Chemistry

MODERN APPROACH TO
Grade XII
Daman Raj Gautam, Ph.D. Bishan Datt Bhatt, Ph.D. Hem Raj Pant, Ph.D.
Associate Professor Assistant Professor Associate Professor
Tribhuvan University Tribhuvan University Tribhuvan University
Amrit Science Campus Tri-Chandra Multiple Campus Pulchowk Engineering Campus
Uday Kumar Jha, M.Sc. Tanka Mukhiya, M.Sc. Deval Prasad Bhattarai, M.Sc.
Former Faculty of Chemistry Assistant Professor Assistant Professor
Tribhuvan University Tribhuvan University Tribhuvan University
Amrit Science Campus Bhaktapur Multiple Campus Amrit Science Campus
MODERN APPROACH TO
Edition: First 2015

Reprint 2016
Reprint 2017
Reprint 2019
Reprint 2020
©Authors
Publishers: Asmita Books Publishers and Distributors (P) Ltd.
Kathmandu, Nepal
Tel. 01-4168216/4168274
website: www.asmitapublication.com.np
facebook: www.facebook.com/asmitapublication
email: [email protected]
Distributors: Kasthamandap Pustak Pasal

Bhotahity, Kathmandu
Tel. 01-4224048
Price: Rs. 795.00
ISBN: 978-9937-615-57-0
Printed: Kathmandu, Nepal
Preface
A dire need of a text book in Chemistry, which can provide an insight of various aspects of
Chemistry in a comprehensive and interactive way, has been felt for a long time. Hence, a noble
strategy for presenting the text in a simple and interesting manner becomes the true motive of the
book for the students to achieve clear chemical concepts and principles. Our dream is to fulfill the
need of students to cover all the curriculum of Chemistry for Higher Secondary Level and
medical and engineering entrance examinations. Having long years of experience in teaching
chemistry in various levels (+2, I. Sc., B. Sc., B. E., Masters and Ph.D. level), it’s our immense
pleasure in bringing out Modern Approach to Chemistry for the students of grade XII of Higher
Secondary Education Board (HSEB), Nepal. This is a text book of chemistry that provides a firm
foundation primarily aimed at delivering concepts of chemistry critically.
Salient features of the book are:
 Simple, systematic and well-organized texts in lucid and comprehensive manner
 Eye catchy photograph in the beginning of each chapter emphasizing its practical
application
 Logically explained concepts
 Illustration of concepts with the help of carefully drawn and well- labeled diagrams
 Well-chosen examples and numerical problems with the solutions
 Proper presentation of reactions with mechanisms for their better understanding
 Exercises along with short and long answer questions from the latest examination question
papers of grade XII of HSEB, Nepal
 Objective questions for different levels of competitive entrance exams
 Self-test questions to evaluate the level of understanding of students after the completion of
each section of different units.
We hope this book will serve its purpose and will be beneficial for chemistry instructors and
students. However, we shall appreciate and acknowledge any valuable suggestions and
constructive criticisms for the betterment of the text book in the best interest of the students.
July 2015
Authors
Syllabus
Full marks: 100 (75T + 25 P)
Pass Marks: 27T + 10P
Teaching Hours: 150T+50P
Course Contents
General & Physical Chemistry (Section A)
Unit 1: Chemical Bonding and Shape of Molecules - 3 teaching hours

 Hybridization and concept of sigma and pi bond  Valence shell Electron Pair Repulsion (VSEPR)
theory  Prediction of molecular geometry (Shape of molecules) on the basis of VSEPR and hybridization.
(BeF2, BF3, NH3, H2O, CH4, H2O, C2H2 C2H4 H2S)
Unit 2: Volumetric Analysis - 8 teaching hours

 Different ways of expressing the concentration of solutions: (i) Molarity, (ii) Normality (iii) Molality
(iv) Gram /Litre (v) Percentage  Titration: (i) Acid-base titration (ii) Redox titration  Primary standard
substances, primary standard solution, secondary standard solution, end point, equivalence point, neutral
point, indicators  Derivation of normality equation  Relation between normality and molarity
 Selection of indicators in acid-base titration and pH curve  Solving related numerical problems
Unit 3: Ionic Equilibrium - 12 teaching hours

 Introduction  Ionization of weak electrolyte (Ostwald's dilution law)  Degree of ionization and
ionization constant  Strength of acids and base interm of Ka, Kb and pKa and pKb values  Acid-base
concept: (i) Arrhenius concept of acids and bases. (ii) Bronsted lowrry concept of acids and bases
(iii) Lewis concept of acids and bases.  Ionization of water, pH and pH scale.  Hydrolysis of salts.
(qualitative concept)  Solubility product principle and its application  Common ion effects and its
application  Application of solubility product principle in qualitative analysis  Buffer Solution (Solving
numerical problems related with solubility, solubility product, pH and pOH)
Unit 4: Electrochemistry - 10 teaching hours

 Introduction  Electrolysis; strong and weak electrolyte  Arrehenius theory of ionization  Faraday's
laws of electrolysis  Criteria of product formation during electrolysis  Electrolytic conduction,
equivalent and molar conductivities  Variation of conductivity with concentration  Electrode potential,
standard electrode potential, standard hydrogen electrode and its applications  Eletrochemical series and
its use to predict the feasibility of redox reactions  Electrochemical cell (Galvanic cell)  EMF of
electrochemical cell in the standard state (Solving related numerical problems)
Unit 5: Energetics of Chemical Reactions - 8 teaching hours

 Introduction, unit of energy  Some thermodynamical terms: system, surrounding, boundary, universe
different types of system, state function, state variables and internal energy  Exchange of energy between
the system and surrounding  Different types of thermodynamic process  The first law of
thermodynamics  Sign convention of heat and work  Enthalpy, enthalpy change in chemical reactions
 Hess's law of constant heat summation  Heat of neutralization, heat of solution, heat of combustion,
heat of vapourization, heat of formation and bond energy (Solving related numerical problems)
Unit 6: Chemical Thermodynamics - 6 teaching hours
 Spontaneous process  Second law of thermodynamics  Entropy and its physical concept  Entropy
change in phase transformation  Entropy and spontaneity  Entropy changes and their calculation
 Gibb's free energy and prediction for the feasibility of reaction  Standard free energy change and
equilibrium constant  Influence of temperature on spontaneous process (Calculation involving in
standard free energy change and equilibrium constant)
Unit 7: Chemical Kinetics - 10 Teaching hours

 Concept of reaction rate  Average rate and instantaneous rate of a reaction  Factors that influences the
rate of reaction  Rate law equation, rate constant and its units  1st order, 2nd order, 3rd order and zero
order reactions  Order and molecularity of a reaction  Integrated rate law for a first order reaction
 Half-life of a reaction (first order)  Explaining the increase in reaction rate with temperature or collision
theory (qualitative concept only)  Concept of activation energy as the energy barrier, activated complex
and effect of catalyst on the rate of reaction (Solving related numerical problems)
Organic Chemistry (Section B)
Unit 8: Aromatic Hydrocarbon - 3 teaching hours

 Definition, characteristics of aromatic compounds, Huckel's rule, structure of benzene, isomerism and
orientation of benzene derivatives  Preparation of benzene from (i) decarboxylation; (ii) phenol;
(iii) ethyne; (iv) chlorobenzene  Physical properties of benzene  Chemical properties of benzene
(i) Addition reaction: hydrogen, halogen and ozone (ii) Electrophilic substitution reactions: nitration,
halogenation, sulphonation, Friedel Crafts alkylation and acylation (iii) Combustion of benzene and uses
Unit 9: Haloalkanes and Haloarenes - 8 teaching hours

Haloalkanes:  Introduction, classification and isomerism  Preparation of monohaloalkanes from
alkanes, alkenes and alcohols  Physical properties of monohaloalkanes  Chemical properties
-Substitution reactions - Elimination reaction (dehydrohalogenation) - Grignard's reactions -Reduction
reactions - Wurtz's reaction  Polyhaloalkane; - Laboratory preparation of trichloromethane from ethanol
and propanone - Physical properties of trichloromethane - Chemical properties: oxidation reduction,
action on Silver Powder, con. nitric acid, propanone, aqueous alkali, Carbylamine reaction, Remer
Tiemann reaction, Iodoform reaction, etc.
Haloarenes: • Preparation of chlorobenzene from (i) benzene (ii) benzene diazonium chloride  Physical
properties  Chemical properties - Low reactivity of haloarene as compared to haloalkane in term of
nucleophilic substitution reaction - Reduction of chlorobenzene - Electrophilic substitution reactions
- Action with Na, Mg and chloral, etc. - uses
Unit 10: Alcohols and Phenols - 10 teaching hours

Alcohols:  Introduction, classification, nomenclature and isomerism  Distinction of primary, secondary
and tertiary alcohol by Victor Meyer's Method  Preparation of monohydric alcohols form (i) haloalkane
(ii) Grignard's reagents using aldehydes and ketones (iii) primary amines (iv) Ester  Industrial
preparation ethanol form: (i) Oxo process ii. Fermentation of sugar (iii) hydroboration of ethane  Physical
properties monohydric alcohols  Chemical properties of monohydric alcohols - Reaction with HX. PX3,
PX5, SOCl2 - Action with reactive metals like Na, K, Li - Esterification process - Dehydration of alcohols. -
Oxidation of primary, secondary and tertiary alcohol with oxidizing agents. - Reduction of alcohols
(Catalyic dehydrogenation) - Laboratory test of ethanol - Absolute alcohol, methylated spirit, rectified
spirit; alcoholic beverage.  Preparation and uses of ethane- 1, 2. diol (glycol)  Preparation and uses of
Propane - 1, 2, 3 triol (glycerol)
Phenols:  Introduction to phenol  Preparation of phenol from (i) chlorobenzene (ii) Diazonium salt and
(iii) benzene sulphonic acid  Physical properties of phenol  Chemical properties - Acidic nature of
phenol - Action with PCl5, PX3, NH3, Zn, Na benzene diazonium chloride and phthalic anhydride -
Acylation reaction, Kolbe's reaction, Reimer Tiemann's reaction - Electrophilic substitution:
halogenation, nitration, sulphonation, brominaiton and Friedal Craft's alkylation - Laboratory test of
phenol - Uses of phenol
Unit 11: Ethers - 4 teaching hours
Aliphatic Ethers:  Introduction, nomenclature classification, isomerism in ether  Preparation of ethers
from (i) alcohol (ii) Williamson's etherification process  Laboratory preparation of ethoxyethane form
ethanol  Physical properties of ether  Chemical properties of ethorxyethane - action with HI, PCl5, con.
HCl, Conc. H2SO4, air and Cl2 - Uses of ethoxyethane 11.2 Aromatic Ether:
Aromatic Ether: - Preparation of methoxybenzene (anisole) - Halogenation, nitration and sulphonation
reactions
Unit 12: Aldehydes and Ketones - 11 teaching hours

Aliphatic Aldehydes and Ketones:  Introduction, structure of carbonyl group, nomenclature and
isomerism in carbonyl compound  Preparation of aldehydes and ketones from (i) Dehydrogenation and
oxidation of alcohol (ii) Ozonolysis of alkenes (iii) Acid chloride (iv) Gem dihaloalkane (v) Catalytic
distillation of fatty acid (vi) Distillaiton of salt of fatty acid (vii) Calalyic hydration of alkynes  Physical
properties  Chemical properties (i) Addition reaction: addition of H2, HCN, NaHSO3 and Grignand's
reagents (ii) Action with ammonia derivatives; NH2OH, NH2-NH2, phenyl hydrazine, semicarbazides and
2, 4-DNP (iii) Reduction properties of aldelydes - Oxidation with Tollen's reagent, Fehling's solution (iv)
Aldol condensation reaction; Clemennson's reduction Wolf- Kishner reduction, Action with PCl5, action
with LiAlH4 (v) Special reaction of methanal; Cannazzaro's reaction, action with ammonia, action with
phenol; formalin and its uses
Aromatic Aldelydes and Ketones: • Preparation of benzaldelyde from toluene • Properties of
benzaldelyde • Important reaction benzaldelyde different form aliphatic aldelydes: - Perkin condensation
- Benzoin condensation - Electrophilic substitution reaction - Cannizzaro's reaction • Preparation of
acetophenone by Friedel Crafts acylation
Unit 13: Carboxylic Acids - 10 teaching hours

Aliphatic Carboxylic Acids: • Introduction, nomenclature, examples • Preparation of monocarboxylic
acids from (i) aldehydes (ii) nitriles (iii) Grignard's reagents (iv) dicarboxylic acid (v) sodium alkoxide.
(vi) trihaloalkanes • Physical properties of monocarboxylic acids • Chemical properties: Action with
alkalies metal oxides, metal carbonates, metal bicarbonates, PCl3, LiAlH4 and dehydration of carboxylic
acid, esterification, halogenation • Effect of constituents on the acidic strength of carboxylic acid
• Laboratory preparation of methanoic acid • Abnormal behaviour of methanoic acid • Uses of
carboxylic acid
Derivatives of Carboxylic Acid:  Nomenclature, preparation and properties of (i) Acid halides (ii) Acid
amides (iii) Acid anhydrides and (iv) Esters
Aromatic Carboxylic Acids:  Preparation of benzoic acid  Physical and chemical properties  Uses of
benzoic acid
Unit 14: Nitrocompounds: - 4 teaching hours

Aliphatic Nitrocompounds (Nitroalkanes):  Introduction and nomenclature  Preparation from
haloalkane and alkane  Physical properties  Reduction of nitroalkane  Uses
Aromatic Nitrocompounds:  Laboratory preparation of nitrobenzene  Physical properties
 Chemical properties - Reduction in different media - Electrophilic substitution reactions - Uses of
nitrobenzene
Unit 15: Amino Compounds (Amines and Aniline) - 7 teaching hours

Aliphatic Amines:  Introduction, nomenclature and classification  Separation of primary, secondary
and tertiary amines by Hoffmann's method  Preparation of primary amines form haloalkane, nitriles,
nitroalkanes and amides  Physical properties  Chemical Properties: basicity of amines, comparative
study of basic nature of 1°, 2° and 3° amines. Reaction of Primary amines with chloroform, conc. HCl, R-X,
RCOX and nitrous acid (NaNO2 / HCl)  Test of 1°, 2° and 3° amines. (nitrous acid test)
Aromatic Amine (Aniline):  Laboratory preparation of aniline  Physical properties  Chemical
properties: basicity of aniline, comparision of basic nature of aniline with aliphatic amines; alkylation,
acylation, diazotization, carbylamine and coupling reaction  Electrophilic substitution: Nitration
sulphonation and bromination  Uses of anitne
Unit 16: Molecules of Life - 8 teaching hours
 Carbohydrates: definition, classification of carbohydrates, various examples of carbohydrate of different
class. structure and glucose and fructose, function of carbohydrates, sugar and non-sugar  Protein:
definition, amino acid, essential and non-essential amino acids, peptide linkage, hydrolysis of amino
acids, denaturation of protein, zwitter ions, functions of amino acids  Nucleic acid: definition, basic
components of nucleic acid; doule helix, difference between RNA and DNA; biological function of nucleic
acid  Lipid: definition, fatty acids, fat as ester of fatty acid and difference between fats and oils, function
of lipid  Enzymes and their functions
Unit 17: Chemistry in Service to Mankind - 10 teaching hours

 Polymer: definition, natural and synthetic polymers, homopolymers and co-polymer, Preparation of
some polymers; PVC, polyethene polystyrene, Teflon, Nylon-66, Bakelite and their uses  Dyes:
definition, natural and synthetic dyes, names and structure of some common drug, drug addiction
 Fertilizer: definition, chemical and organic fertilizers, nitrogen fertilizer, phosphatic fertilizer; fertilizer
as pollution  Pesticides: insecticides, herbicides. weedicides and fungcides (examples and their uses)
Inorganic Chemistry Section C
Unit 18: Heavy Metals -18 teaching hours

General Characteristics of Transition Metals: Copper:  Position in periodic table  Occurrence and
extraction of copper form copper pyrites  Properties and uses  Chemistry of (i) blue vitriol (ii) black
oxide of copper (iii) red oxide of copper. Zinc:  Position in periodic table  Occurrence and extraction of
zinc from zinc blende  Properties and uses of copper  Preparation properties and uses of zinc white and
white vitriol  Galvanization. Mercury:  Occurrence and extraction of Hg from Cinnabar  Properties of
mercury  Mercury poisoning and uses of Hg  Preparation, properties and uses of (i) Calomel
(ii) Corrosive Sublimate. Iron:  Occurrence and extraction  Varieties of Iron  Properties of Iron
 Manufacture of Steel by (i) Bessemer process (ii) Open hearth process  Heat treatment of steel
 Stainless steel  Rusting of iron and its prevention  Uses and biological importance of iron  Structure
and uses of green vitriol, Ferric chloride Mohr's salt. Silver:  Extraction of Silver by cyanide process and
its uses  Preparation and uses of (i) Silver chloride (ii) Silver nitrate
Contents
1. Chemical Bonding and Shape of Molecules
1.1 Introduction 2
1.2 Valence Shell Electron Pair Repulsion (VSEPR) Theory 2
1.2.1 Introduction 2
1.2.2 Postulates of VSEPR Theory 2
1.2.3 Some More Examples 6
1.3 Valence Bond Theory 8
1.3.1 Postulates 8
1.3.2 Types of Overlapping: Types of Covalent Bonds 10
1.3.3 Bonding in H2, HF, F2, O2 and N2 on the Basis of Valance Bond Theory 11
1.3.4 Hybridization 14
1.3.5 Limitations of Valence Bond Theory (VBT) 24
 Solved Questions 26
 Questions 27
 Multiple Choice Questions 28
2. Volumetric Analysis
2.1 Introduction 30
2.2 Concept of Equivalent Weight 30
2.3 Different Ways of Expressing the Concentration of Solution 36
2.4 Primary and Secondary Standard Substances 47
2.5 Law of Chemical Equivalence: Normality Equation 50
2.6 Theoretical Aspects of Volumetric Analysis 52
2.6.2 Titration 56
 Questions 63
 Numerical Problems 64
3. Ionic Equilibrium
3.1 Introduction 68
3.2 Electrolytes and Non-Electrolytes 68
3.3 Arrhenius Theory of Ionization 69
3.4 Factors Affecting the Degree of Ionization 69
3.5 Degree of Ionization () and Ionization Constant (K): Ostwald Dilution Law 70
3.6 Ionization Constant and Relative Strength of Acids and Bases 72
3.7 Autoionization of Water 74
3.8 pH and pH Scale 74
3.9 Buffer Solution 76
3.10 Concept of Acids, Bases and Salts 78
3.10.1 Arrhenius Concept of Acid-Base 78
3.10.2 Bronsted-Lowry Concept of Acid-Base 79
3.10.3 Lewis Concept of Acid-Base 81
3.11 Salt Hydrolysis 82
3.12 Common Ion Effect 84
3.13 Solubility Product and Solubility Product Principle 86
 Questions 92
4. Electrochemistry
4.1 Introduction 96
4.2 Electronic and Electrolytic Conductors 96
4.3 Electrolytes: Strong and Weak Electrolytes 97
4.4 Arrhenius Theory of Ionization 97
4.5 Electrolytic Cells and Voltaic Cells 97
4.6 Electrolysis and Criteria of Product Formation 97
4.7 Quantitative Aspect of Electrolysis 102
4.7.1 Faraday's First Law of Electrolysis 102
4.7.2 Faraday's Second Law of Electrolysis 103
 Solved Numerical Problems 105
 Questions 108
4.8 Electrolytic Conduction 110
4.9 Variation of Conductivities of Electrolyte Solution with Dilution 117
4.10 Effect of Temperature on Conductance 118
4.11 Kohlrausch's Law of Independent Migration of Ions 119
 Questions with Answers 120
 Questions 120
 Numerical Questions 120
4.12 Galvanic Cell 121
4.12.2 Construction of Galvanic Cell 121
4.12.3 Salt Bridge 123
4.13 Electrode Potential and Standard Electrode Potential 125
4.14 Electrochemical Series (ECS) 129
4.15 Nernst Equation 132
4.16 Some Commercial Cells 134
 Solved Numerical Problems 138
 Questions 139
5. Energetics of Chemical Reaction

5.1 Introduction 144
5.2 Some Thermodynamic Terms 144
5.3 State of Equilibrium 150
5.4 Heat and Work (Modes of Energy Transfer) 152
5.5 Internal Energy (E) 153
5.6 The First Law of Thermodynamics 153
5.7 Enthalpy (Greek en = in; thalpos = heat) 155
5.8 Enthalpy 158
5.9 Hess's Law of Constant Heat Summation 163
 Questions 166
6. Chemical Thermodynamics
6.2 Spontaneous and Non-spontaneous Process 170
6.3 Driving Forces for Spontaneity 171
6.4 Measure of Randomness and Concept of Entropy 173
6.5 Probability and Entropy 174
6.6 Entropy Change 175
6.7 Criteria of Spontaneity in Terms of Entropy Change (Entropy and Spontaneous Process) 179
6.8 Limitation of the First Law of Thermodynamics and Dawn of Second Law of
Thermodynamics 181
6.9 The Third Law of Thermodynamics 182
6.10 Concept of Free Energy 182
 Questions 188
7. Chemical Kinetics
7.2 Rate of Chemical Reaction 192
7.3 Concept of Activation Energy and Threshold Energy 195
7.4 Theory of Chemical Reaction 195
7.5 Factors Affecting the Rate of Chemical Reaction 198
7.6 Types of Reaction 202
7.7 Concept of Rate Determining Step 202
7.8 Molecularity of Reaction 203
7.9 Law of Mass Action and the Rate Law Equation 204
7.10 Order of Reaction 205
7.10.1 Zero-Order Reaction 208
7.10.2 First Order Reaction 211
7.10.3 Pseudo-Order Reaction 214
7.10.4 Second Order Reaction 214
7.10.5 Third Order Reaction 217
7.11 Methods of Determination of Order of Reaction 218
 Some Solved Numerical Problems 219
 Questions 223
8. Aromatic Hydrocarbons
8.2 Characteristics of Aromatic Compounds 229
8.3 Nomenclature of Benzene Derivatives 229
8.4 Structure of Benzene 231
8.5 Huckel's (4n+2) Rule for Aromaticity (Theoretical Criteria for Aromatic Character) 235
8.6 Isomerism in Benzene Derivatives 238
8.7 Commercial Source of Benzene 239
8.8 Preparation of Benzene 240
8.9 Physical Properties 241
8.10 Chemical Properties 241
8.11 Uses of Benzene 247
8.12 Electrophilic Aromatic Substitution Reactions in Substituted Benzene 248
 Questions 251
9. Haloalkanes and Haloarenes

9.1 Haloalkanes 254
9.1.2 Monohaloalkanes (Alkyl halides) 254
9.1.3 Dihaloalkanes 277
9.1.4 Trihaloalkales: Chloroform 279
9.1.6 Tetrahaloalkane: Carbon tetrachloride 287
9.2 Haloarenes (Aryl halides) 287
9.2.2 General Methods of Preparation 288
9.2.3 Physical Properties 291
9.2.4 Chemical Properties 291
9.2.5 Some Commercially Important Halogen Derivatives of Hydrocarbons 297
 Questions 300
10. Alcohols and Phenols

10.1 Alcohols 304
10.1.2 Classification of Aliphatic Alcohols 304
10.1.3 Nomenclature 306
10.1.4 Isomerism in Monohydric Alcohols 307
10.1.5 General Methods of Preparation of Monohydric Alcohols 307
10.1.6 Industrial Method of Preparation of Alcohols 311
10.1.7 Physical Properties of Alcohols 314
10.1.8 Important Terms Used in Alcohol Industries 315
10.1.9 Chemical Properties of Alcohols 316
10.1.10 Distinction of Primary, Secondary and Tertiary Alcohols 324
10.1.11 Laboratory Test for Ethanol (Already discussed ) 326
10.1.12 Dihydric Alcohols 326
10.1.13 Trihydric Alcohols 327
 Some Solved Questions 328
 Questions 329
10.2 Phenols 331
10.2.2 Classification 331
10.2.3 Methods of Preparation 333
10.3 Tests for Phenols 346
10.4 Uses of Phenol 346
 Questions 347
11. Ethers
11.1 Aliphatic Ethers 350
11.1.3 Isomerism 351
11.1.7 Diethyl Ether 357
11.1.8 Laboratory Preparation of Diethyl Ether 358
11.1.11 Uses 359
11.2 Aromatic Ethers 359
11.2.2 Preparation of Methoxybenzene/Anisole 360
 Questions 363
12. Aldehydes and Ketones

12.1 Aliphatic Aldehydes and Ketones 366
12.1.2 Structures of Carbonyl Group 367
12.1.3 Nomenclature of Carbonyl Compounds 368
12.1.4 Structural Isomerism in Aliphatic Carbonyl Compounds 369
12.1.5 General Methods of Preparation of Aliphatic Aldehydes and Ketones 370
12.1.8 Uses of Aldehydes and Ketones 391
12.2 Aromatic Aldehydes and Ketones 392
12.2.2 Preparation of Aromatic Aldehyde (Benzaldehyde) 392
12.2.3 Preparation of Aromatic Ketones (Acetophenone) 393
12.2.4 Physical Properties of Benzaldehyde and Acetophenone 394
12.2.5 Chemical Properties of Benzaldehyde and Acetophenone 394
 Questions 400
13. Carboxylic Acids and Their Derivatives
13.1 Aliphatic Carboxylic Acids 404
13.1.3 General Methods of Preparation of Monocarboxylic Acids 408
13.1.4 Physical Properties of Monocarboxylic Acids 412
13.1.5 Chemical Properties of Monocarboxylic Acids 413
13.1.6 Laboratory Preparation 425
13.1.7 Abnormal Behaviour of Methanoic Acid (Comparison of Properties of Formic Acid
with Acetic Acid) 427
13.1.8 Uses of Carboxylic Acids 430
13.2 Aromatic Carboxylic Acids 430
13.2.1 Effect of substituents on acidity of carboxylic acids 433
13.3 Functional Derivatives of Carboxylic Acids 435
13.3.1 Acid Halides (Acyl Halides) 437
13.3.2 Acid Anhydrides 441
13.3.3 Esters 444
13.3.4 Acid Amides 449
 Questions 453
14. Nitro Compounds

14.1 Aliphatic Nitro Compounds (Nitroalkanes) 458
14.1.2 Classification 458
14.1.4 Isomerism 459
14.1.8 Differences between Nitroalkanes and Alkyl Nitrites 463
14.2 Aromatic Nitro Compounds 464
14.2.1 Introduction and Nomenclature 464
14.2.2 Preparation of Aromatic Nitro Compounds 465
14.3 Nitrobenzene (Oil of Mirbane) 465
14.3.1 Laboratory Preparation of Nitrobenzene 465
14.3.4 Uses of Nitrobenzene 471
 Questions 473
15. Amines
15.2 Classification 477
15.3 Structure of Amines 477
15.4 Nomenclature 478
15.5 Salts of Amines 479
15.6 Isomerism 480
15.7 General Methods of Preparation 481
15.8 Separation of Amines 488
15.9 Physical Properties 489
15.10 Chemical Properties 490
15.11 Aromatic Amine (Aniline) 499
15.11.2 Preparation of Aniline 500
15.11.3 Laboratory Preparation of Aniline 501
15.11.4 Physical Properties of Aniline 504
15.11.5 Chemical Properties of Aniline 504
15.11.6 Uses of Aniline 509
15.12 Test for Amines 509
15.13 Diazonium Salts and their Reactions 510
 Questions 517
16. Molecules of Life

16.1 Carbohydrates 520
16.1.2 Classification of Carbohydrates 520
16.1.3 Meaning of (+) and (-): Optically Active Compounds 523
16.1.4 D and L Designations: Relative Configuration 523
16.1.5 (+)-Glucose (Dextrose, Grape Sugar, Blood Sugar) 524
16.1.6 (-)-Fructose (Laevulose, Fruit Sugar) 526
16.1.7 Sucrose (Common Table Sugar) 527
16.1.8 Functions of Carbohydrates 528
16.1.9 Test for Carbohydrates: Molicsh's Test 528
16.2 Proteins 529
16.2.2 Amino Acids 529
16.2.3 Isoelectric Point of Amino Acids 533
16.2.4 Peptides and Peptide Bond 533
16.2.5 Classification of Proteins 535
16.2.6 Structure of Proteins 536
16.2.7 Denaturation of Proteins 536
16.2.8 Enzymes 537
16.2.9 Functions of Proteins 537
16.2.10 Some Visual Tests of Proteins 538
16.3 Nucleic Acids (DNA and RNA) 538
16.3.2 Components of Nucleic Acids 538
16.3.3 Double Helix Structure of DNA 540
16.3.4 Differences between RNA and DNA 541
16.3.5 Biological Functions of Nucleic Acids 541
16.4 Lipids 542
16.4.2 Simple Lipids (Fats and Oils) 542
16.4.3 Differences between Fats and Oils 544
16.4.4 Hydrogenation of Oil 545
16.4.5 Hydrolysis of Fats 545
16.4.6 Phospholipids 547
16.4.7 Waxes 547
16.4.8 Functions of Lipids 547
 Questions 549
17. Chemistry in the Service of Mankind

17.1 Polymers 554
17.1.1 Monomer, Polymer and Polymerization 554
17.1.2 Classification of Polymers 554
17.1.3 Addition and Condensation Polymers 554
17.1.4 Homopolymers and copolymers 559
17.1.5 Natural and Synthetic Polymers 559
17.1.6 Fibers, Elastomers, Thermoplastics and Thermosetting Polymers 560
17.2 Dyes 562
17.2.2 Structural features 562
17.2.3 Classification of Dyes 563
17.2.4 Classification Based on the Source 563
17.2.5 Classification Based on the Chemical Constitution 563
17.2.5 Classification Based on the Mode of Application 564
17.3 Drugs 566
17.3.2 Classification of Drugs 567
17.3.3 Drugs Addiction 571
17.4 Chemical Fertilizers 572
17.4.2 Classification of Fertilizers 573
17.4.3 Nitrogen Fertilizers 573
17.4.4 Phosphorus Fertilizers 573
17.4.3 Potash Fertilizers 574
17.4.4. Mixed (NPK) Fertilizers 574
17.4.5 Fertilizers as Pollutants 574
17.5 Pesticides 575
17.5.2 Classification of Pesticides 575
17.5.3 Pesticides, Environmental Pollution and Human Health 579
 Questions 580
18. Heavy Metals
18.1 Introduction to Transition Metals 584
18.2 Copper 585
18.2.2 Position of Copper in Periodic Table 586
18.2.3 Occurrence 586
18.2.4 Extraction of Copper from Copper Pyrites 586
18.2.7 Uses of Copper 593
18.2.8 Compounds of Copper 593
 Questions 598
18.3 Zinc 600
18.3.2 Position of Zinc in Periodic Table 600
18.3.3 Occurrence of Zinc 600
18.3.4 Extraction of Zinc 601
18.3.5 Properties of Zinc 604
18.3.6 Uses of Zinc 606
18.3.7 Zinc White or Zinc Oxide (ZnO) 606
18.3.8 White Vitriol, ZnSO4.7H2O 607
18.3.9 Galvanization 609
 Questions 610
18.4 Mercury 612
18.4.2 Occurrence of Mercury 612
18.4.3 Extraction of Mercury from Cinnabar 612
18.4.4 Physical Properties of Mercury 614
18.4.5 Chemical Properties of Mercury 615
18.4.6 Uses of Mercury 616
18.4.7 Mercury Poisoning: Health Hazards and Environmental Pollution 616
18.4.8 Calomel (Mercurous chloride or Mercury (I) chloride), Hg2Cl2 616
18.4.9 Corrosive Sublimate (Mercuric Chloride or Mercury (II) Chloride), HgCl2 618
 Questions 620
18.5 Iron 621
18.5.3 Extraction of Iron 621
18.5.4 Different forms of Iron 625
18.5.5 Properties of Iron 626
18.5.6 Some Compounds of Iron 628
18.5.7 Rusting of Iron 633
18.5.8 Steel 636
 Questions 642
18.6 Silver 644
18.6.2 Extraction of Silver from Argentite ore Using Cyanide Process 644
18.6.3 Silver Nitrate AgNO3 647
 Questions 650
 Bibliography 651
 Index 653
Chemical Bonding and
Shape of Molecules
Ball and stick models showing geometries of different molecules.

2 Modern Approach to Chemistry-II
1.1 Introduction
In molecules, atoms are held together by a force of attraction called chemical bond. Ionic bonds are
non-directional i.e., an ion can attract oppositely charged ion in any direction. However, covalent
bonds are directional. Hence, covalent molecules have particular bond angles and shapes. In the case
of diatomic covalent compounds, the molecules are always linear. The molecule having three or
more atoms possesses particular shape. The shape of a particular molecule is determined by
specific arrangement of atoms in it and the bond angles. The shape of molecule depending on the
arrangement of atoms within the molecule in space is called geometry of the molecule.
Depending upon the different orientations of atoms with respect to each other and central atom,
molecules have different geometries.
The modern techniques like X-ray diffraction (XRD), electron diffraction, spectroscopy etc. are used
to determine the geometry of molecules. In order to predict the geometry of molecules and various
aspects of bonds, the following theories have been proposed.
i. Valence Shell Electron Pair Repulsion (VSEPR) Theory
ii. Valance Bond Theory (VBT)
iii. Molecular Orbital Theory (MOT)
1.2 Valence Shell Electron Pair Repulsion (VSEPR) Theory

1.2.1 Introduction
Valence Shell Electron Pair Repulsion (VSEPR) theory is a simple theory to predict and explain the
shape and bond angles in a number of simple covalent molecules and ions. This theory was
proposed by Sedgwick and Powell in 1940 initially and developed by Gillespie and Nyholm in 1957
as VSEPR theory. The main postulates of this theory may be summarized as follows;
1.2.2 Postulates of VSEPR Theory

1. The shape of a covalent molecule or ion is determined by the total number of electron pairs
present in the valence shell of the central atom in the molecule. The electron pairs remain
arranged around the central atom in space so as to get the minimum electrostatic repulsion
hence, determines the shape.
Examples:
i. Beryllium chloride (BeCl2): Here, the central atom Be has two bond pairs in its valence shell.
For this molecule, there may a number of possible structures. Some of them are;
Cl Cl Repulsion
Repulsion Repulsion
Cl Be Cl Cl Be Cl
Cl B
Be Cl
I III
II Linear
Lewis structure 'V' shaped 'L' shaped
Repulsion of bond pairs: I > II > III
The actual structure is the one in which the repulsion of electron pairs is minimum. This is in
structure (III). Hence, BeCl2 is linear molecule.
Chemical Bonding Unit 1 3
ii. Boron trifluoride (BF3): In BF3, the central atom B has three bond pairs in its valence shell. The
repulsion of three bond pairs is minimum in trigonal planar geometry with bond angle 120º.
Hence, BF3 is trigonal planar.
F
F F
B B F
F
F
Lewis structure Trigonal planar shape of BF3.
iii. Methane (CH4): In CH4, the central atom carbon has four electron pairs. All are bond pairs. The
repulsion of four bond pairs is minimum in tetrahedral geometry with bond angle 109º28'.
Hence, CH4 has tetrahedral geometry.
H
H
H C
C H
H H
H H
Tetrahedral geometry of CH4
Lewis structure
Table 1.1: Molecular geometry (ideal shape) on the basis of VSEPR theory if central atom has only bond
pairs. Here, A = central atom and B = atom bonded to central atom.
No. of e- pairs in
Ideal shape of molecule Bond angle Examples
the valence shell
B A B
2 180° BeF2, BeCl2
Linear
B
A B
3 120º BF3, BCl3
B
Trigonal planar
A 109º 28’
4 CH4, CCl4, NH4⊕
(109.5°)
B B
B
Tetrahedral
B
B
120°
A B
5 90º, 120º PCl5
B B
Trigonal bipyramidal
B
B B
A
6 90º SF6
B B
B
Octahedral
B
B
B
A B
7 72°
72º, 90º IF7
B
B
B
Pentagonal bipyramidal
2. If the central atom has lone pair(s), along with bond pairs, the ideal shape is distorted to give
different bond angle than expected. This is because a lone pair (lp) occupies more space
around the central atom than the bond pair (bp) since lone pair is attracted by one nucleus
and the bond pair is shared between two nuclei. Hence, repulsion of electron pairs around
the central atom is in the order: lp-lp > lp-bp > bp-bp.
Examples:
i. Ammonia (NH3): In NH3, the central atom contains four effective electron pairs but only three
of them are bonded pairs. Since one of the electron pair is the lone pair, the molecule will have
trigonal pyramidal geometry. Since, lone pair exerts greater repulsion than the bonded pair, the
bond angle is less than expected in regular tetrahedral bond angle (109°28'). Actual bond angle
is found to be 107.5°.
N
lp-bp lp-bp repulsion

107.5°
H N H H
N H
107°48'
H
H bp-bp bp-bp
H H Trigonal pyramidal shape of NH3
Lewis structure H
ii. Water (H2O): In H2O, the central atom oxygen has four electron pairs hence, expected geometry
is tetrahedral but there are two lone pairs and two bond pairs. Since there are two lone pairs of
electrons around central atom, the actual geometry is bent or angular. Since lone pair exerts
greater repulsion than the bonded pairs, the bond angle is less than the regular tetrahedral bond
angle (109°28'). Actual bond angle is found to be 104.5°.
lp-lp
O O
lp-bp lp-bp repulsion
104.5°
bp-bp H H
H H
Molecular geometry of H2O Bent/angular shape of water
Bond angle = 104°28'
3. The electronegativity of atoms in the molecule also affects the bond angle of the molecule, in
the iso-structural molecules (molecules having same number of bonded and lone pairs
around the central atom).
a. As the electronegativity of the central atom increases, the bond pairs of electrons are pulled
more towards the central atom due to which repulsion between bond pairs increases and
bond angle increases.
Example: H2O and H2S
S O
H H H H
Less repulsion between bond pairs More repulsion between bond pairs
Bond angle = 92.5° Bond angle = 104.5°
Electronegativity of oxygen is greater than that of sulphur.
Table 1.2: Variation of bond angle with change in electronegativity (EN) of central atom
Group 15 Bond angle EN of central atom Group 16 Bond angle
NH3 107°48’ Decreases H2O 104°28’
PH3 93°36’ H2S 92°
AsH3 91°48’ H2Se 91°
SbH3 91°18’ H2Te 90°
b. As the electronegativity (EN) of the atoms bonded to the central atom increases, the bond
pairs of electrons are pulled towards themselves by electronegative atoms due to which
repulsion between bond pairs decreases. As a result, bond angle decreases.
Example: H2O and OF2
O O
H F F
H
More repulsion between bond pairs Less repulsion between bond pairs
Bond angle = 104.5° Bond angle = 102°
Table 1.3: Variation of bond angle with change in electronegativity of atom bonded to central atom
Group 17 Bond angle EN of surrounding atoms
PF3 97°
PCl3 100°
PBr3 101.5°
PI3 102° Decreases
4. The double or triple bond is taken as one effective electron pair, however, the repulsion is in
the order: triple bond> double bond> single bond
Self Test
1.1 Predict the shape of following molecules on the basis of VSEPR theory.
i. BF3 ii. CH4 iii. CCl4 iv. PCl5 v. SF6
1.2 Predict the shape of following molecules on the basis of VSEPR theory.
i. PCl3 ii. NH3 iii. PH3 iv. H2O v. H2S vi. OF2
1.3 BF3 is trigonal planar but PF3 is trigonal pyramidal, explain.
1.4 Arrange CH4, NH3 and H2O in the decreasing order of their bond angle, on the basis of VSEPR
theory.
1.5 How do you account for the fact that bond angle in H2O is greater than that in H2S?
1.6 How do you account for the fact that bond angle in PF3 is smaller than that in PCl3?
1.7 Draw the molecular geometries of NH3 and NF3. Which one is expected to have smaller bond
angle?
1.2.3 Some More Examples

i. Shape of Phosphorous Pentachloride (PCl5): In PCl5, the central atom phosphorous has five
electrons pairs. The repulsion of five electron pairs is minimum when they are arranged in
trigonal bipyramidal shape. Hence, PCl5 is trigonal bipyramidal in shape. However, trigonal
bipyramid is not a regular structure. Here, two axial bonds are longer than three equatorial
bonds.
Cl Cl
Cl
Cl Cl
P
120°
Cl Cl P Cl
Cl Cl
+ +
ii. Shapes of NH4 , NH3 and NH2¯: NH4 is regarded as being formed by adding H+ to NH3 by
coordinate covalent bond. Hence, the central atom nitrogen has four bond pairs in its valence
shell. The repulsion of four bond pairs is minimum when bond angle is 109°28’ with tetrahedral
geometry. Hence, NH4+ is tetrahedral.
In NH3, the central atom nitrogen has four electron pairs; three bond pairs and one lone pair.
The repulsion between lp and bp is greater than bp and bp. Hence, bond angle in NH3 is
smaller than the normal tetrahedral value the shape is trigonal pyramidal.
NH2¯ is regarded as being formed by removing H+ from NH3. Hence, the central atom nitrogen
has two lone pairs and two bond pairs in its valence shell. The repulsion of electron pairs
around the central atom is in the order of lp-lp > lp-bp > bp-bp. Hence, bond angle in NH2¯ is
still smaller than that in NH3 and it is bent or angular shaped. Hence, bond angle is in the order
NH4+ > NH3 > NH2¯.

+ –
H
N
N N
H H H H H H
H H
Shape of NH4+
Shape of NH3 Shape of NH2¯
Tetrahedral
Trigonal pyramidal Bent or angular
iii. Examples involving four electron pairs in the valence shell of central atom: If the central atom
has four electron pairs in its valence shell, three different shapes are possible; tetrahedral,
trigonal pyramidal and bent or angular depending upon number of lone pair as in table 1.4.
Table 1.4: Shapes of molecules having four electron pairs.

B
A A
Molecular Geometry A
B less than less than
B
B 109.5° B 109.58° B 109.58° B
B
B
Total electron pairs 4 4 4
Bond pairs 4 3 2
Lone pairs 0 1 2
Bond angle 109°28’ Less than 109°28’ Less than 109°28’
Shape Tetrahedral Trigonal pyramidal Bent or angular
Type of molecule AB4 AB3L AB2L2
Examples CH4, CHCl3, CCl4, SiF4 NH3, NF3, PH3, PX3 H2O, H2S, OF2, SCl2
iv. Examples involving five electron pairs in the valence shell of central atom: If the central atom
has five electron pairs in its valence shell, the structure is trigonal bipyramidal. If lone pairs occur
in a trigonal bipyramid, they will be located in the equatorial positions rather than the apical
positions, since this arrangement minimizes the electrostatic repulsions
Table 1.5: Shapes of molecules having five electron pairs.

Molecular B B B
Geometry B B
120°
120°
120°
B A A
120°
A B A B
B B B B B
B
Bond pairs 5 4 3 2
Lone pairs 0 1 2 3
shape Trigonal bipyramidal Seesaw T shaped linear
Type of AB5 AB4 L AB3L2 AB2L3
molecule
Examples PX5 SF4,TeCl4 ClF3 –
XeF2, I3 , ICl2
–
v. Examples involving six electron pairs in the valence shell of central atom: If the central atom
has six electron pairs in its valence shell, the structure is octahedral.
Table 1.6: Shapes of molecules having six electron pairs.

B B
B B B B B B
A A A
B B B B B B
B
Bond pairs 6 5 4
Lone pairs 0 1 2
shape Octahedral Square pyramidal Square planar
Type of AB6 AB5L AB4L2
molecule
Examples SF6 IF5, ClF5, BrF5 XeF4, ICl4
–
Self Test
1.8 Predict the geometry of the following molecules on the basis of VSEPR theory.
i. ClF3 ii. XeF2 iii. XeF4 iv. SF4
1.9 Why do lone pair(s) occupy equatorial positions in case of five electrons pairs containing
molecules?
1.3 Valence Bond Theory

Valence bond theory (VBT) was proposed by Heitler and London in 1927 and improved by Linus
Pauling to explain the nature of bonding in covalent molecules. This theory is based on wave
mechanical model of atom. According to this theory, a covalent bond is formed by overlapping of
atomic orbitals having unpaired electrons. The main postulates of this theory are as follows;
1.3.1 Postulates
1. Half filled atomic orbital of one atom overlaps with half filled atomic orbital of another atom to
form a covalent bond.
2. Atomic orbitals undergoing overlap must be sufficiently close to each other with proper
alignment.
3. The strength of bond formed depends upon the extent of overlapping of atomic orbitals.
Greater the overlapping of atomic orbitals, stronger the covalent bond formed.
4. Overlapping lowers the energy of the molecule and excess energy is released. The energy
released per mole is called stabilization energy or bond energy and the equilibrium distance
between two nuclei of bonding atoms is bond length.
5. Number of unpaired electrons in an atom can increase at the time of reaction due to the
excitation of electron from one orbital to the orbital of slightly higher energy.
6. Number of unpaired electrons in ground state or excited state of an atom is called covalency of the
element.
Formation of Hydrogen Molecule

In valence bond theory, the stability of a – Repulsion –
molecule is explained in terms of following Attraction
interactions. +
+ Repulsion
i. Electrons-nucleus attractive interaction
ii. Electron-electron repulsive interaction
Atom HA Atom HB
iii. Nucleus-nucleus repulsive interaction
The attractive and repulsive interactions oppose each other. When attractive interactions are stronger
than repulsive interactions, certain amount of energy is released. Due to lowering of energy, the
molecule becomes stable. The qualitative treatment of valence bond theory can be understood by
describing the formation of hydrogen molecule.
Consider two hydrogen atoms; HA and HB at large separation before formation of bond to each other.
There is no interaction between them. The total energy is equal to sum of energies of two H atoms
(location A in the figure)
When two H atoms approach each other, the attractive and repulsive force begin to operate; electron
in an atom HA is attracted by the nucleus of another atom HB and electron in an atom HB is
attracted by the nucleus of another atom HA. Similarly, there is repulsion between the two nuclei.
The attractive interaction decreases energy. Therefore, when two atoms approach each other, energy
of system goes on decreasing.
When two H atoms HA and HB come still closer there exist electron -electron and nucleus-nucleus
repulsions which tend to increase energy. As large as the attractive interaction is stronger than
repulsion, the energy of the system continue to decrease.
At certain distance between the two
atoms, the attractive and repulsive
interaction balance each other and the
energy of system attains a minimum
value (location C). At this state, the two H 0 kcal
atoms have a fixed distance between Bond energy A
them and form a stable H2 molecule. This –104 kcal
inter-nuclear distance when the energy of

Potential energy →
the system is minimum is called bond B

length which is 0.74Å in H2.
Bond length
If the two H atoms in a H2 molecule 0.74 Å
further come closer then the bond length
C
(0.74Å), the repulsive force predominates
and energy of system increases sharply. 0Å Internuclear distance →
At point C, H2 has 104 kcal less energy
Fig 1.1: Energy profile diagram for formation of H2 molecule
than uncombined state at point A.
Hence, 104 kcal energy is required to separate H atoms from H2. This energy is called bond energy of
H2.
1.3.2 Types of Overlapping: Types of Covalent Bonds

There are two types of covalent bonds depending upon type of overlapping of orbitals; sigma bond
and pi bond.
a. Sigma bond (σ - bond): It is a covalent bond formed by end to end (head on or axial)
overlapping of half filled atomic orbitals. Overlapping takes place along the internuclear axis.
The extent of overlapping is large and the bond formed is strong. It is formed by following
types of overlapping;
i. s-s overlapping
+ or internuclear axis
s-orbital s-orbital σ- bond σ- molecular orbital
ii. s-p overlapping
+ or
internuclear axis
s-orbital p-orbital σ- bond σ- molecular orbital
iii. p-p overlapping
+ or
px-orbital px-orbital σ- bond σ- molecular orbital
where, x is taken as inter-nuclear axis.

b. Pi bond (π - bond): It is a covalent bond formed by sideways or lateral overlapping of half filled
atomic orbitals. Overlapping takes place perpendicular to the internuclear axis. The extent of
overlapping is small and the bond formed is weak. It is formed by following types of
overlapping;
Internuclear axis
+ or
(nodal plane)
p-orbital p-orbital π-bond

Differences between σ-bond and π bond

Sigma (σ) bond Pi (π) bond
i. It is formed by end to end, head on or axial i. It is formed by sideways or lateral
overlapping of half filled orbitals. overlapping of half filled orbitals.
ii Overlapping of orbitals takes place along the ii. Overlapping of orbitals takes place
internuclear axis. perpendicular to the internuclear axis.
iii. The extent of overlapping is large so the bond iii. The extent of overlapping is small so the
formed is strong. bond formed is weak.
iv. It is symmetrical along the internuclear axis iv. It consists two lobes on either side of
so free rotation about sigma is possible. internuclear axis and free rotation about pi
v. It may be present alone or along with pi bond is restricted.
bonds. v. π bond cannot be formed alone. It is formed
vi. It is formed by overlapping of all types of when σ bond is present.
orbitals; s-s, s-p, p-p orbitals. vi. It is formed by other than s orbitals.
Self Test
1.10 Calculate the number of σ and π bonds in the following molecules
H
H—C = C—H H—C ≡ C—H C
H H Ethyne H C C H
a. b. (Acetylene) c.
Ethene H C C H
(Ethylene) C
H—C = C—C = C—H H
H—C = C = C—H
Benzene
d. H H H H e. H H
Buta-1,3-diene Allene
1.3.3 Bonding in H2, HF, F2, O2 and N2 on the Basis of Valance Bond Theory
1. Hydrogen (H2) molecule: Hydrogen atom has one half filled orbital (1s1). Therefore, it can form
a single covalent bond. In the formation of H2, half filled 1s orbital of one hydrogen atom
overlaps with half filled 1s orbital of another hydrogen atom forming a sigma bond.
1s
H=
σ bond
H=
1s
s-s overlapping
+
1s 1s Orbital overlap
H H picture of H2
2. Hydrogen fluoride (HF) molecule: Hydrogen atom has one half filled orbital (1s1). Fluorine
atom has one half filled orbital (1s2 2s2 2px2 py2 pz1). So, each can form a single covalent bond. In
the formation of HF, half filled 1s orbital of one hydrogen atom overlaps with half filled 2pz
orbital of fluorine atom forming a sigma bond (here, Z-axis is considered as inter-nuclear axis).
1s
H=
σ bond
F=
2px 2py 2pz
s-p overlapping
+
1s 2pz Orbital overlap

H F picture of HF
3. Fluorine (F2) molecule: Fluorine atom has one half filled orbital (1s2 2s2 2px2 py2 pz1). So, it can
form a single covalent bond. In the formation of F2, half filled 2pz orbital of one fluorine atom
overlaps with half filled 2pz orbital of another fluorine atom end to end forming a sigma bond
(here, Z-axis is considered as inter-nuclear axis).
2px 2py 2pz
F=
σ bond
F=
2px 2py 2pz
p-p head on overlapping

+
2pz 2pz Orbital overlap

F F picture of F2
4. Oxygen (O2) molecule: Oxygen atom has two half filled orbitals (1s2 2s2 2px2 py1 pz1). So, it can
form two covalent bonds or a double bond. In the formation of O2, half filled 2pz orbital of one
oxygen atom overlaps with half filled 2pz orbital of another oxygen atom end to end forming a
sigma bond. The remanding half filled 2py orbital of oxygen atom which is perpendicular to its
2pz orbital overlaps with that of another oxygen atom laterally forming a pi bond. Hence, O2 has
a double bond, a sigma bond and a pi bond. Sigma bond is strong since overlapping of orbitals
is more and pi bond is weak since overlapping of orbitals is less.
2px 2py 2pz 2py 2py
O=
π bond σ bond
2pz 2pz
O=
2px 2py 2pz
(here, z is taken as internuclear axis) Orbital picture of O2
π
π electron cloud σ electron cloud
5. Nitrogen (N2) molecule: Nitrogen atom has three half filled orbital (1s2 2s2 2px1 py1 pz1). So, it can
form three covalent bonds or a triple bond. In the formation of N2, half filled 2pz orbital of one
nitrogen atom overlaps with half filled 2pz orbital of another nitrogen atom end to end forming a
sigma bond. The remanding half filled 2py orbital which is perpendicular to 2pz orbital overlaps
with that of another nitrogen atom laterally forming a pi bond. The remaining half filled 2px
orbital which is perpendicular to 2pz orbital overlaps with that of another nitrogen atom
laterally forming another pi bond. Hence, N2 has a triple bond, a sigma bond and two pi bond.
Sigma bond is strong since overlapping of orbitals is more and pi bond is weak since
overlapping of orbitals is less.
2px 2py 2pz 2py

2py
N= 2px 2px
π
N=
π π σ bond
2pz 2pz
N σ
π N
2px 2py 2pz
Orbital picture of N2
Self Test
1.11 What are the differences between a sigma bond and a pi bond?
1.12 Draw the orbital picture of following molecules and indicate the number of unpaired electrons
according to VBT.
i. HCl ii. Cl2 iii. O2 iv. N2
1.3.4 Hybridization
The concept of hybridization was introduced to explain the nature of bonding and geometry of
molecules especially in polyatomic molecules. According to this concept, atomic orbitals or orbitals
wave function, undergo mixing to form new orbitals of equivalent energy and identical shape and
size called hybrid orbitals which then participate in bonding. The process is called hybridization.
Characteristics of hybridization
1. Atomic orbitals only in an atom undergo hybridization. It is not mixing of atomic orbitals of
different atoms.
2. Atomic orbitals undergoing hybridization must have nearly equal energy. They should not
have very large difference in their energy.
3. Full filled, half filled as well as empty atomic orbitals undergo hybridization.
4. The number of hybrid orbitals formed is equal to total number of orbitals undergoing
hybridization.
5. Hybrid orbitals formed in a hybridization have new character and are equivalent in energy and
identical in shape and size and take the geometry so as to get minimum electrostatic repulsion.
6. Hybrid orbital has one lobe enlarged, so it overlaps more effectively. Hence, a hybrid orbital
forms stronger bond than the original atomic orbitals.
Hence, hybridization is the process of mixing atomic orbitals of nearly equal energy in an
atom to form new orbitals of equivalent energy and identical shape and size called hybrid
orbitals.
Types of hybridization
There are various types of hybridizations depending on nature and number of atomic orbitals
involved. The s and p orbitals undergo three types of hybridization. Only there types of
hybridizations (sp, sp2 and sp3) will be discussed here through d orbitals can also take part in
hybridization.
1. sp hybridization 2. sp 2 hybridization 3. sp 3 hybridization
1. sp hybridization ( Linear or diagonal hybridization): It is the process of mixing one s and one p
orbital of nearly equal energy in an atom to form two new orbitals of equivalent energy and
identical shape. Each orbital formed is called sp hybrid orbital. Two sp hybrid orbitals take
linear geometry with bond angle 180º. Hence, this type of hybridization is also called linear
hybridization. Each sp hybrid orbital has 50% s-character and 50% p-character.
sp sp
sp hybridization 180°
+
Two sp hybrid orbitals

s-orbital p-orbital Linear geometry
2. sp2 hybridization (Trigonal planar hybridization): It is the process of mixing one s and two p
orbitals of nearly equal energy in an atom to form three new orbitals of equivalent energy and
identical shape. Each orbital formed is called sp2 hybrid orbital. Three sp2 hybrid orbitals takes
trigonal planar geometry with bond angle 120° .Hence, this type of hybridization is also called
trigonal planar hybridization. Each sp2 hybrid orbital has 33.33% s-character and 66.67% p-
character.
sp2
120°
sp2 hybridization
+ +
sp2
sp2
s-orbital p-orbital p-orbital
Three sp2 hybrid orbitals
Trigonal planar geometry
3. sp3 hybridization (Tetrahedral hybridization): It is the process of mixing one s and three p
orbitals of nearly equal energy in an atom to form four new orbitals of equivalent energy and
identical shape and size. Each orbital formed is called sp3 hybrid orbital. Four sp3 hybrid orbitals
take tetrahedral geometry with bond angle 109º28'. Hence, this type of hybridization is also
called tetrahedral hybridization. Each sp3 hybrid orbital has 25% s-character and 75% p-
character. An sp3 hybrid orbitals has one lobe enlarged so it can overlap more effectively than an
s or a p orbital. Hence, sp3 hybrid orbitals form stronger bonds than the original s and p orbitals.
sp3
sp3 hybridization 109°28'

+ + +
sp3
s-orbital px-orbital sp3
py-orbital pz-orbital
sp3
Four sp3 hybrid orbitals

Tetrahedral geometry
Table 1.7: Approximate strength of bonds formed by various orbitals

Orbital Relative bond strengths
s 1
p 1.73
sp 1.93
sp2 1.99
sp3 2.00
Table 1.8: Various bond properties based upon the mode of hybridization
sp sp2 sp3
% of s-character 50 33.33 25
Electronegativity Decreases
Acidic character Decreases
Bond length Increases
Examples involving sp3, sp2 and sp hybridization

1. Examples involving sp3 hybridization
i. Methane (CH4): Carbon has two half filled orbitals in ground state (1s2, 2s2, 2px1 2py1, 2pz0). It has
four half filled orbitals in excited state since one electron is promoted from 2s to empty 2p
orbital during chemical combination (1s1, 2s1, 2px1 2py1, 2pz1) i.e.
2s 2px 2py 2pz
in ground state
sp3
sp3 sp3
2s 2px 2py 2pz
in exited state
sp3
sp3 hybridization Four sp3 hybrid orbitals in

tetrahedral geometry
sp3 sp3 sp3 sp3
Four sp3 hybrid orbitals
Now one 2s and three 2p orbitals undergo sp3 hybridization to form four sp3 hybrid orbitals of
equivalent energy and identical shape and size which take tetrahedral geometry with bond
angle 109º28'.
Each half filled sp3 hybrid orbital of carbon atom overlaps with half filled 1s orbital of four
hydrogen atoms forming four carbon to hydrogen sigma bonds. Hence, all four bonds in
methane are identical with bond angle 109 º28' and methane has a tetrahedral geometry.
1s
sp3
H
sp3 sp3
C
sp3
1s
1s
H H
H
1s
Orbital picture of CH4 Tetratedral geometry
Why is the concept of hybridization needed in CH4?

The answer is to explain the nature of bond and bond angle. In CH4, all four bonds are identical
(same bond length (1.10Å) and bond dissociation energy) with bond angle109º28'. This means all
four half filled orbitals in carbon are equivalent. This is possible only when 2s and three 2p orbitals
undergo mixing forming four new orbitals of equivalent energy during bond formation. If the
concept of hybridization is not introduced, there should have two types of bonds in CH4; one type
of bond due to 2s orbital and another type of bonds due to three 2p orbitals. Similarly, bond angle
in methane should have 90º since three p orbitals are perpendicular to each other.
ii. Ethane (C2H6): Each carbon has four half filled orbitals in excited state since one electron is
promoted from 2s to empty 2p orbital during chemical combination.
Now, one 2s and three 2p orbitals undergo sp3 hybridization to form four sp3 hybrid orbitals of
equivalent energy and identical shape which take tetrahedral geometry with bond angle
109°28'.
1s 1s
H
sp3
sp3 109°28'
C
1s 1s H
H
H
sp3 sp3 H
sp3 sp3 C
sp3 sp3 H
1s 1s
Geometry of Ethane
Orbital picture of ethane molecule
One half filled sp3 hybrid orbital of one carbon atom overlaps with half filled sp3 orbital of
another carbon atom head to head forming a carbon to carbon sigma bond. The remaining three
half filled sp3 orbitals of each carbon atom overlap with half filled 1s orbital of six hydrogen
atoms forming six carbon to hydrogen sigma bonds. Hence, all carbon to hydrogen bonds in
ethane are identical with bond angle 109°28'.
iii. Ammonia (NH3): Nitrogen has three half filled orbitals (1s2 2s2 2px1 2py1 2pz1). Now, one 2s and
three 2p orbitals undergo sp3 hybridization to form four sp3 hybrid orbitals of equivalent energy
and identical shape which take tetrahedral geometry with bond angle 109º28'.
2s 2px 2py 2pz
sp3 hybridization
sp3 sp3 sp3 sp3
sp3
sp3
sp3 sp3
N
sp3 sp3 107.5°
sp3 H H
1s
1s
H
sp3
1s Trigonal pyramidal
Four sp3 hybrid orbitals geometry of NH3
Orbital picture of NH3
Three sp3 hybrid orbitals are half filled and one sp3 orbital is completely filled. Each half filled sp3
hybrid orbital overlaps with half filled 1s orbital of three hydrogen atoms forming three sigma
bonds. Now, there are three bond pairs and one lone pair around the central atom. The
repulsion between lone pair and bond pair is greater than the repulsion between bond pairs.
Hence, bond angle in NH3 is lower than the normal tetrahedral value. NH3 is trigonal
pyramidal in shape with bond angle 107 º48'.
iv. Water (H2O): Oxygen has two half filled orbitals (1s2 2s2 2px2 2py1 2pz1). Now one 2s and three 2p
orbitals undergo sp3 hybridization to form four sp3 hybrid orbitals of equivalent energy and
identical shape which take tetrahedral geometry with bond angle 109°28'.
2s 2px 2py 2pz
O=
sp3 hybridization
sp3 sp3 sp3 sp3
sp3
sp3
sp3 sp3
sp3 sp3 O
sp3 H
104°28
1s
sp3
H
1s
Four sp3 hybrid orbitals Orbital picture of H2O Bent or angular geometry of H2O
Two sp3 hybrid orbitals are half filled and two sp3 orbital are completely filled. Each half filled
sp3 hybrid orbital overlaps with half filled 1s orbital of two hydrogen atoms forming two sigma
bonds. Now there are two bond pairs and two lone pairs around the central atom. The
repulsion between lone pair and lone pair is greater than lone pair and bond pair which in turn
is greater than the repulsion between bond pairs. Hence, bond angle in H2O is lower than the
normal tetrahedral value with bond angle 104º28'. The geometry of H2O molecular is "angular"
or "bent".
2. Examples involving sp2 hybridization
i. Boron trifluoride (BF3): Boron has one half filled orbital in ground state (1s2 2s2 2px1 2py0 2pz0). It
has three half filled orbitals in excited state since one electron is promoted from 2s to 2p orbital
during chemical combination.
Now, one 2s and two 2p orbitals undergo sp2 hybridization to form three sp2 hybrid orbitals of
equivalent energy and identical shape and size which take trigonal planar geometry with bond
angle 120°.
1s 2s 2px 2py 2pz

B= in ground state
2s 2px 2py 2pz

in excited state
sp2 hybridization
sp2 sp2 sp2 2pz
Three sp2 hybrid orbitals
2pz
F
sp2 120°
sp2
2pz
120° B F
sp2
sp2
sp2
sp2 F
Three sp2 hybrid orbitals 2pz

Trigonal planar geometry of BF3
Trigonal planar geometry Orbital picture of BF3
Each half filled sp2 hybrid orbital of carbon atom overlaps with half filled 2pz orbital of three
fluorine atoms forming three boron to fluorine sigma bonds. Hence, all three bonds in BF3 are
identical with bond angle 120° and BF3 is trigonal planar molecule.
Why is the concept of hybridization needed in BF3?
The answer is to explain the nature of bond and bond angle. In BF3, all three bonds are identical
(same bond length and bond energy) with bond angle120°.This means all three half filled orbitals in
boron are equivalent. This is possible only when 2s and two 2p orbitals undergo mixing forming
three new orbitals of equivalent energy during bond formation. If the concept of hybridization is not
introduced, there should have two types of bonds in BF3; one type of bond due to 2s orbital and
another type of bonds due to two 2p orbitals. Similarly, bond angle in BF3 should have 90° since
two p orbitals are perpendicular to each other.
ii. Ethylene (C2H4): Each carbon has two half filled orbitals in ground state (1s2, 2s2, 2px1 2py1, 2pz0).
It has four half filled orbitals in excited state since one electron is promoted from 2s to empty 2p
orbital during chemical combination (1s2, 2s1, 2px1 2py1, 2pz1).
Now, one 2s and two 2p orbitals undergo sp2 hybridization to form three sp2 hybrid orbitals of
equivalent energy and identical shape and size which take trigonal planar geometry with bond
angle 120º. Unhybridized 2pz half filled orbital remains perpendicular to the plane of hybrid
orbitals.
1s 2s 2px 2py 2pz
C= in ground state
2s 2px 2py 2pz

in excited state 2pz
sp2
sp2 hybridization
sp2
sp2 sp2 sp2 2pz
sp2
Three sp2 hybrid orbitals Unhybridized orbital
One half filled sp2 orbital of one carbon atom overlaps with half filled sp2 orbital of another
carbon atom forming carbon to carbon sigma bond. Each half filled sp2 hybrid orbitals of both
carbons atoms overlap with half filled 1s orbital of four hydrogen atoms forming four carbon to
hydrogen sigma bonds. The remaining half filled 2pz orbital of one carbon which is
perpendicular to the plane of hybrid orbitals overlaps with that of another carbon atom laterally
forming carbon to carbon pi bond. Hence, ethene is flat molecule (all carbon and hydrogen
atoms lie in a plane) with pi electron cloud above and below the plane of the molecule. The
geometry is trigonal planar with respect to each carbon.
1s 2pz 2pz 1s
H
H
sp2 σ
sp2 C C
π
sp2 sp2 H
sp2 sp2 H
1s 1s
Orbital picture of ethylene Trigonal planar geometry of ethylene
3. Examples involving sp hybridization

i. Beryllium chloride (BeCl2): Be has no half filled orbitals in ground state (1s2, 2s2, 2px0, 2py0, 2pz0).
It has two half filled orbitals in excited state since one electron is promoted from 2s to empty 2p
orbital during chemical combination (1s2, 2s1, 2px1, 2py0, 2pz0).
i.e.
1s 2s 2px 2py 2pz
Be= in ground state
2s 2px 2py 2pz

in excited state
sp hybridization 180°
sp sp
sp sp 2py 2pz
Two sp hybrid orbitals
3pz sp sp 3pz 180°

σ σ
Cl Be Cl
Cl Be Cl
Orbital picture of BeCl2
Now one 2s and one 2p orbitals undergo sp hybridization to form two sp hybrid orbitals of
equivalent energy and identical shape and size which take linear geometry with bond angle
180º.
Each half filled sp hybrid orbital of Be atom overlaps with half filled 2pz orbital of two chlorine
atoms forming two sigma bonds. Hence, all two bonds in BeCl2 are identical with bond angle
180º and BeCl2 is linear molecule.
ii. Acetylene (C2H2): Each carbon has two half filled orbitals in ground state (1s2, 2s2, 2px1 2py1,
2pz0). It has four unpaired electrons in excited state since one electron is promoted from 2s to
empty 2p orbital during chemical reaction ( 1s2,2s1, 2px1 2py1, 2pz1). i. e.
1s 2s 2px 2py 2pz
C= in ground state
2s 2px 2py 2pz

in excited state
sp hybridization
sp sp 2py 2pz
2py 2py 2py
2pz 2pz 2pz
1s 1s
sp sp sp sp
sp sp
Orbital picture of acetylene

180° 180°
H C C H
Linear shape of acetylene
H C H
Cylindrical electron cloud in acetylene

Now, one 2s and one 2p orbitals undergo sp hybridization to form two sp hybrid orbitals of
equivalent energy and identical shape and size which take linear geometry with bond angle
180º. Unhybridized 2py and 2pz orbitals remain perpendicular to hybrid orbitals.
One half filled sp hybrid orbital of carbon atom overlaps with half filled sp orbital of another
carbon atom forming carbon to carbon sigma bond. The remaining half filled sp orbitals of each
carbon overlaps with half filled 1s orbital of two hydrogen atoms forming two carbon to
hydrogen sigma bonds. Unhybridized and half filled 2py and 2pz orbitals of one carbon overlap
with respective orbitals of another carbon laterally forming two carbon to carbon pi bonds.
iii. Carbon dioxide (CO2):
1s 2s 2px 2py 2pz
C= in ground state
2py
2pz
2s 2px 2py 2pz
in excited state
sp sp
sp hybridization
sp sp 2py 2pz
2py 2py
2pz 2pz
σ σ
2px sp sp 2px O π C π O
O
Linear geometry of CO2
C O
Orbital picture of CO2
Table 1.9: A summary of hybridization

Hybridization Geometry Bond angle Examples
sp Linear 180º Acetylenes, CO2, BeF2, BeCl2, etc.
sp2 Trigonal planar 120º Alkenes, benzene, BF3, etc.
sp3 Tetrahedral 109º28' Alkanes, CH3X, etc.
sp3d Trigonal bipyramidal 90º , 120º PX5,
sp3d2 Octahedral 90º SF6
sp3d3 Pentagonal bipyramidal 72º, 90º IF7
dsp2 Square planar 90º [Cu(NH3)4]2+
1.3.5 Limitations of Valence Bond Theory (VBT)

1. According to VBT, a covalent bond is formed by overlapping half filled orbitals. It can not
explain bonding in electron deficient compounds.
2. It fails to explain the paramagnetic behavior of O2. Paramagnetic behavior is due to unpaired
electrons but according to VBT, O2 has no unpaired electrons.
3. Presence of other nuclei in the molecule should affect the whole electronic arrangement of
atoms in the molecule. This has been neglected in VBT.
A simple way to predict the type of hybridization

The type of hybridization and hence, the shape of covalent molecules and ions can be predicted with
the help of general formula
1
H = 2 (V + M + A - C)
where, H = Hydridization
V = Number of valence electrons of the central atom
M = Number of monovalent atoms
A = Charge on anion
C = Charge on cation.
It is very easy to find number of valence electrons (V) of an element if its group or family is known.
Group 16
Group 14 Group 15 Group 17 Group 18
Chalcogens
Carbon family Nitrogen family Halogens Noble gases
Oxygen family
He*(exception)
C N O F Ne
Si P S Cl Ar
Ge As Se Br Kr
Sb Te I Xe
Bi Po Rn
No. of Valence No. of Valence No. of Valence No. of Valence No. of Valence
e=4 e=5 e=6 e=7 e=8
Examples:
Example i: NCl3
1
H = 2 (V + M + A - C)
Here, V = 5 (N = 2, 5), M = 3 (three Cl atoms), A = 0 (no negative charge), C = 0 (no positive charge).
1
H = 2 (5 + 3+ 0-0) = 4
Hence, hybridization of N in NCl3 is sp3.
Example ii: PCl5
1
H = 2 (V + M + A - C)
Here, V = 5 (It belongs to nitrogen family),

1
M = 5 (five Cl atoms), H = 2 (5 + 5+ 0-0) =5
Hence, hybridization of P in PCl5 is sp3d.
Example iii: SO3
1
H = 2 (V + M + A - C)
Here, V = 6 (It belongs to oxygen family),

M = O (There is no monovalent atoms, oxygen is divalent)
1
H = 2 (6 + 0+ 0-0) = 3
Hence, hybridization of S in SO2 is sp2.
Example iv: ClF3
1
H = 2 (V + M + A - C)
Here, V = 7 (It belongs to halogen family), M = 3 (three F atoms)

1
H = 2 (7 + 3+ 0- 0) = 5
Hence, hybridization of Cl in ClF3 is sp3d.
Example v: XeF4
1
H = 2 (V + M + A - C)
Here, V = 8 (It belongs to group 18), M = 4 (four F atoms)

1
H = 2 (8 + 4+ 0- 0) = 6
Hence, hybridization of Xe inXeF2 is sp3d2.
Example vi: CH3+
1
H = 2 (V + M + A - C)
Here, V = 4 ( C = 2, 4), M = 3 ( three H atoms), A = 0 (no negative charge), C = 1

1
H = 2 (4 + 3+ 0-1) = 3
Hence, hybridization of C in CH3+ is sp2.

Example vii: SO4- -

1
H = 2 (V + M + A - C)
Here, V = 6 (N = 2, 5), M = 0 ( no monovalent atoms), A = 2, C = 0 ( no positive charge).

1
H = 2 (6 + 0+ 2- 0) = 4
––
Hence, hybridization of S in SO4 is sp3.
Solved Questions
1. Predict the molecular geometry of ammonia on the basis of VSEPR theory.
¬ The shape of a covalent molecule or ion is determined by the total number of electron pairs present in the
valence shell of the central atom in the molecule. The electron pairs remain arranged around the central
atom in space so as to get the minimum electrostatic repulsion hence determines the shape.
N
H N H
lp-bp lp-bp repulsion 107.5°
N H H
H 107°48'
bp-bp H
Lewis structure H bp-bp H Trigonal pyramidal shape of NH3
In NH3, the central atom nitrogen has four electron pairs hence, expected geometry is tetrahedral but there
are three bond pairs (bp) only. So, actual shape of ammonia is trigonal pyramidal. Repulsion between lone
pairs (lp) is more than that between a lone pair and a bond pair. Hence, the bond angle in NH3 is less than
normal tetrahedral value (109°28'). Experimentally the bond angle has been found to be 107°28'.
2. Write differences between a sigma and a pi bond.
σ-bond π-bond
i. It is formed by end to end, head on or axial i. It is formed by sideways or lateral overlapping of
overlapping of half filled orbitals. half filled orbitals.
ii. Overlapping of orbitals takes place along the ii. Overlapping of orbitals takes place
internuclear axis. perpendicular to the internuclear axis.
iii. The extent of overlapping is large so the iii. The extent of overlapping is small so the bond
bond formed is strong. formed is weak.
iv. It is symmetrical along the internuclear axis iv. It consists of two lobes on either side of
so free rotation about sigma is possible. internuclear axis and free rotation about pi bond
v. It may be present alone or along with pi is restricted.
bonds. v. It can not present alone.It is always present in
vi. It is formed by overlapping of all types of addition to sigma bond.
orbitals; s-s, s-p, p-p orbitals. 6. It is formed by the overlapping of other than s
orbitals.
3. Define hybridization. Draw the orbital picture of ethylene.

¬ Hybridization is the process of mixing atomic orbitals of nearly equal energy in an atom to form new
orbitals of equivalent energy and identical shape and size called hybrid orbitals. For example: in sp3
hybridization, one s- orbital and three p- orbitals hybridize together giving four sp3 hybrid orbitals.
1s 2pz 2pz 1s
H
H
sp2 σ
sp2 σ C π C
H σ
sp2 sp2 sp2 sp2 H
1s 1s
Orbital picture of ethylene Planar geometry of ethylene
Questions
Very Short Answer Questions:
1. BCl3 is trigonal planar whereas PCl3 is trigonal pyramidal, why?
2. NH3 is trigonal pyramidal whereas NH4+ is tetrahedral. Why?
3. The bond angle in NF3 is 103° whereas in BF3 is 120°. What factor account for this difference in
bond angle?
4. Why is H-O-H bond angle in water molecule comparatively higher than H-S-H bond angle in
H2S molecule?
5. What are the differences between a σ–bond and a π–bond?
6. Define hybridization. What are the characteristic of hybridization?
7. Mention the type of hybridization of underlined atom in the following molecules.
a. CH4 b. C2H4 c. C2H2 d. BF3
e. BeF2 f. NH3 g. H2O h. CO2
8. Nitrogen of ammonia has sp hybridization but ammonia molecule has trigonal pyramidal
3
geometry. Why?
9. Mention with an example of
a. Diagonal hybridization b. Trigonal hybridization
c. Tetrahedral hybridization
10. Draw the orbital picture of following compounds indicating σ and π bond.
a. Ethane b. Ethylene c. Acetylene d. Ammonia
11. Write any two features of sp3 hybrid orbitals with examples.
12. Why do NH3 and BF3 have dissimilar geometries?
13. What is the mode of hybridization in BF3? Write any two important features of this
hybridization.
14. What is the mode of hybridization of the central atom whose molecular geometry is
tetrahedral? Give an example.
15. Draw the orbital picture of a hydrocarbon showing (a) tetrahedral structure (b) Trigonal planar
structure.
16. Draw orbital picture of ethyne and mention σ and π bonds.
Short /Long Answer Questions:
1. Predict the geometry of the following species on the basis of VSEPR model?
+
a. BeF2 b. BF3 c. NH3 d. NH4
e. PCl5 g. SO2 h. SF6 i. ClF3
j. NCl3 k. NO3¯ l. XeF4 m. I3¯
2. How would you interpret that all four C—H bonds of methane are identical?
3. Predict the molecular geometry of the following species on the basis of hybridization?
a. BeF2 b. BF3 c. NH3 d. CH4
e. C2H4 g. C2H2 h. CH3Cl i. CCl4
4. What do you understand by sp2 hybridization? Explain the molecular geometry involved with
an example for the same.
Multiple Choice Questions

1. VSEPR theory is developed by
a. Lewis and Kossel b. Sidgwick and Powell 11. The shape of ClF3 is
c. Gillespie and Nyholm d. Linus Pauling a. T shaped b. Trigonal planar
2. VSEPR theory is useful to explain c. Pyramidal d. Tetrahedral
‐
a. Nature of bond 12. The geometry of BF4 is similar to
b. Number of π electron pairs a. BF3 b. NF3
c. Geometry of molecules c. CH4 d. SF4
d. Number of π and σ electron pairs 13. Which of the followings is trigonal planar?
3. The order of bond angle is a. AlCl3 b. PCl3
a. PH3 >NH3 > AsH3 >SbH3 c. ClF3 d. ICl2-
b. NH3 >PH3 >AsH3 >SbH3 14. Shape of XeF2 is similar to
c. PH3 >AsH3 >SbH3 > NH3 a. OF2 b. I3¯
d. NH3 <PH3<AsH3 <SbH3 c. SCl2 d. None
4. The order of bond angle is 15. Which of the following pairs has identical geometry?
a. H2O > H2S > H2Te> H2Se a. BCl3 and PCl3 b. CH3Cl and CHCl3
b. H2S > H2Te> H2Se >H2O c. CH4 and CCl4 d. XeF4 and SiF4
c. H2O > H2S > H2Se > H2Te
16. CO2 is isostructural with
d. H2O < H2S < H2Se < H2Te
a. C2H2 b. NO2
5. The order of bond angle is c. SO2 d. C2H6
a. PF3 > PBr3 >PCl3 >PI3 b. PF3 >PCl3 > PBr3 >PI3
17. Which of the followings has unequal bond length?
c. PCl3 > PBr3 >PI3 >PF3 d. PF3 <PCl3 < PBr3 <PI3
a. NF3 b. SF4
6. Which of the followings has highest value of bond c. PF5 d. SF6
angle? 18. According to valence bond theory, number of
a. BF3 b. NH3
unpaired electron in O2 is
c. PCl3 d. NCl3
a. 0 b. 1
7. The lowest value of bond angle is in c. 2 d. 4
a. NH3 b. NH4+
19. The number of unpaired electron in O2 is
c. NH2- d. NCl3
a. 0 b. 1
8. If the central atom has three bond pairs and one lone c. 2 d. 4
pair, the expected shape is 20. A pi bond is formed by
a. Tetrahedral b. Square planar a. sideways overlapping of sp2 hybrid orbitals
c. Pyramidal d. Trigonal planar b. axial overlapping of p orbitals
9. If the central atom has three bond pairs and two lone c. lateral overlapping of p orbitals
pairs, the expected shape of the molecule is d. head on overlapping of p orbitals
a. Pentagonal bipyramidal b. Trigonal bipyramidal 21. pi bonds in benzene are formed by
c. T shaped d. Trigonal planar a. sp2-s overlapping b. sp2-sp2 overlapping
10. The central atom has three lone pairs and two bond c. sideways p-p overlapping d. head on p-p overlapping
pairs, the shape of molecule is 22. The number of pi bond in acetylene is
a. Linear b. 'V' shaped a. 1 b. 2
c. Trigonal bipyramidal d. 'L' shaped c. 3 d. 4
1 2 3 4 5 6 7 8 9 10 11
c c b c d a c c c a a
12 13 14 15 16 17 18 19 20 21 22
c a b c a c a c c c b
Volumetric Analysis
Titration is a very simple and efficient method of determining the concentration of solutions.
Nowadays, instrumental methods are being mostly used in titration owing their accuracy and versatility.
2.1 Introduction
Chemical analysis is one of the most important tasks in chemistry. It involves qualitative analysis
and quantitative analysis. Qualitative analysis involves the determination or identification of
chemical substances or radicals present there in. Qualitative salt analysis is an example of this
category. Quantitative analysis involves the estimation of amount of substance present. There are
different methods of quantitative analysis. Some of these methods are volumetric analysis (e.g.,
titrimetric analysis, gravimetric analysis, instrumental analysis, etc.).
Volumetric analysis involves the determination of concentration of one solution comparing with
another standard solution, by measuring their reacting volumes. If concentration of base and acid are
measured with respect to standard acid and standard alkali, these analyses are called acidimetry and
alkalimetry, respectively. This topic is mainly related to acidimetry and alkalimetry. Before
proceeding to this, first we shall discuss about equivalent weight, knowledge of which is the pre-
requisite to understand the acidimetry and alkalimetry.
2.2 Concept of Equivalent Weight

Equivalent weight is the combining capacity of a chemical species by weight. Equivalent weight of
any compound is defined as the number of parts by mass (in gram) of it which reacts completely
with one gram equivalent of another compound. Equivalent weight of compound can be studied
under different headings.
1. Equivalent weight of acid
Equivalent weight of an acid is defined as the number of parts by weight of it which contains 1.008
parts by weight of replaceable hydrogen atom.
In HCl: 36.5 parts by weight of HCl consists 1.008 parts by weight of replaceable hydrogen. Hence
equivalent weight of HCl is 36.5.
Molecular mass of acid
Equivalent weight of acid = Number of replaceable hydrogen atoms
The number of replaceable hydrogen atom(s) present in a molecule of an acid is called its basicity.
Molecular mass of acid
∴ Equivalent weight of acid = Basicity
Self Test
2.1 Calculate the equivalent weight of carbonic acid.
Volumetric Analysis Unit 2 31
Table 2.1: Some acids with their molecular mass (Mol.mass) and equivalent weight (Eq.Wt.).
Molecular Eq.wt. =
Molecular Mol. mass
S.N. Name of acid mass Basicity
formula
(amu) Basicity
1. Hydrochloric acid HCl 36.5 1 36.5
2. Nitric acid HNO3 63.0 1 63.0
3. Acetic acid CH3COOH 60 1 60
4. Formic acid HCOOH 46 1 46
5. Sulphuric acid H2SO4 98 2 49
COOH
6. Oxalic acid (anhydrous) 90 2 45
COOH
7. Oxalic acid (hydrated) COOH.H2O
126 2 63
COOH.H2O
8. Phosphoric acid H3PO4 98 3 32.6
9. Phosphorous acid H3PO3 82 2 41.0
10. Pyrophosphoric acid H4P2O7 178 4 44.5
11. Metaphosphoric acid HPO3 80 1 80
2. Equivalent weight of base or alkali

Equivalent weight of base is defined as the number of parts by weight of it which is exactly
neutralized by one gram equivalent of acid.
Molecular mass of base
Equivalent weight of base = Number of replaceable OH¯ ions
The number of replaceable OH¯ ions present in a molecule is called acidity.

Molecular mass of base
∴ Equivalent weight of base = Acidity
Let us find the equivalent weight of Ca(OH)2
(Molecular mass = 74 amu)
Method 1:
2 replaceable OH¯ ions are present in 74 parts by wt. of Ca(OH)2
1 replaceable OH¯ ion is present in 37 parts by wt. of Ca(OH)2.
Method 2:
Let us take an acid-base reaction
Ca(OH)2 + 2HCl CaCl2 + 2H2O
74 2×36.5
74 2 gequiv
We know 1 gram equivalent (gequiv) of HCl = 36.5 g

2 gequiv of HCl is neutralized by 74 g of Ca(OH)2
74
1 gequiv of HCl is neutralized by 2 g of Ca(OH)2 = 37 g of Ca(OH)2
∴ 1 gram equivalent of HCl is neutralized by 37 g of Ca(OH)2

1 gram equivalent of Ca(OH)2 = 37 g
Hence, Equivalent weight of Ca(OH)2 is 37.
Table 2.2: Some bases with their Molecular masses (Mol.mass) and Equivalent weights (Eq.Wt.).
Mol. Eq.wt. =
Molecular Mol. mass
S.N. Name of base mass Acidity
formula
(amu) Acidity
1. Sodium hydroxide NaOH 40 1 40
2. Ammonium hydroxide NH4OH 35 1 35
3. Potassium hydroxide KOH 56 1 56
4. Calcium hydroxide Ca(OH)2 74 2 37
5. Magnesium hydroxide Mg(OH)2 58 2 29
6. Barium hydroxide (anhydrous) Ba(OH)2 171 2 85.50
7. Barium hydroxide (hydrated) Ba(OH)2.8H2O 315.50 2 157.75
3. Equivalent weight of salts

Equivalent weight of a salt1 is the number of parts by weight of it which is formed by complete
neutralization of 1 gram equivalent of acid with 1 gram equivalent of base.
Molecular mass or formula unit mass of salt
Equivalent weight of salt = Total number of cationic or anionic charge
Let us find the equivalent weight of Na2CO3 [Mol. mass = 106 amu]
Method 1:
Na2CO3 2Na+ + CO3¯ ¯
Total number of cationic charge = Total number of anionic charge = 2
106
∴ Equivalent weight of Na2CO3 = 2 = 53
Method 2:
Let us take a reaction of formation of Na2CO3
2 NaOH + H2CO3 Na2CO3 + 2H2O
2 mole 1 mole 1 mole 2 mole
2 gequiv 2 gequiv 106 g 2 gequiv
1 gequiv 1 gequiv 53 g 1 gequiv
When one gram equivalent of NaOH reacts with one gram equivalent of H2CO3, 1 gram
equivalent of Na2CO3 is formed.
1 gequiv of Na2CO3 = 53 g
∴ Equivalent weight of Na2CO3 = 53
1 Ionic compounds are composed of cations and anions. Some prefer to use the term formula unit rather than molecule. The latter is used
to denote covalent compound. In this sense, formula unit weight is used in preference to molecular mass especially for ionic compound.
Table 2.3: Some salts with their molecular masses (Mol. mass) and Equivalent weights (Eq. Wt.)
Eq.wt. =
Mol. mass or Total number Formula unit mass
Molecular
S.N. Name of salt formula unit of cationic or Total no. of cationic
formula
mass (amu) anionic charge
or anionic charge
1. Sodium chloride NaCl 58.5 1 58.5
2. Potassium chloride KCl 74.5 1 74.5
3. Sodium carbonate Na2CO3 106 2 53
4. Sodium bicarbonate NaHCO3 84 1 84
5. Silver nitrate AgNO3 169.8 1 169.8
6. Potassium nitrate KNO3 101.0 1 101.0
7. Sodium Sulphate Na2SO4 142 2 71
4. Equivalent weight of oxidizing agent and reducing agent

a. Equivalent weight of KMnO4: KMnO4 is oxidizing agent having variable equivalent weight.
Its equivalent weight is different in different media.
[Mol. mass of KMnO4 = 39 + 55 + 4 × 16 = 158 amu]
i. In Acidic medium
reduction
+7 +2
2KMnO4 + 3H2SO4 K2SO4 + 2MnSO4 + 3H2O + 5[O]
2 × 158 5 × 16
Or reduction
+7 +2
MnO−4 + 8H+ + 5e– Mn++ + 4H2O
Method 1:
5 × 16 parts by weight of oxygen is released from 2 × 158 parts by wt. of KMnO4.
2 × 158
8 parts by weight of oxygen is released from 5 × 16 × 8 = 31.6 parts by weight of KMnO4.
So, equivalent weight of KMnO4 in acidic medium = 31.6.
Method 2:
Mol. mass of KMnO4
Equivalent weight of KMnO4 = Total change of oxidation number (O.N.) per molecule
158
= 5 = 31.6
ii. In Neutral medium
reduction
+7 +4
2KMnO4 + H2O 2KOH + 2MnO2 + 3[O]
2 × 158 3 × 16
Or
reduction
+7 +4
Method 1: MnO−4 + 2H2O + 3e– MnO2 + 4[OH-]
3 × 16 parts by wt. of oxygen is released from 2 × 158 parts by wt. of KMnO4

2 × 158
8 parts by wt. of oxygen is released from 3 × 16 × 8 parts by wt. of KMnO4.
158
= 3 = 52.6
Method 2:
Molecular mass of KMnO4 158
Equivalent weight of KMnO4 = Change in oxidation number per molecule = 3 = 52.6
iii. In Alkaline medium

reduction
+7 +6
2KMnO4 + 2KOH 2K2MnO4 + H2O + [O]
2 × 158
Or
reduction
+7 +6
MnO−4 + e– MnO-4 -
Method 1:
16 parts by weight of oxygen is released from 2 × 158 parts by weight of KMnO4
2 × 158
8 parts by weight of oxygen is released from 16 × 8 parts by weight of KMnO4 = 158
Method 2:
Mol. mass of KMnO4 158
Equivalent weight of KMnO4 = Change in O.N. per molecule = 1 = 158
b. Equivalent weight of potassium dichromate

[Mol. mass of K2Cr2O7 = 2 × 39 + 2 × 52 + 7 × 16 = 294 amu]
reduction
+6 +3
K2Cr2O7 + 4H2SO4 K2SO4 + Cr2(SO4)3 + 4H2O + 3[O]
294 3 × 16
Or
Cr2O-7 - + 14 H+ + 6 e− 2 Cr3+ + 7 H2O
Method 1:
3 ×16 parts by weight of oxygen is produced form 294 parts by weight of K2Cr2O7
294
8 parts by weight of oxygen is produced from 3 × 16 × 8 parts by weight of K2Cr2O7
294
= 6 = 49
Method 2:
Molecular mass of K2Cr2O7 294
Equivalent weight of K2Cr2O7 = Change in O.N. per molecule = 2 × 3 = 49
Here, one molecule of K2Cr2O7 consists 2 atoms of chromium.

Change in oxidation number in one molecule of K2Cr2O7
= 2 × change in O.N. of Cr. = 2 × 3 = 6
Self Test
2.2 Calculate the equivalent weight of K2Cr2O7 in the reaction,
K2Cr2O7 + 2KOH 2K2CrO4 + H2O Ans: [M/2]
Table 2.4: Some compounds with their molecular masses and equivalent weights
Name of Mol. Change in O.N. per
S.N. Molecular formula Eq. wt.
compounds mass molecule
1. Potassium KMnO4 5 (in acidic medium) 31.6
permanganate 158 3 (in neutral medium) 52.6
1 (in alkaline medium) 158
2. Potassium K2Cr2O7
294.2 6 49.03
dichromate
3. Potassium iodate KIO3 214 1 214
4. Mohr's salt FeSO4(NH4)2SO4.6H2O 392 1 392
c. Equivalent weight of oxalic acid: Oxalic acid is reducing agent and molecular mass of
anhydrous oxalic acid is 90 amu. Its equivalent weight can be calculated as
+3 +4
C2H2O4 2 CO2 + 2 H+ + 2 e
Molecular mass 90
∴ Equivalent weight = 1×2 = 2 = 45.
Self Test
2.3 Find out the equivalent weight of (a) H2O2 (b) hydrated oxalic acid, (COOH)2.2H2O.
Ans: (a) [M/2] (b) [M/2]
5. Equivalent weight of ions

Ionic mass
Equivalent weight of ion = Charge on ion
60
e.g. Eq. wt. of CO32– ion = 2 = 30
Self Test
2.4 If M is the molecular mass of H3PO4, what will be its equivalent weight in
H3PO4 + 2 NaOH Na2HPO4 + 2H2O [Ans: M/2]
Table 2.5: Equivalent weights of some ions

Ionic mass
S.N. Ions Ionic Mass Charge of ions Eq. wt. =
Charge on ion
+
1. Na 23 1 23
++
2. Ca 40 2 20
3. SO4¯ ¯ 96 2 48
4. HCO3¯ 61 1 61
If a compound is formed by radicals then the equivalent weight of the compound is equal to the
sum of equivalent weight of radicals. For example, Na2CO3 is composed of Na+ and CO3¯ ¯ .
Eqvt. wt. of Na2CO3 = Eqvt. wt of Na+ + Eqvt. wt. of CO3¯ ¯ = 23 + 30 = 53.
2.3 Different Ways of Expressing the Concentration of

Solution
Amount of solute present in the given amount of solution is concentration.
Amount of solute
Concentration = Amount of solution
It can be expressed in different ways:

Depending upon the relative amount of solute and solution, solution can be classified into diluted
solution and concentrated solution.
i. Diluted solution: The solution which consists relatively low amount of solute dissolved in a
given amount of a solution is called diluted solution.
ii. Concentrated solution: The solution which consists relatively more amount of solute dissolved
in a given amount of solution is called concentrated solution.
The terms dilute and concentrate do not express the actual amount of solute dissolved in solution.
These express only relative amount. Hence actual concentrations of solutions are expressed different
ways as follows:
1. Percentage Concentration
Percentage concentration of a solution can be expressed in following three terms.
a. Percentage concentration in mass/volume: It is defined as the mass of a solute in gram present
in 100 mL of the solution.
Mass of solute in gram
% (w/v) = Volume of solution in mL × 100.
For example: when 4 g of sodium chloride is dissolved in water to prepare 100 mL solution then
the strength of solution is said to be 4% (w/v) NaCl.
Self Test
2.5 100 mL of oxalic acid solution consists 2.45 gram of oxalic acid. Calculate the percentage
strength.
b. Percentage by mass or % (w/w): It is defined as the mass of a solute in gram present per 100 g
of solution. Mathematically,
Mass of a solute in gram w × 100 w × 100 %(w/v)

% (w/w) = Mass of solution in gram × 100 = w = = , where ρsoln is the
soln v× ρsoln ρsoln
density of the solution in g/mL (or specific gravity).
When 4 g of NaCl is dissolved to prepare 100 g of its solution, then the strength of NaCl is said
to be 4% (w/w). In other words 4g of NaCl is dissolved in 96 g of water to prepare 100 g
solution.
c. Percentage concentration in volume/volume: If solute and solvent both are liquid then
percentage strength can be expressed in volume/volume. It is defined as the volume of solution
present per 100 volume of the solution.
Volume of solute in mL
% (v/v) = Volume of solution in mL × 100
When 10 mL of ethyl alcohol is mixed with 90 mL of water to prepare 100 mL of solution, then
the strength of solution is 10% V/V.
Self Test
2.6 What do you mean by 90% (v/v) methanol solution in water?
2. Gram per litre

It is defined as the mass of solute in gram present per litre of its solution.
Strength in gram/lit (g/L) = Volume of solution in litre
Mass of solute in gram w × 1000

or, Strength in g/L = Volume of solution in mL × 1000 = v
When 4.9 g of H2SO4 is dissolved to prepare 1 litre solution then the strength of solution is said
to be 4.9 g/L.
Again,
Strength in g/L = Volume of solution in mL × 100 × 10
So, g/L = % (w/v) × 10
Self Test
2.7 Find the strength of 4.5% (w/v) Na2CO3 in terms of g/L?
3. Molarity (M)
It is defined as the number of mole of solute dissolved per litre solution.
Number of moles of solute
Molarity (M) = Volume of solution in litre
If volume of solution is expressed in mL then the above expression becomes.

Number of moles of solute w × 1000 g/L
Molarity (M) = Volume of solution in mL × 1000 = = M
Mw×v w
where Mw=Molecular mass of the solute.

For example, when 1 mole of anhydrous sodium carbonate (i.e. 106 gram) is dissolved to
prepare one litre solution then the strength of solution is said to one molar (written as 1 M or
M).
Semi-molar solution (M/2)

When half mole of solute is dissolved to prepare one litre solution then the strength of solution is
said to be semi-molar. If 49 gram of sulphuric acid is dissolved to prepare one litre solution then the
strength of solution is semi-molar.
Decimolar solution (M/10)
When one-tenth mole of solute is dissolved to prepare one litre solution then the strength of solution
is said to be decimolar. If 9.8 gram of sulphuric acid is dissolved to prepare one litre solution then the
strength of solution is decimolar.
Centimolar solution (M/100)
When 0.01 mole of solute is dissolved to prepare one litre of solution then the strength of solution is
called centimolar. If 0.98 gram of sulphuric acid is dissolved to prepare one litre solution, then the
strength of solution is centimolar.
Different ways of expression of molarity
Molarity = Volume of solution in litre . . . (i)
Number of millimoles of solute

= Volume of solution in mL . . . (ii)

= Volume of solution in mL × 1000 . . . (iii)
We know,
Number of mole = Molar mass (in g/mol)
Now relation (i) becomes,

Molarity = Molecular mass × Volume of solution in litre . . . (iv)
Gram per litre

= Molecular mass . . . (v)
Percentage strength (w/v) × 10

= Molecualr mass [∵ Gram per litre = % (w/v) × 10]. . . (vi)
If volume is expressed in mL then equation (iv) can be expressed as,

Mass of solute in gram × 1000 w × 1000
Molarity = Molecular mass × Volume of solution in mL = Mw × v . . . (vii)
w × 1000
or, M = M × v
w
Example 2.1. Calculate the molarity of 250 mL solution prepared by dissolving 1.375 g of anhydrous sodium
carbonate.
Solution
Molecular mass of anhydrous Na2CO3 = 106 amu
Method 1:
106 g of Na2CO3 in 1000 mL solution = 1M
1
1.375 g of Na2CO3 in 1000 mL solution = 106 × 1.375 M
1 1000
1.375 g of Na2CO3 in 250 mL solution = 106 × 1.375 × 250 = 0.0518 M
Method 2:
1.375
Number of moles of Na2CO3 = 106 = 0.01297 mol
250
Volume of solution in litre = 1000 = 0.25 L
Number of mole 0.01297

Molarity = Volume in litre = 0.25 = 0.0518 M
Method 3:
Mass of solute × 1000 1.375 × 1000
Molarity = Volume in mL × Molecular mass = 250 × 106 = 0.0518 M
Method 4:
250 mL solution consists 1.375 g
1.375
1000 mL solution consist 250 × 1000 g = 5.5 g
Strength = 5.5 g/L

g/L 5.5
Molarity = Molecular mass = 106 = 0.0518 M
Example 2.2 Calculate the amount of NaHCO3 in 500 mL of 0.25 M solution.

Solution
Molecular mass of NaHCO3= 84
Method 1:
Volume in mL × Mol. wt × Molarity 500× 84 × 0.25
Mass of solute = 1000 = 1000 = 10.5 g
Method 2:
Strength in g/L = Molarity × Molecular mass = 0.25 × 84 = 21 g/L
i.e. 1000 mL solution consists 21g
500 mL solution consists 10.5g
(Practice other methods also)
Example 2.3 Calculate the molarity of pure water.
Solution
If density of water is 1 g/mL,
1 litre of water = 1000 mL = 1000 g
For 1 litre of water,
Mass of 1 litre water 1000
Number of moles = Molecular mass of water = 18 = 55.55 mol
∴ Strength of pure water is 55.55 mol/L (55.55 M)

Example 2.4 25 millimole of glucose is present in 250 mL solution. Calculate the molarity of solution.
Solution
Number of millimole of solute 25 1
Molarity = Volume of soluiton in mL = 250 = 10 = 0.1M
4. Formality (F)
Ionic compounds exist in the form the ions rather than in the form of molecules. So the term formula
mass is used instead of molecular mass. That is why the term formality is used for ionic compound
in place of molarity. As the molecular mass is the sum of all atoms present in the molecule, formula
mass is also the sum of all atoms present in the formula. So, mathematically, molarity and formality
will have same values, for a given solution.
Formality of a solution is defined as the number of gram formula mass of solute dissolved per litre of
solution. It is denoted by F.
Number of formula mass in gram
Formality (F) = Volume of solution in litre
5. Molality (m)
Molality is defined as the number of moles of solute dissolved in 1 kg of solvent.
Molality (m) = mass of solvent in kg
Different ways of expression of molality
Molality (m) = Mass of solvent in kg . . . (i)
Number of millimoles of solute

= Mass of solvent in gram . . . (ii)
If mass of solvent is expressed in gram,

Molality (m) = Mass of solvent in gram × 1000 . . . (iii)
We know,
Mass of solute
Number of mole = Molar mass
Now, relation (i) becomes

Molality = Molecular Mass × Mass of solvent in kg . . . (iv)
Strength in gram kg–1 solvent

= Molecular mass . . . (v)
If weight is expressed in gram, relation (iii) changes to

Mass of solute in gram × 1000
Molality = Molecular mass × Mass of solvent in gram . . . (vi)
Relation between molarity (M) and molality (m)

w × 1000 w × 1000 m v
M = M × v and m = M × w . So, M = w . . . (vii)
w w solv solv
Self Test
2.8 Calculate the molarity of 3m NaOH solution having a density 1.1 g/mL.
Ans: 2.95M
Example 2.5 29.25 g of sodium chloride is dissolved in 500 g water. What is the molality of solution?
Solution
Molecular mass or formula mass of NaCl = 58.5 amu
Method 1:
58.5 g of NaCl in 1000 g water makes 1 molal solution
1
29.25 g of NaCl in 1000 g water makes 58.5 × 29.25 molal solution
1 1000
29.25 g of NaCl in 500 g water makes 58.5 × 29.25 × 500 = 1 molal.
Method 2:
29.25
Number of moles of solute = 58.5 = 0.5 mol
500
Mass of solvent in kg = 1000 = 0.5 kg
Number of moles of solute 0.5

∴ Molality = Mass of solvent in kg = 0.5 = 1 m
Method 3:
Mass of solute in gram × 1000 29.25 × 1000
Molality = Molecular mass of solute × mass of solvent in gram = 58.5 × 500 = 1 m
Method 4:
500 g solvent dissolves 29.25 g solute.
29.25
1000 g solvent dissolves 500 × 1000 g = 58.5g
Strength in gram kg–1 solvent 58.5

Strength in molality (m) = Molecular mass = 58.5 = 1 m
Example 2.6 A sulphuric acid solution is 9.8% by mass. Calculate its molality.
Solution
9.8% by mass of sulphuric acid solution means, 9.8 g of sulphuric acid is dissolved to prepare 100 g of its
solution.
∴ Mass of water = 100 – 9.8 = 90.2 g
90.2 g of water dissolves 9.8 g of H2SO4
9.8
1000 g of water dissolves 90.2 × 1000 g of H2SO4 = 108.64 g
Strength in gram kg–1 solvent 108.64

∴ Molality = Molecualr mass = 98 = 1.10 m
Example 2.7 The density of 15% (w/w) H2SO4 solution is 1.1 g/mL.
a. Calculate % (w/v)
b. Calculate molarity
c. Calculate molality
Solution
(a) Method 1:
15% (w/w) H2SO4 means
100 g H2SO4 solution has 15 g H2SO4
Mass of solution = 100 g
Mass of H2SO4 = 15 g
Mass of H2O = 100 – 15 = 85 g
Mass of solution 100
Volume of solution = Density of solution = 1.1 = 90.9 mL
w× 100 15
So, % (w/v) = v = 90.9 × 100 = 16.5% (w/v)
Method 2:
% (w/v) = % (w/w) × Density of solution = 15 × 1.1 = 16.5% (w/v)
(b) 90.5 mL solution has 15 g H2SO4

Method 1:
g/L = % (w/v) × 10
g/L
M = Molecular mass
16.5 × 10
So, Molarity = 98 = 1.69 M
w × 1000 15 × 1000
Molality = Molecular mass × Weight of solution = 98 × 85 = 1.80 m
Method 2:
m Volume of solution
M = Weight of solvent
m 1000 + (1.69 × 98)
or, 1.69 = 1000 × 1.1
So, m = 1.80 m
6. Normality (N)
Normality of a solution is defined as the number of gram equivalent (g equiv) of solute dissolved per
litre of solution.
Mathematically,
Number of gram equivalent of solute
Normality (N) = Volume of solution in litre
If volume of solution is expressed in mL then above expression becomes,
Normality = Volume of solution in mL × 1000
When 49 g of sulphuric acid is dissolved to prepare 1 litre solution, then the strength of solution is
one normal (1 N or N).
Bi-normal solution (2N solution)
The solution in which two gram equivalent solute is dissolved to prepare one litre solution is said to
be bi-normal solution. When 80 g of NaOH is dissolved to prepare 1 litre solution then the strength
of solution is bi-normal.
Semi-normal solution (N/2 solution)
The solution in which half gram equivalent solute is dissolved to prepare one litre solution is said to
be semi-normal solution. When 20 g of NaOH is dissolved to prepare 1 litre solution then the
strength of solution is semi-normal.
Deci-normal solution: (N/10 solution)
The solution in which one tenth gram equivalent of solute is dissolved to prepare one litre solution is
said to be deci-normal solution
When 4 g of NaOH is dissolved to prepare 1 litre of solution then the strength of solution is deci-
normal.
Centi-normal solution (N/100 solution)
The solution in which one-hundredth gram equivalent solute is dissolved to prepare one litre
solution is said to be centi-normal solution.
When 0.4 g of NaOH is dissolved to prepare 1 litre of solution then the strength of solution is centi-
normal.
Self Test
2.9 Define
a. Normal solution (N) b. Binormal solution (2N)
c. Penta-normal solution (5N) d. Deca-normal solution (10N)
e. Semi-nornal solution (N/2) f. Penti-normal solution (N/5)
g. Deci-normal solution (N/10) h. Centi-normal solution (N/100)
i. Milli-normal solution (N/1000)
Different ways of expressing of normality
Normality = Volume of solution in litre . . . (i)
Number of milligram equivalent of solute

= Volume of solution in mL . . . (ii)

= Volume of solution in mL × 1000 . . . (iii)
We know,
Number of gram equivalent = Equivalent weight of solute
Now, relation (i) becomes,

Mass of solute in gram (w)
Normality (N) = Equivalent weight of solute (E) × Volume of solution in litre (V) . . . (iv)
Strength in g/L
N = Equivalent weight . . . (v)
% (w/v) × 10
= Equivalent weight [∵ g/L = % (w/v) × 10] . . . (vi)
If volume is expressed in mL then equation (iv) changes to,

Weight of solute in gram (w) × 1000
Normality (N) = Equivalent weight of solute (E) × Volume in mL (v) . . . (vii)
VEN
or w = 1000
Example 2.8 What amount of anhydrous sodium carbonate should be dissolved to prepare 250 mL of
decinormal solution?
Solution
Molecular mass of anhydrous Na2CO3 = 106 amu
106
Equivalent weight = 2 = 53
Method 1:
To prepare 1000 mL of 1N Na2CO3 solution 53 g Na2CO3 should be dissolved.
53
To prepare 250 mL of 1N Na2CO3 solution 1000 × 250 g should be dissolved.
53 × 250 × 0.1
To prepare 250 mL of 0.1N Na2CO3 solution 1000 g should be dissolved.
= 1.325 g
Method 2:
Normality = Volume in litre
0.1 = 0.250
∴ Number of gram equivalent = 0.1 × 0.250 = 0.025 g equiv.
Mass in gram = Number of gram equivalent × Equivalent weight = 0.025 × 53 = 1.325 g

Method 3:
Gram/lit
Normality = Eq. wt.
Gram/litre = Normality × Equivalent weight = 0.1 × 53 = 5.3 g/L

1000 mL solution consists 5.3 g of Na2CO3
5.3
250 mL solution consists 1000 × 250 g of Na2CO3 = 1.325 g
Method 4:
VEN 250 × 53 × 0.1
w = 1000 = 1000 = 1.325 g
Example 2.9 Calculate the number of milli-equivalent of oxalic acid in 50 mL of 0.2 N oxalic acid solution.
Solution
Number of milli-equivalent = Normality × volume in mL = 0.2 × 50 = 10.0 milli-equivalent (10 m equiv)
Example 2.10 Commercially available concentrated hydrochloric acid contains 36.5% HCl by mass and has
density 1.25 g cm–3. Calculate the normality of solution.
Solution
36.5% HCl means, 100 g of solution consist 36.5 g of dissolved HCl.
Method 1:
100 g of solution consists 36.5 g of HCl
100
1.25 mL of solution consists 36.5 g of HCl [ Mass
∵ V = Density ]
36.5 × 1.25 × 1000
1000 mL of solution consists 100 g of HCl = 456.25 g
Strength is 456.25 g/L

Gram/litre 456.25
Normality = Eq. wt. = 36.5 = 12.5 N
Method 2:
% (w/w) strength × density (sp. gravity) × 10 36.5 × 1.25 × 10
Normality = Eqvt. wt. = 36.5 = 12.5 N
Relation between molarity and normality

We know the relation,
Gram/litre
Normality = Eqvt. wt.
or, Gram/litre = Normality × Eq. wt. . . . (i)

Gram/litre
Molarity = Mol. mass
or, Gram/litre = Molarity × Mol. mass . . . (ii)

From relation (i) and (ii),
Normality × Eqvt. wt. = Molarity × Mol. mass
Mol. mass
Normality = Molarity × Eqvt. wt.
or, N=M× ( )
Mw
Ew . . . (iii)
Note:
( Mol. mass
Eqvt. wt ) represents acidity for base or basicity for acid or total change in oxidation number for oxidizing or reducing
agents, or total + ve charge on cation or total –ve charge on anion for a salt.
7. Mole fraction
Mole fraction is the ratio of number of moles of solute or solvent to the total number of moles of
solute and solvent.
If n1 be the number of moles of solute and n2 be the number of moles of solvent, then
n1
Mole fraction of solute Xsolute = n + n
1 2
n2
Mole fraction of solvent Xsolvent = n + n
1 2
Also, Xsolute + Xsolvent = 1

Example 2.11 5.0g of CaCO3 is mixed with 8.4 g of MgCO3.
a. Calculate the number of moles of CaCO3 in the mixture.
b. Calculate the number of moles of MgCO3 in the mixture.
c. Calculate the total number of moles of components.
d. Calculate the percentage mass of CaCO3 in mixture.
e. Calculate the percentage mass of MgCO3 in mixture.
f. Calculate the mole fraction of CaCO3.
g. Calculate the mole fraction of MgCO3.
h. Calculate the sum of mole fraction of components.
i. What amount of which component should be added to the mixture so that each component
of mixture will have same value of mole fraction?
Solution
a. Molecular mass of CaCO3 = 40 + 12 + 3 × 16 = 100 amu
Molecular mass of MgCO3 = 24 + 12 + 3 × 16 = 84 amu
Mass of CaCO3 5
No. of mole of CaCO3 (n1) = Mol. mass of CaCO = 100 = 0.05 mol
3
Mass of MgCO3 8.4

b. No. of mole of MgCO3 (n2) = Mol.mass of MgCO = 84 = 0.10 mol
3
c. Total no. of mole of components (nt) = n1 + n2 = 0.05 + 0.10 = 0.15 mol

Wt. of CaCO3 5
d. % mass of CaCO3 = Total mass × 100% = 5 + 8.4 × 100% = 37.31%
Mass of MgCO3 8.4

e. % mass of MgCO3 = Total mass × 100% = 5 + 8.4 × 100% = 62.69 %
n1 0.05
f. Mole fraction of CaCO3 (x1) = n + n = 0.05 + 0.10 = 0.33
1 2
n2 0.10
g. Mole fraction of MgCO3 (x2) = n + n = 0.05 + 0.10 = 0.67
1 2
h. Sum of mole fraction = x1 + x2 = 0.33 + 0.67 = 1

i. To have equal mole fraction the mole fraction of each component should be 0.5.
i.e. mole fraction of CaCO3 should be 0.5

let x g of CaCO3 should be added to the mixture.
5+x
No. of mole of CaCO3 = 100
No. of mole of CaCO3

Mole fraction of CaCO3 (x1) = Total no. of mole
1 (5 + x)/100
or 2 =
( 5+x
)
100 + 0.10
1 (5 + x)/100
or 2 = (5 + x + 10)/100
1 5+x
or 2 = 15 + x
or 10 + 2x = 15 + x
or 2x – x = 15 – 10
∴ x =5g
8. Part per million (ppm)

When very small quantity of solute is present in large quantity of solution then it is less significant to
express the concentration in terms of normality or molarity or gram per litre. For very dilute
solution, the concentration is often expressed in terms of part per million. Concentration of ions such
as Hg++, Pb++ etc in solution, and presence of traces amount of gas in atmosphere are also expressed
in terms of ppm.
Concentration of ppm is defined as the weight of solute present in one million parts by weight of
solution.
Mass of solute w ×106
Concentration in ppm = Mass of solution × 106 = w
soln
But for very dilute aqueous solution, the amount of solute is very law so v ≅ wsoln
Mass of solute (in g) w ×106
ppm = vol. of solution (in mL) × 106 = v
and ppm = g/L × 103
Example 2.12 The iodide salt provided by salt trading corporation consists 50 ppm iodine in 1 kg packet.
Calculate the amount of iodine in 1 kg packet salt.
Solution
Method 1:
50 ppm means, 50 parts by mass of iodine is present in 106 parts by mass of salt.
106 kg of salt consists 50 kg iodine
50
1 kg of salt consist 106 kg of iodine = 5 × 10–5 kg = 5 × 10–5 × 1000 g = 0.05 g = 50 mg
Method 2:
Mass of solute
ppm = Mass of solution or mixture × 106
ppm × mass of solution or mixture 50 × 1 kg

Mass of solute = 106 = 106 = 5 × 10–5 kg = 50 mg.
Note: Temperature dependence in concentration units

Normality, molarity, g/L and % (w/v) include volume of solution. If temperature is increased, volume of solution is also
increased (due to expansion), but amount of solute remains constant. So, these concentration units are temperature dependent
units. Their values decrease with increasing temperature. But molality, mole fraction and % (w/w) include masses or number of
moles only in their units. Values of these quantities do not change with the change in temperature. So, these concentration
units are temperature independent units.
2.4 Primary and Secondary Standard Substances

In volumetric analysis, concentration of one solution is determined with the help of another solution
of known concentration by measuring their reacting volumes. Volumetric analysis is likely to be
confused with the measurement of volume of gas or solid. Hence, a better term titrimetric analysis is
used which involves the measurement of volume of solution only used in the titration.
A solution having known concentration is called standard solution. The process of determination of
concentration of a solution with the help of standard solution is called standardization (or titration)
and the solution is called standardized solution.
Standard solution is prepared by dissolving a known mass of pure substance in water and making a
definite volume of solution. These types of solute substances are called primary standard substance.
However, all solutions of the exact concentrations cannot be prepared directly because some
substances interact with air or moisture or may be present in impure form. In such conditions, once
these prepared solutions are required to be standardized and these types of solute substances are
called secondary standard substances.
Primary standard substance is that pure chemical substance which can be used for the direct
preparation of solution of known concentration.
To be a primary standard, a substance should have following requisites.
1. The substance must be easy to obtain and purify. It should be present in pure state.
2. The substance should not be hygroscopic or efflorescent or deliquescent.
3. The substance shouldn't be affected by carbon-dioxide and should not be oxidized by air. The
composition should not change during storage or weighing.
4. It is better to have a high relative molecular mass so that weighing error can be minimized.
5. The substance should be readily soluble under the employed condition.
6. The composition of substance should not change in its solid state or in solution form for
sufficiently long period.
Some examples of primary standard substances include
i. Anhydrous sodium carbonate (Na2CO3) ii. Oxalic acid (COOH)2.2H2O
iii. Potassium chloride (KCl) iv. Arseneous oxide (As2O3)
v. Mohr's salt, FeSO4.(NH4)2SO4.6H2O vi. Potassium dichromate (K2Cr2O7)
vii. Potassium iodate (KIO3) viii. Potassium bromate (KBrO3)
ix. Sodium chloride (NaCl)
The solution which is directly prepared by dissolving primary standard substance and composition
of solution does not vary on prolong standing is called primary standard solution.
Secondary standard substance is defined as that chemical substance whose composition may change
either in solid phase or in its solution phase on long standing and cannot be used to prepare primary
standard solution directly. Secondary standard solutions are also prepared as the primary standard
solutions. But after preparing the solutions, it must be titrated with a primary standard solution to
get its accurate strength. The accurate strength is then utilized for the further calculations.
Hydrated salt as a rule do not make good standard solution (except few like hydrated oxalic acid) as
it is difficult to dry these salt efficiently. The following salts are found to be secondary standard
substances.
i. Copper sulphate (CuSO4. 5 H2O) ii. Sodium tetra borate (Na2B4O7. 10 H2O)
iii. Sodium hydroxide (NaOH) iv. Acids such as HCl, HNO3, H2SO4
v. Potassium permanganate (KMnO4) vi. Ferrous sulphate (FeSO4)
So, the solution whose strength is to be redetermined after its preparation with the help of a primary
standard solution is called secondary standard solution. In such type of solution exact strength can
not be determined on the basis of amount of substance dissolved to prepare solution because this
type of substance may not be present in pure and dry state. Their composition may change while
storing.
Preparation of Primary Standard Solution (Say Na2CO3 Solution)

To prepare primary standard solution of a substance, first we have to determine volume and
strength of solution to be prepared. The mass of the substance required is calculated. The calculated
mass of primary standard substance is taken in volumetric flask and water is added upto mark. The
solution is shaken well. Let us take an example for the preparation of 100mL of decinormal oxalic
acid solution. The solution is prepared in the following steps.
Calculation
Volume (v) × Eqvt. mass (E) × Normality (N) 100 × 63 × 0.1
Mass required (w) = 1000 = 1000 = 0.63 g
Â Weigh out exactly 0.63 g of pure oxalic acid crystals in watch glass.
Â Pour the weighted oxalic acid into 100 mL volumetric flask using funnel.
Â Wash the watch glass by sprinkling water drops through wash bottle into volumetric flask.
Â Wash the funnel upto the brim and allow to fall the wash into volumetric flask.
Â Dissolve the content within volumetric flask by adding little quantity of water.
Â Then add water to make the volume of solution upto the mark.
Â Shake the solution properly to make the solution homogeneous.
Wash bottle
Balance Watch glass Volumetric flask
Fig. 2.1: Schematic diagram of some laboratory instruments and apparatus

Preparation of decinomarmal NaOH solution (Secondary Standard Solution)

Lets suppose, we have to prepare decinormal solution of NaOH (which may be approximately
100 × 40 × 0.1
decinormal solution). Weight out 1000 g = 0.4 g NaOH in a watch glass and transfer and
dissolve it in 100 mL volumetric flask. Add water to make the volume upto the mark. The solution is
approximately decinormal.
Preparation of secondary standard solution (say exactly Decinormal NaOH Solution)

Let us take an example for the preparation of 100 mL of decinormal NaOH solution. The solution is
prepared in the following steps.
Calculation:
Volume (V) × Eqvt. mass (E) × Normality (N)
Weight required of NaOH (W) = 1000
100 × 40 × 0.1
= 1000 = 0.4 g
Step 1: Preparation of approximate 0.1 N NaOH solution.

i. Weigh out slightly more than 0.4 g (say 0.5-0.6 g) of NaOH in watch glass.
ii. Transfer the weighed NaOH into 100 mL volumetric flask using funnel.
iii. Wash the watch glass by sprinkling water drops through wash bottle into volumetric flaks.
iv. Dissolve the content within volumetric flask by adding little quantity of water.
v. Then add water to make the volume of solution upto the mark.
vi. Shake the solution properly to make the solution homogeneous.
Step 2: Standardization of NaOH solution
i. Take NaOH solution in burette and 10 mL of standard oxalic acid solution in conical flask. Then
add about 2 drops of phenolphthalein.
ii. Titrate the solution to obtain end point.
Calculation
Oxalic acid Sodium hydroxide
V1= 10 mL (from pipette) V2 = 8 mL (say, from burette reading)
N
N1 = 10 (say) N2 = ?
Applying normality equation, N1V1 = N2V2

V1N1 10 1 1
N2 = V2 = 8 × 10 = 8 N
Step 3: Dilution of NaOH solution to make it exactly decinormal.
NaOH (Prepared above) NaOH (To be prepared)
V1 =? V2 = 100 mL
1
N1 =8 N2 = 0.1 N
Applying Law of Dilution (C1V1 = C2V2)

V2N2 100 × 0.1
V1 = N = 1/8 = 100 × 0.1 × 8 = 80 mL
1
Take exactly 80 mL of thus prepared NaOH solution in 100 mL measuring flask and add water
to make it exactly 100 mL. Shake the solution to make homogeneous. The solution can now be
used as a decinormal solution.
2.5 Law of Chemical Equivalence: Normality Equation

According to the law of chemical equivalence, one gram equivalent of one chemical substance reacts
exactly with one gram equivalent of another chemical substance or in any chemical reaction,
reactants must react in equal number of gram equivalents. Accordingly, x gram equivalent of
particular compound exactly reacts with x gram equivalent of another compound. For two reacting
substance A and B to have complete reaction,
Number of gram equivalent for A (g1) = Number of gram equivalent for B (g2) . . . (i)
We know,
Number of gram equivalent (n)
Normality (N) = Volume of solution in litre (V)
or, Number of gram equivalent (g) = Normality (N) × Volume in litre (V)
So, g1 = N1V1 and g2 = N2V2
Now relation (i) becomes,
N1V1 = N2V2 . . . (ii)
The relation (ii) is called normality equation. This relation is always true because chemical
substance always react in equivalent proportions,
For molarity equation, the balance chemical equation is required. Example:
aA + bB Products
No. of moles of A a
No. of moles of B = b
M1V1 a
or M2V2 = b
So, the molarity equation is
a(M2V2) = b(M1V1) . . . (iii)
Note:
M1V1 = M2V2 holds true only when reactants react in equal number of moles.
Normality factor
To understand the normality factor, let's take an example of preparation of decinormal 250 mL
solution of anhydrous sodium carbonate 1.325 g should be weighted. If 1.325g of anhydrous Na2CO3
N
is weighted and dissolved to prepare 250 mL solution then the strength is exactly 10 . If weight
N
slightly greater or less is taken, the strength of solution is not exactly 10 . In such condition,
normality factor is calculated. Normality factor (f) is defined as the ratio of mass taken to the mass to
be taken.
Mass taken
Normality factor (f) = Mass to be taken
If normality factor is greater than one then the strength of solution is greater than that to be required.
If normality factor is one then the strength is exactly same as that is required. If normality factor is
less than one then the strength of solution is less than that to be required. To understand more
clearly, let us discuss few cases here
a. If weight taken is 1.350 g.
1.350
Normality factor (f) = 1.325 = 1.01
N
The concentration of solution is expressed as 10 (f = 1.01)
b. If weight taken is 1.325 g.

1.325
Normality factor (f) = 1.325 = 1
In such case, it is not necessary to write normality factor.

N N
The concentration of solution is expressed as 10 (f = 1) or simply 10
c. If weight taken is 1.320 g.

1.320
Normality factor (f) = 1.325 = 0.99
N
The concentration of solution is expressed as 10 (f = 0.99)
In calculation, the normality factor is multiplied

Examples:
N 1
10 (f = 1.01) = 10 × 1.01N = 0.101N
N 1
10 (f = 1) = 10 × 1 N = 0.1N
N 1
10 (f = 0.99) = 10 × 0.99 N = 0.099N
In the days where weight of chemical substance were used to be taken by using, non-digital balance,
the normality factors were mostly used. Now a day's digital balances are used to weigh out the
chemical substance. Hence, normality factors are less commonly used.
2.6 Theoretical Aspects of Volumetric Analysis

2.6.1 Introduction
Volumetric analysis is that analysis in which strength of a solution is determined by reacting it with
standard solution by measuring their reacting volumes. Volumetric analysis is based on the fact that
chemical substances react in their equivalent proportions. Volumetric analysis is carried out by
titration. The principle of volumetric analysis can be outlined as follows.
i. Chemical substances always react in their equivalent proportions. It leads to the normality
equation N1V1 = N2V2. This law is called law of equivalence.
ii. During dilution, if volume of solution is multiplied by x, strength of solution must be divided
by x. For the dilution of a particular solution, the product of C × V remains constant.
This is called law of dilution. The general relation for dilution is C1V1 = C2V2. Where C1 and V1
are the concentration and volume of solution before dilution, C2 and V2 are the concentration
and volume of solution after dilution. Here C is the concentration of the solution in any unit.
1 N
1 mL of 1N NaOH ≡ 10 mL of 10 N NaOH ≡ 20 mL of 20 NaOH
N N
≡ 5 mL of 5 NaOH ≡ 0.1 mL of 0.1 NaOH and so on.
iii. If solutions of reactants have same normality, these react with each other in equal volume. If
acid and base neutralize by equal volume, these should have same normality.
9 mL of 0.1 N HCl ≡ 9 mL of 0.1N NaOH ≡ 9 mL of 0.1N Na2CO3 ≡ 9 mL of 0.1N KOH
iv. When chemical substances of same kind are added then number of gram equivalent increases.
If three different acid solutions having normality N1, N2 , N3 and volume V1, V2, V3, respectively
are mixed then
NV = N1V1 + N2V2 + N3V3
N1V1 + N2V2 + N3V3
or, N = (V1 + V2 + V3)
Where N is normality and V is volume of resulting solution. The same is true for base.
v. If acids and alkalis are mixed, the chemical substance having minimum number of gram
equivalent is completely neutralized and solution possesses the acidic or basic character due to
excess reagent.
If N1 and V1 are normality and volume of acid
N2 and V2 are normality and volume of base.
N and V are normality and volume of resulting solution,
then NV = N1V1 – N2V2 if N1V1 > N2V2
N1V1 – N2V1
or N= V1 + V2
and, NV = N2V2 – N1V1 if N2V2 > N1V1
N2V2 – N1V1
or N= V1 + V2
Example 2.13 0.715 g of Na2CO3⋅xH2O required 20 mL of seminormal hydrochloric acid solution for complete
reaction. Find the value of x.
Solution
Method 1:
1 gequiv of HCl ≡ 1 gequiv of Na2CO3.xH2O.
1000 mL of 1N HCl ≡ E g of Na2CO3⋅xH2O, where E = Equivalent weight of Na2CO3⋅xH2O
E
20 mL of 1N HCl ≡ 1000 × 20 g Na2CO3⋅xH2O
N E 1 E
20 mL of 2 HCl ≡ 1000 × 20 × 2 g ≡ 100 g.
E
∴ 100 g = 0.715 g
∴ E = 71.5
∴ Equivalent wt. of Na2CO3. x H2O = 71.5
∴ Mol. mass of Na2 CO3.x H2O = 71.5 × 2 [ acidity of Na2CO3 ⋅ xH2O is 2] = 143 amu.
Mol. mass of Na2CO3 . x H2O = 2 × 23 + 12 + 3 × 16 + x × 18
143 = 46 + 12 + 48 + x × 18
143 – 106 = 18 x
37 = 18 x
x = 2.05
∴ Value of x = 2.
Method 2:
w× 1000 0.715 × 1000
Equivalent wt. of Na2CO3.xH2O = v × N = 20 × 0.5 = 71.5
∴ Mol. mass = 71.5 × 2 =143

Mol. mass of Na2CO3.xH2O = 106 + x × 18
or, 143 = 106 +18x
143 - 106
∴ x= 18 = 2.05 ≈ 2
Method 3:
No. of gram equivalents of Na2CO3⋅xH2O = No. of gram equivalents of HCl
0.715 1 20 w (in g)
or, E = 2 × 1000 , since number of g equiv = N × V (in L) = E
or, E = 715
Molecular mass of Na2CO3.xH2O = 71.5 × 2 = 143 amu
Now, 143 = 106 + 18x
∴ x=2
Example 2.14 7.35 g of a dibasic acid was dissolved in water and diluted to 250 mL. 25 mL of this solution was
neutralized by 15 mL. of N NaOH solution. What is equivalent weight and molecular mass of the
acid?
Solution
Method 1:
25 mL of acid solution was neutralized by 15 mL of 1N NaOH
Acid solution NaOH solution
v1 = 25 mL v2 =15 mL
N1 = ? N2 = 1N
V2N2 15 × 1
∴ N1 = V = 25 = 0.6 N, where N1 is the normality of the diluted solution.
1
∴ Strength of 25 mL acid solution = strength of 250 mL of acid solution = 0.6N.

0.6 N of 250 mL solution consists 7.35 g dibasic acid

7.35
1N of 250 mL solution consists 0.6 g of dibasic acid
7.35 × 1000
1N of 1000 mL solution consists 0.6 × 250 g = 49 g dibasic acid
So, Eq. wt of dibasic acid = 49.

Since acid is dibasic
Molecular mass = Eq. wt × basicity = 49 × 2 = 98 amu
Alternatively,
7.5 × 1000 7.35 × 1000 × 25
Eq. wt of dibasic acid = 15 × 1 = 15 × 250 = 49
25 × 250
∴ Mol. mass of dibasic acid = 49 × 2 = 98 amu

N
Example 2.15 x g of CaCO3 required 40 mL of 2 HCl for complete neutralization. Calculate x.
Solution
Note:
W (in g)
No. of gequiv of solute = N × V (in L) = E
w (in mg)
No. of mequiv of solute = N × v (in mL) = E
Method 1:
100
1000 mL of 1 N HCl = 50 g CaCO3 (as ECaCO3 = 2 = 50)
N 50 × 40 × 1
40 mL of 2 HCl = 1000 × 2 g CaCO3 = 1 g
Method 2:
No. of g equiv of CaCO3 = No. of g equiv of HCl
x 1 40
So, 50 = 2 × 1000
or, x = 1g
Method 3
No. of mequiv CaCO3 = No. of mequiv HCl
Suppose, mass of CaCO3 = w mg
w 1
50 = 2 × 40
w = 1000 mg = 1 g
N
Example 2.16 1.0 g of CaCO3 was dissolved in 50 mL at 2 HCl solution. The solution was diluted 100 mL.
Calculate the normality and pH of the diluted acid.
Solution
1000
No. of m equiv of CaCO3 = 50 = 20 mequiv
1
No. of m equiv of HCl taken = 2 × 50 = 25 mequiv.
No. of mequiv of HCl that reacted with CaCO3 = 20 mequiv

No. of mequiv HCl left unreacted = 25 – 20 = 5 mequiv in 50 mL of solution
5
Normality of residual and before dilution (N1) = 50 = 0.1 N
Let,
So, normality of diluted acid (to 100 mL) = N2
Using law of dilution, N1V1 = N2V2
0.1 × 50 = N2 × 100
0.1 × 50 5
N2 = 100 = 100 = 0.05 N
pH of diluted acid = – log (Nacid) = – log (0.05) = 1.7

N
Example 2.17 1.5 g of calcium carbonate sample required 40 mL of 2 HCl for complete neutralization. Calculate
percentage purity of the calcium carbonate in the sample.
Solution
Lets suppose: Mass of CaCO3 in the sample = x g
No. of g equiv. of CaCO3 = No. of g equiv of HCl
x 1 40
or, 50 = 2 × 1000
x=1g
1
So, % purity of CaCO3 = 1.5 × 100 = 66.67%
Example 2.18 50 mL of 1M acetic acid is mixed with 50 mL of 0.2 M NaOH. If ka for CH3COOH is 1.8 × 10–5,
calculate
(a) pH of resulting solution
(b) Concentration of salt formed
Solution
Number of millimole of CH3COOH = volume in mL × molarity = 50 × 1 = 50 mmol
Number of millimole of NaOH = V(mL) × molarity = 50 × 0.2 = 10 mmol
The reaction takes place as follows:
CH3COOH + NaOH CH3COONa + H2O
Initially present 50 mmol 10 mmol – –
Changed quantity 10 mmol 10 mmol 10 mmol 10 mmol
Quantity after reaction 40 mmol – 10 mmol 10 mmol
Total volume of solution = 50 + 50 = 100mL
(a) Calculation of pH of resulting solution
number of mmol 40
Molarity of acetic acid in resulting solution (M) = volume in mL = 100 = 0.4 M
The solution is equivalent to 100 mL of 0.4M H3COOH. The acetic acid ionizes as follows:
CH3COOH CH3COO¯ + H+
Initially, C mol lit–1 0 0
At time t c-cα cα cα
From Ostwald's dilution law, ka = α2c
ka
or, α= c
ka
[H+] = cα = c ⋅ c = ka ⋅ c = 1.8 × 10–5 × 0.4 = 2.68 × 10–3
pH = –log [H+] = –log (2.68 × 10–3) = 2.57

(b) Concentration of salt formed
number of mmol of salt 10
Molar concentration of salt = volume of mL = 100 = 0.1 M
2.6.2 Titration
In the previous unit we have discussed that volumetric analysis involves the quantitative
determination of volume of standard solution required to react with the measured volume of
solution of unknown strength. The term volumetric analysis is likely to be confused with the
measurement of volume of gas. Therefore, a clear term titrimetric analysis is introduced which
expresses the process of titration rather than volume measurement.
Titration is the method of quantitative chemical analysis which involves the determination of volume
of standard solution required to react with measured volume of solution of unknown strength. The
solution of known strength is called standard solution. The solution of known strength is also called
titrant. In titration, the standard solution (titrant) is usually added from a burette. The substance
being titrated is called titrand. Titrand is usually taken in conical flask. However, it is not the affix
rule. There are other factors used to determine which solution is to be kept in burette or in conical
flask.
10
20
30
40
50
Conical flask Pipette

Titration (As titration flask)
Fig. 2.2: Burette, conical flask and pipette
In titration process, a fixed volume of solution (usually, the solution whose strength is to be
determined) is taken in a conical flask. Few drops of suitable indicator are added. Then another
solution (usually standard solution) is added from burette into the conical flask. The conical flask is
shaken with swirling motion. During titration, a point will appear at which equivalent quantity of
titrand is neutralized by titrant which is called equivalence point or theoretical end point or
stoichiometric end point. However, this point is not visible in acid base titration. To indicate the
completion of reaction between titrant and titrand usually an auxiliary chemical substance is added
which is called indicator. The completion of titration is detected by some physical change produced
by one of the solution itself or by indicator. Most of the indicators show their colour change either in
acidic medium or in alkaline medium. Therefore, at the equivalence point the indicators are unable
to show their colour change. The point at which indicator show the completion of reaction between
titrant and titrand by the sharp visual change in colour or the appearance of turbidity is called end
point of the titration. In the ideal titration, end point coincides with equivalence point but in practice
the value of end point is slightly different than the value of stoichiometric end point or equivalence
point. The difference between end point and equivalence point of titration is called titration error. In
titration, indicator should be chosen in such a manner that it would avoid or minimize the titration
error.
While conducting the titrimetric analysis the following points are to be considered.
i. The chemical substances react completely in equivalent proportion.
ii. The reaction should be relatively fast. If rate of reaction is slow, a suitable catalyst should be
added or solution can be heated.
iii. There must be some sort of physical change at the end point. The change may be in colour or
the formation of precipitate.
iv. If indicator fails to indicate the end point, other alternative methods are adopted to find out the
equivalence point. The alternative methods may be conductometric titration, (measuring the
change in conductance of ions in solution), potentiometric titration (measuring the potential
between indicator electrode and reference electrode), coulometric titration (developing the
titrant by electrolysis) or amperometric titration (measurement of current under constant
applied voltage). These methods of titration are not discussed here. This is beyond the scope of
this text.
Differences between equivalence point and end point

Equivalence point End point
1. The point in titration at which equivalent 1. The point in titration at which neutralization of
quantity of titrand is exactly neutralized titrand by titrant is shown by sharp change in
by titrant is called equivalence point visual colour of solution is called end point.
2. Equivalence point is not visible in acid- 2. End point is visible in acid base titration using
base titration involving burette and burette and pipette system.
pipette system.
3. It is determined by using (conductometer 3. It is determined by observing the colour change
or potentiometer) instrumental method. of indicator in solution.
4. It is exact point where the reactants are 4. It is practical point where the completion of the
completely reacted. reaction is indicated by the change in colour.
Classification of Titration Reactions in Titrimetric Analysis

The titration involved in titrimetric analysis can be classified into following types:
a. Acid-base titration or neutralization titration.
b. Redox titration or oxidation-reduction titration.
c. Complexometric titration or complex formation titration.
d. Precipitation titration.
a. Acid-base titration
The titration which involves the reaction of free acid and free base or base formed from salt of weak
acids by hydrolysis (e.g. Na2CO3) is called acid-base titration. Some of the acid-base reactions
involved in acid-base titration are as follows.
HCl + NaOH NaCl + H2O
2 HCl + Na2CO3 2 NaCl + H2O + CO2
The reaction of HCl and Na2CO3 is also regarded as acid-base reaction although Na2CO3 is salt
because Na2CO3 undergoes hydrolysis to give alkali NaOH.
Na2CO3 + 2 H2O 2 NaOH + H2CO3
In this type of titration, end point is detected by the use of acid-base indicator or pH indicator. It will
be discussed in next unit.
b. Redox titration
The chemical reaction which involves change in oxidation number or transfer of electron among the
reacting chemical species is called redox reaction or oxidation-reduction reaction. In this type of
reaction standard solution is either oxidising or reducing agent. It means if titrant is oxidising agent,
titrand should be reducing agent and vice-versa. Titration involving such type of reaction is called
redox titration. The commonly used oxidising agents are KMnO4, K2Cr2O7, I2, KIO3, KBrO3, etc. The
commonly used reducing agents are iron (II) compounds such as Mohr's salt
(FeSO4.(NH4)2SO4.6H2O), sodium thiosulphate (Na2S2O3), arseneous oxide (As2O3), oxalic acid
(COOH)2 etc.
The reaction between acidified KMnO4 solution and oxalic acid is discussed below.
KMnO4 is strong oxidising agent and it oxidises oxalic acid to carbondioxide. KMnO4 is reduced
while oxalic acid is oxidised.
The oxidation half reaction of KMnO4 in acidic medium is,
2 KMnO4+ 3 H2SO4 K2SO4+ 2 MnSO4 + 3 H2O + 5 [O] . . . (i)
Ionic reaction,
MnO4¯ + 8 H+ + 5 e¯ Mn++ + 4 H2O . . . (ii)
The reduction half reaction of oxalic acid is,
COOH + [O] 2CO2 + H2O
COOH
Ionic reaction is,

COO¯ 2CO2 + 2 e¯
COO¯
To obtain overall reaction, oxidation half and reduction half reaction are added.
The molecular reaction is
2 KMnO4 + 3 H2SO4 K2SO4 + 2MnSO4 + 3H2O + 5 (O)
COOH + [O] 2CO2 + H2O] ×5
COOH
+7 +2
2 KMnO4 + 5COOH + 3H2SO4 K2SO4 + 2MnSO4 +10 CO2 + 8H2O
COOH
The ionic reaction is,
MnO4¯ + 8 H+ + 5 e¯ Mn++ + 4 H2O ] × 2
COO¯ 2CO2 + 2 e¯ ] × 5
COO¯
2MnO4¯ + 16 H+ + 5COO¯ 2Mn++ + 10 CO2 + 8 H2O
COO¯
Note:
1. The titration involving potassium permanganate is called permanganometric titration.
2. Potassium permanganate is not primary standard substance because it is not obtained in pure state. It may consist MnO2 as
impurity. The KMnO4 solution is not so soluble in aqueous solution. The aqueous solution of KMnO4 is boiled for some time,
cooled and filtered. Then it is standardised by either oxalic acid or by Mohr's salt. In this titration KMnO4 is taken in burette.
3. KMnO4 is acidified by dilute H2SO4 but not by dilute HCl or HNO3 because KMnO4 may oxidise HCl. Whatever may be the
strength, HNO3 acts as oxidising agent.
4. In the titration of KMnO4, no external or internal indicator is required because disappearance of pink colour indicates the
completion of reaction. So KMnO4 acts as self indicator.
5. When KMnO4 is reduced to Mn++, the Mn++ acts as catalyst and increases the rate of reaction. For example, in the titration of
acidified KMnO4 and oxalic acid, initially the the rate of disappearance of pink colour of KMnO4 is relatively slow. After few
readings Mn++ is sufficient in solution to catalyse and rate of disappearance of pink colour of KMnO4 is fast in the same pace of
titration.
6. Since the reaction between KMnO4 and oxalic acid is slow, so the acidified oxalic acid must be heated to about 600C, before
running down the KMnO4 from burette.
c. Complexometric titration
The titration which involves the formation of complex compound is called complexometric titration.
The most commonly used reagent in this type of titration is disodium salt of EDTA (Ethylenediamine
tetra-acetic acid). In such case, the equivalence point is determined by the use of metal ion indicator
such as Eriochrome black-T. This type of titration can be used in the estimation of hardness of water.
Ca++ + Disodium EDTA Calcium EDTA complex + 2Na+
d. Precipitation titration
This type of titration involves the formation of precipitate by the combination of ions of titrant and
titrand.
Example:
NaCl + AgNO3 AgCl ↓ + NaNO3
White ppt
The formation of precipitate is guided by solubility product principle. (This is discussed in ionic
equilibria). In the titration of AgNO3 and NaCl, potassium chromate solution can be used as indicator.
At end point:
2Ag+ + CrO42– Ag2CrO4 (red)
Indicators in acid-base titration

The auxiliary chemical substance which is used to indicate the completion of reaction by the sharp
change in colour of solution or of precipitate is called indicator. The indicator used in acid-base
reaction is called acid-base indicator. There are different theories about the action of indicator. Acid-
base indicators are either organic weak acids or organic weak bases. These show one colour in
certain pH range and show another type of colour in another pH range. Every acid-base indicator
has its own colour changing pH range called pH transition. If equivalence point of reaction falls in
this pH range, equivalence point coincides with colour changing pH range of indicator and end
point is attained accurately.
The choice of indicator depends upon the nature of titrant and titrand. However the basic principle
and common feature is that the indicator should be chosen in such a way that end point should
coincide with equivalence point and titration error should be zero. This condition may not be
achieved exactly and very small difference usually occurs. The indicator and experimental condition
should be chosen in such a way that the difference between end point and theoretical end point is as
small as possible.
In case of acid base titration, acid-base indicator is used. Every acid-base indicator has a certain
effective pH range within which it shows sharp change in colour. The pH value at the end point of
titration depends upon the relative strength of acid-base under titration. The pH value at the end
point of titration and pH range of indicator should have proper matching. The suitable indicator and
effective pH range for acid-base titration are as follows:
Table 2.6: Choice of indicators in acid-base titration

Approx. pH range near Approximate pH transition
Acid Base Indicator
equivalence point of indicator
Strong Strong 3 - 11 Methyl orange 3.2 - 4.4
phenolphthalein 8 - 10
Strong Weak 3-8 Methyl orange 3.2 - 4.4
Weak Strong 6 to 11 phenolphthalein 8 - 10
Weak Weak about 6 to 8 None ––––
Table 2.7: Colour of indicators in different media

Colour in
Indicator
Acidic medium Basic medium
Methyl orange Pink or red Light yellow
Litmus paper Red Blue
Phenolphthalein Colourless Pink
Following titration curve is useful to choose acid base indicator.
12
11
B Phenolphthalein (8-10)
10 •
pH =11
9
8
C
7 • pH = 8
pH
6
D
5 • pH = 6
4
Methyl orange (3.2 - 4.4)
3
A
2 • pH = 3
1
Volume of alkali added
Fig. 2.3: Titration curve
A curve obtained by plotting a graph of pH of solution versus volume of alkali added is called
titration curve. When acid is taken in a conical flask with few drops of indicator and alkali is added
gradually from burette, H+ ions of acid is neutralized by OH¯ ion of base. In this condition there is
smooth increase in pH value of resulting solution. Near the end point or equivalence point there is
sudden rise in pH value. After this, again there is smooth rise in pH value. The sudden rise or steep
rise in pH value during titration indicates the neutralization in acid-base reaction. The nature of
titration curve depends upon the nature of acid and base used.
a. Titration of strong acid and strong base: In the titration of strong acid such as HCl and strong
base such as NaOH, the steep rise of curve occurs at pH 3 to 11. Any indicator capable of
changing colour within this range is a suitable indicator.
The colour changing pH range of methyl orange is 3.2 to 4.4 and that of phenolphthalein is 8 to
10. So either methyl orange or phenolphthalein can be used as indicator.
12
11
B
10 • pH =11
9
8 Phenolphthalein (8.0-10)
7
pH 6
5
4
3 Methyl orange (3.2 - 4.4)
A
2 •pH = 3
1
Volume of alkali added

Fig. 2.4: Titration curve of strong acid and strong base
b. Titration of strong acid and weak base: In the titration of strong acid such as HCl and weak
base such as NH4OH, the steep rise of curve occurs at pH 3 to 8.
HCl + NH4OH NH4Cl + H2O
Any indicator capable of changing its colour within this pH range is a suitable indicator.
The colour changing pH range of methyl orange is 3.2 to 4.4. So methyl orange is a suitable
indicator in the titration of strong acid and weak base.
12
11
10
9
C
8 • pH = 8
pH 7
6
5
4 Methyl orange (3.2 - 4.4)
A
3 • pH= 3
2
1
Volume of base added
Fig. 2.5: Titration curve of strong acid and weak base

Self Test
2.10 Why is phenolphthalein not used as indicator in the titration of strong acid and weak base?
c. Titration of weak acid and strong base: In the titration of weak acid such as CH3COOH and
strong base such as NaOH the steep rise of curve occurs at pH 6 to 11.
CH3COOH + NaOH CH3COONa + H2O
Any indicator capable of changing its colour within this pH range is a suitable indicator. The
colour changing pH range of phenolphthalein is 8.0 to 10.0. So phenolphthalein is a suitable
indicator in the titration of weak acid and strong base.
12
B
11 • pH =11
10
9 Phenolphthalein (8.0-10)
8
pH 7
D
6 pH = 6
5
4
3
2
1

Fig. 2.6: Titration curve of weak acid and strong base
d. Titration of weak acid and weak base: In the titration of weak acid such as CH3COOH and
weak base such as NH4OH there is no enough steep rises in the curve. The tapering of curve
takes place within pH value of 6 to 8.
CH3COOH + NH4OH CH3COONH4 + H2O
12
11
10
9
C
8 •H
p =8
pH 7
D
6 •
pH = 6
5
4
3
2
1
Fig. 2.7: Titration curve of weak acid and weak base

The colour changing pH range of methyl orange is 3.2 to 4.4 and that of phenolphthalein is 8.0
to 10.0. Therefore, neither methyl orange nor phenolphthalein is suitable indicator. Hence end
point of weak acid-weak base titration is not determined by acid-base titration which may be
determined by other methods such as conductometric titration.
Solved Questions
1. Define decinormal solution.
¬ A solution containing one tenth gram equivalent of dissolved solute per litre solution is said to be deci-
normal solution (N/10). Example: 5.3 g Na2CO3 dissolved in 1 L solution gives decinormal Na2CO3
solution.
2. What do you mean by equivalent weight of an element?
¬ Equivalent weight of an element may be defined as the number of parts by weight of it which combines
with or displaces directly or indirectly 1.008 parts by weight of hydrogen, 8 parts by weight of oxygen and
35.5 parts by weight of chlorine or its equivalent. For example: Equivalent wt. of Mg = 12
3. What is primary standard solution?
¬ The solution which can be prepared directly by dissolving calculated amount of solute to prepare specified
volume of solution and can be stored for a sufficiently long period without any change in concentration, is
called primary standard solution. Primary standard solution is prepared by dissolving primary standard
substance. e.g., Oxalic acid, anhydrous sodium carbonate, Mohrs salt, etc. can be used to prepare primary
standard solution.
4. What is secondary standard solution?
¬ The standard solution, whose strength is to be redetermined after its preparation is secondary standard
solution. The solution whose strength is determined first by titrating it with standard solution then
afterward it can be used for titration purpose is called secondary standard solution. Solution of potassium
permanganate is an example of secondary standard solution.
5. What is an acid-base indicator?
¬ The organic compound either weak acid or weak base which acts as auxiliary reagent and shows the
completion of acid-base reaction by the sharp change in visual colour of solution or of precipitate is called
acid-base indicator. Example: Methyl orange and phenolphthalein are the examples of acid-base indicators.
Questions
1. What is normality? How is it related with molarity?
2. Why are the concentration units like g/L, M, N etc. temperature dependent?
3. Define acidimetry and alkalimetry.
4. Write an example of redox titration. Why is it called so?
5. Differentiate primary and secondary standard solutions.
6. What are the requisites for a substance to be a primary standard?
7. Define secondary standard solution with a suitable example
8. What is normality factor? How does it arise during the preparation of standard solution?
9. Why are the following substances not taken as primary standard substances (a) NaOH
(b) Na2CO3.10H2O (c) FeSO4 (d) conc. H2SO4 (e) KMnO4
10. Write down the differences between equivalence point and end point.
11. Why is chemical indicator method not suitable for the titration between weak acid and weak
base?
12. What is normality equation? Derive it.

1. Define: (a) normality factor (b) binormal solution (c) semi-molar solution (d) centimolar solution
(e) molarity (f) decinormal solution (g) decimolar solution (h) end point (i) equivalence point (j)
indicator.
2. What is an indicator? How is a suitable indicator selected for a particular acid-base titration?
3. Write short notes on (a) choice of indicators in acid base titration (b) law of equivalence.
Numerical Problems
1. What volume of water should be added to 500 mL of 2 N (f = 0.98) Na2CO3 to make it exactly
N/10?
Ans: 9.3 litres
2. X cc of 5 N HCl was diluted to one litre to make normal solution. Calculate the value of x.
Ans: 200cc
3. What mass of Na2CO3 is required to make 50cc of its seminormal solution?
Ans: 1.325 g
4. What volume of 5% NaOH is required to neutralize 2 litres of decinormal H2SO4?
Ans: 160 mL
5. 0.715 g of Na2CO3 x H2O required 20 mL of seminormal hydrochloric acid solution for complete
reaction. Find the value of x.
Ans: x = 2
6. 7.35 g of a dibasic acid was dissolved in water and diluted to 250 mL. 25 mL of this solution was
neutralized by 15 mL of N NaOH solution. What is equivalent weight and molecular mass of the
acid?
Ans: Eqvt. wt. = 49, Molecular wt. = 98
7. x g of a metal (eq. wt = 12) was completely dissolved in 100 cc of N/2 HCl. The volume was
then made up to 500 cc. 25 cc of this diluted acid required 17.5 cc N/10 NaOH for complete
neutralization. Find the value of x.
Ans: x = 0.18g
8. 100 mL of 0.1 M HCl is mixed with 50 mL of 0.1M KOH. Calculate the concentration of acid in
terms of g/L in the resulting solution.
Ans: Gram/Litre = 1.21
9. If 20 mL of 0.5 N NaOH is mixed with 30 mL of 0.3 N HCl, is the resulting solution acidic or
basic? Calculate the normality with respect to the acidic or basic final solution.
Ans: Basic, 0.02 N
10. What is the normality of 50 mL of 3 M H3PO4 solution?
11. What volume of 10 M and 5 M NaOH solutions must be mixed to prepare 6L of 6M NaOH
solution
Ans: 1.2 L and 4.8 L
N
12. What mass of 50% pure CaCO3 is required to neutralize 40 mL of 2 HCl?
Ans: 2.0 g
13. Calculate the molarity and normality of 36.5% (w/w) HCl solution having a density 1.15 g/mL.
Ans: 11.5 N, 11.5 M
14. How many moles of H2SO4 are required to prepare 4 L of 2N NaOH solution?
Ans: 4 mol
15. 0.8 g of a divalent metal was dissolved in 100 cc of 1.28 NHCl and the solution was diluted to
200 cc. 50 cc of this dilute solution required 54.6 cc of 0.22 N NaOH for neutralization. Calculate
the atomic mass of the metal.
Ans: 20
16. 4 g of NaOH was added to 20 cc of 2N H2SO4 solution and solution was diluted to 1 L. Predict
whether the solution is acidic, basic or neutral. Calculate the normality of the resulting solution.
Ans: Basic, 3 N
17. 30 g of NaOH was dissolved in 500 mL of its solution, Determine the concentration of the
solution in terms of (a) g/L (b) Normality (c) Molarity (d) % (w/v).
Ans: 60 g/L, 1.5 N, 1.5 M, 6%
18. 5 g of diacidic base is completely neutralized by 50mL of 2N HCl. Find the molecular mass of
the base.
Ans: 100 amu.
19. 100 mL of 0.1 N HCl and of 0.3 N NaOH are mixed. Calculate (a) normality of NaCl formed
(b) Mass of NaOH (in g).
Ans: 0.067 N, 0.585 g

1. The number of milli‐moles of HCl required to 6. The normality of 7.3% solution of HCl is
neutralize 10 mL of 0.2 M Na2CO3 is a. 0.2 N b. 2.0 N
a. 2.0 mmol b. 4.0 mmol c. 7.3 N d. 0.1 N
c. 0.2 mmol d. 0.4 mmol 7. The normality of 1% solution of sulphuric acid is
2. 100 mL of 0.5 M H2SO4 solution and 0.1 litre of 1 M nearly
HCl were mixed. The normality of the resulting a. 1.0 N b. 0.1 N
solution will be, c. 0.2 N d. 1.5 N
a. 1.5 N b. 0.75 N 8. What is the molarity of a solution containing 34.2 g
c. 2.0 N d. 1N of cane sugar (C12H22O11) in 1 litre of its aqueous
3. The molarity of a solution obtained by mixing 50 mL solution?
of 24 N sulphuric acid with 50 mL of water is a. 1.0 M b. 3.42 M
a. 12 M b. 18 M c. 0.1 M d. 34.2 M
c. 6M d. 9M 9. 2 g of CaCO3 sample is required for the complete
4. 20 mL of 1N HCl reacted with 30ml of 0.5 N NaOH. e neutralization of 10mL of 2N HCl. The % purity of
normality of resulting solution is CaCO3is
a. 0.1 N HCl b. 0.1 N NaOH a. 50.00% b. 100.00%
c. 0.5 N HCl d. 0.5 N NaOH c. 66.67% d. 33.33%
5. The equivalent weight of divalent metal is 12. Find 10. 1.5g of mixture of NaCl and CaCO3 requires 40mL of
the molecular mass of the metal oxide, N/2 HCl for neutralization. The % NaCl in the
a. 40 b. 16 mixture is
c. 28 d. 32 a. 66.67% b. 50.00%
c. 33.33% d. 80.10%
1 2 3 4 5 6 7 8 9 10
b d c a a b c c a c
Ionic Equilibrium
pH meters are very useful devices to determine the acidic and basic nature of various solutions.
3.1 Introduction
The equilibrium state existing in reversible chemical reaction is discussed under the chapter
Chemical Equilibrium (chapter 9 of modern approach to chemistry I). Such phenomenon existing in
aqueous solutions of electrolytes are studied under ionic equilibrium. Since, some of the most
important processes in biological and industrial systems consist of ionic species of acids, bases or
salts in aqueous solutions, the concept of ionic equilibrium helps us to understand the nature of
different electrolytes in aqueous solution for different applications. The equilibrium among ions and
undissociated or unionised electrolytes is ionic equilibrium.
3.2 Electrolytes and Non-Electrolytes

Any substances which are ionized in water and can conduct electricity through their aqueous
solution are known as electrolytes whereas those which are not ionized in aqueous solution and
cannot conduct electricity are known as non-electrolytes. The electrolytes are further categorized
into two types according to the extent of ionization in aqueous solution; (i) strong electrolytes and (ii)
weak electrolytes.
Strong electrolytes are those electrolytes which are almost completely ionized in any concentration of
solution. Mineral acids (HCl, HBr, HI, HNO3, H2SO4), alkalies (LiOH, NaOH, KOH), and water
soluble ionic compounds (NaCl, KCl, KNO3, K2SO4, Na2SO4) are the common examples of strong
electrolytes. The ionization or dissociation of strong electrolyte is given as
NaCl Na+ + Cl¯
The reversibility sign is necessary for strong electrolytes even as the ionization is not exactly 100%.
Weak electrolytes are those which are feebly (partially) ionized in a certain concentration of solution.
Almost all organic acids (e.g. HCOOH, CH3COOH), some inorganic acids (HCN, HClO, H2CO3) and
some bases (NH4OH, Al(OH)3, Fe(OH)3) are the common example of weak electrolytes. The
ionization of weak electrolyte is given as
+
CH3COOH CH3COO¯ + H
The ionization or dissociation of electrolyte also depends upon the nature of solvent. If solvent is
changed, the extent of ionization may be changed and the concept of strong electrolyte and weak
electrolyte is also changed. That is why a weak electrolyte in one solvent system may behave as
strong electrolyte in another solvent system. The behaviour of strong electrolyte can be explained in
the same way.
Moreover, electrolytes can be classified into two types according to their bonding nature. They are;
(i) true electrolytes and (ii) potential electrolytes. A true electrolyte is a substance which consists of
ions in its purest form. They dissociate to give free ions when dissolved in water. The ionic
compounds such as Na+Cl¯, K+Cl¯, Ba++SO4¯ ¯ etc., are true electrolytes.
A potential electrolyte is a highly polar covalent compound which gets dissolved in water and gives
ions in solution. In their purest form, these electrolytes do not contain any ions. However, they can
easily form ions after dissolution in water. For example HCl and CH3COOH are covalent
compounds. They can interact with water to produce ions as in this reaction.
O H O
CH3—C—O—H + O CH3—C—O¯ + H3O+
H
Note:
True electrolytes dissociate in aqueous solution whereas potential electrolytes ionize in aqueous solution.
Ionic Equilibrium Unit 3 69
3.3 Arrhenius Theory of Ionization

Svante Arrhenius postulated the theory of ionization in 1887. The basic postulates of this theory are:
1. When an electrolyte is dissolved in water, it gives two types of species in which one carries
positive charge and another carries negative charge. Such charged particles are called ions and
process is called ionization.
2. The ions which carry positive charges are called cations and those which carry negative charges
are called anions.
3. In any electrolytic solution, the total number of positive charges is equal to the total number of
negative charges. Therefore, given electrolytic solution is electrically neutral.
4. The ions present in the solution constantly reunite to form neutral molecules and thus there is a
state of dynamic equilibrium between the dissociated and undissociated molecules.
AB A+ + B¯
5. The properties of an electrolyte in the solution are due to the ions given by it in the solution.
6. When an electric current is passed through the solution of an electrolyte, the positive ions
(cations) move towards the cathode and the negative ions (anions) move towards the anode.
7. The electrical conductivity of an electrolyte depends on the number of ions present in the
solution which is determined by the term degree of ionization (α) which is defined as
Number of moles of electrolyte ionised/dissociated
α= Total number of moles of electrolyte taken
The degree of ionization depends upon temperature, concentration, and nature of the
electrolyte and solvent.
Limitations of Arrhenius Theory
1. Arrhenius assumed that ions are formed when electrolytes are dissolved in water but ionic
electrolytes are previously in ionized form. They only dissociate when dissolved in water.
2. According to Arrhenius, water or solvent is must for ionization but X-ray diffraction studies
have revealed that ionization occurs even in molten state.
3. According to Arrhenius, ionization increases due to dilution but strong electrolytes are almost
completely ionized even in concentrated solution.
4. The increase in equivalent conductance and molar conductance of strong electrolyte is not due
to increase in dissociation but it is due to increase in ionic mobility with dilution.
3.4 Factors Affecting the Degree of Ionization

Number of moles of electrolyte ionised or dissociated
Degree of ionization (α) = Total number of moles of electrolyte taken
The important factors that affect the degree of ionization are:
1. Nature of electrolyte: Nature of electrolyte is the most important factor that affects the degree
of ionization. For example, ionic compounds such as NaCl, KI, etc. dissociate almost completely
even in moderately concentrated solution. Such compounds are called strong electrolytes.
However, organic acids such as CH3COOH, HCOOH can ionize partially, and are called weak
electrolytes. For strong electrolytes, α ≈ 1 and for weak electrolytes, α <<< 1.
2. Nature of solvent: The degree of ionization of an electrolyte is directly proportional to the

dielectric constant of the solvent. For example, dielectric constant of water is greater than that of
dimethyl sulfoxide (DMSO). Therefore, degree of ionization of given electrolyte is higher in
water than in DMSO.
3. Temperature: The degree of ionization increases with increase in temperature because at higher
temperature the kinetic energy of solute molecules increases which helps in increasing the
effective collisions between molecules, increasing the degree of ionization.
4. Concentration of electrolyte: The degree of ionization increases with increase in dilution (or
decrease in concentration). This is strikingly found in weak electrolytes because they can almost
completely ionize at infinite dilution which is explained by Ostwald dilution law.
5. Common ion effect: The presence of a strong electrolyte in the solution of a weak electrolyte
having a common ion greatly suppresses the ionization of weak electrolyte. For example,
ionization of CH3COOH (weak acid) is decreased in presence of CH3COONa (strong
electrolyte). This effect is simply called common ion effect and its detail explanation is given in
section 3.12.
3.5 Degree of Ionization (α) and Ionization Constant (K):

Ostwald Dilution Law
Ostwald dilution law relates the degree of ionisation (α) with concentration of a weak electrolyte. Let
us consider the ionization of a binary electrolyte AB in the solution of concentration C mol/L. Suppose
the degree of ionization of electrolyte is α.
AB A+ + B¯
Initial concentration C 0 0
Change in concentration – Cα + Cα + Cα
Concentration at equilibrium (C – Cα) Cα Cα
Applying the law of mass action at equilibrium state of this ionization, the equilibrium constant of
the electrolyte is given by,
[A+] [B¯]
K= [AB] . . . (i)
Here, K = ionisation or dissociation constant of the electrolyte.

Substituting their concentration, we get,
αC × αC
K=
C(1 – α)
α2C
or, K= . . . (ii)
(1- α)
Equation (iii) is the mathematical form of Ostwald dilution law. For weak electrolyte, the degree of
ionization is very small. Since, 1 – α ≈ 1. Now equation (iii) becomes
K = α2C . . . (iii)
K
or, α2 = C
K
or, α= C . . . (iv)
We know,
Number of mole of solute (n)
Molar concentration (C) = Volume of solution in litre (V)
1
If one mole of solute is used to prepare V liter of solution then, C = V .
α2
Now equation (iii) becomes, K = . . . (v)
V(1 – α)
α2
Taking 1 – α = 1, equation (iv) becomes, K = V . . . (vi)
or, α= KV . . . (vii)
Equation (vii) reveals that the degree of ionization is directly proportional to the square root of
dilution.
Therefore, according to Oswald dilution law:
"Degree of ionisation of an electrolyte is inversely proportional to square root of the concentration
of the electrolyte." Or
"Degree of ionisation of an electrolyte is directly proportional to the square root of dilution."
K
α= C or α = KV
Applications of Oswald Dilution Law

1. To calculate degree of ionisation (α): The above mentioned equation can be utilized as:
Ka
* For weak acids: α = C , where Ka = ionisation constant of an acid.
Kb
* For weak bases: α = C , where Kb = ionization/dissociation constant of a base.
Kh
* For salt hydrolysis: h = C , where h is degree of hydrolysis and Kh = hydrolysis constant
2. To determine equilibrium molar concentration of ions like H+, OH– etc.: Molar concentration
of ions formed by the ionisation of an electrolyte is Cα. For example, [H+] = Cα, [OH–] = Cα etc.
3. To calculate pH and pOH of weak acids and bases: The molar concentrations of H+ and OH–
can be determined as given in the example above. Thus, pH and pOH of weak acid and bases
can be determined as:
pH = – log [H+], pOH = – log [OH–]

Also, pH = 14 –pOH (for 25°C)
(iv) To determine the relative acidic or basic nature of acids or bases: The relation is:
α1 K1
=
α2 K2
Limitation of Ostwald's dilution law

Ostwald dilution law is only applicable for weak electrolytes. Strong electrolyte ionise/dissociate
almost completely. For strong electrolyte, 1 – α cannot be approximated as 1. So, the equation
α2C
number (iii) as given above becomes K = 0 = Undetermined. This means, Ostwald's dilution law
is not applicable for the strong electrolytes.
Example 3.1 At 25°C, ionisation constant of CH3COOH is 1.8 × 10–5. For 2 M CH3COOH solution,
calculate:
(a) degree of ionisation (b) % ionisation, and (c) molar concentration of H+ ions in
equilibrium. d) pH of the solution
Solution
Ka 1.8 × 10–5
a. Using Oswald dilution law: α = C = 2 = 9 × 10–6 = 3 × 10–3
b. % ionisation = α × 100 = 3 × 10–3 × 100 = 0.3%

c. [H+] = Cα = 2 × 3 × 10–3 = 6 × 10–3 mol/L
d. pH = -log[H+] = -log(6 × 10–3) = 2.2
Note:
For weak acid, [H+] = Cα and for weak base, [OH–] = Cα. This is because, out of 1 mol electrolyte, α mol of acid or base are
ionized. So for C mol/L Cα mol of acid or base are ionised giving Cα mol [H+] or [OH¯]
Self Test
–4 –6
3.1 How many times an acid with Ka = 10 is stronger than an acid with Ka = 10 ? (Ans. 10)
3.6 Ionization Constant and Relative Strength of Acids and

Bases
The relative strengths of weak acids can be compared in terms of their ionization constant (Ka or Kb).
The smaller the value of Ka, the weaker will be the acidic strength. This fact can be explained with
the help of Ostwald's dilution law.
We have, Ka = α2C
Stronger the weak acid, higher will be the value of degree of ionization for a given concentration and
therefore, higher is the value of Ka. For example, Ka values for acetic acid, formic acid, and
hypocholorous acid at 25°C are 1.8 × 10–5, 2.0 × 10–4, and 3.5 × 10–8, respectively. Therefore, the order
of acidic strength should be formic acid > acetic acid > hypocholorous acid.
Table 3.1: Ionization constants of some weak acids at 25°C

Name of acid Formula Ka
Formic acid HCOOH 1.7 × 10–4
Hydrofluoric acid HF 7.1 × 10–4
Nitrous acid HNO2 4.5 × 10–4
Acetic acid CH3COOH 1.8 × 10–5
Benzoic acid C6H5COOH 6.5 × 10–5
Asorbic acid C6H8O6 8 × 10–10
Hydrocynanic acid HCN 4.9 × 10–10
Phenol C6H5OH 1.3 × 10–10
Similarly, higher the value of Kb, higher is the degree of ionization and hence, stronger will be the
base. For example, Kb values for weak bases ammonia, aniline, and methylamine at 25°C are 1.8 × 10–
5, 5 × 10–10 and 5.1 × 10–4, respectively. Therefore, the order of basic strength should be methylamine
> ammonia > aniline.
Table: 3.2: Ionization constants of some weak bases at 25°C

Name or base Formula Kb
Caffeine C8H10N4O2 4.1 × 10–4
Methylamine CH3NH2 4.4 × 10–4
Ethylamine C2H5NH2 5.6 × 10–4
Ammonia NH3 1.8 × 10–5
Pyridine C5H5N 1.7 × 10–9
Aniline C6H5NH2 3.8 × 10–10
Urea N2H4CO 1.5 × 10–14
Since, the value of Ka and Kb for weak acid and base is very small, the term pKa and pKb is used to
compare the acidic and basic strength. The terms pKa and pKb are given by
pKa = – log Ka, and pKb = – log Kb
We have seen that the magnitude of Ka indicates the strength of an acid. Another measure of the
strength of an acid is its percent ionization, which is defined as
Percent ionization = α × 100%.
Stronger the acid, greater will be the percent ionization. For a monoprotic acid HA, the concentration
of the acid that undergoes ionization is equal to the concentration of the H+ ions or the concentration
of the A– ions at equilibrium. Therefore, we can write the percent ionization as
[H+]
Percent ionization = [HA]0 × 100%
Where, [H+] is the molar concentration of H+ at equilibrium and [HA]0 is the initial concentration of
the acid taken.
Polybasic acid undergoes ionization in different successive steps. Each step has its own ionization
constant. The first ionization constant is always greater than the second ionization constant and so
on. For example, orthophosphoric acid undergoes ionization in three steps as follows
H3PO4 H+ + H2PO4¯ Ka1 = 7.5 × 10–3
H2PO4¯ H+ + HPO4¯ ¯ Ka2 = 6.2 × 10–8
HPO4¯ ¯ H+ + PO4¯ ¯ ¯ Ka3 = 4.8 × 10–13
Here, it is to be noted that Ka1 > Ka2 > Ka3
Self Test
3.2 First ionization constant of an acid is always greater than second ionization constant. Do you
agree this? Give reason for your answer.
3.7 Autoionization of Water

Pure water ionizes to a very small extent. Its autoionization can be expressed as,
H2O (l) + H2O (l) H3O+ (aq) + OH¯ (aq)
By applying the law of mass action:

[H3O+] [OH¯]
Keq =
[H2O]2
Here, Keq is called ionization constant of water.
Concentration of water can be taken to be constant.
or, Keq × [H2O]2 = [H3O+] [OH¯]
or, Kw = [H3O+] [OH¯]
or, Simply: Kw = [H+] [OH¯]
Here, Kw is a constant called ionic product of water which depends upon temperature only.
At 25°C, 10–7 mol/L water ionises producing 10–7 mol/L of H+ ions and 10–7 mol/L of OH¯ ions.
For pure water, [H3O+] and [OH¯] ions are formed in equal numbers. Therefore, at 25°C,
[H3O+] = [OH¯] = 1.0 × 10–7 mol/L.
Therefore, Kw = (1.0 × 10–7) × (1.0 × 10–7)
or, Kw = 1.0 × 10–14
Since, pKw = – log (Kw)
or , pKw = – log (10–14)
or, pKw = 14
Therefore, at 25°C, pH + pOH=14
Effect of temperature on auto-ionization of water
Increase in temperature increases the degree of ionization of water consequently concentration of H+
and OH¯ increases and ionic product of water also increases. As result of this pKw value decreases.
At different temperatures the values of Kw and pKw are given below. This means, on increasing
temperature, there is decrease in pH, pOH and pKw.
Example:
For pure water at 25°C: pH=7, pOH=7, pKw=14 and pKw= 14. Here, pH + pOH=14.
For pure water at 50°C: pH=6.63, pOH=6.63 and pKw=13.26. Here, pH+pOH=13.26.
Temperature 0°C 25°C 50°C 60°C

–15 –14 –14 –14
Kw 1.14 × 10 1.00 × 10 5.47 × 10 9.60 × 10
pKw 14.94 14 13.26 13.01
3.8 pH and pH Scale

Because the concentration of H+ and OH¯ ions in aqueous solution are very small numbers which
makes inconvenient to work with, Sorensen in 1909 proposed a more practical measure, called pH.
Simply, pH is defined as the negative common logarithm of molar concentration of H+ ions.
pH = – log10 [H+]
In aqueous solution, H+ ion mostly exists in hydrated form. More correctly, pH = –log10 [H3O+]
Similarly, for basic solution

pOH = – log10[OH¯]
The relationship between pH and pOH can be established from autoionization of water.
We know, [H3O+] [OH¯] = 1.0 × 10–14 at 25°C
Taking log of both sides
log[H3O+] + log[OH¯] = log (1 × 10–14)
or, –log[H3O+] – log[OH¯] = – log (1 × 10–14)
pH + pOH = 14
Because pH is simply a way to express hydrogen ion concentration, nature of the solution (acidic,
basic or neutral) can be distinguished by their pH values expressed in pH scale.
For acidic solutions at 25°C
The concentration of H+ ion is greater than 10–7 M and hence the pH value is less than 7.
For basic solution at 25°C
The concentration of H+ ion is less than 10–7 M and hence the pH value is more than 7.
For neutral solution at 25°C
The concentration of H+ ion is equal to 10–7 M and hence the pH value is 7.
[H+] 1 10–1 10–2 10–3 10–4 10–5 10–6 10–7 10–8 10–9 10–10 10–11 10–12 10–13 10–14
pH 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
pOH 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0
Acidic Neutral Basic

solution solution solution
Fig. 3.1: pH scale at 25°C
Example 3.2 Calculate the pH of 0.04N H2SO4 solution (Assume complete ionization)
Solution
Method 1:
Since basicity of H2SO4 is 2, its molarity
M = N/2 = 0.04/2 = 0.02 M and it is completely ionized
H2SO4 2H+ + SO4¯
Initial concentration 0.02 M 0 0
Change after ionization –0.02 M 2 × 0.02 0.02
Concentration at equilibrium ≈0 0.04 M 0.02 M
Now,
pH = – log [H+] = – log (0.04) = 1.398
Method 2: In case of complete ionization of acid or base,
pH = – log (Nacid) and pOH = – log (Nbase)
So, pH = – log (0.04) = 1.398
Example 3.3 Calculate the pH of 0.01M solution of ammonia (Kb = 1.8 × 10–5)
Solution
Since ammonia is weak base, it is partially ionized. The degree of ionization of ammonia is calculated by
Ostwald's dilution law.
Method 1:
NH4OH NH4+ + OH¯

Initial concentration 0.01 M 0 0
Change at equilibrium -0.01 α +0.01 α +0.01 α
Concentration at equilibrium (0.01-0.01 α) M + 0.01 α M +0.01 α M
Now,
[NH4+] [OH¯] 0.01 α × 0.01 α 0.01 α2
Kb = [NH4OH] = (0.01 – 0.01 α) = (1 – α)
For weak electrolyte 1 – α ≈ 1
So, Kb = 0.01 α2
Kb 1.8 × 10–5
or α= 0.01 = 0.01 = 0.042
and [OH¯] = 0.01 × 0.042 = 0.00042 M
pOH = – log[OH¯] = – log(0.00042) = 3.377
pH = 14 – pOH = 14 – 3.377 = 10.623
Method 2:
Kb 1.8 × 10–5
Using Ostwald's dilution law: α = C = 0.01 = 0.042
[H+]=Cα = 0.01 × 0.042 = 0.00042 M
pOH = – log[OH¯] = – log(0.00042) = 3.377
pH = 14 – pOH = 14 – 3.377 = 10.623
3.9 Buffer Solution or Buffered Solution

The literal meaning of buffer is "to resist". A buffer solution resists the change in pH value on
addition of small amount of acid or base. Generally, a buffer solution is a mixture of a weak acid and
its salt with strong base or a mixture of weak base and its salt with strong acid. For example, if we
mix CH3COOH solution (solution 1) and its salt CH3COONa solution (solution 2), the resultant
mixture is called acidic buffer. The solution has the ability to resist changes in pH upon the addition
of small amounts of either strong acid or base. Buffers are very important to chemical and biological
systems. The pH in the human body varies greatly from one fluid to another; for example, the pH of
blood is about 7.4, whereas the gastric juice in our stomachs has a pH of about 1.5. A buffer solution
must contain a relatively large concentration of acid to react with any OH– ions that are added to it,
and it must contain a similar concentration of base to react with any added H+ ions. Furthermore, the
acid and the base components of the buffer must not consume each other in a neutralization reaction.
There are two types of buffer solutions;
i. Acidic buffer: It is the mixture of weak acid and its salt with strong base. Example: Mixture of
CH3COOH and CH3COONa solutions.
ii. Basic buffer: It is the mixture of weak base and its salt with strong acid. Example: mixture of
NH4OH and NH4Cl solutions.
Besides these two types of buffered solutions, solution of the salt of weak acid and weak base can
also act like a buffered solution, which can be termed as a single buffer. For example, the solution of
ammonium acetate (CH3COONH4) can act as a single buffer. In the text, we shall only be discussing
about the first two types only.
Buffer action can be understood with the help of common ion effect and Le-Chatelier principle. The
following diagram illustrates how basic buffer of ammonia and ammonium chloride can maintain
the pH almost constant upon the addition of small amount of strong acid (HCl) or strong base
(NaOH).
When small quantity of acid (H+) is added, it combines with OH¯ ion of buffer system to give H2O
molecules, which is feebly ionized. Therefore, OH¯ ion concentration is decreased which causes the
disturbance of equilibrium state of ionization of NH4OH. However, according to Le-Chatlier's
principle, this disturbance is minimized by shifting this equilibrium towards forward direction i.e.
more NH4OH molecule will be ionize to fulfill the, amount of OH¯ ion and therefore pH remains
constants. In this way addition of small quantity of acid does not change the pH of solution
appreciably.
Addition of acid H+
NH4OH NH4+ + OH¯

H2O
NH4Cl NH4+ + Cl¯
NH4OH
Addition of base OH¯
When small quantity of base (OH¯) is added, it combines with NH4+ ion of buffer solution to furnish
NH4OH, which is feebly ionized. Due to this addition of small quantity of base does not change the
pH of solution appreciably.
Now, let us take an example of acid buffer to study how pH is maintained on addition of small
quantity of acid or base.
Addition of base OH¯
H2O
CH3COONa CH3COO¯ + Na+
CH3COOH
Addition of acid H+
When small quantity of base is added, OH¯ ion of base is neutralized by H+ of buffer solution to give
H2O, which is feebly ionized. Therefore, H+ ion concentration is decreased which causes the
disturbance of equilibrium sate of ionization of CH3COOH. However, according to Le-Chatelier's
principle, this disturbance is minimized by shifting this equilibrium towards forward direction i.e.
more CH3COOH molecule will be ionized to fulfill the, amount of H+ ion and therefore pH remains
constant.
When small quantity of acid (H+) is added, H+ ion combines with CH3COO¯ ion of solution to give
CH3COOH, which is feebly ionized. Hence there is no appreciable increase in H+ ion concentration in
buffer solution.
pH of buffer solution can be calculated by Henderson equation, which is
[salt]
For acidic buffer: pH = pKa + log [acid]
[salt]
For acidic buffer: pOH = pKb + log [base]
Self test
3.2 Give two examples of basic buffer solution.
Example 3.4 Calculate the pH of mixture that contains 0.03 M NH4OH and 0.04M of NH4Cl. (Kb for
ammonia is 1.8 × 10–5)
Solution
Since mixture contains weak base and its salt, it is basic buffer and its pH can be calculated by using
Henderson equation.
[salt] [salt] 0.04
pOH = pKb + log [base] = -log Kb + log [base] = 4.74 + log 0.03 = 4.865
pH = 14 – pOH = 14 – 4.865 = 9.135
3.10 Concept of Acids, Bases and Salts

Classically, a compound containing replaceable hydrogen atom (s), which has sour taste, has a
capacity to neutralize base and turns blue litmus paper red, is called an acid.
For example HCl is acid because;
i. it contains hydrogen which can be replaced by treating with active metal like sodium
2 HCl + 2 Na 2 NaCl + H2
ii. it can be neutralized by base like as NaOH to give salt and water
iii. Its aqueous solution turns blue litmus paper to red, methyl orange to pink and it has sour taste.
Similarly, the oxides or hydroxides of metals, which have a capacity to neutralize acid, turn red
litmus paper blue and have bitter taste, are called bases. Water soluble bases are called alkalis. All
alkalis are bases but all bases are not alkalis. Fe(OH)3, Cu(OH)2, etc. are bases but are not alkalis.
For example, NaOH is alkali because;
i. It is water soluble hydroxide of metal
ii. It neutralize acid to give salt and water
iii. Its aqueous solution turns red litmus paper into blue and phenolphthalein to pink.
iv. It is bitter in taste and soapy to touch (such types of bases should never be tasted !).
The important acid-base concepts are explained here.
3.10.1 Arrhenius Concept of Acid-Base

Depending upon the Arrhenius theory of ionization, clear definition of acids, bases and salt have
been given.
An acid is a compound which ionizes to give hydrogen ion as only the positive ion in aqueous
solution. For example, hydrochloric acid and acetic acid are acids because they furnish hydrogen ion
when dissolved in water.
HCl Cl¯ + H+
A base is a compound which ionizes to give hydroxide ion as only the negative ion in aqueous
system. For example, sodium hydroxide and calcium hydroxide are bases (alkalies) because they
furnishes OH¯ ion when dissolved in water.
NaOH Na+ + OH¯
Ca(OH)2 Ca++ + 2 OH¯

The acidic or basic properties explained above are due to the presence of H+ or OH¯ ions of acid or
base, respectively.
A salt is a compound which gives positive ion excepting hydrogen ion and negative ion, excepting
hydroxide ion, when taken in aqueous solution.
Neutralization is a process through which H+ of acid combines with OH¯ of the base to give neutral
water molecule.
H+ + OH¯ H2O
or more correctly
H3O+ + OH¯ 2 H2O
Limitations of Arrhenius Concept

Arrhenius theory suffers from many serious defects, which are given below;
1. Arrhenius theory does not explain the nature of hydrogen ion in aqueous solution. Actually, H+
ion does not exist independently in solution. It combines with water molecule to give
hydronium ion.
H+ + H2O H3O+
2. This theory does not explain the acidic or basic properties of those compounds which do not
consist H+ or OH¯ ions. For example, CO2 does not contain H+ ion but behaves as an acid.
CO2 + 2 NaOH Na2CO3 + H2O
Similarly, NH3 is base eventhough it does not contain OH¯ ion in its molecule.
NH3 + HCl NH4Cl
3. Arrhenius theory explains the acids and bases in terms of their aqueous solution (i.e., this
concept is limited to water soluble compounds only) but it does not say anything about the
acidic or basic properties of substance themselves.
4. Some salts such as AlCl3, FeCl3, etc, show acidic behaviour. But this theory does not explain
about their acidic nature.
3.10.2 Bronsted-Lowry Concept of Acid-Base

Arrhenius definitions of acids and bases are limited in aqueous solutions. Broader definitions were
proposed by Johannes Bronsted and T. M. Lowry in 1932; a Bronsted-Lowry acid is a proton donor
and a Bronsted-Lowry base is a proton acceptor.
Therefore, any hydrogen containing species (molecule, cation or anion) which is capable of
donating one or more protons (H+) to any substance is called an acid and that which is capable of
accepting proton from an acid is called a base. Note that this definition of acid-base does not
require acids and bases to be in aqueous solution. Moreover, an important feature of this concept is
interdependent acid-base pair. This means, for a substance to act as an acid, there should be another
substance to act as a bas such that there is a proton transfer from the acid to base.
This concept of acid and base is illustrated below. Hydrochloric acid is a Bronsted acid since it
donates a proton in water:
HCl (aq) + H2O (l) H3O+ (aq) + Cl¯ (aq)
Here, HCl donates a proton and becomes Cl¯ whereas H2O accepts this proton to become H3O+.
Thus, HCl is an acid and H2O is a base. If we consider the reverse reaction, H3O+ can donate its
proton to Cl¯. Hence H3O+ is also a Bronsted acid and Cl¯ is a Bronsted base. It is clear that every
acid must form a base on donating its proton, and every base must form an acid on accepting a
proton. Therefore, we can write,
(a conjugate acid-base pair)
HCl (aq) + H2O (l) H3O+ (aq) + Cl¯ (aq)

acid 1 base 1 acid 2 base 2
(a conjugate acid-base pair)
Here, HCl donates a proton to water, and water accepts a proton, hence HCl is an acid and water is a
base. In reverse process, the Cl¯ ion accepts a proton from H3O+, hence Cl¯ ion acts as a base and
H3O+ acts as an acid. The pair of substances which can be formed from each other by gain or loss of
proton is called a conjugate acid-base pair. Therefore, acid1 and base-2 (i.e., HCl and Cl¯) is one
conjugate acid-base pair and base-1 and acid-2 (i.e., H2O and H3O+) is another conjugate acid-base
pair. Simply, acid after loss of proton becomes conjugate base while a base after gaining a proton
becomes a conjugate acid.
Conjugate acid Conjugate base + H+
Therefore, a pair of an acid and base which differ from one another by a proton is called a
conjugate acid-base pair.
Interestingly, according to this concept neutralization means the formation of corresponding
conjugate acid-base pair. For example, neutralization of acetic acid by ammonia as in this reaction
CH3COOH + NH3 CH3COO¯ + NH4+

acid 1 base 1 base 2 acid 2
The strength of acid or base is related to the tendency of donating or accepting of proton. A strong
acid has a greater tendency to donate its proton, while a strong base has a greater tendency to accept
the proton. From conjugate acid-base pair, if given acid is strong, its conjugate base must be weak
and vice versa. In above example, acetic acid is weak acid and therefore its conjugate base
(CH3COO¯ ion) should be strong base.
Relative strength of conjugate acid-base pairs
Perchloric acid (HClO4) ClO4¯
Sulphuric acid (H2SO4) HSO4¯
Strong acid
Hydroiodic acid (HI) I¯

Hydrobromic acid (HBr) Br¯
Base strength increases
Acid strength increases
Hydrochloric acid (HCl) Cl¯

Nitric acid (HNO3) NO3¯
Hydrofluoric acid (HF) F¯
Nitrous acid (HNO2) NO2¯
Formic acid (HCOOH) HCOO¯
Weak acids
Acetic acid (CH3COOH) CH3COO¯

Hydrocyanic acid (HCN) CN¯
Water (H2O) OH¯
Ammonia (NH3) NH2¯
Acids Conjugate bases
This theory is much broader than Arrhenius theory because it is found that all Arrhenius acids and
bases are also Bronsted-Lowry acids and bases, but the reverse may not be true. For example,
ammonia has no OH group and is not Arrhenius base. However, it can accept proton from water to
give NH4+ ion and therefore is Bronsted base. Moreover, NH4+ ion is Bronsted acid as it can donate
proton in reverse direction of given reaction.
NH3 + H2O NH4+ + OH¯
In this reaction water acts as acid. However, if we consider the dissolution of hydrochloric acid in
water, water acts as base as it accepts proton from HCl as:
HCl + H2O H3O+ + Cl¯
Therefore, H2O in first reaction acts as an acid, while in second reaction it acts as a base. It is
concluded that Bronsted acid or base can be identified from the given reaction where they donate or
accept a proton. As it is clear from above, with NH3, water acts as an acid, while with HCl water acts
as a base. Water is therefore an amphoteric substance.
The substances which can act as proton donor as well as proton acceptor are called amphoteric
substances
Self Test
3.3 HCO3¯ is amphoteric. Explain
3.4 Explain acid-base properties of water based upon Bronsted-Lowry concept.
Significance of Bronsted-Lowry concept of acid and base
This concept is capable of explaining the acidic and basic natures of some compounds (like NH3,
HCl, etc.) in non-aqueous medium also. Besides this, it provides an excellent way of comparing the
relative acidic strengths considering their ionizations in water and determining their ionization
constant values.
Example:
CH3COOH + H2O CH3COO- + H3O+
(l)
[CH3COO-][H3O+]
For this ionization: Ka=[CH COOH][H O] = 1.8 × 10-5, at 250C
3 2
HCOOH + H2O HCOO- + H3O+
[HCOO-][H3O+]
For this ionization: Ka=[HCOOH][H O] = 1.7 × 10-4, at 250C
2
The above data shows that HCOOH is stronger acid than CH3COOH.
Limitation of Bronsted Lowry concept of acid and base
1. The Bronsted-Lowry concept is not applicable for non-protonic chemical species. For example,
SO2, CO2, NO2, etc. are acidic in nature but these do not have proton. Similarly, CaO, MgO,
BaO, etc. are basic in nature but these do not accept proton.
2. There are some acid-base reactions where there is no transfer of proton. The example includes,
MgO + CO2 MgCO3
CaO + SO3 CaSO4

These types of reactions can not be explained by Bronsted-Lowry concept.
3. Some salts such as BF3, AlCl3, FeCl3, etc. are acidic in nature but these do not have proton.
3.10.3 Lewis Concept of Acid-Base

G. N. Lewis proposed a more general theory about acids and bases. This concept is based on electron
rather than proton. A Lewis base is a substance which can donate a pair of electrons. A Lewis acid is
a substance which can accept a pair of electrons. For example, in the protonation of ammonia, NH3
acts as a Lewis base because it donates a pair of electrons to the proton H+, which acts as a Lewis acid
by accepting the pair of electrons. A Lewis acid-base reaction, therefore, is one that involves the
donation of a pair of electrons from one species to another. Such a reaction does not produce a salt
and water.
H H +
H+ + N—H H←N—H
H H
Here, a lone pair of electron is donated by ammonia to hydrogen ion, hence ammonia is a Lewis
base, and hydrogen ion that accepts the lone pair of electron is a Lewis acid.
Examples of Lewis acid:
i. Cations (NO2+, Cl+, Ag+, Cu2+ etc.)
ii. Compounds having incomplete octet in their molecules (e.g. BCl3, BF3, AlCl3, FeCl3 etc.)
iii. Some molecules with multiple bonds (e.g., CO2, SO3, H–C ≡ N etc.)
Examples of Lewis bases:
i. All anions (e.g. Cl–, I–, OH–, CN–, etc.)
ii. Molecules having at least one lone pair electrons. (e.g. H2O, NH3, ROH, ROR etc.)
Lewis acids have an electron deficient centre and it attract electron pair where as Lewis base has the
electron rich centre and it looks for electron deficient species. Hence, Lewis acids are electrophiles
and Lewis bases are nucleophiles.
Self Test
3.5 Identify Lewis acid and base in the following reaction
+ 2+ 2+
i. Ag (aq) + 2NH3 (aq) = Ag(NH3) (aq) ii. Cd (aq) + 4I¯ (aq) = CdI4¯ ¯ (aq)
Limitations of Lewis concept of acid and base

Even though this is the advanced concept of acid-base, it still has following limitations.
1. In Lewis acid-base reaction, there is formation of coordinate covalent bond which is very slow
process. But true acid-base reactions are very fast.
H H H H
F—B + N—H F—B N—H
H H H H
Coordinate covalent bond
2. This concept cannot tell anything about the strength of acid and base.
3. This concept does not consider about ionization process of acid and base.
Self Test
3.6 With the help of Lewis dot formula how can you show that CO2 in water acts as Lewis acid.
3.11 Salt Hydrolysis

A salt is an ionic compound formed by the combination of basic radical and acid radical. Most of the
salts are strong electrolytes that completely dissociate into ions in water. The term salt hydrolysis
describes the reaction of an anion or a cation of a salt, or both, with water. Salt hydrolysis usually
affects the pH of a solution. Depending upon the origin of salt and its nature (acidic, basic or neutral)
in aqueous solution, salt hydrolysis can be categorized into following types.
1. Salts of strong bases and weak acids
The solution of a salt obtained from a strong base and a weak acid is basic. For example, the
dissociation of sodium acetate (CH3COONa) in water is given by
CH3COONa (s) + (H2O) CH3COO¯ (aq) + Na+ (aq)
The hydrated Na+ ion has no acidic or basic properties. The acetate ion CH3COO¯, however, is the
conjugate base of the weak acid CH3COOH and therefore has an affinity for H+ ions. The hydrolysis
reaction is given by
CH3COO¯ (aq) + H2O (l ) CH3COOH (aq) + OH¯ (aq)
Because this reaction produces OH¯ ions, the sodium acetate solution will be basic. In fact this is
anionic hydrolysis.
For simplicity, this hydrolysis can be shown as:
CH3COONa + H2O CH3COOH + NaOH
Weak acid Strong base
2. Salts of weak bases and strong acids

When a salt obtained from a strong acid such as HCl and a weak base such as NH3 dissolves in
water, the solution becomes acidic. For example, consider the process
NH4Cl (s) + (H2O) NH4+ (aq) + Cl¯ (aq)
The Cl¯ ion, being the conjugate base of a strong acid, has no affinity for H+ and no tendency to
hydrolyze. The ammonium ion NH4+ is the conjugate acid of weak base NH3 and ionizes as follows:
NH4+ (aq) + H2O (l) NH4OH (aq) + H+ (aq)
Since H+ ions are produced, the pH of the solution decreases. In fact this is cationic hydrolysis
For simplicity this hydrolysis can be shown as:
NH4Cl (s) + (H2O) NH4OH + HCl
Weak base Strong acid
3. Salts of weak acids and weak bases

So far we have considered salts in which only one ion undergoes hydrolysis, for salts obtained from
a weak acid and a weak base; both the cation and the anion hydrolyze.
Example: CH3COONH4 + H2O CH3COOH + NH4OH
However, whether a solution containing such a salt is acidic, basic, or neutral depends on the relative
strengths of the weak acid and the weak base.
• Kb > Ka: If Kb for the anion is greater than Ka for the cation, then the solution must be basic
because the anion will hydrolyze to a greater extent than the cation. At equilibrium, there will
be more OH¯ ions than H+ ions.
• Kb < Ka: Conversely, if Kb for the anion is smaller than Ka for the cation, the solution will be
acidic because cation hydrolysis will be more extensive than anion hydrolysis.
• Ka ~ Kb: If Ka is approximately equal to Kb, the solution will be nearly neutral.
4. Salts of strong acids and strong bases

This type of salt in water gives cation and anion, and both of these ions do not hydrolyze. Therefore,
the aqueous solution of such type of salt is neutral. For example, potassium chloride (KCl) when
dissolved in water dissociates to give K+ and Cl¯ ions. Neither of these ions hydrolyze and therefore
resulting solution will be neutral.
3.12 Common Ion Effect

It is previously discussed that weak electrolytes ionizes feebly while strong electrolytes ionize almost
completely. What will happen to the ionization of weak electrolyte if strong electrolyte having one
common ion is added?
Weak electrolytes are partially ionized and these are in equilibrium with their ions. If we consider a
weak electrolyte acetic acid, then equilibrium of acetic acid with its ions is represented as,
Now applying the law of mass action,
[CH3COO¯][H+]
Ka = [CH3COOH]
In such equilibrium condition, if strong electrolyte having a common ion (say CH3COONa) is added
then some sort of change takes place.
The concentration of CH3COO¯ increases. To keep the value of Ka constant either the concentration
of H+ should decrease or the concentration of CH3COOH should increase or both take place
according to Le-Chatelier's principle. This happens with H+ ions of solution combine with CH3COO¯
ions to furnish undissociated CH3COOH. This type of phenomenon takes place only when there is
ion common to that furnished by weak electrolyte. The addition of common ion acts as stress in the
equilibrium and the equilibrium shifts to LHS. This type of phenomenon is often called common ion
effect which is defined as the suppression of ionization of weak electrolyte by the addition of strong
electrolyte having a common ion.
Let us illustrate this by following example.
Acetic acid ionizes as follows.
When sodium acetate is added to the equilibrium,

Equilibrium
Shift
CH3COONa CH3COO¯ + Na+

Common ion
The concentration of acetate ion increases which consumes more H+ ions of solution to give more
undissociated acetic acid. In this way ionization of acetic acid is suppressed. In this above case, if
HCl is added instead of sodium acetate, the same type of phenomenon takes place due to common
H+ ions.
Equilibrium
Shift
HCl Cl¯ + H+
Common ion
Self Test
3.7 What happens when (a) NH4Cl (b) NaOH is added into the following equilibrium reaction?
Effect of common ion on solubility

When a highly soluble salt is added to a sparingly soluble salt having at least one ion common then
the solubility of sparingly soluble salt is deceased. This forms the fundamental principle in
qualitative salt analysis. For example, when small amount of NaCl is added to AgCl solution then
more precipitation of AgCl occurs. This is due to common chloride ion. In other words, the degree of
dissociation of AgCl is suppressed due to common ion, which is also the decrease in the solubility of
AgCl.
Application of common ion effect
The applications of common ion effect are as follows:
1. Salting out of sodium chloride: When dry HCl gas is passed into the saturated sodium chloride
solution then chloride ions act as common ion and equilibrium shifts towards the back side.
Due to this precipitation of NaCl takes place.
Equilibrium
Shift
NaCl Na+ + Cl ¯
HCl H+ + Cl¯
Common ion
2. Salting out of soap: Soap is sodium salt of higher fatty acid. Sodium chloride is added into
saturated soap solution to precipitate the soap. Here, Na+ ion acts as common ion.
Equilibrium
Shift
RCOONa RCOO¯ + Na+
NaCl Cl¯ + Na+

Common ion
3. In qualitative salt analysis: Qualitative salt analysis is based on common ion effect and
solubility product principle. This is discussed in solubility product principle.
3.13 Solubility Product and Solubility Product Principle

Solubility
Solubility of a substance is defined as the amount of solute (in gram) dissolved per hundred gram of
solvent at a particular temperature to make it a saturated solution. At 25°C temperature 36 gram of
sodium chloride is dissolved in 100 gram water to make it a saturated solution of sodium chloride.
Here, solubility of NaCl at 25°C is 36.
Weight of solute in gram
Solubility (s) = Weight of solvent in gram × 100
Solubility of a substance depends upon the property of solvent, nature of solute, temperature and
presence of common ion. Chemists work so much with aqueous solution and hence need the
knowledge of solubility of salt. In fact no salt is completely insoluble in water. Hence it is difficult to
define a salt as soluble salt or insoluble salt. However, a salt can be said to be soluble if it can make a
solution more concentrated than 0.01M (centimolar) near room temperature. On the same basis, a
salt is said to be insoluble if its solubility is much less than 0.01 M.
Since no salt is completely insoluble in water, it is advisable to call it a sparingly soluble salt rather
than insoluble salt.
Ionic product and solubility product
When a sparingly soluble salt such as AgCl is added into water, very small amount of it should be
dissolved and that dissolved part of salt is almost completely dissociated in solution. The solubility
of salt is often expressed in terms of mole per liter. Let us take an example of solubility of AgCl.
For the equilibrium, AgCl (solid) +
Ag (aq) + Cl¯ (aq)
We can apply law of mass action ,
[Ag+ [Cl¯ ]
Equilibrium constant (K) = [AgCl ] . . . (i)
Since concentration of solid silver chloride is almost constant,
K.AgCl = [Ag+] [Cl¯ ]

or Ksp = [Ag+] [Cl¯] . . . (ii)
+
For simplicity, we write, Ksp = [Ag ] [Cl¯] . . . (iv)
If S mole lit–1 be the solubility of AgCl, equilibrium concentration of both Ag+ and Cl¯ ions will be S
mol lit–1, then Ksp = S mol. lit–1 × S mol. lit–1 = S2 mol2. lit–2
Here, Ksp is solubility product of AgCl. Since solubility of a salt is constant at a particular
temperature, so does the solubility product.
The quantity [Ag+] [Cl–] is ionic product. The ionic product is defined as the product of molar
concentration of the constituent ions, each concentration term raised to the power equals to the
stoichiometric coefficient present in balanced ionic equilibrium.
Note:
At equilibrium (in saturated solution of sparingly soluble salt), solubility product is equals to the ionic product.
Let us take another example to write solubility product expression.

CaF2 (s) Ca++ (aq) + 2 F¯ (aq)
[Ca++] [F¯]2
K= [CaF2]
or K[CaF2] = [Ca++] [F¯]2

Since concentration of CaF2 is almost constant, we write Ksp for K[CaF2]. So,
–
Ksp = [Ca2+] [F ]2 ... (v)
–
The quantity [Ca2+] [F ]2 is ionic product is CaF2.
–
If molar solubility of CaF2 is S mol/L, at equilibrium [Ca2+] = S mol/L and [F ] = 2S mol/L. Putting
these values in equation (v), we get
Ksp = S × (2S)2 = 4S3
For a general type of salt BxAy
x y
The solubility product is, Ksp = [By+] . [Ax–]
Hence, solubility product of a sparingly soluble salt is defined as the product of molar concentration
of its constituent ions in its saturated solution, each concentration term being raised to power equal
to stoichimetric coefficient present in balanced ionic equilibrium. Simply speaking, ionic product of
saturated solution of sparingly soluble salt is solubility product of the salt.
In the above illustration, we considered the case of saturated solution. However, if we consider the
case of unsaturated or supersaturated solution, the case will be different.
In case of unsaturated solution, molar concentration of each ion is less than that in case of saturated
solution. In such cases the ionic product is obviously less than in the case of saturated solution.
In case of supersaturated solution, the molar concentration of each ion is greater than that on
saturated solution and hence ionic product is obviously greater than that the saturated solution.
Self Test
3.8 Write solubility product expression for
Ag2CrO4 (s) 2 Ag+ (aq) + CrO4¯ ¯ (aq)
a.
b. PbSO4 (s) Pb++ (aq) + SO4¯ ¯ (aq)
c. AgBr (s) Ag+ (aq) + Br ¯ (aq)
BxAy (s) x By+ (aq) + yAx– (aq)
Relation between solubility and solubility product

Relation between solubility and solubility product of some different types of salt are given below:
1. For AB types of salt: Some examples of this type of salts are AgCl, AgBr, AgI, PbSO4, BaSO4,
etc.
Let us take an example of AgCl. where S mol L–1 be the solubility of AgCl. It furnishes S mol L–1
which will be the solubility of AgCl. Then it furnishes S mol L–1 of Ag+ and Cl¯ ions in solution.
AgCl Ag+ + Cl¯
Concentration (in
S S S
mol/L) at equilibrium)
Now, Solubility product, Ksp = [Ag+] [Cl¯] = S mol L–1 × S mol L–1 = S2 mol2 L–2
Solubility (S) = Ksp

2. For A2B or AB2 type of salt: Some examples of this type are Ag2S, Ag2CrO4, CaF2, BaF2,
Cu(OH)2, etc. Let us take an example of Ag2S, where solubility of Ag2S be S mol L–1. One mole
--
of Ag2S furnishes 2 mole of Ag+ ions and one mole of S ions.
Now, Solubility product, Ksp = [Ag+]2 [S¯ ¯]
Ag2S 2 Ag+ + S¯ ¯
Concentration (in mol/L S 2S S
at equilibrium)
= (2S)2 (S) = 4S3
3 Ksp
Solubility (S) = 4
3. In general: for Ax By salt:
Ksp = xx, yy, sx+y
5 Ksp
Example, for Bi2S3: Ksp = 22. 33. s2+3 or Ksp = 108 S5 or S = 108
Example 3.5 The solubility product of CaCO3 is 9.3 × 10-8. Calculate its solubility in gram per litre.
Solution
CaCO3 ionizes as
CaCO3 Ca++ + CO3¯ ¯
Concentration (in
mol/L at equilibrium) x x x
Where x is the solubility of CaCO3

Solubility product Ksp = [Ca++] [CO3¯ ¯]
9.3 × 10-8 = x . x
∴ x = 3.049 × 10–4 mol/L
Note:
Molar concentration of Ca2+ in equilibrium = molar solubility of CaCO3 = x mol/L
Mol. wt. of CaCO3 = 100
Solubility in g/L = molarity × Mol.wt. = 3.09 × 10–4 × 100 = 3.049 × 10-2 g/L
Example 3.6 The solubility of AgCl in water at 298 K is 1.43 × 10–3 gL–1, calculate its solubility in 0.5
M KCl solution.
Solution
Method 1:
Solubility of AgCl = 1.43 × 10-3 g/L
Mol. wt. of AgCl = 108 + 35.5 = 143.5
g/L 1.43 × 10-3
∴ Solubility of AgCl in mole/L = Mol. wt = 143.5 = 9.965 × 10–6 mol/L
–
Solubility product of AgCl (Ksp) = [Ag+] [Cl ] = (9.9654 × 10–6) × (9.965 × 10–6) = 9.930 × 10–11
AgCl Ag+ + Cl ¯
Solubility 9.966×10–6 9.966×10–6 9.966×10–6
KCl K+ + Cl ¯
Initially 0.5 M – –
After ionization – 0.5 M 0.5 M
–
Total concentration of Cl = (9.965 × 10-6 + 0.5)
Now, solubility product of AgCl (Ksp) = [Ag+] [Cl¯ ]
(9.965 × 10-6)2 = (9.965 × 10-6 + 0.5) [Ag+]
(9.965 × 10-6)2
∴ [Ag+] = (9.965 × 10-6 + 0.5) = 1.985 × 10-10 mol/L.
Method 2:
Since molar solubility of AgCl in pure water is 9.965 × 10–6 mol/L
its Ksp = [Ag+] [Cl–]
= 9.965 × 10–6 × 9.965 × 10–6
= 9.930 × 10–11
Lets suppose the molar solubility of AgCl in 0.5 M KCl is S mol/L,
Equilibrium concentrations of different ions will be
[Ag+] = S mol/L
[Cl–] = S + 0.5 M (S mol/L from AgCl are 0.5 mol/L from KCl)
≈ 0.5 M (as S in very very small and can be neglected)
So, Ksp = [Ag+] [Cl–]
or, 9.930 × 10–10 = S × 0.5
9.930 × 10–11
or, S= 0.5 = 1.98 × 10–10 mol/L
Example 3.7 A sample of AgCl is treated with 5 mL of 2 M Na2CO3 solution to produce Ag2CO3.
The remaining solution contained 0.003 gram Cl¯ per litre. Calculate the solubility
product of AgCl. (ksp of Ag2CO3 = 8.2 × 10–12)
Solution
2AgCl + Na2CO3 → 2NaCl + Ag2CO3
Gram lit–1 0.003
Concentration of Cl¯ = Gram ionic weight. = 35.5 = 8.45 × 10–5 mol lit–1
For Ag2CO3
Ag2CO3 2Ag+ + CO3¯ ¯

2
ksp = [Ag+] [CO3¯ ¯]
ksp 8.2 × 10–12
[Ag+] = [CO3¯ ¯] = 2 = 2.024 × 10–6 mol lit–1
For AgCl
ksp = [Ag+] [Cl ¯]
= [2.024 × 10–6] [8.45 × 10–5] mol2 lit–2
= 1.71 × 10–10 mol2 lit–2
Example 3.8 A 500 mL of saturated solution of Ca(OH)2 is mixed with equal volume of 0.4 M
NaOH. What mass of Ca(OH))2 is precipitated? (ksp of Ca(OH)2 = 4.42 × 10–5 at 25ºC)
Solution
Strategy: Number of mol of Ca(OH)2 precipitated = number of mol Ca(OH)2 dissolved initially – number
of mol of Ca(OH)2 dissolved after adding 0.4 M NaOH.
(a) For Ca(OH)2 = Ca(OH)2 Ca++ + 2(OH) ¯
Solubility s s 2s
− 2
ksp = [Ca++] [OH ]
= s ⋅ (2s)2 = 4s3
3 ksp
Solubility (s) = 4 …(i)
3 ksp 3 4.42 × 10–5

(b) For 500 mL of saturated Ca(OH)2 = 4 = 4 = 0.022273 mol lit–1
When NaOH is added to Ca(OH)2 solution then some Ca++ or Ca(OH)2 get precipitated
Initial volume
After dilution concentration of solution = Initial concentration × Final volume
0.022273 × 500
Concentration of Ca++ after mixing (M2) = 1‚000 = 0.011136 = 1.1136 × 10–2 mol/lit
One mole of Ca(OH)2 gives 2 mole of OH– ions

− − −
Total [OH ] = [OH ] from Ca(OH)2 + [OH ] from NaOH
500 500
= (2 × 0.022273) × 1‚000 + 0.4 × 1‚000
= 0.2223 M
But due to addition of NaOH, Ca(OH)2 precipitates due to common ion effect and concentration of
Ca++ is suppressed. Then concentration of Ca++ in solution is calculated as;
Even after the precipitation, the Ksp value remains same while [Ca++] is solution change.
Ksp = [Ca++ dissolved] [OH–]2
Ksp 4.42 × 10–5
[Ca++ dissolved] = – 2 = (0.2223)2 = 8.84 × 10 mol/lit
–4
[OH ]
No. of mol. of Ca(OH)2 precipitated = No. of mol. of Ca++ precipitated
= No. of mol. of Ca++ before precipitation – No. of mol. of Ca++
after precipitation
= 1.1136 × 10–2 – 8.84 × 10–4
= 0.010252 × 10–4 mol
= 0.010252 × 10–4 × 74 g [weight = No. of mol. × mol. wt.]
= 0.758 gram
Solubility Product Principle

An unsaturated solution has a capacity to dissolve more amount of solute at the same temperature.
A saturated solution neither dissolves more amount of solute nor gives precipitate. A supersaturated
solution gives precipitate of a salt. The same case can be studied in terms of ionic product and
solubility product (Ksp).
♦ When ionic product is less than solubility product, the solution is unsaturated and can dissolve
more amount of solute at the same temperature. Dissolution takes place here.
♦ When ionic product is equal to the solubility product, the solution is saturated and the solution
neither dissolves more solute nor gives precipitate.
♦ When ionic product is greater than the solubility product the solution is supersaturated and
precipitation takes place. This principle is called solubility product principle.
When two solutions are mixed, precipitate of a salt is formed if ionic product is greater than
solubility product (Ksp).
Application of solubility product principle in salt analysis (in identification of
basic radicals)
Solubility product principle helps to predict whether a solution gives or does not give precipitate in
qualitative salt analysis. In presence of a common ion, the ionic product in solution is changed. When
ionic product is greater than solubility product, precipitation of salt takes place.
Common ion effect provides the most important method to monitor the concentration of precipitant
for the selective precipitation of metallic ions in qualitative analysis.
1. Precipitation of sulphides of group II metal ions: Group II metal ions are Cd++, Hg++, Cu++,
Pb++, Sn++, As+++ Sb+++, Bi+++. These metal ions are precipitated in the form of their sulphide (their
sulphides have low solubility product). Therefore, H2S gas is passed in presence of HCl. In
absence of HCl, not only of group II but also of group IIIB metal ions are precipitate in the form
of their metal sulphides due to high concentration of S– – ion. Precipitation of metal salt is based
on the fact, if ionic product is greater than solubility product, precipitation occurs. To
precipitate only group II metal ions the concentration of S – – should be decreased in such an
extent that the ionic product would be greater than solubility product for sulphides of group II
metal ions, while ionic product would be less than solubility product for sulphides of group IIIB
metal ions. To suppress the concentration of S – – from H2S, a strong electrolyte HCl is used.
−−
H2S 2 H+ + S
weak acid
−
HCl H+ + Cl
strong acid common ion
Therefore, presence of HCl suppresses the ionization of H2S and concentration of S– – would be
decreased which is still sufficient to precipitate group II metal ions and insufficient to
precipitate group IIIB metal ions (Ksp of group II metal sulphide is less than that of group III B
metal sulphide) as their sulphides.
2. Precipitation of group III A metal ions: Group III A includes Fe++, Fe+++, Cr+++, Al+++ as basic
radicals. In group IIIA, NH4Cl is added along with NH4OH to the solution. Here NH4OH is
precipitating agent. If only NH4OH is used without NH4Cl, not only of group IIIA metal ions
are precipitated but also metal ions of subsequent group (eg. Mn++, Mg++ etc.) are also
precipitated out. The Ksp of hydroxides of group IIIA metal ion is relatively low. Therefore,
−
suppressed concentration of OH ions still maintain IP > Ksp, hence they get precipitated. For
Mg(OH)2, Mn(OH)2 etc. it becomes IP < Ksp as they have high Ksp values.
Therefore, the amount of OH– ion in the solution is sufficient to precipitate group IIIA metal
ions but not others. Presence of NH4Cl suppresses the ionization of NH4OH due to common ion
effect. The reaction takes place as
NH4OH −
NH+4 + OH
weak electrolyte
NH4Cl −
NH+4 + Cl
strong electrolyte common ion
–
As the OH concentration is decreased, ionic product value of system is also decreases.
3. Precipitation of group IV metal ions: Group IV metals ions are Ba++, Sr++, Ca++. These basic
radicals are precipitated in the form of their carbonate salt. (NH4)2CO3 is the precipitating
reagent. The reaction takes place in alkaline medium (NH4OH is required). NH4Cl suppresses
the degree of ionization of (NH4)2CO3 by common ion effect which decrease the concentration
of
CO3− − ions which is sufficient to precipitate Ba++, Sr++, Ca++ (Ksp of group IV metal carbonate is
fairly low). This concentration of CO23 − ion is not sufficient to precipitate MgCO3 as it has high
solubility product.
Solved Questions
1. What is degree of ionization?
¬ Degree of ionization or dissociation (α) of an electrolyte is defined as the ratio of number of molecules which
undergoes ionization or dissociation to the total number of molecules taken.
No. of molecules which undergo ionization or dissociation
α= Total no. of molecules present
2. What is pH? How pH and pOH are related at 25°C?
¬ Negative common logarithm of molar concentration of hydrogen ion is called pH. The term pH is originated
from the word potenz de hydrogen.
pH is defined as pH = – log [H+]
1
or, pH = + log [H+]
at 25°C pH + pOH = 14
3. Why is aq. Na2CO3 basic?
¬ Aqueous Na2CO3 is basic due to anionic hydrolysis which can be explained as follows.
Na2CO3 dissociates as
––
Na2CO3 2Na+ + CO3 . . . (i)
+
Water also ionizes partially as H2O H + OH¯ . . . (ii)
+ H2CO3
The CO3¯ ¯ and H+ combine to form H2CO3 as 2 H + CO3¯ ¯ . . . (iii)
The hydrogen ions necessary for equation (iii) is provided by further ionization of water in equation (2). Now
adding equation (ii) and (iii) we get
+
H2O H + OH¯ ] × 2
+ H2CO3
2 H + CO3¯ ¯
CO3¯ ¯ + 2 H2O H2CO3 + 2 [OH¯]

. . . (iv)
+
Due to further ionization of water, thus produced H are consumed by CO3¯ ¯ to form H2CO3 and solution
contains excess OH¯. Therefore, the solution is basic. From equation (iv) it is seen that the alkaline nature of
Na2CO3 is mainly due to hydrolysis of anion.
4. What is solubility product principle?
¬ The solubility product principle states that," when two solutions containing ions are mixed together if ionic
product is greater than solubility product, the precipitation takes place, otherwise not." It can be expressed as
i. If I.P. < KSP, the solution is unsaturated and can dissolve further salt at the same temperature.
ii. If I.P. = KSP, the solution is saturated and can't dissolve further salt at the same temperature.
iii. If I.P.> KSP, the solution is supersaturated solution which gives precipitation on slight disturbance.
Questions
1. What is Ostwald's dilution law? How is degree of ionization related to concentration of
solution?
2. Why is Ostwald's dilution law not applicable for strong electrolyte?
3. What is auto ionization of water?
4. What are pH and pOH? How are they related?
5. Define Bronsted-Lowry concept of acid and base. Give examples.
6. Define Lewis concept of acid and base with examples.
7. What is conjugate acid base pair? Give an example.

8. What is buffer solution? Define buffer action and buffer range?
9. What are solubility, solubility product, ionic product?
10. What will happen when HCl gas is passed over a saturated solution of NaCl? Also explain the
principle involved.
11. Write suitable example to show that water acts as Bronsted-Lowry acid and base.
12. Write the conjugate acid and conjugate base of NH3.
13. Why is aqueous solution of NaCl neutral whereas that of Na2CO3 is basic?
14. How do the following vary with temperature (a) Degree of ionization (b) ionisation constant (c)
pH (d) Ionic product of water (Kw)?
15. Why is NH4Cl added before adding NH4OH in the salt analysis of group IIIB metal ions?
16. Why is HCl added before adding H2S in the salt analysis of group II metal ions?

1. Explain common ion effect? Write its applications.
2. What is solubility product principle? How is this principle helpful in the qualitative salt
analysis?
3. Write notes on:
a. Degree of ionization b. Salt hydrolysis c. pH and pH scale
d. Ionic product of water e. Solubility product principle
f. Common ion effect g. Ostwald Dilution Law
4. Whether aqueous solution of the following compounds are acidic, basic or neutral. Give reason.
a. CuSO4 b. FeCl3 c. Na2CO3
d. NH4Cl e. CaCl2 f. KCN
5. State and explain Ostwald's dilution Law. Why is it not applicable for the strong electrolytes?
Numerical Problems
1. What will be the H+ ion concentration of a solution having pH 5.5?
–6 –1
Ans: 3.16 × 10 mole L
2. 10–2 mol of KOH is dissolved in 10 litres of water. What will be the pH of the solution?
Ans: pH = 11
3. Two litres of 1M HCl is mixed with one litre of 1M NaOH solution. Calculate the strength of the
salt formed and the pH of the resulting solution.
Ans: Strength = 0.33M, pH = 0.48
4. The solubility of CaF2 in water at 18°C is 2.05 × 10-4 mol L–1. Calculate its solubility product.
Ans: 3.446 × 10–11 mol/L
5. The solubility product of BaSO4 in water at 25°C is 1×10-10 mol L–1. Calculate the solubility of
BaSO4 in g/L. [Ba = 137]
Ans: Solubility of BaSO4 = 2.33 × 10–3 g/L
6. A 500 mL of a saturated solution of Ca(OH)2 is mixed with equal volume of 0.4 M NaOH. What
mass of Ca(OH)2 is precipitated. (Ksp of Ca(OH)2 is 4.42 × 10-5.)
Ans: 0.754g
7. 4.9 g of H2SO4 is present in 1000 ml of its solution. What is the pH of the solution?
Ans: 1
8. Equal volumes of the solutions with pH = 2 and pH = 4 are mixed together. Calculate the pH of
the resulting solution.
Ans: 2.3
9. Equal volumes of the solutions with pH = 8 and pH = 10 are mixed together. Calculate the pH
of the resulting solution.
Ans: 9.7
10. What mass of NaOH should be dissolved in 1L of solution to prepare solution having pH = 12
at 25°C?
Ans: 0.4 g
11. Calculate the pH of 1 g/L NaOH solution
Ans: 12.4
12. A sample of AgCl is treated with 5 mL of 2 M Na2CO3 solution to produce Ag2CO3. The
remaining solution contained 0.003 g of Cl– per litre. Calculate the solubility product of AgCl
(Ksp of Ag2 CO3 = 8.2 × 10–12)
–10
Ans: 1.20 × 10
13. The pH of 0.1 M HCN solution is 5.2. What is the value of ionization constant for the acid?
Ans: 3.98×10–10
14. Calcualte the hydroxide ion concentration having pH = 10.5.
Ans: 3.16 × 10-4 mol/L
15. A solution having pH 6 is diluted 100 times. Calculate the pH of the resulting solution.
Ans: 6.96

1. The degree of dissociation of an electrolyte, 8. The solubility product of a sparingly soluble salt A2B
–12
a. decreases with dilution is 4.0 × 10 at 298 K. Its molar solubility will be,
b. increases with dilution a. 4.0 × 10–3 b. 4.0 × 10–6
c. may increase or decreases with dilution c. 1.0 × 10–6 d. 1.0 × 10–4
d. is not affected by dilution 9. Which of the following can act as a base according
+
2. In the reaction NH3 + H2O NH4 + OHˉ, which to the Lewis concept?
of the following constitutes conjugate acid base a. Cl¯ b. Na+
pair? c. H d. K
a. NH3 and H2O b. NH4+ and OH¯ 10. The degree of ionization of an electrolyte does not
c. H2O and OH¯ d. NH3 and OH¯ depend upon on,
–12
3. The pH of 10 M HCl is a. temperature
a. 12.0 b. <7 b. nature of the solute
c. 7.0 d. –12 c. size of the solvent molecules
4. Which of the following can act both as Lowry ‐ d. concentration of the solution
Bronsted acid and base? 11. pH of 0.001 M NaCl solution is
a. CO3 –2 b. HSO4¯ a. 7 b. <7
c. >7 d. can't be decided
c. BF3 d. H3O+
H 12. 10mL of 0.1N NH4OH and 20 mL of 0.05 N HCl are
5. The p of 0.015 N NaOH is
a. 1.82 b. 8.23
mixed together. The pH of resulting solution is:
c. 12.18 d. 10.57 a. 7 b. <7
c. >7 d. can't be decided
6. The sum of pH and pOH at 25°C,
a. 7 b. 0
13. Solubility of AgCl is minimum in
c. –7 d. 14 a. water b. 0.1 M NaCl
c. 0.1 M KCl d. 0.1 M BaCl2
7. The solution is 1% ionized having concentration 1 M.
Find the dissociation constant:
a. 1 × 10–2 b. 1 × 10–4
c. 1 × 10–3 d. 1 × 10–5
1 2 3 4 5 6 7 8 9 10 11 12 13
b c b b c d b d a c a b D
Electrochemistry
Galvanic cell is a device which converts chemical energy into the useful work (electrical energy).
4.1 Introduction
If a spoon is to be copper plated, assemble of electrodes and electrolyte is made in such a way that
copper is made anode, spoon is made cathode and one of the soluble salt of copper is made
electrolytic solution. Here copper is connected to the positive terminal and spoon is connected to the
negative terminal of battery. Then electrolysis process is allowed to take place for hours. In this
example, electricity produced from battery is used to cause chemical change. This type of cell is
called electrolytic cell.
On the other hand, if a dry cell is considered, electricity is produced in the cost of electrochemical
reaction within it. Dry cell is electricity generator. This type of cell is called galvanic cell or voltaic
cell.
Both electrolytic cell and Galvanic cell is the domain of electrochemistry. Electrochemistry is that
discipline which deals on the relationship between electrical energy and chemical change (redox
reactions). The conduction in electrochemical cell is carried out either by electronic conductor or by
electrolytic solution. Electrochemistry is important from theoretical as well as practical aspects.
Purification of metals, electroplating of articles, commercial production of a number of chemicals
such as Na, NaOH, Cl2 etc. involve the principle of electrochemistry.
Galvanic (voltaic) cells have been used in torches, cell phones, digital cameras, hearing aids, digital
watches, etc. Fuel cells, which utilize the redox reactions between the supplied gases to produce
electricity have gained enormous amount of interest nowadays owing their high fuel efficiency,
environment friendly operation and ease of maintenance.
4.2 Electronic and Electrolytic Conductors

The substances which allow the passage of electricity through them are called conductors. Metals,
some alloys, graphite, acids, bases and salts can conduct electricity though in different extent. On the
basis of mechanism of conduction the conductors can be classified into electronic (metallic)
conductors and electrolytic (ionic) conductors.
Differences between electronic and electrolytic conductors

Electronic Conductors Electrolytic Conductors
1. Those conductors which conduct electricity by 1. Those conductors which conduct electricity by
the flow of electrons are called electronic the flow of cations or anions are called
conductors. electrolytic conductors.
2. Metals, some alloys and graphite are examples 2. Acid, bases and salt solutions are example of
of electronic conductors. electrolytic conductors.
3. Electronic conduction is faster than electrolytic 3. Electrolytic conduction is slower than
conduction. electronic conduction.
4. During electronic conduction no chemical 4. During electrolytic conduction chemical
change takes place. change takes place.
5. Transport of matter does not take place except 5. Transport of matter (ions) takes place.
the migration of electrons.
6. On increasing the temperature, the electronic 6. On increasing the temperature, the
conduction decreases due to increase in electrolytic conduction increases usually due
hindrance in the flow of electrons. to decrease in viscosity of medium and
increase in the velocity of ions.
Electrochemistry Unit 4 97
4.3 Electrolytes: Strong and Weak Electrolytes

Refer Unit 3.2 (Page no. 68)
4.4 Arrhenius Theory of Ionization

Refer Unit 3.3 (Page no. 69)
4.5 Electrolytic Cells and Voltaic Cells

An electrochemical cell is an assemble of two electrodes dipped in same or different electrolyte
solutions in which either electrical energy is produced as a result of chemical reaction or chemical
reaction is driven by external supply of electrical energy. Simply speaking, the devices in which the
electrochemical phenomena take place are called electrochemical cells. There are two types of
electrochemical cells.
1. Electrolytic cell: The cell in which chemical reaction is performed by the external supply of
electric current is called electrolytic cell. e.g. cell used in purification of metal and in electrolysis.
2. Galvanic or voltaic cell: The cell in which electrical energy is produced due to spontaneous
chemical reaction (redox reaction) is called galvanic cell or voltaic cell. Panel cell, dry cell etc.
are the examples of galvanic cell.
Differences between electrolytic cell and galvanic (voltaic) cell
Electrolytic cell Galvanic cell

1. The cell in which chemical change is 1. The cell in which electrical energy is produced as a
brought by the application of electrical result of chemical reaction is called galvanic cell.
energy is called electrolytic cell.
2. The redox reaction is non-spontaneous. 2. The redox reaction is spontaneous.
3. Two electrodes are dipped in the same 3. Two electrodes with their respective electrolytes are
solution with in a same container. usually set up in two container or these are
separated by porous membrane.
4. Anode is positive and cathode is negative 4. Anode is negative and cathode is positive electrode.
electrode.
5. Only one electrolytic solution is used. 5. Usually two different electrolytic solutions are used
6. No salt bridge or porous plug is used. 6. Salt bridge or porous plug is used.
4.6 Electrolysis and Criteria of Product Formation

(Electro = electricity, lysis = break down)
Electrolysis is the process of decomposition of electrolytes by the passage of electricity through its
aqueous solution or molten form.
The apparatus used to carryout electrolysis is called electrolytic cell or voltameter.
DC source Ammeter
+ –
– + + +
+
+ – – –
+ Cathode
+ +
Anode – + +
– – +
+ – +
+ Electrolytic solution
+ + –
+
– – – +
– +
Fig. 4.1: Schematic diagram of electrolytic cell
Electrolytic cell consists two metallic rods or metallic plates dipped into electrolyte solution. The
metallic rods or metallic plates are called electrodes. These electrodes are connected to the source of
direct current. The electrode which is connected to the positive terminal of cell is called anode and
the electrode which is connected to the negative terminal of cell is called cathode. The electrolytic
solution may be aqueous solution or molten or fused state of electrolytes. The process of electrolysis
can be explained on the basis of Arrhenius theory of ionization. When electric current is passed, the
ions migrate towards the oppositely charged electrodes. It means, the anions (negatively charged
ions) migrate towards anode (positive electrode) and cations (positively charged ions) migrate
towards the cathode (negative electrode). Then these ions get discharged and become neutral
chemical species.
Anions reach to anode and get oxidized by the loss of electrons. Oxidation takes place at anode. On
the other hand cations reach to cathode and get reduced by the gain of electrons. Hence reduction
takes place at cathode. The conversion of ions into corresponding neutral chemical species in
corresponding electrode is called primary change. Thus obtained products may remain as such or
they may undergo change to give final products. If products formed from primary change in
electrolysis process further undergo change to give final products, it is called secondary change.
It is discussed that the products obtained in electrolysis are the substances obtained by the discharge
of ions in corresponding electrodes. If molten or fused electrolyte is taken then the ions are cations
and anions of electrolyte. If aqueous solution of electrolyte is taken then the ions present are some H+
and OH¯ ions obtained by ionization of water along with the cations and anions of electrolyte. When
electric current is passed then cations of electrolyte and H+ ions from water move towards cathode.
Out of these two cations only one cation is discharged. Similarly anions of electrolyte and OH¯ ions
from water move towards anode at that condition. Here out of two anions, only one anion is
discharged. Out of the different ions which one gets discharged depends upon relative discharge
potentials and nature of electrode used.
In summary, the products obtained during electrolysis depend upon the following factors.
i. Nature of electrolytes (Types of electrolytes)
ii. State of electrolytes (Molten or aqueous solution)
iii. Concentration of electrolyte solution
iv. Nature of electrodes (Attackable or non-attackable)
v. Charge density flown during electrolysis.
Examples:
i. Electrolysis of molten NaCl in presence of graphite anode and iron cathode (or Pt electrodes):
The platinum electrodes don't take part in oxidation reduction reaction with electrolyte solution
so they are not-attackable electrode. When electricity is passed through molten NaCl then the
ions are discharged at the corresponding electrodes.
NaCl Na+ + Cl¯
Half-reaction at anode (Oxidation)
2Cl¯ Cl2 + 2e–
Half-reaction at cathode (Reduction)
Na+ + e+ Na
Cell Reaction, electrolysis
2NaCl 2Na + Cl2
At cathode at anode
As a result of electrolysis of molten NaCl, chlorine is obtained at anode and sodium is

obtained at cathode. This forms the basis of Down's process in the extraction of sodium.
ii. Electrolysis of aqueous NaCl solution in presence of platinum electrodes: Aqueous NaCl
solution consists Na+ ions and Cl¯ ions in addition with some H+ ions and OH¯ ions obtained
by the ionization of H2O
NaCl Na+ + Cl¯ (Completely ionized)
H2O H+ + OH¯ (Feebly ionized)
When electricity is passed through aqueous NaCl solution both cations (Na+ and H+) ions move
towards the cathode. Out of these two, H+ ion has lower discharge potential (The potential at
which ions are converted into neutral atom is called discharged potential) than Na+ ion (If the
electrode is inert). So H+ ions are discharged in preference to Na+ ions.
Similarly both Cl¯ and OH¯ ions move towards anode. Here Cl¯ has lower discharge potential
and is discharged in preference to OH¯ ions. So, following discharge reaction takes place.
Half–reaction at anode (Oxidation)
2Cl¯ Cl2 + 2e¯
Half reaction at cathode (Reduction)
2H+ + 2e¯ H2
Cell Reaction: electrolysis
NaOH + H2 + Cl2
NaCl + H2O
in solution At cathode at anode
Therefore, when aqueous solution of NaCl is electrolysed, Cl2 is obtained at anode and H2 is
obtained at cathode.
If very dilute solution of aqueous NaCl is electrolysed, the concentration of Na+ and Cl¯ is very
low. So this type of electrolysis is almost equivalent to electrolysis of water. Here OH¯ gets
preference over Cl¯ for discharge.
NaCl Na+ + Cl¯ (Very low concentration)
H2O H+ + OH¯
Half reaction at anode (Oxidation)

4 (OH¯) 2H2O + O2 + 4 e¯
4 H+ + 4 e¯ 2 H2
Cell Reaction electrolysis
NaCl + 2 H2O NaCl + 2 H2 + O2
excess
iii. Electrolysis of aqueous NaCl solution using graphite anode and mercury cathode: The
aqueous NaCl solution consists Na+ and Cl¯ ions along with some H+ and OH¯ ions.
NaCl Na+ + Cl¯
H2O H+ + OH¯
Out of Cl¯ and OH¯ ions, the Cl¯ ions have lower discharge potential and are discharged in
preference to OH¯ ions.
2Cl¯ Cl2+ 2e¯
The discharge potential of H+ ions is lower than that of Na+ ions under ordinary condition. If
mercury is used as cathode, the discharge potential of H+ ion will be high and it is discharged
only at high voltage. This is called over voltage of hydrogen. In this condition Na+ will be
discharged in preference to H+ ions. For Hg electrode, ease of discharge of cations: Na+ > H+
2 Na+ + 2 e¯ 2 Na
Thus obtained Na reacts with Hg of cathode and forms amalgam.
Na + Hg NaHg. (Sodium amalgam)
The sodium amalgam if reach to another chamber having mercury anode reacts with water to produce NaOH and H2.
2 NaHg + 2 H2O 2 NaOH + 2 H2 + 2 Hg
This forms the basic principle of manufacture of NaOH in Castner Kellner Cell.
iv. Electrolysis of CuSO4 solution using non attackable electrodes (Pt electrodes)
Reaction:
CuSO4 Cu++ + SO4¯ ¯
H2O H+ + OH¯
Half reaction at anode
SO4¯ ¯ and OH¯ ions migrate to anode. Discharge potential of OH¯ is less than that of SO4¯ ¯.
So OH¯ ions are discharged in preference to SO4¯ ¯.
4 (OH¯) 2 H2O + O2 + 4 e¯
∴ Oxygen is released at anode or: Water is oxidized at anode.

Half reaction at cathode
Cu++ and H+ migrate to cathode. Discharge potential of Cu++ is less than that of H+. So Cu++ is
discharged in preference of H+.
2 Cu++ + 4 e¯ 2 Cu
∴ Copper is deposited at cathode.

v. Electrolysis of CuSO4 solution using attackable electrodes
If copper electrodes are used then it act as attackable electrode.
Reaction:
CuSO4 Cu++ + SO4¯ ¯
H2O H+ + OH¯
DC source Ammeter
+ –
Pure copper (Cathode)

Impure copper (Anode)
CuSO4 solution
Fig. 4.2: Electrolysis of copper sulphate solution using attackable electrodes

Reaction:
2 SO4¯ ¯ S2O8 + 4 e¯ (Very difficult)
4 (OH¯) 2 H2O + O2 + 4e— (Does not occur at Cu electrode)

Cu Cu+++ 2 e¯
(Preference because it is attackable electrode)
So, Cu anode undergoes dissolution.
Cu++ and H+ go to cathode. Discharge potential of Cu++ is lower than of H+ ions. So Cu++ ions
are discharged in preference to H+.
Cu++ + 2 e¯ Cu
So, copper is deposited at cathode.

Note:
If the electrode is inert (non-attackable)
Discharge potential: Na+> K+ > Ca2+ > Mg2+ > Zn2+ > Fe2+ > H+ > Cu2+ > Ag+ > Au3+
Ease of discharge at cathode: Na+< K+ < Ca2+ < Mg2+ < Zn2+ < Fe2+ <H+ < Cu2+ < Ag+ < Al3+
Discharge potential: SO42– > NO¯3 > OH¯ > X¯
Ease of discharge at anode: SO42– < NO¯3 < OH¯ < X¯
4.7 Quantitative Aspect of Electrolysis

The quantitative relationship between the amount of electricity passed and the mass of ion
discharged in the voltameter was first investigated by Michael Faraday and he enunciated the
following two laws in 1833. These laws are known as Faraday's law of electrolysis.
4.7.1 Faraday's First Law of Electrolysis

Faradays first law of electrolysis states "The amount of substance discharged or liberated at the
electrode during electrolysis is directly proportional to the quantity of electricity (charge) passed
through the electrolyte solution."
Amount of substance discharged ∝ charge supplied
W ∝ Q.
or, W = ZQ . . . (i)
or, W = ZIt [Charge (Q) = current (I) × time (t)] . . . (ii)
where Z = proportionality constant and known as electrochemical equivalent. (ECE)
W = Amount of substance discharged,
Definition of Electrochemical Equivalent
We have, W = ZIt
If 1 ampere current is passed through the electrolyte solution for 1 sec (i.e. one coulomb charge)
then, W = Z
Hence, electrochemical equivalent of a substance is defined as the mass of substance (in
gram) deposited or liberated by the passage of one coulomb charge.
1 Faraday (96,500 coulomb) charge deposits 1 gram equivalent of any substance.
Let E be the equivalent weight of a substance
96,500 coulomb deposits E g of substance
E
1 coulomb deposits 96500 g of substance.
E
By definition, Z =
96,500
Unit of Z is gram coulomb–1 or gram ampere–1 sec–1
∴ Faraday's first law can be mathematically expressed as,
W = ZIt.
EIt
W= 96‚500
1.008
∴ Electrochemical equivalent of H = 96500 = 0.0000104 g/coulomb
31.75
Electrochemical equivalent of Cu = 96500 = 0.0003290 g/coulomb
107.7
Electrochemical equivalent of Ag = 96500 = 0.0011160 g/coulomb
32.6
Electrochemical equivalent of Zn = 96500 = 0.0003378 g/coulomb
4.7.2 Faraday's Second Law of Electrolysis

It is dealt that when electric current is passed into the electrolytic solution then certain amount of
substances are discharged or liberated at the electrode.
If such voltameters are connected in series, the amount of substance deposited or liberated at the
respective electrodes depends upon the equivalent weight or chemical equivalent of the respective
substance. This is the Faraday's second law of electrolysis.
It states, When same quantity of electricity is passed through different electrolytic solution
connected in series, the mass of substance deposited or liberated at the respective electrodes is
directly proportional to its chemical equivalent or equivalent weight.
Mass of substance discharged (W) ∝ chemical equivalent (E)
W∝E
or, W = kE (k is proportionality constant)
W
or, E = k.
Mass of substance deposited
i.e. Chemical equivalent = Constant.
W1 W2 W3
Accordingly, E = E = E
1 2 3
Let the same quantity of electricity be passed through the different voltameters connected in series
containing acidulated water, CuSO4 and AgNO3 as shown in the figure.
+ –
A
O2
H2
Cu electrode Ag electrode
Acidified water
CuSOAnod AgNO3
CuSO4 e solution
Pt electrode solution
Cell-A Cell-B Cell-C
Fig. 4.3: Schematic diagram for the verification of Faraday's second law of electrolysis
Since the connection is in series, the same quantity of electricity is passed to all the voltameters.
So, according to Faraday's second law of electrolysis,
For cell A: Mass of hydrogen displaced ∝ Chemical equivalent (or Equivalent weight) of hydrogen.
Mass of hydrogen displaced
∴ Equivalent weight of hydrogen = Constant . . . (i)
For cell B: Mass of copper deposited ∝ Equivalent weight of Cu

Mass of Cu deposited
∴ Equivalent weight of Cu = Constant . . . (ii)
For cell C: Mass of silver deposited ∝ Equivalent weight of Ag

Mass of Ag deposited
∴ Equivalent weight of Ag = Constant . . . (iii)
From equation (i), (ii) and (iii)

Mass of hydrogen displaced Mass of Cu deposited Mass of Ag deposited
Equivalent weight of hydrogen = Equivalent weight of Cu = Equivalent weight of Ag
Relation between electrochemical equivalent (Z) and chemical equivalent (E)

From Faraday's first law of electrolysis, W = ZIt.
When Q = 1 coulomb then W = Z. Hence electrochemical equivalent can be defined as the mass of
substance deposited by passing one coulomb of charge in voltameter. The amount of substance in
gram liberated or deposited by passing 96,500 coulomb charges is chemical equivalent or
equivalent weight.
Also we know,
One Faraday or 96500 coulomb charge deposits one gram equivalent of any substance (E) g of
substance.
E
or, 1 coulomb charge deposits = 96‚500 g of the substance
E
By the definition of electrochemical equivalent, Z = 96‚500
1
Also, Z = 96‚500 × E.
1
Z ∝ E where 96‚500 is constant.
For two substance 1 and 2.

Z1 ∝ E1 and Z2 ∝ E2
Z1 Z2
∴ E1 = E2
∴ Electrochemical equivalent of element is directly proportional to its equivalent weight.
Alternatively,
From Faraday's first law of electrolysis,
For two different substances in the voltamenter if same quantity of charge is passed,
W1 = Z1Q . . . (i)
W2= Z2Q . . . (ii)
Now equation (i) is divided by equation (ii), we get
W1 Z1
= . . . (iii)
W2 Z2
From Faraday's second law of electrolysis,
W1 E1
= . . . (iv)
W2 E2
From equation (iii) and (iv)
Z1 E1
=
Z2 E2
Z
or = constant
E
or Z = constant × E
or Z ∝ E
Note:
96500 C (1F) charge can discharge or deposit or liberate one gram equivalent of any substance.
Solved Numerical Problems

Example 4.1 Show that 1 Faraday charge is approximately equal to 96,500 coulombs.
Solution
One Faraday is the charge of one mole of electrons
1F = Charge of one mole of electrons
= 1 mole of electron × charge of one electron.
= 6.023 × 1023 × 1.60 × 10–19 C.
= 96488.46 Coulomb.
≈ 96500 Coulomb.
Example 4.2 5 Ampere current is passed into a voltameter containing CuSO4 solution for 15 minutes
(having Cu-electrode): (a) Calculate the mass of copper metal deposited. (b) If mass of
each electrode is 5 g initially what will be the masses of anode and cathode after
electrolysis? (c) What will be the mass of Cu metal deposited if current efficiency is
only 75%?
Solution
(a) Method 1:
Total quantity of electricity (Q) = Current × time in second
= 5 A × (15 × 60 sec.)
= 4500 coulomb.
Atomic mass of Cu = 63.5
65.3
Equivalent mass of Cu = 2 = 31.75
We know,
96500 coulomb charge deposits 31.75g of Cu
31.75
4500 coulomb charge deposits 96500 × 4500 = 1.480 g
Method 2:
EIt 31.75 × 5 Ampere × (15 × 60 sec)
W = 96500 = 96500 = 1.480 g
(b) After electrolysis mass of anode is decreased and mass of cathode is increased
∴ Mass of anode = 5 – 1.48 g = 3.52 g
∴ Mass of cathode = 5 + 1.48 g = 6.48 g
(c) If current efficiency is 75%
The quantity of electricity (Q) = Current × time in second × current efficiency
75
Q = 5A × (15 × 60 sec) × 100
= 3375 coulomb
96500 coulomb charge deposits = 31.75 g of Cu.
31.75
3375 coulomb charge deposits = 96500 × 3375 g
= 1.110 g
Example 4.3 Calculate the number of coulomb of electricity required:
a. to discharge 0.3 mol of Zn2+
b. to deposit 4g of Mg from MgSO4.
Solution
(a) Method 1:
Zn++ + 2 e¯ Zn
1 mol 2 mol
1 mole of Zn++ is discharged by 2 moles of electrons.

0.3 mole of Zn++ is discharged by 2 × 0.3 mol of electrons.
= 0.6 mol of electron = 0.6 Faraday = 0.6 × 96500 coulomb
= 57900 coulomb
[Charge of 1 mol of electron is 1 F or 96500 coulomb]
Method 2:
1 mole of Zn++ = 65.3 g, Eq. wt. of Zn = 32.65
∴ 0.3 mole of Zn++ = 0.3 × 65.3 g
EQ
W = 96500
W × 96500 0.3 × 65.3 × 96500

Q= E = 32.65 = 57900 coulombs.
(b) 1 gram equivalent of Mg = 12 g

Since, 1 g equivalent of metal is deposited by 96500 coulomb of charge,
12 g of Mg is deposited by 96500 coulomb.
96500
4 g of Mg is deposited by 12 × 4 = 32166.66 coulomb
[Do yourself by using second method]
Example 4.4 Calculate the charge involved to oxidize 2 moles of Mn3O4 to MnO4¯ ¯ in alkaline
medium.
Solution
The balanced chemical equation is
Mn3O4 + 16 (OH¯) 3 MnO4¯ ¯ + 8 H2O + 10 e¯
1 mole 10 mole
2 mole 20 mole
From the above balance chemical equation,

Oxidation of 1 mole of Mn3O4 involves 10 mole of e¯
Oxidation of 2 mole of Mn3O4 involves 20 moles of e¯ = 20 Faraday = 20 × 96500 coulomb
= 1930000 coulombs
Example 4.5 75 milliampere current was passed through acidified water and metal nitrate solution
for same time. 60 cc of H2 at NTP and 0.57 g of metal deposited were measured.
Calculate the equivalent weight of metal.
Solution
From the Faraday's second law of electrolysis, mass of hydrogen evolved = volume of H2 in cc × 0.000089
g/cc
2
[... Density of H2 = 22400 g/cc = 0.000089 g/cc]
= 60 × 0.000089 g = 0.00534 g
Mass of hydrogen evolved Mass of metal deposited
Eq. wt. of hydrogen = Equivalent weight of metal
0.00534 0.57
or, 1.008 = Equivalent weight of metal
0.57 × 1.008
∴ Equivalent weight of metal = 0.00534 = 107.59
Example 4.6 Same quantity of electricity is passed though acidified water and a metal sulphate
solution. The volume of H2 gas produced is 55.30 cc at 730 mm Hg and 17°C. The mass
of metal deposited is 0.0397 g. The specific heat of the metal is 0.236. Find the formula
of the metal sulphate.
Solution
For H2 gas
At given condition At NTP
P1 = 730 mm Hg P2 = 760 mm Hg
V1= 55.30 cc V2 = ?
T1 = 17 + 273 T2 = 273 K
= 290 K
From combined gas equation, we have
P1V1 P2V2
T1 = T2
P1V1 T2 730 × 55.30 273
or V2 = T × P = 290 × 760 = 50.00 cc
1 2
2
Mass of H2 = Vol. of H2 at NTP in cc × 22400 g/cc = 50 × 0.000089 g = 0.00445 g
From Faraday second law of electrolysis,

Mass of H2 displaced Mass of metal depsoited
Equivalent weight of hydrogen = Equivalent weight of metal
0.00445 0.0397
or 1.008 = Equivalent weight of metal
0.0397 × 1.008
∴ Equivalent weight of metal = 0.00454 = 8.99
From Dulong and Petit's law, we have

Approximate atomic weight × specific heat ≈ 6.4
6.4 6.4
∴ Approximate atomic weight = sp heat = 0.236 = 27.11
Approximate atomic weight 27.11

Valency = Equivalent weight = 8.99 = 3.016
Valency of metal can't be fractional. Therefore, valency of metal = 3

∴ Formula of metal sulphate M2(SO4)3.
Example 4.7 A metallic spoon is coated with silver by passing a current of 5 ampere through AgNO3
solution for 5 hrs. What is the thickness of silver plating if the area of the spoon is 12
cm2 (density of silver is 10.5 g cm−3).
Solution
If ρ is the density of metal, θ is thickness of plating and A is surface area of the tray
EIt
W= F
EIt
or, ρ×V= F
EIt
or, ρAθ = F
EIt 108 × 5 × (5 × 60 × 60)

θ= = 10.5 × 12 × 96500 = 0.799 cm
ρAF
Solved Questions
1. What is E.C.E. (Electro-chemical Equivalent)?
¬ Electrochemical equivalent of a substance is defined as the mass of substance deposited or liberated by the
1.008
passage of 1 ampere current for one second. Example: e.c.e of H2=96500 g/coulomb
OR
Electrochemical equivalent of a substance is defined as the mass of substance deposited or liberated by the
passage of 1 coulomb charge.
2. State Faraday's first law of electrolysis
¬ The amount of substance discharged or liberated at the electrode during electrolysis is directly proportional
to the quantity of charge or electricity passed through the electrolyte.
Mathematically,
Amount of substance discharged (W) ∝ quantity of charged passed (Q)
W ∝ Q.
W = ZQ
W = ZIt [charge (Q) = current (I) × time (t)]
where z = proportionality constant and known as electrochemical equivalent. (ECE)
3. State Faraday's second law of electrolysis.
¬ It states that "when the same quantity of electricity is passed through the different electrolytes connected in a
series, the amount of substance deposited or liberated at the respective electrodes are proportional to their
chemical equivalent."
Mathematically,
Amount of substance discharged (W) ∝ chemical equivalent (E)
W∝E
W = kE
W
E = k.
Mass of substance deposited
i.e. Chemical equivalent = Constant.
Questions
1. Define the following terms:
a. Electro-chemical equivalent b. Chemical equivalent
c. One Faraday charge d. One ampere current
e. Electrochemical cells
2. Write the differences between electronic conduction and electrolytic conduction.
3. Justify the fact that value of 1 F is 96500 C
4. Define the term electrochemical equivalent (ECE). Derive its relation with chemical equivalent.
5. Calculate the charge on:
a. 1 mol of Cr2 O7−2 b. 4 g equivalent of Na+ c. 3 × 1023 electrons

1. State and explain Faraday's first law of electrolysis.
2. State and explain Faraday's second law of electrolysis.
3. Distinguish between (a) Electrolytic and voltaic cell (b) Electrochemical equivalent and chemical
equivalent.
4. Write short notes on: (a) Faraday's laws of electrolysis (b) Arrhenious theory of ionization (c)
Electronic and electrolytic conductors.
Numerical Problems
1. How many coulombs of electricity are required to discharge 0.1 mole of Na+?
[1 Faraday = 96500 coulomb]
Ans: 9650 coulomb
2. How long a current of 3 ampere has to be passed through a solution of AgNO3 to coat a metal
surface of 80 cm2 with 0.005 mm thickness? (density of Ag = 10.5 g/cc).
Ans: 125.09 seconds
3. What current is required to deposit whole copper from 1 litre of 1M CuSO4 solution by passing
electricity through it for 10 minute.
Ans: 321.66 A
4. A current of 2.5 ampere is passesed through the solution of a metal sulphate for 30 minutes and
deposits 1.52 g of metal at cathode. Find the equivalent weight of the metal.
Ans: 32.59
5. How many grams of silver could be plated out on a serving tray by passing electricity through a
solution of Ag (I) salt for 8 hours at a current of 9 ampere? What is the area of the tray, if
thickness of the silver platting is 0.002 cm? Density of silver is 10 g/cm3. (atomic mass of
Ag = 107.8).
Ans: Weight of Ag = 289.5 g; Area of tray = 14475 cm2
6. 1.52 g of a trivalent metal M was deposited at cathode by passing a current of 2.5 ampere
through its salt solution (metal sulphate) for 30 minutes. What is the atomic mass of M?
Ans: 97.78 amu
7. How many number of coulombs are required to deposit 81 g of aluminium when the electrode
reaction is: Al++++ 3e- → Al?
Ans: 868,500 coulombs
8. Equal amount of current was passed through an aqueous solution of trivalent metallic salt and
dil. H2SO4. The volume of H2 liberated was 96.5 mL at 27°C and 765 mm Hg pressure and mass
of metal deposited was 0.74 g. Calculate atomic mass of the metal.
Ans: 284.45 amu
4.8 Electrolytic Conduction

In the previous heading we have discussed about conductors. The conductor may be electronic or
electrolytic. When current is passed the electrolytic conductors undergo decomposition due to the
discharge of ions. Some electrolytes ionize almost completely and furnish more number of ions
which are called strong electrolytes. The example includes strong acid (HCl, H2SO4, HNO3, etc.),
strong base (NaOH, KOH, etc.), most of the inorganic salts (NaCl, KCl, etc.). Some electrolytes
undergo feeble ionization and furnish low number of ions in solution and offer poor conduction.
These are called weak electrolytes. These include weak acid (CH3COOH, HCN, H2CO3), weak base
(Cu(OH)2, Zn(OH)2, Al(OH)3, NH4OH etc.) and few inorganic sparingly soluble salts.
Electrolytic conduction not only depends upon the nature of electrolytes but also to the nature of
solvents. When electrolytes are added into solvents, some sort of interaction take place between ions
and solvent. Electrolytes ionize more in polar solvent than in non-polar solvent. The viscosity of
solvent is another contributing factor. Inter-ionic attraction, solvation of ions and viscosity of
solvents are influenced by temperature. Therefore, effect of temperature can't be ruled out.
Another most important factor that affects the electrolytic conduction is concentration of solution.
Before discussion about this we should be familiar with Ohm's law and related terms which are
given below.
Self Test
4.1 Write factors that affect electrolytic conduction.
Ohm's Law: Every substance offers resistance to the flow of electricity to some extent. The hindrance
offered by a substance to the flow of electric charge through the solution is called resistance. It is
denoted by R. The relationship among voltage or emf (E), resistance (R) and current flowing (I) is
shown by Ohm's law. Ohm's law states, "physical conditions (temperature, mechanical strain, etc.)
remaining constant, the current flowing through a conductor is directly proportional to the
potential difference (V) of the two points."
I∝V
1 V
or I = R .V
I R
Where R is proportionality constant and is called resistance of the conductor
or V = IR
The resistance (R) of a conductor is
i. Directly proportional to the length of the conductor (l) i.e. R ∝ l
. . . (i)
1
ii. Inversely proportional to the area of cross-section of the conductor (A). i.e., R ∝ A . . . (ii)
From equation (i) and (ii)

l
R∝ A
l
or R=ρ A . . . (iii)
Where ρ is proportionality constant and is called resistivity or specific resistance.

Definition of resistivity
When l = 1 cm and A = 1 cm2 then from relation (iii), we get R = ρ.
Hence, specific resistance or resistivity of a wire is defined as the resistance offered by the wire of
unit length and unit area of cross section.
From above relation,
RA
ρ= l
The S.I. unit of resistance is Ohm (Ω ), area of cross-section is m2 and length of wire is m, therefore,
the unit of resistivity is Ohm meter.
Ohm × meter2
ρ= meter = Ohm meter = Ω m
Graphical representation of Ohm's law

1
The equation I = R V is in the form of y = mx.
So, if a graph of current (I) versus voltage (V) is plotted, a straight line passing through the origin is
obtained. This justifies the validity of Ohm's law. The metallic conductor is called Ohmic conductor.
↑ ↑
I I
V→ V→
(a) (b)
Fig. 4.4: A graph of current versus voltage for (a) Ohmic conductor (b) Non-Ohmic conductor
In case of electrolytic solution (e.g. CuSO4 solution, NaCl solution etc.) the graph of current versus
voltage is not straight line. This type of conductor is called non-Ohmic conductor.
Resistance in electrolytic solution: Like ohmic conductor, electrolyte solution also obeys Ohm's law.
With respect to electrolyte solution, the Ohm's law can be stated as "the current flowing through an
electrolyte solution is directly proportional to the emf or potential difference applied".
Specific Resistance (ρ )
It is already mentioned that like Ohmic conductor electrolyte solutions also obey the Ohm's law.
If electrolyte solution is kept in a tube having length l cm and area of cross-section A cm2 then
resistance (R) offered by electrolyte solution is directly proportional to the length (l) of tube and
inversely proportional to the area of cross-section (A) of the tube.
When l = 1 cm and A = 1 cm2 then R = ρ
Hence, specific resistance or resistively (ρ) is defined as the resistance offered by electrolyte
solution kept in a tube having unit length and unit area of cross-section.
A tube having unit length and unit area of cross-section will have unit volume. Hence, alternatively,
specific resistance is defined as the resistance offered by electrolyte solution kept in a cube
having unit volume.
In short, the resistance offered by 1 cc electrolyte solution is specific resistance.
Conductance (G)
The reciprocal of resistance is called conductance. It may be represented by G.
1
Conductance (G) = Resistance (R)
In case of electrolyte solution, the term conductance is frequently used rather than resistance.
Unit of conductance
The unit of conductance is Ohm-1 or Ω –1 or mho or siemens.
Types of conductance
Electrolytic conduction depends upon number of ions and their mobility in the solution. For pure
electronic conductor the number of atoms per unit volume is fixed. However, electrolyte solution is
prepared by dissolving electrolyte into solvent. The degree of ionization is also different for different
electrolyte. Therefore, it is convenience to study conductance in terms of,
1. Specific conductance or conductivity (κ)
2. Equivalent conductance (λ)
3. Molar or molecular conductance (μ)
1. Specific conductance or conductivity (κ)

The reciprocal of specific resistance is called specific conductance and it is denoted by κ
(kappa). From the above relation,
l
R=ρA
1 1 ⎛l⎞
= .
ρ R ⎝A⎠
l 1 1
κ=GA [Where κ = and G = R ]
ρ
When length between two parallel electrodes (l) = 1 cm and area of cross-section of electrode
(A) = 1 cm2 then κ = G.
Hence, specific conductance may be defined as the conductance offered by a solution kept
between two parallel electrodes each of cross-sectional area 1 cm2 and separated by 1 cm
length.
or
Specific conductance of a solution may be defined as the conductance offered by 1 cc
(centimeter cube) electrolyte solution.
electrolyte solution
+ –
1cm
1cm
Fig.4.5: Diagrammatic illustration of specific conductance
Conductance of 1 cc electrolytic solution = Specific conductance.

Unit of Specific conductance
l
R=ρA
1 1 l
= .
ρ RA
1 l 1 Cm
κ = R . A = Ohm . Cm2
∴ Unit of κ = Ohm–1 cm–1 or mho cm–1 or simens cm–1.
2. Equivalent conductance (λ)

The conductance offered by 1 cc solution is not much informative because 1cc solution is not
well defined in terms of the amount of electrolyte present in that volume. Therefore, it is a
common practice to express of the solution in terms of its concentration. If electrolyte solution is
prepared by dissolving certain number of gram equivalent of electrolyte in particular volume of
solution, conductance is measured in terms of equivalent conductance. Equivalent conductance
is the measure of conducting power of all ions produced by one gram equivalent of electrolyte
in solution.
Hence, it is defined as the conductance offered by solution prepared by dissolving 1 gram
equivalent of solute when the whole solution is placed between two parallel electrodes at
1 cm apart with area of cross-section 1 cm2 of each electrode.
Equivalent conductance (λ) is calculated from the specific conductance and concentration of the
solution.
Let 1 gram equivalent electrolyte is dissolved to prepare V cc of solution and κ be the specific
conductance.
Now, by definition of specific conductance
conductance of 1 cc solution = κ.
conductance of V cc solution = κ ×V.
Equivalent conductance λ = κ × V . . . (i)
Number of g eqvt. (n)
Concentration in normality (N) = Vol. of solution in litre (V)
V
If 1 gram equivalent of electrolyte is dissolved to prepare V cc ⎛or 1000 liter⎞ solution,
⎝ ⎠
1
N = V/1000
1000
or N = V
1000
or V = N
Putting the value of V in equation (i), we get

κ × 1000
λ = N . . . (ii)
l
Also, κ = R.A
Now putting the value of κ in equation (ii)

l × 1000
∴ λ = R.A.N . . . (iii)
[Where, l= length, R= resistance, N = normality of solution, A = area of cross section]
Unit of Equivalent conductance

Simens cm–1 . cm3
λ= equiv = Simens cm2 eqaiv-1
3. Molecular conductance or molar conductance (μ)

Molecular conductance is the measure of conducting power of all ions produced by one mole of
electrolyte in solution.
Hence, it is defined as the conductance offered by solution prepared by dissolving 1 mole of
solute when the whole solution is placed between two parallel electrodes at 1 cm apart with
area of cross-section of each electrode 1 cm2.
Molar conductance is calculated from specific conductance and concentration of the solution.
Let one mole of solute be dissolved to prepare V cc of solution and κ be the specific
conductance.
Conductance of 1 cc solution = κ
Conductance of V cc solution = κV
By definition μ = κV . . . (i)
Number of moles (n)
Concentration in Molarity (M) = Volume of solution in litre (V)
V
If 1 mole of electrolyte is dissolved to prepare Vcc ⎛or 1000 liter⎞ solution then,
⎝ ⎠
1
M = V/1000
1000
or M = V
1000
or V = M
Putting the value of V in equation (i), we get

κ × 1000
μ = M . . . (ii)
l
Also, κ = R.A
Now putting the value of κ in equation (ii)

l × 1000
∴ μ = R.A.M [Where, l= length, R= resistance, M = molarity of solution] . . . (iii)
Unit of molar conductance:

Simens cm–1 . cm3
μ= mol = Simens cm2 mol–1
Relationship between equivalent conductance (λ) and molar conductance (μ)

From the above relation, we have
l × 1000
Equivalent conductance λ = RAN . . . (i)
l × 1000
Molar conductance μ = RAM . . . (ii)
Now equation (i) is divided by equation (ii), we get

λ M
= N
μ
or λ× N = μ × M
or Eqvt. conductance × Normality = Molar conductance × Molarity
Conductivity Cell and Cell Constant

We know,
l
R = ρ A.
Where R = resistance
ρ = specific resistance
l = distance between electrodes
A = cross-sectional area of electrode.
For a given cell, the cross-sectional area of electrode and length between two electrode is fixed.
l
Therefore, A remains constant which is called cell constant.
l
∴ Cell constant = A
Hence, cell constant is defined as the ratio of the distance between the plates of two electrodes to
the area of cross-section of electrode plate.
l
Here, R=ρA
1 1 ⎛l⎞
=
ρ R ⎝A⎠
κ = G × cell constant
κ
∴ Cell constant = G
Specific conductance (κ)

∴ Cell constant = Observed conductance (G)
Alternatively, cell constant is the ratio of specific conductance to the observed conductance.
Unit of cell constant
l cm
Cell constant = A = cm2 = cm–1
In fact cell constant is determined by measuring specific conductance and observed conductance
rather than by measuring the distance between two parallel plates and area of cross- section of
electrodes. A solution of known specific conductance is taken and observed conductance is
determined. KCl solution is mostly used for this purpose. Its conductance has been measured with
sufficient accuracy (calibration of the conductivity cell).
The conductance of electrolyte solution is measured by using conductivity cell. In market, different
types of conductivity cells are found. Some models of conductivity cells are shown in figure 4.6.
+ –
Copper wire + –
Ebonite cover
l cm A
Mercury
Platinum plate A
l cm
Fig. 4.6: Conductivity cells
Conductivity Water
For the measurement of the conductance of electrolyte solution pure water should be used to prepare
solution. Distilled water has also certain level of conductance. Conductivity water is prepared by
double distillation of distilled water containing small amount of KMnO4 and KOH so that volatile
impurities are oxidised. The specific conductance of the conductivity water is 8 × 10–5 Ohm–1m–1 at
298 K. This conductivity is mainly due to dissolved CO2 from air. The conductivity water is also
called equilibrium water. Purest water free from air is called ultra pure water. The specific
conductance of ultra pure water is 5.8 × 10–6 Ohm–1m–1 at 298 K. For precise experimental work ultra
pure water is used.
4.9 Variation of Conductivities of Electrolyte Solution with

Dilution
Conductance of electrolyte solution mainly depends upon the following two factors.
1. Number of ions present in the solution
2. Mobility of ions
Other factors such as temperature, viscosity of solvent, hydration of ions, concentration or dilution of
solution ultimately affect the above factors. The effects of dilution on different types of conductivities
of solution are discussed in different headings.
1. Effect of dilution on specific conductance
Specific conductance of a solution is the conductance offered due to the conduction of ions in 1cm3 of
the solution. When the solution is diluted the following changes occur.
a. Degree of ionization increases in case of weak electrolyte. Therefore, number of ions in solution
increase.
b. The number of ions per centimeter cube decreases.
c. As the number of ions per centimeters cube decreases they become far apart from one another.
But the effects of increase in number of ions due to ionization and increase in mobility due to
decrease in inter-ionic interaction are far less than the effect caused by decrease in number of ions
per unit volume due to dilution.
Overall effect is decrease in specific conductance with increase in dilution.
In brief, specific conductance decreases on dilution due to decrease in number of ions per unit
volume of the solution.
2. Effect of dilution on equivalent conductance or molar conductance
On dilution, equivalent and molar conductance increase whether the solution is of strong electrolyte
or weak electrolyte. But the reasons for increase in conductance are different.
a. Increase in equivalent or molar conductance on dilution for weak electrolyte: Molar or
equivalent conductance is the total conductance of all ions present in a solution containing 1
mole (for molar conductance) or 1 g equivalent (for equivalent conductance) electrolyte,
assuming that their ions are present in unit volume of solution. Therefore, the total volume of
solution has no effect on their values. But when the solution of weak electrolyte is diluted, the
degree of ionization is increased and number of ions in the solution is increased which increases
the equivalent or molar conductance.
The variation of equivalent conductance (or molar conductance) with dilution for weak
electrolyte can be shown graphically as in figure 4.7.
↑
λ
Weak electrolyte
C
Fig. 4.7: Variation of equivalent conductance with concentration for weak electrolyte
b. Increase in equivalent or molar conductance with dilution for strong electrolyte: Strong
electrolytes are ionized almost completely at all dilution. Therefore, increase in equivalent or
molar conductance with dilution for strong electrolytes is not due to the increase in degree of
ionization but due to some other factors.
At concentrated solution, the ions are sufficiently near to one another and inter-ionic forces are
predominant. It tends to decrease the mobility of ions. When strong electrolyte solution is
diluted, the ions are dispersed in large volume and inter-ionic distance increases. This decreases
the electrostatic forces of attraction.
q1q2
F ∝ r2
Due to decrease in inter-ionic forces of attraction, the mobility of ions towards the
corresponding electrode increases and equivalent or molar conductivity increases.
The variation of equivalent conductance with dilution for strong electrolyte solution can be
shown graphically as in figure 4.8.
λ∞
λ
Strong electrolyte
C
Fig. 4.8: Variation of equivalent conductance with concentration for strong electrolyte solution
The molar or equivalent conductivity of strong electrolyte solution varies with concentration according to equation.
λ c = – b C + λ∞
Where, λc = Equivalent conductance of electrolyte at concentration C.
λ∞ = Equivalent conductance of electrolyte at infinite dilution.
C = Equivalent concentration
b = Constant, the value of b depends upon the type of electrolyte used, nature of solvent and temperature.
In fact the above equation is simplified form of Debye – Huckel – Onsager equation.
The increase in equivalent or molar conductance of strong electrolyte solution on dilution is due to decrease in asymmetric
effect or relaxation effect and electrophoretic effect. So, mobility of ions increases. These terms are not described here. This is
beyond the scope of this text.
4.10 Effect of Temperature on Conductance

There are mainly two types of conductances. These are
a. Electronic conductance or metallic conductance
b. Electrolytic conductance
The electronic conductance decreases with the increase of temperature. This can be explained as
follows. Electronic conductance is due to flow of electrons. When temperature is increased, the drift
velocity of electron is increased and these electrons tend to move randomly in several directions
rather than in particular direction with particular orientation. On the other hand, the electrolytic
conductance increases with increasing temperature. The reason is explained as: The extent of
increase in conductance of electrolyte solution is due to increase in temperature vary from one
condition to another condition. There is in average, 2-3% increase in conductance of electrolyte
solution for each degree rise in temperature. The conductance of an electrolyte solution depends on
two factors.
i. The number of ions present in unit volume of solution.
ii. The speed of ions towards the respective electrode.
For strong electrolytes, due to increase in temperature there is hardly any increase in number of ions
in unit volume of solution but the speed of ions increases due to decrease in viscosity of solvent.
For weak electrolyte, the effect of temperature on the conductance depends upon enthalpy change
accompanying the process of ionization.
If the process of ionization is exothermic, the degree of ionization is decreased due to increase in
temperature and conductance is decreased. If the process of ionization is endothermic, the ionization
is increased due to increase in temperature and conductance is increased.
4.11 Kohlrausch's Law of Independent Migration of Ions

In 1875, Kohlrausch studied the equivalent conductance of different electrolyte pairs with common
cation and common anion. On the basis of these observations, he gave a law which is called
Kohlrausch's law of independent migration of ions.
It is defined as "At infinite dilution, where dissociation of all electrolytes is complete and inter-ionic
effects fade out, each cation or anion migrates independently of its counter ion and contributes a
definite share to the total equivalent conductance."
OR,
Kohlrausch's law states "at infinite dilution, the equivalent conductance of an electrolyte is equal to
the sum of equivalent conductance of its cation and anion."
Mathematically,
λ0 = λ0+ + λ0–
λ0 = Equivalent conductance at infinite dilution.
λ0+ = Equivalent conductance of cation at infinite dilution
λ0– = Equivalent conductance of anion at infinite dilution
For example,
At infinite dilution, the equivalent ionic conductance of Na+ is 50.0 Sm2 eqvt–1 and equivalent
ionic conductance of Cl¯ ion is 76 Sm2 eqvt–1. The equivalent conductance of NaCl at infinite
dilution is 126 Sm2 eqvt–1.
λ0NaCl = λ0Na+ + λ0Cl–

126 = 50 + 76
Solved Questions
1. Define specific conductance.
¬ Specific conductance of a solution may be defined as the conductance offered by 1 cc (centimeter cube)
l
electrolyte solution. Mathematically, κ = G × A
2. Define equivalent conductance.

¬ It is defined as the conductance offered by solution prepared by dissolving 1 gram equivalent of solute when
the whole solution is placed between two parallel electrodes at 1 cm apart with area of cross-section of each
l × 1000
electrode 1 cm2. Mathematically, λ = κ × V or, λ = RAN
3. Define molecular conductance.

¬ It is defined as the conductance offered by solution prepared by dissolving 1 mole of solute when the whole
solution is placed between two parallel electrodes at 1 cm apart with area of cross-section of each electrode 1
l × 1000
cm2. Mathematically, μ = κ × V or, μ = RAM
Questions
a. Conductance b. Resistivity
c. Specific conductance d. Equivalent conductance
e. Molecular conductance f. Cell constant
g. Electrolytic conductance
2. Why do specific conductance decrease and equivalent conductance increase with dilution?
3. Write graphical representation showing variations of conductance with concentration.
1. Write short notes on variation of electrolytic conductance with concentration.
2. Write short notes: (a) conductance of solutions (b) molar and equivalent conductance.
Numerical Questions
1. Find the molar conductivity of 0.01 M acetic acid having specific conductivity 1.46 × 10-4 Ohm-1
cm-1.
Ans: 14.6 s cm2 mol–1
2. Calculate the equivalent conductivity of 0.12 (N) solution of an electrolyte, whose conductivity
is 0.024 S cm–1.
Ans: 200m–1 cm2 eqv–1 (200 Scm2 eqv–1)
3. Calculate the equivalent conductance of 0.1N KCl solution having specific resistance 83.3 Ohm
cm−1.
Ans: 120 ohm–1 cm2 eqvt.–1
4. The conductivity of electrolytic solution is 0.3704 S cm−1 at 298K. A conductivity cell when filled
with this solution gave a resistance of 1.5 ohm, find out the cell constant of this cell.
Ans: 0.556 cm−1
5. 0.028 N KCl solution has specific conductance of 0.00277 S cm−1
having resistance of 520 ohm.
0.04N solution of unknown salt kept in the same cell showed the resistance of 300 Ohm at same
condition. Calculate (i) cell constant of the cell and (ii) equivalent conductance of unknown salt.
Ans: (i) 1.44 cm−1 (ii) 119.5 S cm2 eq−1
4.12 Galvanic Cell

4.12.1 Introduction
If a zinc rod is immersed into CuSO4 solution, the solution is found to be warm due to following
reaction.
Zn (s) + CuSO4 (aq) ZnSO4 (aq) + Cu (s)
The above reaction is redox reaction where metallic zinc is oxidized to Zn++ (or ZnSO4) and Cu++ (or
CuSO4) is reduced to metallic copper. The reaction is exothermic which makes solution warmer.
But the reaction does not provide a useful work done. If the reducing agent (Zn) and oxidising agent
(Cu2+) are taken in separate containers connected by external metallic conductor (as shown in Fig.
4.9), the electron flow takes place through Zn electrode to Cu electrode. Now, the same reaction can
be utilized for useful work and such cell is called galvanic cell.
An electrochemical device which converts chemical energy into electrical energy is called galvanic
cells or voltaic cell. Galvanic cell is named in the honour of Luigi Galvani (1780) and voltaic cell is
named in the honour of Alessandro Volta (1800) who were the pioneer to perform experiments on
the conversion of chemical energy into electrical energy.
4.12.2 Construction of Galvanic Cell

Let us take an example where zinc rod is immersed into aqueous solution of zinc sulphate and
copper rod is immersed into aqueous solution of copper sulphate as shown in figure 4.9. These two
half cells are externally connected to emf measuring device such as voltmeter or potentiometer and
internally connected by salt bridge as shown in figure 4.9.
Conventional direction of current
Flow of electron
Potentiometer
e
Salt bridge
ZnSO4 CuSO4
Cu electrode
Zn electrode
Anode half Cathode half

ll ll
Fig. 4.9: Diagram of galvanic cell
Cell notation
It is inconvenient to draw the diagram of galvanic cell. Therefore, this cell can be represented in
symbolic form which is called cell notation. While writing cell notation, the following pattern is
adopted (According to IUPAC recommendation).
Anode/ Electrolyte solution of anode // Electrolyte solution of cathode/ Cathode
In the above format, the state of anode, cathode and electrolyte solution should be mentioned
whether these are in solid, liquid or gaseous state. In case of electrolyte solution it is customary to
mention the concentration of the solution too. If gas electrode is used then pressure of gas is written
in bracket. In the above cell notation a single vertical slash line is used to distinguish different phases
such as solid-liquid or liquid-gas. The double vertical slash lines indicate salt bridge. In the galvanic
cell of Zn and Cu(Daniell cell), the cell notation is given below.
Zn(s) / ZnSO4 (1M) CuSO4 (aq) (1M)/Cu(s)
Anode half cell Cathode half cell
Zn (s) Zn(s)
/ ZnSO/ 4ZnSO 4 (aq.)(1M)
(aq.) (1 M ) ||CuSO
CuSO4 4(aq) (1M)(1M)
(aq) / Cu(s)
/ Cu (s)
Cathode is +ve
Cu is +ve polepole
Cu is solid
Cu is cathode
The slash line is used to differentiate solid and solution phase
Strength of CuSO4 solution is 1M
CuSO4 is used in aqueous solution phase

Electrolyte of cathode half cell
Anode half cell and cathode half cell are joined by salt bridge
Strength of ZnSO4 solution is 1M
ZnSO4 is used in aqueous solution phase
Electrolyte of anode half cell
The slash line is used to differentiate solid and solution phase
Zn is solid electrode
Zn is anode
Anode is negative pole.
Electrode reactions
An anode (Oxidation-Half reaction): Electrode having lower reduction potential acts as anode. At
anode half cell, oxidation reaction takes place. The electrode reaction taking place at anode half cell
of above cell is given below.
Zn Zn++ + 2 e¯ (zinc is oxidised)
At cathode (Reduction–Half reaction): Electrode having higher reduction potential acts as cathode.
At cathode half cell, reduction reaction takes place. The electrode reaction taking place at cathode
half cell is given below.
Cu++ + 2 e¯ Cu (Cu2+ is reduced)
The complete cell reaction is obtained by adding anode half reaction and cathode half reaction.
Zn Zn++ + 2 e¯
Cu++ + 2 e¯ Cu
Complete cell Reactions: Zn + Cu++ Zn++ + Cu
This is the ionic reaction that takes place in galvanic cell. The molecular reaction is,
Zn + CuSO4 ZnSO4+ Cu
The above reaction informs that when zinc rod is immersed into ZnSO4 solution and copper rod is
immersed into CuSO4 solution followed by joining these two half cells by salt bridge, the zinc rod
gradually becomes thinner while copper rod gradually gets thickened. Zinc atom from zinc metal
goes into the solution in the form of zinc ions while copper ions accepts electron and get reduced to
form metallic copper. As a result of chemical reaction following changes take place.
a. Mass of metal at anode decreases.
b. Concentration of metal ion at anode increases.
c. Concentration of metal ion at cathode decreases.
d. Mass of metal at cathode increases.
e. As the metallic atoms of anode pass into the solution in the form of ions leaving behind the
electrons at anode, the anode is rich in electron and acts as negative electrode. Consequently,
the cathode acts as positive electrode.
f. The electrons flow from anode to cathode but the conventional direction of flow of current is
from cathode to anode.
If the cell reactions are carried out without using salt bridge, the production of current is stopped
after sometimes. The role of salt bridge in electrochemical cell is discussed below.
4.12.3 Salt Bridge

Salt bridge is 'U' shaped glass tube containing inert electrolyte solution such as KCl, KNO3 or
NH4NO3 in agar-agar or jelly medium. To understand its importance in a galvanic cell, let us take an
example of Daniell cell where Zn strip is dipped in ZnSO4 solution and Cu strip is dipped into
CuSO4 solution.
Potentiometer
Zn++ Zn++ SO4¯ ¯ SO4¯ ¯

ZnSO4 Zn++ CuSO4
Zn++
SO4¯ ¯ SO4¯ ¯
Zn electrode Zn++ Zn++ Cu electrode
SO4¯ ¯ SO4¯ ¯
Fig. 4.10: Galvanic cell without salt bridge
Convention direction of current

Flow of electron
Potentiometer
e
Salt bridge
ZnSO4 CuSO4
Zn electrode Cu
l t d
Fig. 4.11: Galvanic cell with salt bridge

Initially, here we discuss what will happen if salt bridge is not used in cell. Then, we will discuss
how the salt bridge avoids the undesirable circumstances in the galvanic cell. Out of Zn and Cu strip,
Zn has more tendency to get oxidized while Cu2+ has more tendency to get reduced. Therefore, zinc
atoms lose electrons and zinc ions pass into solution. This makes zinc electrode rich in electrons and
it acts as negative electrode. The electrolyte solution of anode half cell will be rich in Zn++ ions. The
solution of anode half cell consists more cations than anions in average. Therefore, the electrolyte
solution can be considered to be positively charged in net. On the other hand, electron driven by
anode will be consumed by copper ions of cathode half cell to form metallic copper. As copper ions
get reduced the cathode solution will be rich in sulphate ions in average.
Maintenance of this type of charge reparation requires high amount of energy and therefore, the flow
of electrons stops. Therefore, salt bridge is used to balance this unbalanced charge between these two
compartments. The anion present in salt of salt brings (e.g. Cl¯) migrates towards anode half-cell to
balance excess positive change there. On doing so, heavily crowded of positively changed particles
are counter-balnced. Similarly, anion present in the salt of salt bridge (e.g. K+) migrates towards
cathode half-cell to balance excess negative charge there. On doing so, heavily crowded negatively
changes particles are counter-balnced.
It is believed that the salt bridge balances unbalanced charges solutions without extensive
intermixing of the ions. Therefore, the external circuit is completed by metallic conduction where as
the internal circuit is completed by salt bridge.
The function of salt bridge can be summarized as,
i. Salt bridge avoids or minimizes the liquid-liquid junction potential. Due to different mobility of
ions in electrolyte solution, different ions migrate at different speeds. Due to this, there is
separation of charge and formation of two layers of liquid. A potential is developed at the
junction of two liquid layers which is called liquid-liquid junction potential or simply junction
potential.
ii. Salt bridge helps to complete the internal circuit of galvanic cell.
iii. Salt bridge maintains electrical neutrality without direct mixing of electrolyte solution.
iv. Salt bridge avoids the crowding of ions around electrodes.
The criteria of electrolytes used in salt bridge are given below.
i. The electrolyte solution should be inert towards electrode reaction i.e., the electrolyte of salt
bridge should not take part in reaction. For example: KCl cannot be used in salt bridge, if
electrolyte solution contains Ag+ ions as there is the formation of insoluble AgCl.
ii. The transport number or mobility of cations and anions should be same or nearly same. In salt
bridge, KCl is preferred because the transport number of K+ ions is nearly equal that of Cl¯ ions.
The fraction of current carried by an ion is called its transport number.
iii. The concentration of electrolyte should be preferably high.
4.13 Electrode Potential and Standard Electrode Potential

A metal dipped in the solution of its own ion constitutes an electrode. When a metal is immersed
into its soluble salt solution, three cases may arise as shown in fig. 4.12.
i. The metal atoms of electrode pass into the solution in the form of positive ion leaving behind
electron on the electrode and the electrode becomes negative.
M Mn+ + ne– (Oxidation)
ii. The metal ions of electrolyte solution accept electrons from electrode and get reduced. This
makes electrode electron deficient and the electrode becomes positive.
Mn+ + ne¯ M (Reduction)
iii. Neither the metal atoms loses electron nor the metal ions gain electron.
Mn+
M Mn++ ne¯ M
ne¯
Metal atoms of electrode Metal ions accept Neither metal atoms lose
loses electrons and metal electron and deposit on electron nor metal ions
ions go into the solution electrode. gain electron
Fig. 4.12: Schematic diagram to show the fate of metal atom or ion in an electrode
When an electrode is immersed into electrolyte solution, the fate of atom of electrode or ions of
solution is discussed above. This will be more clear from the Nernst theory of electrode potential. It
will be discussed in the next heading.
When an electrode is dipped into electrolyte solution of its soluble salt, either the metal atom loses
electrons and positive ions dive into the electrolyte solution or the ions of electrolyte accept electrons
and deposit on the electrode. During this process, there is separation of charge on the electrode and
electrolyte interface. Potential difference exists across the double electrical layer of electrode system.
This potential developed in electrode electrolyte
Metal
interface due to the formation of an electrical double
layer is called single electrode potential or simply Double layer
electrode potential.
The adjoining figure portrays how single electrode
potential is developed. To explain this, let us take an Solution of metal salt
example. When zinc rod is immersed into zinc sulphate
solution, zinc atoms lose electrons and zinc ions are
formed. These ions are pulled towards the solution by Fig. 4.13: Diagram of show the origin of
single electrode potential.
the attraction of SO4¯ ¯ ions. Then zinc ions dive into the
solution leaving behind electrons on the electrode.
When the process continues, electrode acquires negative charge while electrolyte solution acquires
net positive charge. Later on, the positively charged ions of electrolyte solutions are attracted
towards the negative electrode and a double layer of charge is developed at the solid liquid interface.
This double layer of charge develops potential. In this way single electrode potential is originated.
On contrary, there is probability of deposition of zinc ions on electrode from electrolyte solution by
accepting electrons. In such situation the electrode becomes electron deficient and it is regarded as
positive electrode. In this case electrolyte interface develops net negative charge. To know, whether
zinc atoms lose electrons and get oxidized or zinc ions gain electrons and get reduced, we should
know about another half cell in the circuit. It will be more clear after studying electrochemical series.
Electrode potential is defined as the potential developed at the electrode electrolyte interface
when an electrode is dipped into electrolyte solution having its ions. It is denoted by E. Electrode
potential is the measure of the tendency of an electrode to lose or gain electrons to or from electrolyte
solution of its salt. The electrode potential varies with the nature of electrode, concentration of
electrolyte solution, pressure (in case of gas electrode) and temperature.
If electrode potential is measured for an electrode at its 1 molar concentration of electrolyte
solution at 25°C, it is called standard electrode potential which is denoted by E°. If electrode
potential is developed due to loss of electron (oxidation) by electrode, it is called oxidation potential.
Or, oxidation potential shows a capacity of the electrode material to be oxidised (or to lose e–). If
oxidation potential is measured at standard condition, it is called standard oxidation potential. It is
denoted by Eoxo . The standard oxidation, potential of zinc electrode is + 0.76 volt (EZn/Zn
o
++ = 0.76 V).
Zn (s) Zn++ (aq) + 2e¯ E°ox= + 0.76 volt.

If electrode potential is developed due to reduction, it is called reduction potential. Reduction
potential at standard condition is called standard reduction potential. Reduction potential shows a
capacity of the electrode material to be reduced or to gain electron. It is denoted by Eored. The
o
standard reduction potential value of zinc electrode is – 0.76 V. (EZn++/Zn = −0.76 V).
Zn++ + 2 e Zn, E°cell = – 0.76 volt.

Since oxidation is the reverse process of reduction the oxidation potential for an electrode will have
same magnitude to that of reduction potential but with opposite sign.
According to IUPAC conventions, reduction potential value is used in electrochemical calculation.
Nernst theory of electrode potential

In Galvanic cell, anode is negative electrode and cathode is positive electrode. A much deeper
insight about the polarity can be realized from Nernst theory of electrode potential. According to
this theory, all metals and non-metals have definite tendency to pass into ionic state by the loss of
electrons when it is dipped into electrolyte solution.
The property of atoms of electrode to pass into solution in the form of positive ion is called
solution pressure. When a positive ion tends to enter into solution, it is opposed by similar ions of
electrolyte solution. Therefore, cations develop a tendency to get deposited on the electrode. The
property of ions of electrolyte which creates pressure to get deposited at the electrode by
accepting electrons is called osmotic pressure. When an electrode is immersed into electrolyte
solution, the solution pressure tends to develop positive ion by the loss of electrons while osmotic
pressure opposes this phenomenon. The electrode potential of an element or electrode is equal to
the difference between the solution pressure and the osmotic pressure of ions. Depending upon
the magnitude, three cases may arise here.
i. Solution pressure > Osmotic pressure: When solution pressure is greater than osmotic
pressure, atoms of electrode become positive ions and pass into the solution leaving behind
electrons at the electrode until the charge in the electrolyte solution oppose further action. In
such situation the electrode acquires negative charge while electrolyte solution acquires net
positive charge. Oxidation takes place here.

M Mn+ + ne¯
The potential developed in this condition is called oxidation potential.
ii. Solution pressure < Osmotic pressure: When osmotic pressure is greater than solution
pressure, the electrode fails to send the positive ions in solution. Further the positive ions of
solution acquire electrons and get deposited. Due to this, electrode acquires positive charge
while electrolyte solution acquires net negative charge. Oxidation takes place here.
Mn+ + ne¯ M
The potential developed in this condition is called reduction potential.
iii. Solution pressure = Osmotic pressure: When solution pressure is equal to osmotic pressure,
no charge separation occurs at electrode-electrolyte interface without developing any
potential difference. This type of electrode is often called null electrode.
Measurement of Electrode Potential

Potentiometer or voltmeter is used to measure the
H2 gas at 1 atm pressure
potential difference. Therefore, the electrode for which
the electrode potential is measured should be connected
to the reference electrode (electrode whose electrode
1M HCl solution
potential is known) by means of potentiometer or
voltmeter and solutions are connected by a salt bridge. Platinized platinum foil
Standard hydrogen electrode (SHE) is the primary
reference electrode, whose standard electrode potential
Fig. 4.14: Schematic diagram of hydrogen
is assigned to be 0.00V. electrode
Standard hydrogen electrode: Hydrogen electrode is a gas electrode. It is reversible to H+ ions of
solution. A platinum foil is connected to a conducting wire and whole of this part is covered by glass
jacket having an inlet. The platinized platinum foil is immersed in lM HCl solution. Pure and dry H2
gas is admitted through the narrow inlet maintaining 1 atm pressure (more correctly 1 bar pressure).
The hydrogen gas is preferentially adsorbed by platinized platinum foil and desorbed in the form of
tiny bubbles as if the platinized foil were the sources of hydrogen gas. This hydrogen gas is
reversible to H+ ions of solution. Depending upon the counter electrode, hydrogen electrode acts as
anode half cell or cathode half cell. If hydrogen gas is maintained at 1 atm pressure, 25°C temperature
and platinized platinum foil is immersed into 1M HCl solution, hydrogen electrode is called
standard hydrogen electrode (SHE) or normal hydrogen electrode (NHE).
If hydrogen electrode acts as anode half cell, the half cell notation is, Pt, H2(g, 1 atm)/H+ (1M)
and oxidation half reaction is
1
2 H2 (g) H+ + e¯
If hydrogen electrode acts as cathode half cell, the half cell notation is, H+ (1 M)/H2 (g, 1 atm), Pt
and reduction half reaction is
1
H+ + e¯ 2 H2 (g)
Electrode potential of hydrogen electrode at 25°C, 1 atm pressure and 1M concentration of HCl
solution is arbitrarily taken as zero. In fact, electrode potential of hydrogen electrode is neither
zero nor independent of temperature. All other electrodes are calibrated with respect to
standard hydrogen electrode.
Hydrogen electrode is some what difficult to handle and can't be used in presence of oxidising
or reducing agent. The platinum black is easily poisoned by substance such as mercury and
hydrogen sulphide. Therefore, other reference electrodes such as calomel electrode and silver-
silver chloride electrode are used. Such electrodes are called secondary reference electrodes.
Measurement of standard electrode potential: Standard electrode potential of an electrode is
measured by coupling it with standard hydrogen electrode. The emf of cell is measured by
potentiometer or voltmeter. The electrode whose emf is to be measured is immersed into its
electrolyte solution at 1M concentration. A salt bridge is used to complete internal circuit
between the electrode and standard hydrogen electrode. The circuit is complete and emf of cell
is read as shown figure 4.15.
Here, measurement of electrode potential of Zn and copper electrodes is illustrated.
Measurement of electrode potential of Zn electrode: A pure zinc electrode is immersed into
1M ZnSO4 solution at 25°C. Then it is coupled with standard hydrogen electrode as shown in
figure. Out of zinc and hydrogen, zinc has more tendency to lose electron and get oxidised.
Therefore, zinc electrode acts as anode half cell while standard hydrogen electrode acts as
cathode half cell.

Flow of electron
Potentiometer
e
Salt bridge
H2 gas at 1 atm
ZnSO4 1M HCl
Zn electrode
Platinized platinum foil
Anode half cell
(Zinc electrode) Cathode half cell
(Hydrogen electrode)
Fig. 4.15: Measurement of standard electrode potential of zinc electrode.
Cell notation of this combination is

Zn(s) /ZnSO4 (aq. 1M) || H+ (aq.)/ H2 (g, 1 atm) Pt
The driving force for electron to move from one electrode to the another one is called emf of the
cell or cell potential.
The cell potential of this combination is measured 0.76 V.
E°cell = E°cathode – E°anode
0.76 V = 0 – E°anode
∴ E°anode = – 0.76 volt (Reduction potential)
Measurement of electrode potential of Cu electrode: A pure copper electrode is immersed into
1M CuSO4 solution at 25°C. Then it is coupled with standard hydrogen electrode as shown in
Fig. 4.16. Out of copper and hydrogen, hydrogen has more tendency to loss electron. Therefore
hydrogen electrode acts as anode while copper electrode acts as cathode.

Flow of electron
Potentiometer
e
Salt bridge
H2 gas at 1 atm pressure
1M HCl solution CuSO4 solution
Platinized platinum foil

Cu electrode
Anode half cell
(Hydrogen electrode) Cathode half cell
(Copper electrode)
Fig. 4.16: Measurement of standard electrode potential of Cu electrode
Cell notation: Pt, H2 (g, 1 atm)/H+ (aq, 1 M) // CuSO4 (aq, 1M) /Cu(s)
The cell potential is found to be 0.34V
E°Cell = E°cathode – E°anode
= + 0.34 = E°cathode – 0
∴ E°cathode = + 0.34 volt (Reduction potential)
4.14 Electrochemical Series (ECS)

A series of electrode materials which is arranged on the basic of increasing reduction potential or
decreasing oxidation potential value is called electrochemical series. It is also called activity series.
The electrochemical series is given below.
Table 4.1: Electrochemical series

Electrode reaction E°red E°oxd
+
Li + e¯ → Li – 3.05 + 3.05
+
K + e¯ →K – 2.92 + 2.92
++
Ba + 2e¯ → Ba – 2.90 + 2.90
++
Sr + 2e¯ → Sr – 2.89 + 2.89
++
Ca + 2e¯ → Ca – 2.87 + 2.87
+
Na + e¯ → Na – 2.71 + 2.71
++
Mg + 2e¯ → Mg – 2.37 + 2.37
+++
Al + 3e¯ → Al – 1.66 + 1.66
++
Mn + 2e¯ → Mn – 1.18 + 1.18
++
Zn + 2e¯ → Zn – 0.76 + 0.76
+++
Cr + 3e¯ → Cr – 0.76 + 0.76
++
Fe + 2e¯ → Fe – 0.44 + 0.44
++
Cd + 2e¯ → Cd – 0.40 + 0.40
++
Co + 2e¯ → Co – 0.27 + 0.27
++
Ni + 2e¯ → Ni – 0.25 + 0.25
++
Sn + 2e¯ → Sn – 0.13 + 0.13
++
Pb + 2e¯ → Pb – 0.12 + 0.12
+
2H + 2e¯ → H2 0.00 0.00
++
Cu + 2e¯ → Cu + 0.34 – 0.34
I2 + 2e¯ → 2I¯ + 0.54 – 0.54
++
Hg + 2e¯ → Hg + 0.78 – 0.78
+
Ag + e¯ → Ag + 0.80 – 0.80
Pd + 2e¯ → Pd + 0.98 – 0.98
Br2 + 2e¯ → 2Br¯ + 1.07 – 1.07
++
Pt + 2e¯ → Pt + 1.20 – 1.20
Cl2 + 2e¯ → 2Cl¯ + 1.36 – 1.36
+++
Au + 3e¯ → Au + 1.50 – 1.50
F2 + 2e¯ → 2F¯ + 2.87 – 2.87
Applications of electrochemical series

1. To compare the strength of oxidising and reducing agents. Lower the reduction potential of an
electrode material, greater is the reducing strength. For example, the standard reduction
potential of lithium is – 3.05 volt. Therefore, the reduced form Li has more reducing strength.
Similarly, the standard reduction potential of fluorine is highest. Therefore, it has lower
reducing or most oxidising strength.
Similarly, Li is better reducing agent than K and K+ is better oxidising agent than Na+.
In ECS, the reducing character goes on decreasing while oxidising character goes on increasing
on moving from top to bottom. From the above table, it is concluded that Li is best reducing
agent (in aqueous medium) and F2 is best oxidising agent.
2. To predict whether a metal can or cannot liberate H2 gas from water or acid.
a. Elements upto Na in electro chemical series (ECS) react with cold water to produce H2 gas.
2Na + H2O 2NaOH + H2 ↑
b. Elements upto iron react with steam on heating to liberate hydrogen gas.
Δ
3 Fe + 4 H2O Fe3O4 + 4H2 ↑
c. Elements lying above hydrogen in electrochemical series can displace H2 gas from dilute,
mineral and non-oxidising acid.
Mg + dil. H2SO4 MgSO4 + H2 ↑
Zn + dil. H2SO4 ZnSO4 + H2 ↑
Points (a), (b) and (c) show that reactivity of elements go on decreasing from top to bottom in
the electrochemical series which is applicable for metal only.
3. To predict whether a metal can or cannot displace other metals form their salt. Metals having
lower reduction potential can displace those metals having higher reduction potential from
their salt. It means, metal lying above in electrochemical series can displace only those metals
from their salts which lie below in ECS. For example,
i. Zn + CuSO4 ZnSO4 + Cu
ii. Cu + ZnSO4 No reaction
This can be understood as,

Zn++ + 2e¯ Zn E°red = – 0.76 volt
Cu++ + 2e¯ Cu E°red = + 0.34 volt
Zn++ has low tendency to get reduced or Zn has more tendency to get oxidised. In reaction (i)
Zn displace Cu from Cu++ or CuSO4 because Zn has more tendency to get oxidised. In reaction
(ii) Zn is already in oxidised state and Cu can't displace it.
4. To determine anode and cathode in galvanic cell. Electrode material having lower reduction
potential gets easily oxidised and becomes anode while metal having higher reduction potential
gets easily reduced and becomes cathode. In other words, element lying above in ECS acts as
anode and electrode lying below in series acts as cathode during the construction of galvanic
cell.
Example,
Zn++ + 2 e¯ Zn E°red = – 0.76 volt
Cu++ + 2 e¯ Cu E°red = + 0.34 volt
Zn has lower reduction potential while Cu has higher reduction potential. If a galvanic cell of
Zn and Cu is to be constructed, Zn becomes anode while Cu becomes cathode. Anode is the
electrode where oxidation takes place and cathode is the electrode where reduction takes place.
Therefore, the element which has lower reduction potential (higher oxidation potential) get
oxidised in preference and acts as anode while metal having higher reduction potential (lower
oxidation potential) get reduced in preference and acts as cathode.
5. To calculate cell of emf. Standard emf of cell is calculated from the following relation.
E°cell = E°cathode – E°anode
In this relation, all electrode potentials will be in terms of reduction.
In the galvanic cell of Zn and Cu,
E°cell = E°cathode – E°anode = E°Cu – E°Zn
= + 0.34V – (- 0.76) V [Taking both reduction potential value]
= (0.34 + 0.76) V = 1.10 Volt.
6. To Predict whether a cell reaction is spontaneous or not. If emf of cell reaction is positive, the
cell reaction is feasible in the given direction. If emf of cell reaction is negative, cell reaction is
not feasible or non-spontaneous in the given direction.
In above cell, the emf of cell is positive, therefore, the reaction is spontaneous. In some cases, if
emf of cell is found to be negative it shows that the redox reaction is taking place non-
spontaneously i.e. the cell is under charging.
7. Calculation of Gibbs free energy (ΔG). The Gibbs free energy change is related with emf of cell
as ΔG = – nFE
At standard condition, ΔG° = – nEF°
Where, ΔG = change in Gibbs free energy
n = number of moles of electrons lost or gained
F = Faraday constant, (96500 C)
E= Emf of cell
In the galvanic cell of Zn and Cu, two moles of electrons are lost by Zn and that are gained by
Cu. In this case,
n=2 F = 96,500
E°= 1.10 volt
∴ ΔG = – 2 × 96,500 coulomb × 1.10 volt
= – 212300 Joule (∴ coulomb × volt = Joule)
= – 212.3 kJ
8. To calculate equilibrium constant (Keq).
We have the relation, ΔG = – RT ln Keq.
From the relation the value of Keq for a reaction can be calculated.
Work done by Galvanic Cell

In a galvanic cell emf is produced as a result of redox reaction. This emf can be utilized for useful
work. If nF coulombs of charge is produced against applied potential difference, the work done is
givev by,
Work (W) = Number of coulomb of charge × Potential difference
= nF coulombs × E volts
W = nFE joule [∴ Joule = volt × coulomb] . . . (i)
At stantard condition, W = nFE°
According to thermodynamics, the net work done is related with change in Gibbs free energy
as,
W = – ΔG . . . (ii)
From relation (i) and (ii)
ΔG = –nFE . . . (iii)
If the redox reaction is carried out under standard condition, equation (iii) can be expressed as
ΔG° = – nFE° . . . (iv)
4.15 Nernst Equation

The emf of cell depends upon electrode potential value. The electrode potential value of an electrode
depends upon the following factors.
i. Nature of electrode
ii. Concentration of electrolyte solution
iii. Temperature
Nernst derived an expression to calculate emf of cell in the conditions other than standard one. A
mathematical expression which shows the relationship between emf of a cell under ordinary
condition to emf at standard condition, temperature and concentration is called Nernst equation.
For a general reduction half reaction,
Mn+ + ne– M
According to Nernst equation, the reduction potential is given by

RT [M]
E = E° – nF ln [Mn+] . . . (i)
Where, E = Emf of cell at non standard condition.

E° = Standard emf of cell
R = Universal gas constant, R = 8.314 JK–1 mol–1
n = Number of mole of electrons transferred
F = Faraday constant, F = 96,500 C
[M] = Molar concentration of reduced species
[Mn+]= Molar concentration of oxidized species.
In terms of common logarithm, equation (i) can be expressed as,
2.303 RT [M]
E = E° – nF log [Mn+] [∵ ln x = 2.3031 log x] . . . (ii)
2.303RT
At 25°C, the value of F is 0.0591
Now, equation (ii) becomes

0.0591 [M]
E = E°– n log [Mn+] . . . (iii)
In the case of metal-metal ion electrode, the activity or molar concentration of pure metal is
taken as one.
Example 4.8 Calculate the emf of given cell.

++ ++
Fe|Fe (1M)||Cu (1M)|Cu
Given, EoFe++/Fe = −0.44V
EoCu++/Cu = +0.34 V
Solution
EoCell = EoC − EoA
= + 0.34 − (−0.44) V
= + 0.78 V
Example 4.9 What will be the electrode potential of Cu electrode when it is immersed in decimolar
concentration of CuSO4 solution at 20°C? Given standard electrode potential of Cu = +
0.34 V.
Solution
For a reaction,
Cu++ + 2e– Cu
Temperature (T) = (20 + 273) K = 293 K
Concentration of Cu++ = 0.1 M
Activity or molar concentration of pure metal is arbitrarily taken as 1.
Now applying the Nernst equation,
RT [Cu] 8.314 × 293 1
ECu = E°Cu – nF ln [Cu++] = 0.34 – 2 × 96500 ln (0.1)
= 0.34 – 0.01262 × ln 10 = 0.34 – 0.01262 × 2.302 = 0.34 – 0.029 = 0.31 volt.

Example 4.10What will be the electrode potential of Zn electrode when it is immersed in decimolar
concentration of ZnSO4 solution at 25°C? (Standard reduction potential of Zn is – 0.76
volt).
Solution
Since standard reduction potential is given. Here we write reduction reaction.
Zn++ + 2e– Zn
Applying the Nernst equation,
RT [Zn]
E = E° – nF ln [Zn++]
Also 25°C,
0.0591 [Zn]
E = E° – n log [Zn++]
For pure metal, the activity or molar concentration is arbitrarily taken as one
0.0591 1
E = E° – n log [Zn++]
0.0591 1
= – 0.76 – 2 log (0.1) = – 0.76 – 0.02955 log 10 = – 0.76 – 0.02955 = – 0.789 volt.
Example 4.11 You are given electrode reactions

(a) Zn ⎯→ Zn++ (1M) + 2e, E° = + 0.76 V
(b) Sn++ (1M) + 2e ⎯→ Sn, E° = − 0.14 V
Calculate the emf of this combination and write down the cell notation.
Solution
Before using the formula, EoCell = EoC − EoA , we have to find out which one is anode and which
one is cathode. For this, single electrode potential values should be in terms of reduction. Here,
electrode potential of electrode (b) is terms of reduction, however, that of (a) is in terms of
oxidation. Therefore, we have to change electro potential of (a) in terms of reduction as,
Zn++ + 2e– Zn , E° = − 0.76 V
Now, it is clear that electrode (a) has low value of standard reduction electrode potential and it
becomes anode whereas electrode (b) has high value of standard reduction electrode potential
and it becomes cathode. Therefore, cell notation is
++ ++
Zn|Zn (1M)||Sn (1M)|Sn, and
emf of cell is, EoCell = EoC − EAo
= −0.14 − (−0.76) V
= 0.62V
Self Test
4.2 Calculate the emf of cell having Zn and Cu when both electrodes are immersed in their
corresponding metal sulphate electrolyte at 0.1 M concentration at 25°C.
4.16 Some Commercial Cells

In the previous units, we have discussed that every redox reaction can be used to produce electrical
energy. However, every such redox reaction can not be suitable to develop commercial cells. This is
because electrochemical cells having salt bridge have high internal resistances. If large quantity of
current is to be produced, voltage drops sharply. Besides this such types of cells may not be portable.
Commercial cells should be easy to carry and drop in voltage should be negligible during its use.
When a number of cells are connected in series, it is termed as battery.
The commercial cells are classified as follows.
1. Primary cells
2. Secondary cells
3. Fuel cells
1. Primary cells: Primary cells are those electrochemical devices where spontaneous cell reaction
occur in only one direction and become dead after reaching to equilibrium state. The
electrochemical cell reactions can not be reversed. It means the primary cells can't be recharged.
The examples of primary cells are dry cells and botton cells. Here, working principle of dry cell
is described.
Dry cell was invented by a French engineer George Leclanche in 1866. This type of cell is much
familiar and is used in torches, toys, tape recorders and many other devices. It is one of the most
widely used primary cell.
Construction of cell: Dry cell consists of zinc cylinder which acts as anode. A graphite rod is
kept at the centre which acts as cathode. A paste of NH4Cl and ZnCl2 is filled (in the form of
paste in water) near to the zinc electrode.
The graphite rod is surrounded by black paste of MnO2 and carbon powder. A porous paper
separates the electrolyte and zinc container. The zinc cylinder may have an outer insulation.
Graphite cathode (Carbon

Zinc anode
MnO2 + C
Paste of ZnCl2 & NH4Cl
Fig. 4.17: Schematic diagram of dry cell.
Electrode reactions
Zn (s) Zn++ (aq) + 2 e–
Reaction at anode:
Reaction at cathode: 2MnO2 + 2 NH4+ + 2e– Mn2O3 + 2 NH3 + H2O
Complete cell reaction: Zn + 2MnO2 + 2 NH4+ Zn++ + Mn2O3 + 2 NH3 + H2O

Zn++ + 2NH3+ 2Cl¯ [Zn (NH3)2]Cl2
or Zn++ + 4NH3 [Zn (NH3)4]++
When the cell is in operation, zinc loses electrons to form Zn++ ions which dissolve in electrolyte
solution. The released electrons pass to the external circuit and are taken by MnO2. At the
cathode manganese is reduced from oxidation state of +4 to +3. Besides this, NH4+ ions are
discharged at the cathode to form NH3. However, ammonia is not liberated as gas but it
combines with Zn++ to form diammine zinc (II) complex (poisonous).

Â The cell produces a potential of 1.5 volt.
Â The dry cell has no indefinite life because, NH4Cl being acidic continuous corrodes the zinc
container even when the cell is not in operation.
Â In alkaline version of dry cell, NH4Cl is replaced by NaOH or KOH. The alkaline cells have
longer life. The electrode reaction taking place can be interpretated as
Zn Zn++ + 2 e–
Zn++ + 2 OH¯ Zn(OH)2
Zn + 2 (OH¯) Zn(OH)2 + 2 e–
2MnO2 + H2O+ 2 e– Mn2O3 + 2 (OH¯)
Complete cell reaction is obtained by adding reaction at anode and at cathode.
Zn + 2 (OH¯) Zn (OH)2 + 2 e–
2MnO2 + H2O+ 2 e– Mn2O3 + 2 (OH¯)
Zn + 2MnO2 + H2O Zn(OH)2 + Mn2O3
2. Secondary cells: Those electrochemical cells whose electrode reaction can be reversed by the
application of external electric energy and can be recharged are called secondary cells. The
example includes lead storage cell, nickel cadmium cell etc.
Lead storage cell acts as galvanic cell during discharge and electrolytic cell during charging.
During the discharge process, the products are insoluble so that they adhere to the electrode
and don't fall into the electrolyte solution.
Construction: A lead storage cell or lead acid accumulator contains a number of voltaic cell in
series to form a battery. Usually, 3 to 6 voltaic cells are connected in series to get 6 to 12 volt
battery.
Spongy lead acts as anode and a grid of lead packed with PbO2 acts as cathode. An aqueous
solution of H2SO4 having specific gravity 2.15 is used as electrolyte.
Source of electricity Load
+ —
— +
H2SO4 increasing
Pb H2O decreasing PbO2 H2SO4 decreasing
Pb H2O increasing PbO2
PbSO4 decreasing
PbSO4 increasing
Charging Discharging
Fig. 4.18: Charging and discharging of lead storage cell
Pb Pb++ + 2 e–
Pb++ + SO4– – PbSO4
Pb + SO4– – PbSO4 + 2 e–
PbO2+ H2SO4 + 2H+ + 2 e– PbSO4 + 2H2O
The complete cell reaction is

Pb + PbO2+ 2H2SO4 2PbSO4 + 2H2O + Energy
During this process PbSO4 precipitates at both anode and cathode and the potential of each cell
is about 2V.
Â In the above reaction, it found that
• The weight of anode (Pb) and cathode (PbO2) go on decreasing.
• Concentration of H2SO4 goes on decreasing.
• The amount of product PbSO4 and H2O go on increasing.
Here, the cells deliver electrical energy. Hence, it acts as voltaic cell during discharging (or
working). When both anode and cathode are covered by PbSO4, the cell reaction stops and no
more energy is obtained.
Recharging of battery: To recharge the battery, it is connected to external source of direct
current. The positive pole of battery is connected to the positive pole of source of current and
negative pole of battery is connected to the negative pole of source of current. In this stage, the
cell gain the electric current and acts as electrolytic cell.
The following reaction takes place:
To the previous anode (Now cathode)
PbSO4 Pb++ + SO4––
Pb++ + 2 e– Pb
PbSO4 + 2 e– Pb + SO4––
To the previous cathode (Now anode)
PbSO4 + 2H2O PbO2+ H2SO4 + 2H+ + 2 e–

2PbSO4 + 2H2O + Energy Pb + PbO2+ 2H2SO4
During the recharging process,

• The electrodes of the cell are restored to their original conditions.
• Concentration of H2SO4 is increased.
3. Fuel Cells
Fuel cell is a device in which chemical energy of fuels are directly converted into electricity.
Fuel + Oxygen Redox reaction product + electricity
In ordinary combustion reaction, oxidation of fuels takes place and heat energy is produced which is
converted into other forms of energy. In case of fuel cell, electric energy is directly produced by the
oxidation of fuel. Examples of fuel cells are as,
i. Hydrogen-oxygen fuel cell ii. Propane-oxygen fuel cell
iii. Methyl alcohol-oxygen fuel cell iv. Phosphoric acid fuel cell
v. Biochemical fuel cell.
Here, hydrogen-oxygen fuel cell is described. It is simplest form of fuel cell. The cell consist of two
porous electrodes. The electrodes are made of graphite impregnated with finely divided platinum or
alloy of palladium and silver. Nickel electrodes can also be used. Whatever may be the electrodes
used, these should fulfill the following requirements.
• Electrodes should be good electron sources or sinks.

• Electrode should not be affected by electrode reactions.
• The electrodes should behave as catalyst for the reactions which take place on the surface of
electrodes.
The electrolytes used may be KOH or H2SO4 or ion exchange resins saturated with water. Pure H2
and O2 gases are bubbled through anode and cathode compartment, respectively under a pressure of
50 atm at 250°C. The gases and electrolyte diffuse through the electrode pores and chemical reaction
takes place. Electric current is obtained from anode and cathode source.
– +
Cathode
Anode
Electrolyte
Fuel Oxidiser
(Hydrogen) (Oxygen)
H2O
Fig. 4.19: Hydrogen-oxygen fuel cell
The electrode reaction takes place as follows.

Half-Reaction at anode: 2 H2(g) + 4 (OH¯) (aq) 4 H2O (l) + 4 e¯
Half-Reaction at cathode: O2(g) + 2 H2O (l) + 4 e¯ 4 (OH¯) (aq)
Complete cell reaction: 2 H2(g) + O2(g) 2 H2O (l)
Standard emf of cell E° = E°cathode – E°anode (Both Reduction Potential)

= 0.40 – (–0.83) = 0.40 + 0.83 = 1.23 volt.
In practice emf of cell obtained is 0.80 to 1.0 volt.
Application
• It is auxiliary source of energy in spacecraft, submarine or in military vehicles.
• Fuel cell has higher efficiency than that in thermo-chemical reaction.
• The weight of fuel battery is relatively low in comparison to engine-generator set.
• In H2–O2 fuel cell, the product is water which can be used for drinking purpose. So it is
environmently friendly.
Solved Numerical Problems

1. The standard electrode potential for the following electrode are;
Zn+++2 e- Zn, Eo = - 0.76V Fe++++e- Fe++, Eo = 0.77V
i. Represent a suitable galvanic cell and point out which one will be cathode?
ii. Write cell reaction and cell notation.
iii. With 1 M solutions of the ions what will be emf?

iv. Will the reaction Zn+++2Fe++ Zn+2Fe+++occur? Give reason.
Solution
(i) Here Zn2+/Zn has lower reducing potential value than Fe3+/Fe2+ electrode. So, Zn2+/Zn
electrode is an anode and Fe3+/Fe2+ electrode is a cathode.
(ii) Electrode and cell reactions:
At anode: Zn ⎯⎯→ Zn2+ + 2e– (Oxidation)
At cathode: Fe3+ + e– ⎯⎯→ Fe2+ ]× 2 (Reduction)
Cell reaction: Zn + 2Fe3+ ⎯⎯→ Zn2+ + 2Fe2+ (Redox reaction)
The cell notation is
Zn/Zn2+ (1M) // Fe3+(1M) /Fe2+, Pt
(iii) E°Cell (Emf of cell) = E°C – E°A = 0.77 – (–0.76) = 1.53 V
(iv) For Zn2+ + 2Fe2+ ⎯⎯→ Zn + 2Fe3+, oxidation should take place on Fe3+/Fe2+ electrode and
reduction must take in Zn2+/Zn electrode. In such case,
E°Cell = E°C – E°A = –0.76 – 0.77 = – 1.53V
Since, Emf is negative, the above reaction is non-spontaneous. The reaction will not be feasible.
Solved Questions
1. What is electrode potential?
¬ Electrode potential is defined as the potential developed at the solid liquid interface when a metal rod is
dipped into its electrolyte solution. This arises due to the formation of electrical double layer between
electrolyte and electrode interface. Example: Standard electrode potential of Zn2+/Zn electrode is –0.76 V.
2. How is single electrode potential originated?
¬ When an electrode is dipped into electrolyte solution of its soluble salt then either the metal atom loses
electrons and positive ions dive into the electrolyte solution or the ions of electrolyte accept electrons and
deposit on the electrode. During this process there is separation of charge on the electrode and electrolyte
interface and single electrode potential is originated.
3. What is electrochemical series?
¬ A series of electrode materials which is arranged on the basic of increasing reduction electrode potential or
decreasing oxidation electrode potential value is called electrochemical series. It is also called activity series.
In this series active metals lie above the series and less active metals lie below in this series.
4. What is SHE?
¬ If hydrogen gas is passed through 1M HCl solution at 1 atm pressure and 25°C by using platinized platinum
foil immersed into 1M HCl solution, it is called standard hydrogen electrode (SHE) or normal hydrogen
electrode (NHE). Its standard electrode potential is 0 volt. Therefore, it is used as reference electrode the
measure the standard single electrode potential of different electrode.
Questions
a. Electrode b. Electrode potential
c. Standard electrode potential d. Standard oxidation potential
e. Standard reduction potential f. Salt bridge
g. Primary cell h. Secondary cell
i. Fuel cell
2. Construct a galvanic cell in which the cell reaction is:

Fe(S) + H2SO4(aq) → FeSO4(aq) + H2(g)
3. Standard hydrogen electrode can act as both anode or cathode. Explain.
4. Mention one important application of standard hydrogen electrode giving example.
5. What is meant by single electrode potential? Name any two factors which affect its magnitude.
6. What is the important application of standard hydrogen electrode (SHE)
7. Discuss the origination of single electrode potential.
8. Discuss the meaning of standard oxidation potential of Cu/Cu2+ is –0.34V.
9. Why can't the CuSO4 solution be stored in Zn vessel? (E°Zn2+/Zn = – 0.76 V, E°Cu2+/Cu = +0.34V)
1. Write short notes on (a) Standard electrode potential (b) electrochemical series.
2. What is electrochemical series? Discuss its applications.
Numerical Problems
1. Can a solution of 1M CuSO4 be stored in a vessel made of nickel metal? If not, why?
Given: E°Ni++/Ni = −0.25 V; E°Cu++/Cu = 0.34 V
Ans: No, Ni dissolves spontaneously
2. Will the reaction occur: Zn++ + 2Fe++ → Zn + 2Fe+++
Given standard reduction potentials are:
E°Zn++ /Zn = −0.76V, E°Fe2+/Fe3+ = + 0.77 V
Give reason.
Ans: No. E° is negative
3. Can a solution of 1M ZnSO4 be stored in a vessel made up of Nickel?
Given
E°Ni++/Ni = - 0.25 V E°Zn++/Zn = - 0.76 V
Ans: Yes. Ni does not dissolve
4. Predict which one of the following reactions occur spontaneously?
i. 2Fe2+ + Sn4+ ⎯⎯⎯→ 2 Fe3+ + Sn2+
ii. 2 Fe3+ + Sn2+ ⎯⎯⎯→ 2 Fe2+ + Sn4+
Given standard reduction potentials of
Fe3+/Fe2+ and Sn4+/Sn2+ are + 0.77V and + 0.15V, respectively.
Ans: ii, E° = Positive
5. You are given zinc rod, copper rod, zinc sulphate and copper sulphate solutions and standard
electrode potential of zinc and copper are –0.76V and 0.34V respectively.
a. Represent an electrochemical cell indicating anode and cathode
b. Write net cell reactions
c. What will be the emf of the cell?
Ans: c 1.10 V
6. You are given standard reduction potential of Cu2+/Cu and Fe2+/Fe as + 0.34V and – 0.44V
respectively.
a. Construct a Galvanic cell indicating anode and cathode
b. Write the cell reaction and calculate the standard emf of the cell.
Ans: Standard EMF of the cell = 0.78V
7. Construct a Galvanic cell in which the cell reaction is
Fe(s) + H2SO4 (aq) FeSO4 (aq) + H2 (EFe2+/Fe = –0.44 V)
8. Design a Galvanic cell in which the cell reaction is
Zn(s) + 2Ag+ (aq) Zn2+ (aq) + 2Ag (s).
Predict
a. Which of the electrode is negatively charged?
b. Electrode reactions.
9. Consider the following standard electrode potential values:
Al3+ + 3e– Al E° = – 1.66 V
Zn2+ + 2e– Zn E° = – 0.76 V
Answer the following questions:
a. Construct the Galvanic cell
b. Identify anode and cathode of the cell
c. Write electrode reactions and cell reaction
d. Calculate emf of the cell
e. Write the reaction involved during charging of the cell.

1. The number of coulombs of electricity required to cupric salt? (At. wt. of Cu= 63.5)
++
deposit 0.3 mole of Cu is a. 31.50 g b. 2.00 g
a. 9650 b. 2 × 9650 c. 4.00 g d. 63.5 g
c. 4 × 9650 d. 6 × 9650 7. Given that,
++
2. By passing 0.50 A current to an aqueous solution Zn + 2eˉ Zn [E° = –0.763]
++
half gram of an element is liberated. The time of Mg + 2eˉ Mg [E° = – 2.363]
passing the current in seconds is (Eq., Wt. = 96.5) When Zn dust is added to MgCl2 solution then
a. 1000 s b. 500 s a. Zn is dissolved b. ZnCl2 is formed
c. 1000 s d. 2000 s c. Mg Crystallize out d. No reaction
3. Electricity can be passed through molten lead (II) 8. One Faraday of electricity is equivalent to:
bromide because of the presence of a. 1602 × 10–12 coulombs b. 96500 coulombs
a. free electron b. moveable ions c. 95.5 coulombs d. 22400 coulombs
c. moveable atoms d. lead in molten state 9. In a cell, oxidation takes place in……..
4. In Faraday's law, the relation between a. anode b. cathode
electrochemical equivalent (ECE) and chemical c. electrolyte d. none of these
equivalent (C.E) is 10. CuSO4 can not be safely stored in
a. C.E. = F × ECE b. ECE = F × CE a. Al vessels b. Ag vessels
F F c. Au vessels d. Pt vessels
c. ECE = CE d. CE = ECE 11. In non‐spontaneous reaction, Ecell is
5. The electrode reaction on the left hand side a. Zero b. positive
electrode of an electro‐chemical cell with positive c. negative d. can't be decided
cell potential is 12. On electrolysis of CuSO4 solution using copper
a. displacement reaction b. oxidation reaction anode, mass of the anode
c. reduction reaction d. decomposition reaction a. increases b. decreases
6. What weight of copper will be deposited by passing c. remains constant d. can't be decided
two faradays of electricity through a solution of
1 2 3 4 5 6 7 8 9 10 11 12 13
d c b a a b d d b a a b b
Energetics of
Chemical Reaction
Combustion of hydrocarbons like methane is an exothermic reaction. So, this reaction can be used to produce heat.
5.1 Introduction
Any physical or chemical transformation is accompanied by change in energy. Flow of energy takes
place from system to the surrounding and vice-versa. Measurement of change in temperature,
pressure, concentration, volume etc of a system from initial state to final state can provide the
information about change in energy and its related quantities such as heat and work. Different forms
of energy are convertible from one to another and these are related quantitatively.
The branch of science which deals with the study of different forms of energy and their quantitative
aspect is called thermodynamics. When study of different forms of energy is limited to chemical
change, it is termed as chemical thermodynamics. Initially the term thermodynamics was introduced
by mechanical engineers who were concerned mainly in the conversion of heat into mechanical
work. In this sense thermo means heat and dynamics means motion which results into mechanical
work.
Now, the study of thermodynamics is broad and it is based on different generalizations. Three laws
of thermodynamics are first, second and the third law. In this Unit, we will discuss about the first
law of thermodynamics. In the next (Unit 6), we shall discuss about the second law of
thermodynamics with a brief account of the third law.
5.2 Some Thermodynamic Terms

Every discipline has its own terminology. Some basic terms involved in thermodynamics are briefly
discussed below.
1. System: System is a part of the universe which is under consideration for the purpose of
theoretical or experimental study.
2. Surrounding: Surrounding is a part of the universe with which a system can interact. A space
of immediate vicinity of the system under study is surrounding.
3. Boundary: A real or imaginary interface which
separates the system from surrounding is called
boundary.
Boundary
Let us consider a gas is taken in a cylinder fitted with Gas (System)
piston. Let the cylinder is kept in a water bath Water bath Water bath
(Surrounding) (Surrounding)
maintained at 25°C. In this case the gas within
cylinder is system. The wall of cylinder is boundary Fig. 5.1: Schematic diagram to illustrate
and the water bath is surrounding. The boundary system, surrounding and boundary
may be permeable or impermeable or rigid.
A permeable wall allows the passage of matter and energy. An impermeable wall prevents the
flow of mass.
Classification of System on the Basis of Exchange of Energy between System and

Surrounding
Depending upon the mode of exchange of heat and energy, a system can be classified into
following types.
a. Open system: A system which can exchange matter as well as energy with the
surrounding across the boundary is called open system e.g, solution in an open beaker.
Energetics of Chemical Reaction Unit 5 145
b. Closed system: A system which can exchange energy but cannot exchange matter with
the surrounding across the boundary is called closed system. e.g. hot solution in stoppered
volumetric flask.
c. Isolated system: A system which can neither exchange energy nor exchange matter with
the surrounding across the boundary is called isolated system. e.g. hot water kept in
thermos flask.
Matter
Energy
Energy
Matter Matter
Energy
Solution in beaker Solution in volumetric flask Solution in thermos flask
Change in mass, dm ≠ 0 Change in mass, dm = 0 Change in mass, dm = 0

Change in internal energy, dE≠ 0 Change in internal energy, dE≠ 0 Change in internal energy, dE= 0
Open system Closed system Isolated system
Fig. 5.2: Schematic diagram to illustrate different types of systems
Classification of System Based Upon the Composition

On the basis of composition of system, it can be classified into homogeneous and heterogeneous
system.
a. Homogeneous system: The system which is uniform throughout the given mass is called
homogeneous system. e.g., pure solid, pure liquid, pure gas, alloys, true solution of solute
in solvent, mixture of gases etc. A homogenous system consists only one phase. A phase is
a homogeneous, physically distinct and mechanically separable portion of a system.
b. Heterogeneous system: The system which is not same throughout the given mass is called
heterogeneous system. A heterogeneous system consists of two or more phases. Ice in
contact with water has two phases; one phase is ice and another phase is water. Therefore,
it is heterogeneous system. Similarly, water in contact with water vapour is also
heterogeneous system.
4. Universe: The whole part of system, surrounding and boundary is called universe.
System + surrounding = universe
5. State functions (or state variables): If we say water is in a beaker, it is not well defined term
because different questions arise to define the system completely. These questions may be,
What is the volume of water?
What is the temperature of the water?
At what pressure, the system (water) is measured?
If all these questions are answered, the water in the beaker is well defined. A system is defined
by measurable properties such as temperature (T), pressure (P), volume (V) and amount of
substance or number of moles (n) which are called state variables. These properties are called
state variables because these define the state of a system.
A thermodynamic system is said to be in a particular state when all of its properties are fixed.
The state of a system is particularly defined in terms of temperature (T), pressure (P), volume
(V) and composition. Change in the magnitude of these properties alters the state of a system.
Let us consider an example of 1 kg ice at 0°C and 1 atm pressure. If temperature is increased, it
undergoes into another state i.e. water. If temperature is further increased upto 100°C, the
liquid form changes to vapour form. Besides temperature, when pressure is changed, the
normal boiling point is also changed. In this way change in magnitude of state variables
changes a system from its one initial state to another state. Hence, these thermodynamic
variables are also called state variables or state functions. It can also be justified that when a
system is brought from initial state to final state, it is accompanied by change in state variables.
It does not matter how is the changes brought about.
State functions can also be defined as those thermodynamic properties which depend upon
only initial and final states of a system but not upon the path of the change. Therefore, state
function is also called path independent function. For example when a sample of water is
heated from 10°C to 25°C, the change in temperature is equal to the difference between final
temperature and initial temperature.
ΔT = Tfinal – Tinitial = 25°C – 10°C = 15°C
It does not matter how the change in temperature is brought about.
For pure substance, the composition is always hundred percent. The remaining state variables
are T, P and V. For ideal gas, these are related by equation of state as, PV = nRT. Here R is
universal gas constant and n is number of mole of gas. Out of three variables, P, V and T, if two
variables are known then the remaining variables are determined by the equation of state. The
variables, P and T must be specified to define a system. These are called independent state
variables. Then the remaining variable, volume, is determined by using the equation PV = RT.
Volume depends upon value of pressure and temperature. Here volume is dependent function
of temperature and pressure, i.e. V = f(T, P). State variables can be integrated between the
E2
approximate limits e.g. ⌠
⌡ = E2 – E1.
E1
Table 5.1: Some state functions

Name of state function Symbol
Temperature T
Pressure P
Volume V
Number of mole n
Internal energy E
Enthalpy H
Entropy S
Gibbs free energy G
Helmholtz free energy A
Chemical potential µ
Heat capacity Cp and Cv
6. Path functions (Path variables): Heat (q) and work (w) are thermodynamic variables but not
state function because their values depend upon the path via which the change is brought
about. Work done carried out reversibly is greater than the work done carried out irreversibly.
Similarly, reversibly exchanged heat is greater than the irreversibly exchanged heat. These facts
can be proved mathematically. However, this is beyond the scope of the text in this book.
An analogy of state function can be exemplified in mountain climbing. Suppose we have to
climb Mount Everest from its base camp. There may be various paths to climb up the mountain
but the vertical distance from the base camp to the peak of the Mount Everest is same. The
height of the mountain peak cannot be changed by changing the climbing path. The amount of
work done and extent of fatigue depends upon the path chosen. In this example, height of the
mountain peak from its base camp is analogous to state function while work done to climb up
the mountain is not analogous to the state function. Path variables cannot be integrated between
w2
⌠ ≠ w2 – w1.
the approximate limits. e.g. ⌡
w1
7. Extensive and intensive properties: The macroscopic properties of a system can be classified
into two types;
a. Extensive properties
b. Intensive properties
a. Extensive properties: Those properties which depend upon the amount of substance (or
number of moles) present and are additive in nature are called extensive properties. For
example, mass of a system is extensive property because sum of masses of each subsystem
is equal to the total mass of the system. If 40 g of NaOH is divided into three parts each
having 20 g, 15 g and 5 g then total mass (20 + 15 + 5 = 40 g) remains same.
b. Intensive properties: Those properties which do not depend upon the amount of
substance (or number of moles) present and are non-additive in nature are called
intensive properties. When a system is divided into n parts or subsystem and each part
has the same value of property equal to that of the system, then these properties are
intensive properties. For example, if 500 mL of water at 100°C is divided into five vessels at
constant temperature then temperature of water in each vessel is also 100°C. Here each
drop of water has 100°C temperature. Therefore, temperature is intensive property. If
extensive properties are expressed in terms of per mole or per gram, etc., these become
intensive properties.
Table 5.2: Some examples of some extensive and intensive properties

Extensive property Intensive property
Volume Molar volume
Number of moles Temperature
Mass Density
Energy Specific gravity
Internal energy Boiling point, freezing point
Enthalpy Molar enthalpy
Entropy Molar entropy
Heat capacity Specific heat capacity
Free energy Refractive index
Chemical potential
Free energy per mole
Pressure
8. Thermodynamic processes: It is obvious that when liquid is heated it is changed into vapour.
Here, state is changed from liquid to vapour. This is one of the examples of thermodynamic
process. Any process which brings about the change in the state of a system is called
thermodynamics operation or process. Various operations such as contraction, expansion,
freezing, sublimation, vaporization, etc. are thermodynamic processes.
The thermodynamic processes can be classified on the following basis.
a. Classification of thermodynamic processes on the basis of constant variable: During
thermodynamic process, some variables can be kept constant. Accordingly
thermodynamic processes are classified as follows.
i. Isothermal process: If temperature is kept constant during various operations, the
process is called isothermal process. To keep the temperature constant, heat is either
removed or supplied. For isothermal process dT = 0 but dq ≠ 0.
ii. Adiabatic process: If no heat is exchanged (supplied or lost) between system and
surrounding during various operations, the process is called adiabatic process. To
keep the heat constant, temperature must be changed. Hence, adiabatic process is
always accompanied by change in temperature. In adiabatic process dq = 0 but dT ≠ 0.
Joule-Thomson expansion is an example of adiabatic process.
iii. Isobaric process: If pressure is kept constant during various operations then the
process is called isobaric process. In isobaric process dp = 0.
Conversion of 1 mole of water at 20°C and 1 atm pressure into 100°C and 1 atm
pressure is isobaric process. All the reaction carried out in open vessels are said to be
carried out in isobaric condition as the pressure (atmospheric pressure) is constant.
iv. Isochoric process: If volume is kept constant during various operations, the process is
called isochoric process. In isochoric process dV = 0.
Combustion of chemical substance in a bomb calorimeter is an example of isochoric
process.
v. Cyclic process: If a system undergoes various changes and ultimately returns into
initial state, the process is called cyclic process.
For cyclic process dE = 0, dH = 0. Here, dE and dH are infinitesimal change in internal
energy and enthalpy respectively.
These thermodynamic processes are shown diagrammatically as follows.
Isobaric
Isochoric
Pressure
Isothermal Pressure
Adiabatic
Cyclic process
Volume Volume
Fig. 5.3: Diagram to show various thermodynamic processes

b. Classification of thermodynamic processes on the basis of way of achieving the final

state: When a thermodynamic process is carried out, the final state of the system can be
achieved either in single step or in multiple steps. On the basis of this, there are two types
of thermodynamic processes. These are;
i. Reversible process. ii. Irreversible process.
i. Reversible process: The process which takes place infinitesimally slowly such that its
direction at any point can be reversed by infinitesimal change in the state of the
system is called reversible process. In actual practice, it is difficult to perform
experiments under reversible condition. However, the concept of reversibility serves
as a means to study many thermodynamic processes which are of immense
importance to chemists.
Evaporation of liquid within a closed vessel at constant temperature can be
considered as reversible process. Chemical reactions taking place in dry cell, batteries,
etc. are very near to the reversible process. Reversible processes are carried out slowly
so they can be considered to be carried out in infinitesimal number of steps. At each
step, the system is at equilibrium because the infinitesimal change in the state of the
system has negligible effect.
To illustrate the concept of reversible process, let us take an example of compression
and expansion of gas.
Let us take a sample of gas in a cylinder fitted with weightless and frictionless piston.
Sand particle
Sand particle
Many steps
Gas (System) Gas (System)
A. Initial stage B. Final stage
Fig. 5.4: Change in state of a system
Let the gas be at initial state as shown in the figure 5.4 (A). The amount of sand particles
is gradually increased into the piston at different time interval. At each time, the weight
of particle pushes the piston downward as equivalent to W = mg. Due to this, the
pressure of gas within the cylinder increases but infinitesimally at each step. When the
process is repeated till large amount of sand (say 500 gram) particles are added then the
piston reaches at final step as shown in figure B. In this example, the final state is
reached reversibly from initial state in infinitesimally large number of steps. If each
particle of sand is removed one at each time, previous stage can be achieved. This
illustrates an example of reversible process.
ii. Irreversible process: When a process is carried out rapidly such that the system
does not get a chance to attain equilibrium between initial and final state, it is called
irreversible process. Such types of processes are carried out in single step or in few
steps. Equilibrium stage can be achieved only in the initial and final states. All
natural processes are irreversible processes. In the above example of reversible
expansion of gas, if 500 g sand is added in single step, the piston goes down and
reaches to stage B. When the sand is removed suddenly, the piston goes up
accordingly. This illustrates the irreversible expansion of gas. Expansion of gas
against vacuum is an example of irreversible expansion.
Table 5.3: The differences between reversible process and irreversible process
Reversible process Irreversible process
1. When a process takes place infinitesimally 1. When a process takes place rapidly from
slowly through a succession of equilibrium initial to final step, it is called irreversible
steps, it is called reversible process. process.
2. It is slow process. It takes place in infinite 2. It is fast process. It takes place in single step
number of steps. or in few steps.
3. All steps in the operation are at equilibrium. 3. Only initial and final steps are at
equilibrium.
4. Work done in reversible process is maximum 4. Work done in irreversible process is lower
than that in reversible process.
5. Heat exchanged reversibly is maximum. 5. Heat exchanged irreversibly is lower than
that in reversible process.
5.3 State of Equilibrium

A state of a reversible process in which a macroscopic property (eg, temperature, pressure,
concentration, density, etc.) does not change with time is called state of equilibrium. A system
undergoes changes until it achieves the state of equilibrium. In the light of thermodynamics, an
equilibrium condition must satisfy the following two conditions.
i. The macroscopic properties should not change with time. The properties of a system due to
bulk of mass rather than atomic or molecular nature are called macroscopic properties.
Properties such as temperature, pressure, concentration, density etc are macroscopic properties.
However, the submicroscopic properties may change continuously. For example, in equilibrium
of colloidal system, the Browniam motion is not stopped.
ii. The system should be at equilibrium without any external assistance.
For a system to be at equilibrium both of the criteria mentioned above should be fulfilled. To
illustrate this let us take an example of a water tank through which 10 mL water is lost in one hour by
leakage. The same volume of water is obtained by leakage from tap into this tank in the same rate.
Here, the level of water remains same. Its macroscopic properties do not change with time. The first
condition is satisfied. But second condition is not satisfied because the level of water is maintained
from external supply (leakage of water from tap into the tank) rather than the system itself. Hence,
the above example signifies a steady state or stationary state, equilibrium state and steady state.
Both are seen dynamic in nature. An insight view reveals that an equilibrium state is static on
macroscopic level and dynamic on microscopic level while the steady state is dynamic on
macroscopic as well as microscopic level.
In thermodynamics, the equilibrium state is attained to balance temperature, pressure and
concentration. Accordingly, the thermodynamic equilibrium involves the following equilibria.
i. Thermal equilibrium
ii. Mechanical equilibrium
iii. Chemical equilibrium
i. Thermal equilibrium: When equilibrium condition is obtained due to difference in
temperature, it is called thermal equilibrium. In thermal equilibrium each part of a system is at
same temperature and this temperature is equal to the temperature of surrounding. When hot
water and cold water are mixed, hot water loses temperature while cold water gains
temperature until equilibrium temperature is obtained. Ultimately, the temperature of mixture

should be equilibrium with the temperature of surrounding.
ii. Mechanical equilibrium: When equilibrium condition
is obtained due to difference in pressure, it is called
mechanical equilibrium. In mechanical equilibrium,
there is no unbalanced force in the interior part of the
High pressure Low pressure
system. Besides this, there is no unbalanced force
between system and surrounding. If there exist
unbalanced forces in the interior part of the system, the
state of the system changes on passing the time. If Fig. 5.5: Schematic diagram to
unbalanced forces exist between system and illustrate mechanical equilibrium
surrounding, system as well as surrounding undergoes
a change.
When two gases at different pressure are separated followed by its removal, gases intermix till
equilibrium.
iii. Chemical equilibrium: When equilibrium condition is obtained due to difference in chemical
composition, it is called chemical equilibrium. After attaining chemical equilibrium, the
chemical composition of the system becomes uniform. Thermodynamically, a system is said to
in chemical equilibrium when chemical potential (µ) of each part of the system remains same.
For example, when a concentrated solution and dilute solution are mixed then their
concentration undergo change until each part of the mixture has same concentration.
Types of equilibrium based upon stability
Equilibrium condition can be classified into following types.
i. Stable equilibrium ii. Unstable equilibrium iii. Metastable equilibrium
i. Stable equilibrium: A system is said to be in a state of stable
equilibrium if it returns to its original state on removing the
constraint causing to displace it. The adjoining figure shows a
ball resting in a shallow pit. This illustrates stable equilibrium.
If the ball is attempted to displace in either direction, ultimately Fig. 5.6: Stable equilibrium
it comes to its original position.
ii. Unstable equilibrium: A system is said to be in a state of
unstable equilibrium if it does not return to its original state on
removing the constraint causing to displace it. In fact, this type
of equilibrium is not real equilibrium. A ball resting on a hillock
in the adjoining figure illustrates unstable equilibrium.
Fig. 5.7: Unstable equilibrium
iii. Metastable equilibrium: A system is said to be in a state of
metastable equilibrium if the system lies between the stages of
stable and unstable equilibria. For a small disturbance the
system remains at equilibrium. If the disturbance is extensive,
the system is at unstable equilibrium. Supersaturated solution
is an example of metastable equilibrium. For a very small
Fig. 5.8: Metastable equilibrium
disturbance the supersaturated solution remains intact. If the
level of disturbance is increased, precipitation takes place instantly. Similarly, a super cooled
liquid is also an example of metastable equilibrium. The adjoining figure depicts an example of
metastable equilibrium.
5.4 Heat and Work (Modes of Energy Transfer)

Change in state of a system is always accompanied by transfer of energy. The energy is transferred
either in the form of heat or in the form of work.
Unit of Energy: SI unit of energy is joule (J). It can also be expressed in terms of kJ, calorie (cal), kcal
etc.
Transfer of energy in the form of heat
When a system and surrounding are at two different temperatures, the energy is transferred in the
form of heat. If system is at higher temperature, the surrounding, heat is lost from the system. If
surrounding is at higher temperature than the system, heat is gained by the system.
Sign convention of heat exchanged Heat absorbed q is positive
If heat is gained by a system, it is taken as positive.

If heat is lost by a system, it is taken a negative.
Thermodynamic system
Unit of heat The S.I. unit of heat is joule. It is also
expressed in calorie 1 calorie = 4.184 Joule Heat lost q is negative
Transfer of energy in the form of work

If system and surrounding are at two different pressures, energy is exchanged in the form of
mechanical work. Let us consider a certain volume of gas enclosed in a container having a weightless
and frictionless piston. If the pressure of gas is more than the external pressure, the piston is pushed
outward. Here, work is done by the system. On the other hand if external pressure is greater than the
pressure of gas inside the vessel, the piston is pushed inward. Here, work is done on the system. In
both cases, energy is transferred in the form of work.
Work (W) = Force (F) × displacement (d) . . . (i)
Force (F)
We know, Pressure (P) = Area (A)
or, Force (F) = Pressure (P) × Area (A)

Now, Relation (i) becomes Work (W) = Pressure (P) × Area(A) × Displacement (d)
or, Work (W) = Pressure (P) × change in volume (ΔV)
or, W = P. ΔV .
Here, change in volume (ΔV) = Area (A) × Displacement (d)
Unit of work: In CGS system, the unit of work is erg. The S.I. unit of work is joule (J). The units erg and
joule are related as, 1 Joule = 107 erg
Sign convention of work done
a. In terms of energy: When work is done on the system by surrounding, the internal energy of
the system is increased and work done on the system is taken as positive. If work is done by the
system to the surrounding, the energy of the system is decreased and work done by the system
is taken as negative. IUPAC recommends this system.
b. In terms of volume: When work is done on the system by surrounding, the volume of the
system is decreased. Let V1 be the initial volume and V2 be the final volume of gas enclosed in
cylinder. If work is done on the system V2 becomes smaller than V1 then V2 – V1 becomes
negative. Therefore, W = P . ΔV = negative value
If work is done by the system, then volume of system is increased. It means V2 becomes greater
than V1. In this case V2 – V1 becomes positive. Therefore, W = P . ΔV = positive value
Sign convention: Heat gained by the system = Positive Heat lost by the system = Negative
In terms of energy change

Work In terms of volume change
(IUPAC convention)
Work done on the system + ve – ve
Work done by the system – ve + ve
5.5 Internal Energy (E)

Every substance is associated with energy. Each atom, ion or molecule of a chemical substance has a
definite quantity of energy within it. Molecule of a chemical substance possesses translational energy
(Et), rotational energy (Er), vibrational energy (Ev), electronic energy (Ee), bond energy (Eb),
intermolecular interaction energy (Ei). Hence, total energy of molecule is given by
Total energy (E) = Et + Er + Ev + Ee + Eb + Ei
Energy of a system includes both kinetic energy and potential energy.
The sum of all kinds of energy including kinetic energy and potential energy associated with a
system is called internal energy or intrinsic energy. It is denoted by E or U (IUPAC recommends
U). In thermodynamics, internal energy is dealt rather than energy of individual chemical species.
Some points about internal energy are given below,
i. Internal energy is a state function. It does not depend upon the path. It only depends upon the
state variables such as temperature (T), pressure (P) and volume (V). Out of these three
variables, when two variables are known, the third variable can be found by using equation of
state (PV = RT). Therefore, internal energy is a function of any two variables out of T, P and V.
ii. Internal energy is extensive property. Its value depends upon the amount of substance taken.
For example, if amount of substance is increased, the energy of the system is also increased.
iii. The absolute value of internal energy cannot be determined. However, change in internal
energy (ΔE), can be determined. If E1 be the initial internal energy and E2 be the final internal
energy, change in internal energy is given by, ΔE = E2 – E1
5.6 The First Law of Thermodynamics

In any physical or chemical transformation, there is change in energy. In some cases, energy is lost by
a system to the surrounding while in some other cases energy is gained by a system from the
surrounding. During these transformations, one form of energy may change into another form of
energy. But the total energy of system and surrounding does not change. It means total energy of the
universe remains conserved. This forms the basis of the first law of thermodynamics. The first law of
thermodynamics can be defined in different ways as:
♦ The total energy of a system and surrounding remains conserved.
♦ Energy can neither be created nor be destroyed but one form of energy can be converted into
equivalent amount of other form of energy.
♦ Whenever a particular type of energy is disappeared, an equivalent amount of another form of
energy must be reappeared.
♦ It is impossible to construct a perpetual motion machine which can produce work without
spending energy on it.
Formulation of the first law of thermodynamics
The first law of thermodynamics is nothing but it is an application of law of conservation of energy
to the thermodynamics system. Suppose a thermodynamic system possesses internal energy E1
initially. Let q quantity of heat is supplied to it. Thus supplied heat is used to increase the internal
energy of the system or does some work or both. Let E2 be the internal energy in the final state of the
system.
So, increase in internal energy = E2 – E1 . . . (i)
Heat absorbed = Increase in internal energy + work done by the system.
or q = (E2 – E1) + W
or q=ΔE+W . . . (ii)
Here, work done by the system is taken as positive and heat gained by the system is also taken
as positive.
W includes all types of works which may be mechanical work, electrical work, gravitational
work and work to increase the surface area or work in the magnetic field. If mechanical work is
considered, W = P.ΔV holds true.
Now, equation (ii) becomes, q = Δ E + P. ΔV . . . (iii)
For infinitesimal change equation (iii) can be expressed as, dq = dE + P.dV . . . (iv)
Where, dq = infinitesimal increase in heat.
dE = infinitesimal increase in internal energy.
dV = infinitesimal change in volume.
Different forms of the first law of thermodynamics
Mathematically, the first law of thermodynamics is defined as q = ΔE + P.ΔV
Case I: For isobaric process, there is no change in pressure. Hence, qp = Δ E + P ΔV
Case II: For isothermal process, ΔE = 0, ∴ q = W
Case III: For isochoric process dV = 0, ∴ qv = ΔE
In this case the supplied heat is converted to increase the internal energy of the system. In
isochoric process there is no work of expansion.
Case IV: For adiabatic process, q = 0
In adiabatic process, there is no heat gained or lost. Therefore, the above equation change to
q = ΔE + W
0 = ΔE + W
or W = – ΔE
In adiabatic process work is done by the compensation of internal energy.
5.7 Enthalpy
When we consider the first law of thermodynamics at constant volume and at constant pressure we
get the following relations.
At constant volume, qv = Δ E
At constant pressure, qp= ΔE + P. ΔV
From these relations, it is revealed that besides internal energy, molecules also possess some
additional energy in the form of pressure-volume work done. Here, it is to the remembered that
work done is also a form of energy. Therefore, total heat content of a system at constant pressure is
equal to sum of internal energy and pressure-volume work. The total heat content of a system is
called enthalpy.
Mathematically, enthalpy is defined as, H = E + PV
Where,
H = Enthalpy, E = Internal energy, P = Pressure, V = Volume
Chemical reactions are usually carried out at constant pressure. Therefore, it is better to express
energy change in terms of enthalpy rather than internal energy.
Some points about enthalpy
i. Enthalpy is a state function. It depends upon the state variables of a system. It does not depend
upon the path.
ii. Enthalpy is extensive property. It depends upon the amount of substance taken.
iii. The absolute value of enthalpy cannot be determined but change in enthalpy for a reaction can
be determined.
At constant pressure, let enthalpy, internal energy and volume of the system change from H1, E1
and V1, to H2, E2 and V2 respectively, then
Initially, H1= E1 + PV1 . . . (i)
Finally, H2 = E2 + PV2 . . . (ii)
Subtracting relation (i) from relation (ii), we get
H2 = E2+ PV2
H1 = E1+ PV1
– – –
(H2–H1) = (E2 – E1) + P(V2 – V1)
ΔH = Δ E + P.ΔV . . . (iii)
For infinitesimal change, dH = dE + P.dV . . . (iv)
iv. For a chemical reaction, ΔH = ∑ HProduct – ∑ Hreactant
For exothermic reaction, ∑ HProduct < ∑ Hreactant, ΔH becomes negative
For endothermic reaction, ∑ Hproduct > ∑ Hreactant, ΔH becomes positive.
v. Enthalpy change at constant pressure and volume
From the first law of thermodynamics, q = ΔE + P.ΔV . . . (i)
At constant volume, ΔV = 0 and q is replaced by qv. Now expression (i) becomes qv = Δ E . . . (ii)
At constant pressure, the equation (i) remains same. q is replaced by qp.

qp = ΔE + P.ΔV
= (E2 – E1) + P(V2 – V1) [ΔE = E2 – E1 and ΔV = V2 – V1]

= E2 – E1 + PV2 – PV1
= (E2 + PV2) – (E1 + PV1)
= H2 – H1 [∵ H =E + PV]
∴ qp =ΔH ... (iii)

If H2 is the enthalpy of products and H1 is the enthalpy of reactants, ΔH is enthalpy change of
reaction or heat of reaction. Hence heat of reaction is the measure of heat of a process at
constant pressure.
Self Test
5.1 How are ΔH and ΔE related?
5.2 What are qp and qv ? How are they related?
Relation between enthalpy change and internal energy change:
Let H1, E1 and V1 be the enthalpy, internal energy and volume of a reactant system. At constant
pressure, when reactants are changed into products then enthalpy, internal energy and volume
becomes H2, E2 and V2, respectively.
Here,
H1= E1+ PV1 . . . (i)
H2= E2 + PV2 . . . (ii)
The enthalpy change for the reaction can be obtained by subtracting the enthalpy of reactants
from the enthalpy of products.
Now subtracting equation (i) from equation (ii)
H2 = E2+ PV2
H1 = E1+ PV1
– – –
(H2–H1) = (E2 – E1) + P(V2 −V1)
ΔH = ΔE + P ΔV . . . (iii)
The equation (iii) holds good at constant pressure.
♦ At constant pressure: Enthalpy change of a reaction is equal to the sum of internal energy
change and pressure volume work.
♦ At constant volume: ΔV = 0. Now equation (iii) becomes ΔH = ΔE . . . (iv)
At constant volume, enthalpy change is equal to internal energy change
♦ At constant temperature: For ideal gas PV= nRT
Now enthalpy of a system can be expressed as, H=E + nRT
Let a system changes from initial condition to final condition at constant temperature. Here, H1,
E1, and n1 are enthalpy, internal energy and number of moles of the system initially whereas H2,
E2 and n2 are enthalpy internal energy and number of mole of the system finally.
H1= E1+ n1RT . . . (v)
H2= E2 + n2RT . . . (vi)

Subtracting equation (v) from equation (vi)
H2 = E2 + n2RT
H1 = E1 + n1RT
– – –
(H2–H1) = (E2 – E1) + (n2 −n1)RT
ΔH = ΔE + ΔnRT . . . (vii)
Endothermic and Exothermic Process
Physical change involves the change in state of matter although the constituents of matter are
unaltered. The example includes melting of ice into water, vaporization of water, condensation of
water vapour etc. Although the phase of the system changes, the chemical constituent H2O remains
same.
Chemical change involves breaking of some or all pre-existing bonds with the formation of new
bonds. In chemical change totally new constituent of matter is formed.
Both physical and chemical changes are accompanied by change in energy. These involve breaking
of all or some pre-existing bonds with the formation of new bonds. Breaking of bonds requires
energy while formation of bond releases the energy. If energy absorbed is greater than the energy
released, net energy is absorbed in the system and this type of reaction is called endothermic
reaction. On the other hand if energy absorbed is less than the energy released, net energy is
released from the system and this type of reaction is called exothermic reaction.
The endothermic and exothermic reactions are shown by energy profile diagram (fig. 5.9).
Potential Energy
Potential Energy
Reactant Product
ΔH Product ΔH
Reactant
Progress of reaction Progress of reaction

(a) (b)
Fig. 5.9: Energy profile diagram for (a) exothermic reaction and (b) endothermic reaction.
In chemical transformation, reactants don't directly change into products. The reactants have to
surmount the higher energy path and ultimately change into products. Whatever may be the change,
reactants initially absorb energy (endothermic process) and reach to high energy content, often called
activated complex, then the energy rich complex changes into product with the release of energy
(exothermic process). The net change in the energy is the key factor which determines whether the
reaction is exothermic or endothermic.
The process which involves the gain of energy is called endothermic process. In endothermic
process the energy of product (HP) is higher than the energy of reactant (HR).
Enthalpy change of reaction (ΔH) = HP – HR = + ve [∵ HP > HR]

Example:
N2(g) + O2(g) 2NO(g) ΔH = + 43.2 kcal.
Since heat is absorbed, the reaction is endothermic. Melting of ice is also endothermic process.
The process which involves the loss of energy is called exothermic process. In exothermic process,
the energy of product is lower than the energy of reactant.
The enthalpy change of reaction (ΔH) = HP – HR
For example,
N2(g) + 3H2(g) 2NH3(g) ΔH = – 11.2 kcal mol–1
Since heat is liberated the reaction is exothermic.
5.8 Enthalpy Change

When a chemical reaction takes place heat is either evolved or absorbed. The quantity of heat
change involved when specified numbers (number of moles of reactants in a balanced chemical
equation) of reactants are completely reacted under the given set of condition is called heat of
reaction or enthalpy of reaction. The following points are to be noted while studying the enthalpy of
reaction.
i. To express the enthalpy of reaction, the chemical equation must be balanced.
ii. While balancing the chemical equation, the coefficients of chemical species need not always to
be whole number. For example, for the formation of CO from carbon and oxygen the chemical
equation is:
1
C(s) + 2 O2(g) CO(g) ΔH = – 26 kcal
iii. In a chemical equation, the physical state of all the chemical constituents must be written
because heat change will be different for different states of matter.
Example,
1
H2 (g) + 2 O2(g) H2O(l) ΔH = – 68.4 kcal
1
H2 (g) + 2 O2(g) H2O(g) ΔH = – 57.8 kcal
When one mole of hydrogen gas reacts with half mole of oxygen gas to give one mole of liquid
water, energy released is 68.4 kcal at 25°C. But, when one mole of hydrogen gas reacts with half
mole of oxygen to give one mole of water vapour, energy released is 57.8 kcal. This suggests
conversion of 1 mole of liquid water into 1 mol of water vapour is endothermic process and it
demands 10.6 kcal energy at 25°C.
iv. For exothermic process, the enthalpy change of reaction is negative and for endothermic
process, the enthalpy change of reaction is positive.
v. The value of ΔH should correspond to the balance equation. Enthalpy change is usually
expressed in per mole.
H2 (g) + Cl2 (g) 2HCl (g) ΔH = – 44.0 kcal for 2 mole of HCl
Since two moles of HCl (g) are formed, the ΔH value corresponds for the formation of 2 moles of
HCl (g).
The enthalpy of formation of 2 mol of HCl = – 44 kcal

The enthalpy of formation of 1 mol of HCl = – 22 kcal
Therefore, enthalpy of formation of HCl is – 22 kcal per mol.
In practice, the term per mole is omitted. Enthalpy of formation of HCl is –22 kcal means
–22 kcal energy is released when one mole of HCl is formed from half mole of hydrogen and
half mole of chlorine.
1 1
i.e., 2 H2 (g) + 2 Cl2(g) HCl (g) ΔH = – 22.0 kcal
vi. The same chemical equation can be expressed in different ways. For example,
1 1
2 H2 (g) + 2 Cl2(g) 2HCl (g) ΔH = – 22.0 kcal
1 1
or, 2 H2 (g) + 2 Cl2(g) HCl (g) + 22 kcal
1 1
or, 2 H2 (g) + 2 Cl2(g) –22 kcal HCl (g)
vii. Enthalpy of reaction will be different at different temperature and pressure. To compare, the
enthalpy of reactions at 25°C temperature, 1 atmospheric pressure are taken as standard
reference state and the chemical substance should be in pure and standard state. Enthalpy of
one mole of pure substance at 25°C and 1 bar pressure is called standard enthalpy. It is denoted
by H°.
The quantity of heat change involved when the number of mole of reactants of balanced
chemical equation are completely reacted at 25°C and 1 bar pressure is called standard heat of
reaction or standard enthalpy of reaction. It is denoted by ΔH°.
A. Enthalpy Change in Physical Transformation
The arrangement of constituent particles and mode of cohesion determines the state of matter.
Accordingly, the three states of matter possess different magnitude of interparticle forces. When heat
energy is supplied solid changes to liquid and liquid changes to vapour. Thus supplied energy is
used to break the interparticle forces. Hence, change in state of matter involves enthalpy change. The
enthalpy changes in different phase transformations are given below.
a. Enthalpy of fusion (ΔHfus) or heat of fusion. It is defined as the quantity of heat change
involved when 1 mole of pure solid is converted into liquid state at its melting point.
H2O (s) H2O (l) ΔHfus = + 1.43 kcal. [ΔHofus at 273 K= +6.01 kJ mol–1]
Ice water
Higher value of heat of fusion indicates the higher magnitudes of intermolecular forces of
attraction.
b. Enthalpy of vaporization (ΔHV) or heat of vaporization. It is defined as the quantity of heat
change involved when one mole of pure liquid is converted into vapour state at its boiling
point.
Δ Hovapat 373 K = + 40.66 kJ mol–1
H2O (l) H2O (g) ΔHv = + 9.71 kcal.
Δ Hovap at 298 K = +44.01 kJ mol–1
Water vapour
Higher value of heat of vaporization indicates the higher magnitude of intermolecular forces of
attraction.
c. Enthalpy of sublimation (ΔHS) or heat of sublimation. It is defined as the quantity of heat

change involved when 1 mol of pure solid is directly converted into vapour state below its
melting point.
I2 (s) I2 (g) ΔHs = + 14.92 kcal.
d. Enthalpy of transition (ΔHt) or heat of transition. It is defined as the quantity of heat change
involved when 1 mol of an element changes from its one allotropic form to another allotropic
form at its transition temperature.
C (diamond) C (graphite) ΔHt = + 3.3 kcal.
P (white) P (red) ΔHt = – 1.0 kcal.
B. Enthalpy Change in Chemical Reaction
Chemical reactions are accompanied by change in energy. The enthalpy changes in chemical
reactions are given below.
a. Heat of formation or enthalpy of formation.
b. Heat of combustion or enthalpy of combustion
c. Heat of neutralization or enthalpy of neutralization.
d. Heat of solution or enthalpy of solution
e. Heat of hydration or enthalpy of hydration.
Some of these are discussed below
a. Enthalpy of formation: (Heat of formation) ΔHform : It is defined as the quantity of heat change
involved when one mole of chemical substance is formed from its constituent elements.
Example:
1 1
2 H2 (g) + 2 Cl2(g) HCl (g) ΔHf = – 22.0 kcal
♦ Enthalpy of pure compound is taken as enthalpy of formation from its constituent elements at
standard state.
♦ By convention, the standard heat of formation of all elements in their most stable form is taken
as zero. If enthalpy of formation of a substance is positive, the compound is energetically less
stable than its elements at its standard state.
♦ Standard heat of reaction can be calculated from the standard heat of formation as
ΔH° = Total ΔHf° of product – Total ΔHf° of reactant.
or ΔH° = ∑(ΔHf°)P – ∑(ΔHf°)R
The quantity of heat change involved when one mole of chemical substance is formed from its constituent elements under
standard conditions of all the reactants and products is called standard heat of formation. It is denoted by is ΔHf°or ΔfH°.
Table 5.4: Standard heat of formation of some compounds at 25°C and 1 atm:
Chemical substance ΔHf° in kJ mol–1
H2 (g) 0.0
H2O (g) – 241.8
H2O (l) –285.8
HCl (g) –92.3
HBr (g) – 36.23
HI (g) + 26.48
NH3 (g) – 46.2
CO (g) – 110.5
CO2 (g) – 393.5
NH4NO3 (s) –368.0
NaCl (g) –411.0
CH4 (g) –74.85
C2H6 (g) –83.85
C6H6 (g) + 82.93
C6H6 (l) + 49.03
C6H6(g) + 82.93
C2H5OH (l) – 277.6
Example 5.1 The standard heat of formation of C2H5OH (l), CO2(g) and H2O(l) are – 277.6, – 393.5
and – 285.8 kJ, respectively. Calculate the standard heat of reaction for the reaction
given below:
C2H5OH (l) + 3O2 (g) 2CO2 (g) + 3H2O (l)
Solution
The ΔHf° for O2 is arbitrarily taken as zero.
ΔH° = ∑ (ΔHf°)Product –∑ (ΔHf°)Reactant
= [2 × (ΔHf° for CO2) + 3 × (ΔHf° for H2O)] – [ΔHf° for C2H5OH]
= [2 × (–393.5) + 3 × (–285.8)] – [–277.6]
= (–787 – 857.4] + 277.6
= – 1366.8 kJ
b. Enthalpy of combustion (Heat of combustion): Heat of combustion is defined as the quantity
of heat change involved when one mole of chemical substance is burnt completely with oxygen.
It is denoted by ΔHc. For example,
CH4 (g) + 2O2(g) CO2(g) + 2H2O (l) ΔHc = – 210.00 kcal
♦ Heat of combustion is always negative because combustion is exothermic reaction.
Self Test
5.3 Study the following reaction.
1
C (s) + 2 O2 (g) CO (g) ΔHc = – 26.00 kcal
C (s) + O2(g) CO2(g) ΔH = – 94.3 kcal

What is the heat of combustion of carbon? Why?
6.4 If CH4 (g) + 2O2(g) CO2(g) + 2H2O (l) ΔH = – 210.00 kcal
H2O (l) H2O (g) ΔH = 9.71 kcal
What is the enthalpy change for
CH4 (g) + 2O2(g) CO2(g) + 2H2O (g)
Ans ΔH = – 190.58 kcal
Calorific value of food and fuel: Food acts as biofuel. Food and fuel both are used for the
production of energy. The energy released in the oxidation of food and fuel is usually measured
in terms of energy per gram rather than per mole. This is because, food and fuel are mostly
mixture of different composition and it is difficult to calculate molecular mass of each kind of
molecule present in food. For example, if one takes rice, it does not consist only glucose but a
mixture of varieties of constituents.
Calorific value of food or fuel is defined as the quantity of heat energy released in calories
(or in joules) when one gram of the substance is burnt completely.
Greater the calorific value of fuel, better is the fuel. To understand calorific value of fuel let us
take an example of combustion of methane and ethane in the following self test.
Self Test
5.5 Study the following reactions and answer the questions given below.
CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (l) ΔH = – 210.0kcal
7
C2H6 (g) + 2 O2 (g) 2CO2 (g) + 3H2O (l) ΔH = – 372.6 kcal
a. Out of methane and ethane which one has higher heat of combustion?
b. Calculate the energy released when one gram of
i. Methane is completely burnt. [Ans: 13.12 kcal]
ii. Ethane is completely burnt. [Ans: 12.42 kcal]
c. Out of methane and ethane which has better fuel efficiency? [Ans: Methane]
c. Heat of neutralization or enthalpy of neutralization: The quantity of heat change involved

when one gram equivalent of acid is neutralized by one gram equivalent of base or vice-versa is
called heat of neutralization.
HCl(aq.) + NaOH(aq.) NaCl (aq.) + H2O (l) ΔH = – 13.68 kcal
Heat of neutralization is exothermic reaction. Therefore, heat is released during neutralization
reaction. One mole of acid may or may not be neutralized by one mole of base but one gram
equivalent of acid is always neutralized by one gram equivalent of base.
The heat of neutralization of strong acid by strong base is always constant and it is – 13.68 kcal
at 25°C and 1 atm pressure whatever may be the acid or base. This fact is explained on the basis
of theory of ionization.
Let, HA is strong acid and BOH is strong base. Since these are strong electrolytes, they undergo
complete dissociation and react as follows.
HA (aq) + BOH (aq) BA (aq) + H2O (l)
Strong acid Strong Base Salt Water
or, H+ (aq) + A– (aq) + B+ (aq) + OH– (aq) B+ (aq) + A–(aq) + H2O(l)

Disregarding the ions present in both sides,
H+ (aq) + OH– (aq) H2O(l), Δ H = – 13.68 kcal

Thus heat of neutralization of acid and base is the heat of formation of water from hydrogen ion
and hydroxyl ions.
If one or both of the varieties of acid and base are weak then the heat of neutralization is less
than 13.68 kcal. This is because, the combination of one mole of H+ (aq) ions and one mole of
OH– (aq) ions involve the release of 13.68 kcal heat but weak electrolytes are not ionized
completely. Some quantity of released heat is consumed for the ionization of weak electrolyte.
Hence, the energy released is less. Now, let us see some neutralization reaction.
HCl (aq) + NaOH (aq) NaCl (aq) + H2O (l) ΔH = – 13.68 kcal
HCOOH (aq) + NH4OH (aq) HCOONH4(aq) + H2O (l) ΔH = –11.9 kcal
Justify the enthalpy of neutralization of strong acid and strong base is nothing but the
enthalpy of formation of water.
Bond Energy or Bond Enthalpy

When bond is formed between two atoms, energy is released because these two atoms have to come
near to each other and work is done. On the contrary when bond is broken, energy must be supplied.
Hence, formation of bond is exothermic process while breaking of bond is endothermic process.
The bond energy is defined as the average amount of energy required to break all bonds in one mole
of particular substance. It is measured in kcal mol–1 or kJ mol–1
Bond energy (ΔH) = Bond energy of reactant – Bond energy of product
Table 5.5: Bond energies of some common bonds:

Bond Bond energy
Cl—Cl 243 kJ mol–1
O=O 499 kJ mol–1
C—H 414 kJ mol–1
O—H 460 kJ mol–1
H—H 24.85 kJ mol–1
Example 5.2 Calculate the heat of reaction for the following reaction:
1
H2 (g) + 2 O2 (g) H2O (g)
Given bond energy:
H—H = 104 kcal mol–1 O=O = 118 kcal mol–1 O—H = 109 kcal mol–1
Solution
Heat of reaction (ΔH) = Bond enthalpy of reactants – Bond enthalpy of products
1
or ΔH = (ΔH of H—H) + 2 (ΔH of O = O) – 2(ΔH of O—H).
1
= 104 + 2 × 118 – 2 × 109 = 104 + 59 – 218 = – 55 kcal mol–1
∴ The heat of reaction is – 55 kcal mol–1.
5.9 Hess's Law of Constant Heat Summation

Enthalpy change (ΔH) depends upon only the initial state and final state of the system and it does
not depend upon the ways through which it is brought. Enthalpy is state function or it is path
independent function. This fact was first generalized by G.H. Hess in 1840 and gave a law which is
called Hess's law of constant heat summation. It states that at constant pressure the amount of heat
evolved or absorbed in a chemical reaction is always the same, regardless of the path by which the
change occurs. This law is concerned with conservation of energy.
To reach upto the conclusion of Hess's law, we can add or subtract the chemical reactions
algebraically whose enthalpy values are known in order to obtain the desired reaction. To balance
the chemical equation, we can multiply by some number to a reaction so as to cancel out the
intermediate product. Accordingly, we calculate the values of ΔH of these reactions to obtain the
enthalpy of the net reaction.
Let us take a general reaction where A changes to Z.

When reactant A changes directly to Z
A Z + Q1 ΔH = – Q1 , where Q1 is heat evolved.
When reactant A changes to product Z by many steps
(i) A B + q1 ΔH = – q1 A Path I
Z
Q1 q3
(ii) B C + q2 ΔH = – q2 q1
C
q2
(iii) C Z + q3 ΔH = – q3 B
Path II
Total heat evolved in this case is Q2 = q1 + q2 + q3.
According to Hess's law Q1 = Q2.
Hess's law is the consequence of the first law of thermodynamics. This fact can also be justified as
follows.
When, Q1 > Q2, (where Q2 = q1 + q2 + q3)
If reaction change is carried out by converting reactant (A) through high energy releasing path (i.e.
path I) and converting the product back through a low energy releasing path (i.e. path II), in each
complete cycle there is some release of energy i.e. energy released in one cycle
= Q1 – Q2.
If the process is repeated many times, tremendous amount of heat is released which is against the
first law of thermodynamics. Hence even according to the first law of thermodynamics Q1 must be
equal to Q2.
Illustration of Hess's law of Constant Heat Summation
Let us take the example of burning of carbon to CO2. Carbon can be burnt to give CO2 directly or it
may be changed first it to carbonmonoxide then only to carbondioxide as shown in figure 5.10.
CO
1 1 Path I
O2(g)
2 O2(g) ΔH2 ΔH3 2
ΔH1 Path I I
C CO2
+O2, path (I)
Fig. 5.10: Different paths for the formation of carbondioxide from carbon and oxygen.
Path I: C (s) + O2 (g) CO2 (g) ΔHI = – 94.00 kcal

1
Path II: C (s) + 2 O2 (g) CO (g) ΔH1 = – 26.00 kcal
1
CO (g) + 2 O2 (g) CO2 (g) ΔH2 = – 68.00 kcal
C(s) + O2 (g) CO2 (g), ΔH1 + ΔH2 = – 94.0 kcal, ΔHII = – 94.0 kcal
Where, ΔHII = ΔH1 + ΔH2
From the above examples, it is found that total heat evolved is same whatever may be the path. This
example justifies the Hess's law of constant heat summation.
Self Test
st
5.6 Explain the Hess's law of constant heat summation in the light of 1 law of thermodynamic.
Applications of Hess's Law
Hess's law is very useful in the field of chemistry for the determination of heat of a reaction. The
applications are as follows.
a. Determination of heat of formation of substances which otherwise can't be measured
experimentally: Substance like carbon monoxide, methane, benzene can't be prepared by
combining their constituent elements. Therefore, it is not possible to determine the heat of
formation directly. Instead the heat of formation is calculated by applying Hess's law.
b. Determination of heat of transition: The heat of transition of one allotropic form of element to
another allotropic form can be calculated by applying Hess's law.
c. Determination of heats of various reactions: By using Hess's law, enthalpies of many reactions
can be calculated which otherwise can't be found out.
Solved Questions
1. Entropy is extensive property but temperature is intensive property. Explain.
¬ Entropy is extensive property because it depends upon the amount of substance present. Larger the mass,
larger will be the entropy. Entropy is the measure of randomness or disorder of a system. It is additive
property.
Temperature is intensive property. It does not depend upon the quantity of substance. It is non-additive
property. For example in a water system at 50°C every water drop is at 50° C.
2. State first law of thermodynamics.
¬ First law of thermodynamics states "Whenever energy of a particular type is disappeared, equivalent amount
of another type of energy must be produced". Or ""Energy can neither be created nor be destroyed"
If a quantity of heat (q) is supplied to a system, part of it goes to increase the internal energy (ΔE) of the
system and part of it will be spent for the work done (W) by the system on the surrounding. Accordingly,
q=ΔE+W . . . (i)
Where,
q = heat supplied to a system
Δ E = change in internal energy of a system = E2 – E1
W = work done by the system
3. State Hess law of constant heat summation.
¬ Hess law of constant heat summation states "The amount of heat evolved or absorbed in a chemical reaction
is always the same, regardless of whether the process takes place in a single step or in a series of steps".
Example: write a suitable example.
4. What is meant by enthalpy of formation?
¬ The amount of heat involved when one mole of compound is formed from its constituent elements is called
heat of formation.
Heat of formation of a compound is equal to its enthalpy of the compound.
Example
1 1
HCl (g) ΔH = – 22.0 kcal.
2 H2 (g) + 2 Cl2 (g)
(1 mole)
∴ Heat of formation of hydrogenchloride gas is – 22.0 kcal mol-1.

Questions
1. Define the terms:
a. Extensive properties b. Intensive properties c. State function
d. Internal energy e. Enthalpy f. Isothermal process
2. State the first law of thermodynamics.
3. How are enthalpy change and internal energy change related?
4. Neither heat nor work is a state function but their difference is state function. Comment it.
5. Draw energy profile diagrams for exothermic and endothermic reactions.
6. Define bond enthalpy.
7. Define the terms:
a. Enthalpy of combustion b. Enthalpy of formation
c. Enthalpy of neutralization
8. State whether the following properties are extensive or intensive:
a. Temperature b. Molar volume
c. Internal energy d. Entropy
d. Enthalpy
9. Deduce the relation ΔH = ΔE + PΔV, where the symbols have their usual meanings.
1. State and explain first law of thermodynamics and hence deduce H = E + PV, where all the
symbols have their usual meanings.
2. State and explain Hess's Law of constant heat summation. Also mention the applications of
Hess's law of constant heat summation.
3. Distinguish between:
a. Internal energy and enthalpy
b. Exothermic and endothermic reaction.
c. Reversible process and irreversible process
4. State the first law of thermodynamics. What is its main limitation?
Numerical Problems
1. Calculate the enthalpy of formation of NH3 from the following equation.
N2 (g)+3H2 (g) 2 NH3 (g) Δ H = -93 kJ
Ans: ΔHF = − 46.81 kJ
2. The standard heat of formation of SO2 (g) and SO3 (g) are - 296.6 kJ and –396 kJ respectively.
Calculate ΔH for the reaction:
1
SO2 (g) + 2 O2 (g) SO3 (g)
Ans ΔH = −99.4 kJ
3. Calculate the heat of combustion of glucose from the following data:
C(s) + O2 (g) CO2 (g), ΔH = −395 kJ
1
H2 (g) + 2 O2 (g) H2O (l), ΔH = −269 kJ
6 C(S) + 6 H2 (g) + 3 O2 (g) C6H12O6 (s), ΔH = −1169 kJ

Ans: −2815 kJ
4. Calculate the heat of formation of naphthalene (C10H8) from the following data:
C(s) + O2 (g) CO2 (g) ΔH = −94.405 kcal
1
H2 (g) + 2 O2 (g) H2O (l) ΔH = −68.3 kcal
C10H8 (s) + 12 O2 (g) 10 CO2 (g) + 4 H2O (l) ΔH = −1231.6 kcal

Ans: Heat of formation of naphthalene = 14.35 kcal
5. Estimate the enthalpy change for the reaction
H2 (g) + Cl2 (g) 2 HCl
Given:
bond energy of H−H. = 435 kJ/mol,
bond energy of Cl−Cl = 243 kJ/mol,
bond energy of H – Cl = 430 kJ/mol
Ans: –182 kJ
6. Calculate the standard enthalpy of formation of H2O (l) in the following reaction:
2H2 (g) + O2(g) 2 H2O (l) ΔH = – 136 kCal
Ans: –68 kcal mol–1
7. Enthalpy of formation of benzene, water and carbondioxide are 55 kJmol-1,
–395 kJ mol-1 and
–285 kJ mol , respectively. Calculate the enthalpy of combustion of benzene.
-1
Ans: –2950 kJ mol–1

8. Calculate the enthalpy of formation of ethane at 298 k, if the enthalpies of combustion of carbon,
hydrogen and ethane are –94.14, –68.47 and –373.3 kCal mol–1 respectively.
Ans: –20.39 kCal mol–1

1. In an adiabatic process 5. In isothermal process
a. pressure is constant a. dq = 0 b. dq ≠ 0
b. the gas is expanded isothermally c. dT ≠ 0 d. dV = 0
c. there is perfect heat insulation 6. Which of the following is a path function?
d. system exchanges heat with surrounding
a. Enthalpy b. Entropy
2. Hess's law deals with: c. Heat d. Temperature
a. change in heat of reaction 7. ΔH is
b. rate of reaction
a. qp b. qv
c. influence of pressure on volume of a gas
c. ΔE d. Δn
d. emf of redox reaction.
3. According to the first law of thermodynamics. 8. Enthalpy change of combustion is
a. +ve b. –ve
a. heat can be flown from colder body to hotter body
c. 0 d. +ve or –ve
b. energy can neither be created nor be destroyed
c. the efficiency of a heat engine can never be 100% 9. Direction of the spontaneous process is predicted by
d. entropy of universe is increasing day by day a. First law b. Hess law
4. H, E, P & V are related as, c. Second law d. Third law
a. H=E+P–V b. H = E + PV
c. H = E – PV d. H = P – EV
1 2 3 4 5 6 7 8 9
c a b b b c a b c
Chemical
Thermodynamics
An Internal Combustion Engine: Knowledge of thermodynamics is necessary

to explain the working of internal combustion engine.
6.1 Introduction
The first law of thermodynamics is concerned with the law of conservation of energy as it explains
about the exact equivalence of different forms of energy. If a hot iron ball at 100°C is connected to
cold iron ball at 10°C, heat flows from hot ball to cold ball. The first law of thermodynamics explains
that heat lost by hot ball is equal to heat gained by cold ball. But it does not tell us about the direction
of flow of heat. There are so many natural phenomena which occur along a particular direction only.
In one direction, these processes are spontaneous but not in opposite direction. To answer the
feasibility of a process along a particular direction, second law of thermodynamics is required.
Before discussing about the second law of thermodynamics, we shall discuss about spontaneous
process and criteria for spontaneity.
6.2 Spontaneous and Non-spontaneous Process

A process which takes place itself (or by initiation at once) is called spontaneous process. All
processes occurring in nature are spontaneous processes or it can be said that all the irreversible
processes are spontaneous processes. Here, it is to be noted that the term spontaneous does not
mean the process occurs at any time but the process occurs only under the given set of conditions.
The time factors and mechanism of reaction are the domain of chemical kinetics but not the domain
of thermodynamics.
Dissolution of glucose into water and burning of petrol in air both are spontaneous process. When
glucose is kept in water it undergoes dissolution. On the other hand, petrol does not burn itself
below its ignition temperature. It demands initiation. When a burning flame is exposed to the petrol,
then only combustion starts. The reason behind this is inflammable substances such as diesel, petrol
and kerosene are energy rich compounds and these are thermodynamically less stable. These require
relatively higher activation energy to burn. When heat is supplied initially, the fuel starts to burn
with the release of energy and that energy sustains activation energy required for further steps. It
means fuels are thermodynamically less stable because these have high potential energy but these
are kinetically stable because these require more activation energy.
Some examples of spontaneous process are given below.
i. Neutralization of acids and bases
ii. Rusting of iron
iii. Evaporation of water
iv. Dissolution of ammonium nitrate in water.
v. Condensation of water vapour into water.
vi. Freezing of water into ice.
vii. Mixing of gases
Those processes which neither take place themselves nor take place by initiation are called non-
spontaneous processes. Some examples of non-spontaneous processes are given below.
i. Flow of water from lower level to upper level.
ii. Flow of heat from cold body to hot body.
iii. Flow of gases from low pressure region to high pressure region etc.
Chemical Thermodynamics Unit 6 171
6.3 Driving Forces for Spontaneity

In the previous unit we have discussed about spontaneous and non-spontaneous processes. It arises
a question to us that why some processes are spontaneous while some are not. The answer is, there
must be some driving forces which are responsible for a process to be spontaneous. These driving
forces for spontaneity are discussed below.
1. Decrease in enthalpy and spontaneity: When a system loses energy, it will have minimum
energy and becomes more stable. It means, to be stable, a system loses energy and the process is
more likely to be spontaneous. This is understood by the following examples.
High P.E.
i. Rolling down of a stone form top of hill is
spontaneous process because while doing
so the potential energy of the stone
decreases. Low P.E.
Fig. 6.1: Showing P.E. of a stone at

higher and lower level (P.E. = mgh)
ii. Water flows down spontaneously from a height because the potential energy of water at
lower height is minimum.
iii. Heat flows spontaneously from hot body to cold body because heat content of hot body
decreases.
iv. The following reactions are some examples of exothermic reactions. The heat content of
the products are less than that of reactants. Therefore, exothermic reactions are more likely
to be spontaneous.
1
H2 (g) + 2 O2 (g) H2O (l) ΔH = – 6.01 kJ mol–1 at 273 K
N2(g) + 3H2 (g) 2NH3(g) ΔH = – 46.2 kJ mol–1 at 298 K

C(s) + O2 (g) CO2 (g) ΔH = – 40.66 kJ mol–1 at 373 K
From these examples, it can be concluded that decrease in enthalpy might be responsible for a
process to be spontaneous or feasible. But it suffers from following limitations.
Limitations
i. There are some endothermic reactions which are spontaneous. These include,
Melting of ice, H2O (s) H2O (l) ΔH = + 5.86 kJmol–1
Evaporation of water H2O (l) H2O (g) ΔH = + 44.0 kJmol–1
Dissolution of some salt such as NH4Cl + water NH4Cl (aq) ΔH = +15.1 kJmol–1
ii. All exothermic reactions may not proceed to completion.
iii. There are some spontaneous processes which do not involve remarkable enthalpy change.
Examples: mixing of water and milk, mixing of gases, etc.
Conclusion
Decrease in enthalpy is not the sole criterion for predicting the spontaneity of a process. There
must be some other factors for a process to be spontaneous.
2. Randomness and spontaneity: There are some spontaneous processes which do not involve
remarkable enthalpy change. Therefore, enthalpy change only cannot be the sole criterion for
the spontaneity of reaction. If such processes are visualized, it is found that there occurs
increase in the randomness or disorder of the system. For example,
i. Mixing of gases involve the increase in randomness or disorders of the system.
A A A B B B A B A B A B
Mixing A B
A A A A A B B B B B B A B B A A B A
A A B B A B B A
Gases after mixing
Gases before mixing
Fig. 6.2: Diagram showing mixing of gases.
Before mixing two types of gases, A and B are at their corresponding bulb. When the stop
cock is opened both gases diffuse and disperse randomly.
ii. Many endothermic spontaneous processes are accompanied by increase in randomness or
disorder. Some examples are given below.
• In melting of ice, molecules experience more randomness in liquid state than in solid state.
H2O (s) + heat H2O (l) ΔH° = 6.01 kJmol–1
• Evaporation of water, H2O (l) + heat H2O (g) ΔH° = 44.01 kJmol–1
• Dissolution of glucose into water is spontaneous process because in solid state the glucose
molecules are fixed but in aqueous solution each molecule achieves more randomness.
• In the decomposition of N2O5, two molecules of reactant yield five molecules of products.
So the process is accompanied by increase in randomness.
2N2O5(g) 4NO2(g) + O2(g)
From these discussions, it is revealed that increase in randomness might be responsible for
a process to be spontaneous. But it suffers from following limitations.
Limitations
If the randomness factor were the only criterion for spontaneity, the process like liquefaction of
gases or condensation of vapour and solidification of liquid or freezing of liquid would not
have been spontaneous processes. In liquefaction of gases and solidification of liquid
randomness decreases, still these are spontaneous processes.
Conclusion
Just as decrease in enthalpy cannot be the sole criterion for predicting spontaneity as well as
increase in randomness cannot be the sole criterion for a process to be spontaneous.
3. Decrease in enthalpy, increase in randomness and spontaneity: From the above study, it is
found that exothermic as well as some endothermic reactions are spontaneous. On the other
hand, some processes accompanied by increase in randomness as well as some processes
accompanied by decrease in randomness are spontaneous. Hence neither the decrease in
enthalpy nor the increase in randomness alone is the criterion for spontaneity but the resultant
of the two factors may be the criterion for a process to be spontaneous.
Hence, overall tendency for a process to be spontaneous is the resultant of tendency to have
minimum energy and maximum randomness (or disorder) of the system.
6.4 Measure of Randomness and Concept of Entropy

To measure the degree of randomness (or disorder) of a system, a new term was introduced by
Clausius which is called entropy. It is denoted by the symbol S.
Definitions of entropy
1. Entropy is the measurement of randomness (or disorder) of a system. Higher the randomness
or disorderness of a system, greater will be the entropy. In solid, the atoms, ions or molecules
are compactly close to each other and solid state has lower entropy. When solid is converted
into liquid, randomness of atoms, ions or molecules is increased and increase in entropy. On the
same background gaseous state have highest entropy.
Ssolid < Sliquid < Sgas
2. Entropy is the measurement of unavailable heat energy. Let us take an example of heating of
water. When water is heated, the heat absorbed is utilized to increase the temperature. This
happens upto boiling temperature. As soon as the boiling point reaches, thus supplied heat is
not utilized to increase the temperature rather it changes the phase of the system from liquid to
gas. It can be said that some amount of heat are not available to increase the temperature of the
system but are utilized to increase the randomness of a system.
3. In terms of probability, entropy is mathematically defined as, S = k ln W
where, S = entropy; k = Boltzmann constant; W = Probability (number of ways of change that
can be carried out)
4. Mathematical definition of entropy.
qrev
Mathematically, entropy is defined as, S = T
Unit of entropy
qrev
We know, S = T
The unit of entropy in CGS system is calorie per Kelvin (cal K–1). It is also called entropy unit (eu).
In S.I. system, the unit of entropy is Joule per Kelvin (J.K-1).
Some points about entropy
• Like internal energy (E) and enthalpy (H), the entropy is also a state function.
• Entropy is an extensive property
• Unlike internal energy (E) and enthalpy, the absolute value of entropy of a substance can be
calculated. It is dealt in the third law of thermodynamics.
If S1 and S2 are entropies of a substance at initial and final condition, the change in entropy is
given by, ΔS = S2– S1
qrev
Also, ΔS = T
dqrev
In terms of infinitesimal change dS = T .
Entropy change during a process is defined as the quantity of heat changed reversibly divided
by absolute temperature at which the heat change occurs.
Self Test
6.1 Write the physical significance of the term entropy.
6.5 Probability and Entropy

It is discussed that entropy is the measurement of randomness of a system. Increase in randomness is
one of the driving forces to cause spontaneity and randomness is directly related to probability. A
highly ordered state is less probable while a highly disordered state is more probable. For a system
to be highly ordered, there is only one way (or few ways) while for the system to be highly
disordered, there are plenty of ways. In the nature, that event takes place which has high probability
to occur. An ordered state has low probability and small entropy while a disordered state has high
probability and high entropy. This fact can be understood from the following examples.
Example 1
Let us consider one colour playing cards are arranged in sequence and tossed. These are collected
and again reshuffled. Will we get the state of previous sequence? Obviously no. Is it impossible to
attain the previous state? The answer is, possible but highly improbable. Mathematically, it can be
understood as, the 13 cards can be arranged by 13! ways. Out of these ways, to achieve the previous
sequence there is only one way. So there is only one way to achieve previous state while there are
(13! –1) ways not to achieve the previous state. Disordered state is highly probable state.
Example 2
Let us consider two glass bulbs connected by a glass tube fitted with stop cock. When two different
types of gases are enclosed in two bulbs and stop cock is opened, these gas molecules undergo
intermixing and randomness of molecules is increased. Will all the gas molecules collect only at bulb
A? It is not impossible but highly improbable. This can be understood by taking an example of three
gas molecules.
If we consider 3 gas molecules A, B, C these can be arranged by 23 ways i.e 8 ways as given below.
AB C
Bulb II
Bulb I
Molecules in Bulb
Way of arrangement
I II
1 A, B, C –
2 A, B C
3 A, C B
4 B, C A
5 .. A, B, C
6 A B, C
7 B A, C
8 C A,B
In case of 3 gas molecules out of 9 chances, there is only one chance for all the gas molecules to be
occupied at bulb I. When number of gas molecules increases tremendously the improbable chance
also increases accordingly. If we consider 1000 gas molecules, the probability of finding all gas
molecules in bulb II even when the stop cock is opened is one out of 21000 chances.
From the above examples, it is clear that highly ordered state is less probable and highly disordered
state is more probable. Mathematically, entropy is related to probability as,
S = k ln W
(Where, S = entropy, k = Boltzmann constant, W = number ways in which change can occur or
probability)
Self Test
6.2 Find out whether the following processes involve increase or decrease in entropy.
A. i. Melting of ice ii. Evaporation of water
iii. Condensation of vapor iv. Liquefaction of gas
v. Sublimation of gas vi. Sublimation of camphor
B. i. 2KClO3(s) 2KCl (s) + 3O2 (g)
+ –
ii. NH4Cl (s) + water NH4 (aq) + Cl (aq)
iii. CaCO3 CaO (s) + CO2 (g)

Δ
iv. N2(g) + 3H2(g) 2NH3
C. i. Gathering of students in canteen from classroom after ringing the bell.

ii. Sitting of students in their seats in classroom after returning from playing ground.
iii. Running of football players to goal football from their initial standing position.
6.6 Entropy Change

Physical or chemical transformations are accompanied by change in entropy. Here entropy change in
phase transformation and chemical transformation are discussed in separate headings.
A. Entropy change in phase transformation
Melting of solid, evaporation of liquid, condensation of vapour, freezing of liquid, sublimation of
solid substance, allotropic modification, etc. are the examples of physical changes. Such changes take
place at constant temperature. For example, when ice is heated, it starts to melt. During melting,
temperature does not rise and heat is absorbed reversibly. If qrev heat change takes place at
temperature T in a process, the entropy is given by
qrev
S= T …(i)
Phase transformation takes place at constant temperature and pressure. At constant pressure
qrev = ΔH holds true according to the first law of thermodynamics. Now equation (i) becomes,
ΔH
S= T …(ii)
The different types of phase transformations are given below.

1. Entropy of fusion: (ΔSfusion): When a solid melts, there exists equilibrium between solid
and its liquid phase at melting point. The entropy change involved when one mole of
solid changes into its liquid state at melting point is called entropy of fusion. It is
denoted by ΔSfusion.
At melting point, the heat absorbed (qrev) is equals to latent heat of fusion (ΔHf).
ΔHf
ΔSfusion= T …(iii .a)
m
Where, Tm = melting temperature in Kelvin scale

For a change,
Melting or
Solid Liquid
M.Pt.
or ΔSfusion = Sliquid – Ssolid …(iii .b)
Where, ΔSfusion= entropy of fusion, Sliquid = molar entropy of liquid and Ssolid is molar entropy of
solid.
Self Test
6.3 Calculate the entropy change for the conversion of 1 mole of ice into water at its melting point.
–1
Melting point of ice is 0°C. The enthalpy of fusion of ice is 6.025 kJ mol
Ans: 22.06 JK-1 mol–1
6.4 In the above case, calculate the entropy change for 2 gram of ice.
Ans: 2.45 JK–1
–1 –1
6.5 30.39 kJ energy is required to melt one mole of NaCl. The entropy of fusion is 28.4 J mol K .
Calculate the melting point of sodium chloride.
Ans: 797°C
2. Entropy of vaporization (ΔSvaporisation): When liquid is heated, it boils at boiling point. At

that temperature liquid and vapour phase attain equilibrium condition.
The entropy change involved when one mole of liquid is changed into its vapour state
at boiling point is called entropy of vaporization. It is denoted by ΔSvaporisation.
At boiling point, the heat absorbed reversibly (qrev) is equal to the latent heat of
vaporization or enthalpy of vaporization (ΔHvaporisation)
ΔHv
ΔSvaporisation = T …(iv. a)
b
Where,
Tb is boiling point of liquid.
For a change,
vapourisation
Liquid Vapour
B.Pt.
or, ΔSv = Svapour – Sliquid …(iv. b)
where,
ΔSv = entropy of vaporization
Svapour= molar entropy of vapour phase
Sliquid = molar entropy of liquid phase.
Self Test
–1
6.6 The boiling point of ethanol is 78.5°C. If its enthalpy of vaporization is 38.59 kJ mol what will
be the molar entropy change?
Ans: 109.78 JK-1 mol–1
6.7 Calculate the entropy change for 0.25 mole of ethanol.
Ans: 27.445 JK-1
–1 –1
7.8 If entropy of vaporization of water is 109 JK mol what will be the latent heat of vaporization?
Ans: 40.657 kJ mol–1
3. Entropy of sublimation (ΔSsublimation): Entropy of sublimation is defined as the entropy

change involved when one mole of solid substance is directly converted into vapour
state below the melting point of solid. It is denoted by ΔSsublimation.
ΔHsublimation
ΔSsublimation = Ts …(v. a)
Where,
ΔHsublimation = enthalpy of sublimation
Ts = sublimation temperature
For a change,
Sublimation
Solid (s) Vapour (g)
ΔSsublimation= Svapour – Ssolid …(v. b)
Where,
ΔSsublimation = entropy of sublimation
Svapour = molar entropy of vapour phase
Ssolid= molar entropy of solid phase
4. Entropy of transition (ΔStransition): At a particular temperature, two allotropes of an element
exist at equilibrium and this temperature is called transition temperature (Tt).
Entropy of transition is defined as the entropy change involved when one mole of one
allotropic form of an element is changed into another allotropic form at transition
temperature.
ΔHtransition
ΔStransition= Tt …(vi. a)
Where, ΔStransition = entropy of transition, ΔHtransition= enthalpy of transition, Tt= transition

temperature
For a change, Diamond Graphite

ΔSt= Sgraphite – Sdiamond
Where, ΔSt= entropy of transition, Sgraphite = molar entropy of graphite, Sdiamond = molar
entropy of diamond
B. Entropy change in chemical reaction
In a chemical reaction, one type of chemical species are entirely changed into another type. This
involves change in entropy in a chemical reaction. Entropy change of a chemical reaction is
calculated by subtracting the sum of entropy of all reactants from the sum of entropy of all products.
For a general reaction, a A + b B cC+dD
Let SA, SB, SC and SD are entropies of chemical species A, B, C and D respectively. Here, a, b, c and d
are stoichiometric coefficients for these chemical species. The entropy change for the reaction is given
by
ΔS = Σ Sproducts – Σ Sreactants
or, ΔS = (c SC + d SD) – [a SA + b SB]
If standard entropies are taken for each chemical species, entropy change in a reaction is called
standard entropy change. It is denoted by ΔS°.
ΔS° = Σ S°products – Σ S°reactants
Entropy of 1 mole of pure substance at 25°C and 1 atmosphere pressure is called standard entropy.
Since, absolute value of entropy of a pure solid substance at 0K is zero, the standard entropies of all
substances above 0K are always greater than zero. The standard entropies of some elements and
compounds are given in table 6.1.
Table 6.1: Standard entropies (at 25°C and 1 atm) of some substances
Chemical Substance S° in cal K-1mol-1 S° in JK–1 mol–1
H2 (g) 32.21 130.6

H2O (g) 45.11 188.7
H2O (l) 16.72 69.96
HCl (g) 44.62 186.7
HNO3 (l) 37.19 155.6
H2SO4 (l) 37.50 157.0
N2 (g) 45.77 191.5
NH3 (g) 46.01 192.5
Na (s) 36.72 153.6
NaCl (s) 17.30 72.88
O2 (g) 49.0 205.0
S (s) 7.62 31.9
SO2 (g) 59.40 248.5
Cl2 (g) 53.29 223.0
CO2 (g) 51.06 213.6
Self Test
6.9 Calculate the entropy change for the reaction
N2 (g) + 3H2 (g) 2NH3 (g)
–1 –1
Given S° of N2, H2 and NH3 are 191.5, 130.6, 192.5 JK mol , respectively.
[Ans –198.3 JK–1 mol–1]
6.10 Calculate the standard entropy for the reaction,
H2 (g) + Cl2 (g) 2HCl (g)
Consult data from Table 7.1.
C. Entropy change of system, surrounding and universe

System interacts with surrounding. In such interactions, heat or energy is exchanged. This causes the
change in entropy of system and surrounding. System and surrounding comprise universe. So
interaction of system and surrounding causes entropy change of universe too. Let us consider some
examples to understand entropy change of system and surrounding.
• Spreading of red dyes, in water within beaker does not involve any exchange of matter and
energy with surrounding. Here the mixture of red dyes and water forms a system. Since no heat
or energy is exchanged to the surrounding, it is regarded as isolated system. Such processes
always involve increase in entropy. For spontaneous processes in an isolated system, the
entropy change is positive.
• Let hot water is taken in a breaker and it is regarded as system. The outer part (i.e. with which
the hot water interacts) forms surrounding. In this case, system loses energy as well as matter
and its entropy is decreased. In this case energy is gained by surrounding and its entropy is
increased. In all spontaneous processes, entropy keeps on increasing till equilibrium is
achieved. At equilibrium the entropy is maximum and change in entropy is zero.
• Depending upon the nature, entropy change of system or surrounding may be positive or
negative. But for a process to be spontaneous, the sum of entropy change of system and
surrounding must be positive.
ΔSuniverse = ΔSsystem + ΔSsurroudning
a. Study the following data for the process, H2O (l) H2O(S) at different temperature at 1 atm pressure.
Temperature Entropy change in JK–1 mol–1
ΔSsys ΔSsurr ΔSuniv
–1°C –21.85 + 21.93
0°C –21.99 + 21.99
+1°C –22.13 + 22.05
i. Calculate ΔSuniv at the mentioned temperature above.

ii. At what temperature, freezing of water is spontaneous?
iii. At what temperature freezing of water is non-spontaneous?
6.7 Criteria of Spontaneity in Terms of Entropy Change

(Entropy and Spontaneous Process)
For a process to be spontaneous in isolated system, the entropy change should be positive. In case of
an open system, spontaneity of the process depends upon the entropy change of system and entropy
change of surrounding. Entropy change of system, surrounding and universe is related as
ΔSuniverse = ΔSsystem + ΔSsurrouding
For a process to be spontaneous, the total entropy change of system and surrounding should be
positive or the entropy change of universe should be positive. A process may be spontaneous even if
the entropy change of system is negative as exemplified by condensation of vapour and freezing of
liquid into solid. This is possible because in these cases, the entropy change of surrounding becomes
positive and it outweighs the entropy change of system. This makes entropy change of universe
positive. [See the following interplay table].
The various possibilities of entropy change of system and surrounding can be justified from the
following interplay of ΔSsys and ΔSsurr. Here, ΔSsys is entropy change of system, ΔSsurr is entropy
change of surrounding, ΔSuniv is entropy change of universe. |ΔSsys|is modules value of ΔSsys. Its
magnitude value is considered.
S.No. ΔSsys ΔSsurr ΔSuniv= ΔSsys + ΔSsurr Fate of the process

1. + ve + ve +ve Spontaneous
2. + ve – ve i. +ve if |ΔSsys| > |ΔSsurr| Spontaneous
ii. 0 if |ΔSsys| = |ΔSsurr| Equilibrium
iii. – ve if |ΔSsys| < |ΔSsurr| Non spontaneous
3. –ve – ve – ve Non spontaneous
4. – ve + ve i. + ve if |ΔSsys| < |ΔSsurr| Spontaneous
ii. 0 if |ΔSsys| = |ΔSsurr| Equilibrium
iii. – ve if |ΔSsys| > |ΔSsurr| Non spontaneous
From the above table following points are concluded

i. If entropy changes of system as well as that of surrounding are positive, the entropy change of
universe becomes positive. The process is obviously spontaneous.
ii. If entropy change of system is positive and entropy change of surrounding is negative, the
process is spontaneous only when system suffers larger entropy change than do the
surrounding.
If entropy change of system and surrounding have same magnitude then entropy change of
universe becomes zero. The process attains thermodynamic equilibrium. If entropy change of
surrounding is greater than entropy change of system, the entropy change of universe becomes
negative and the process is non-spontaneous in the given direction. However, the process is
spontaneous or feasible in opposite direction.
iii. If entropy change of system and surrounding both are negative, the entropy change of universe
is negative. The process is obviously non-spontaneous in the given direction.
iv. If entropy change of system is negative and entropy change of surrounding is positive, three
cases arise (explain as in (ii) points).
Melting of ice at 1 atm and above 0°C is spontaneous process. Justify the statement.
Solution
When surrounding is at higher temperature than system, heat is absorbed by ice from surrounding
to melt.
Let, Tsys is temperature of system. Tsurr is temperature of surrounding. ΔH is latent heat of fusion or
enthalpy of fusion.
The entropy change of system is
ΔH
ΔSsys = + (Positive sign indicates that heat is gained by the system) …(i)
Tsys
Entropy change of surrounding is
ΔH
ΔSsurr= – (Negative sign indicates that heat is lost by the surrounding) …(ii)
Tsurr
Now, ΔSuniverse = ΔSsys + ΔSsurr =

ΔH
Tsys
+ (
–
ΔH
)
Tsurr
ΔH ΔH
ΔSuniv = – …(iii)
Tsys Tsurr
= + ve [∵ TSurr > Tsys]

Since entropy change of universe is found to be positive, the melting of ice is spontaneous at 1 atm
pressure and above 0°C.
Self Test
6.6 Show that melting of ice and freezing of water is in equilibrium at 0°C and 1 atm pressure.
6.7 Freezing of water at 1 atm pressure and below 0°C is spontaneous
6.8 Freezing of water at 1 atm pressure and above 0°C is non-spontaneous.
6.9 Melting of ice at 1 atm pressure and below 0°C is non-spontaneous
6.8 Limitation of the First Law of Thermodynamics and

Dawn of Second Law of Thermodynamics
The first law of thermodynamics suffers from the following limitations.
a. It does not answer, why is natural process unidirectional?
b. It does not explain anything about the source of heat and direction of flow of heat.
c. It does not explain why some chemical reactions do not proceed to completion.
d. The first law states that one form of energy changes into another form but it does not define the
extent of convertibility.
To solve the limitations of the first law of thermodynamics, the necessity of the second law of
thermodynamics was felt. The most important aspect of the second law of thermodynamics is that it
forms a basis to predict whether a particular process occurs or not under the given set of conditions
and if they do occur, to what extent. The second law of thermodynamics is defined in different ways.
In terms of entropy the second law of thermodynamics is defined as entropy of the universe is
increasing. In thermodynamics, the term universe means system and surrounding. Hence, entropy
of universe is defined as,
ΔSuniv= ΔSsys + ΔSsurr
According to the second law of thermodynamics, a process will occur spontaneously if entropy of
the universe is increased.
Some other statements of the second law of thermodynamics
1. Clausius and Kelvin statement: "It is impossible to construct a heat engine which will continuously
abstract heat from a body and convert the whole heat energy into work without leaving changes in the
working system"
2. Planck statement: "It is impossible to construct a machine operating in cycles that will convert heat
into work without producing any other changes in the surroundings."
3. "Heat cannot spontaneously pass from a colder to a warmer body" (R.J.E. Clausius)
4. "Every system which is left to itself will, on the average, change toward a condition of maximum
probability" (G.N. Lewis)
5. "The state of maximum entropy is the most stable state for an isolated system" (Enrico Fermi)
6. "There is a general tendency in nature for energy to pass from more available to less available form"
(J.A.V. Butter)
If an isolated process is considered (e.g. mixing of a drop of ink into water in a beaker), the process
proceeds in the forward direction so long as the entropy goes on increasing. The entropy of the
system become maximum then entropy change becomes zero. This is the state where equilibrium
condition is achieved.
Maximum entropy
Equilibrium
Total entropy Energy

Equilibrium
Minimum energy
Extent of change Extent of change

(a) (b)
Fig. 6.3: Conditions for equilibrium (a) Maximum entropy (b) Minimum energy
If entropy change of universe is negative the process is obviously non-spontaneous. It is summarized

as follows.
Entropy change of universe Sign Fate of the process
ΔSuniv + ve Spontaneous
ΔSuniv 0 Equilibrium
ΔSuniv – ve Non-spontaneous
Application of the second law of thermodynamics

On the basis of validity of the second law of the thermodynamics Carnot theorem is deduced. The
possibility of obtaining mechanical work from heat energy led to the development of that engines
which may be external combustion engine or internal combustion engines. Carnot cycle is used to
demonstrate the maximum convertibility of heat into work. The consequences of Carnot theorem led
to calculate the efficiency of heat into work transformation. It introduced the concept of entropy and
Kelvin scale of temperature.
6.9 The Third Law of Thermodynamics

We have discussed in the earlier topics that on increasing the temperature, the molecular motions
and randomness increase. On the contrary, if temperature of a substance is decreased, the
randomness is decreased and entropy of substance at 0 Kelvin is the minimum value. This forms the
basis of the third law of thermodynamics. The third law of thermodynamics states "the entropy of
perfectly crystalline substance at absolute zero temperature is zero."
lim
T → 0 S= 0
This statement implies that every substance has finite positive entropy above absolute zero
temperature. At absolute zero all perfect crystals1 have same entropy.
6.10 Concept of Free Energy

1. Gibbs Free Energy (G)
The concept of entropy (S) is the fundamental consequence of the second law of thermodynamics.
There is another thermodynamic function which makes use of the entropy in its derivation. This
thermodynamic function is 'free energy function (G)'.
1 A perfect crystal is that where each point of the crystal must be at a crystal lattice point and it should have lowest energy. On the other
hand perfect order means zero entropy. A perfect crystal has no disorder and has zero entropy at absolute zero. Glassy solids or liquids,
ice etc. are not perfect crystals because there exist some randomness in the arrangement of atoms or molecules. Entropy of such type of
substance can't be zero at absolute zero temperature.
We have dealt that energy can be converted into work. But it does not mean that all the energy can
be converted into work. The energy which can be converted into useful work is called available
energy. The available energy performs the operation on engine or motor. The energy which is not
converted into useful work but consumed against friction, operation of piston etc is called
unavailable energy. The measure of unavailable energy is entropy while the measure of available
energy present in a system is free energy.
Total energy = isothermally available energy + isothermally unavailable energy
The isothermally available energy present in a system is called free energy or Gibb's free energy. It is
denoted by the symbol G. Mathematically Gibbs free energy is defined as,
G=H–TS …(i)
Where,
G = Gibbs free energy; H = enthalpy; T = Temperature; S = Entropy
Gibbs free energy is also extensive property. It is state function too. It means the value of Gibbs
free energy depends upon initial and final condition of a system but not upon the path.
Let G1, H1 and S1 are Gibb's free energy, enthalpy and entropy of a system initially. At constant
temperature, when enthalpy and entropy are changed from H1 and S1 to H2 and S2 respectively
then Gibbs free energy changes from G1 to G2.
Initially, G1 = H1 – TS1 …(ii)
Finally, G2= H2 – TS2 …(iii)
Now equation (ii) is subtracted from equation (iii), we get,
G2– G1 = (H2 – H1) – T(S2 – S1)
or ΔG = ΔH – T.ΔS …(iv)
Equation (iv) is also called Gibb's-HelmHoltz equation. It is very useful equation in chemical
thermodynamics.
2. Standard Free Energy of Formation (ΔG°f)

It is defined as the change in free energy when 1 mole of substance is formed from its constituent
element provided that all reactants and products are at their standard state (i.e. one bar pressure and
25ºC). It is denoted by (ΔG°f)
The standard free energy of formation of an element in standard state is taken as zero. The standard
free energy of formation of some common substances are given in table 6.2.
Table 6.2: Standard free energy formation (ΔG°f).

Chemical Substance (ΔG°f) in kJ mol–1
C (graphite) 0
H2 (g) 0
H2O (g) –228.6
H2O (l) –237.2
HCl (g) –95.3
HBr (g) –53.22
HI (g) +1.30
NH3(g) –16.63
B2H6 (S) +82.1
P4 (g) +24.35
CO2(g) –394.4
CO (g) –137.3
CH4 (g) –50.80
C2H6 (g) – 32.90
C2H2 (g) + 209.20
C2H4 (g) +68.12
C6H6 (g) +129.60
C2H5OH (l) –104.76
Free energy change can also be calculated by using the relation ΔG = ΔH – T. ΔS. Since ΔH°f for
element is taken as zero, we cannot calculate ΔG°f for an element using the relation
ΔG° = ΔH° – T.ΔS°.
3. Standard Free Energy Change (ΔG°)

Free energy depends upon temperature and molar concentration of chemical species. The standard
state chosen for the measurement of Gibbs free energy are 25°C temperature and 1 molar
concentration of reactants as well as products. Standard free energy change is defined as the free
energy change involved when all the reactants in their standard states are changed into products
in their standard states. It is denoted by ΔG°. When standard free energy of all reactants and
products are known, standard free energy of reactions can be calculated as,
Standard free energy of reaction (ΔG°) = Standard free energy of formation of products (G°f)p
– Standard free energy of formation of reactants (G°f)R.
or ΔG° = Σ(ΔG°f)product – Σ(ΔG°f)Reactant
4. Relation between Standard Free Energy Change (ΔG°) and Equilibrium

Constant (Keq)
The Gibbs free energy change depends upon the concentration of reactants and products. If a
reaction takes place in non-standard condition then the free energy change (ΔG) of reaction is
different from the standard free energy change (ΔG°). ΔG and ΔG° are related as
ΔG = ΔG° + RT ln Keq … (i)
At equilibrium change in Gibbs free energy (ΔG) is zero. So, relation (i) becomes
ΔG° = – RT ln Keq ...(ii)
This is very useful equation in the field of thermodynamics. It helps to calculated standard Gibbs free
energy change from equilibrium constant and vice-versa.
An equilibrium reaction at 25°C and 1 atm pressure is given below.
1
NO (g) + O (g) NO2(g)
2 2
Given,
ΔH°f of NO2 (g) = 33.85 kJmol–1 . NO(g) = 90.37 kJ mol–1
ΔS° at 25°C for the reaction = – 70.8 JK–1 mol–1
Calculate
a. Standard heat of formation
b. Standard Gibbs free energy
c. Equilibrium constant
Solution
(a) Standard heat of formation of element (eg O2) is zero.
ΔH°f for reaction = Σ (ΔHf)products – Σ(ΔHf)reactants
1
= (ΔHf)NO2 – [ (ΔHf)O2 + (ΔHf)NO]
2
1
= 33.85 – [ × 0 + 90.37] = 33.85 – 90.37 = – 56.52 kJ = –56520 Joule
2
(b) Gibbs Helmholtz equation is
ΔG° = ΔH° – T ΔS°
= (–56520) – 298 × (–70.8) = – 56520 + 210984 = – 35421.6 J mol–1
(c) Standard Gibbs free energy is related to equilibrium constant as,
ΔG° = – RT ln Keq
ΔG°
ln Keq =–
RT
–(–35421.6)
or lnKeq = = 14.296
8.314 × 298
Taking anti ln we get Keq = e14.296 = 1.618 × 106
5. Physical Significance of Free Energy

Decrease in Gibbs free energy is the measurement of useful work done. This can be proved as
follows.
From the first law of thermodynamics, qrev= ΔE + Wrev …(i)
When a quantity of heat is supplied to a system, it increases the internal energy and performs some
work. Work done reversibly is greater than work done irreversibly. Wrev is sum of maximum work of
expansion (P.ΔV) and net useful work (e.g. electrical work, etc.) done. Now equation (i) becomes,
qrev= ΔE + Wexpansion + Wuseful
or qrev = ΔE + P.ΔV + Wuseful
or qrev= ΔH + Wuseful [∵ ΔH = ΔE + P.ΔV] …(ii)
If the process is carried out reversibly then according to the second law of thermodynamics,
qrev
ΔS = T
Note:
or qrev = T.ΔS …(iii) qrev = ΔE + wrev
From equation (ii) and (iii), we get qrev =ΔE + wexp + Wuseful
T.ΔS = ΔH + Wuseful qrev = ΔE + P ⋅ ΔV + Wuseful
or – ΔH + T.ΔS = Wuseful T ⋅ ΔS = ΔH + Wuseful

–(ΔH – T ⋅ ΔS) = Wuseful
or –(ΔH – T.ΔS) = Wuseful
– ΔG = Wuseful
or –(ΔG)T.P = Wuseful …(iv)
Equation (iv) reveals that decrease in Gibbs free energy is the measurement of net work or useful
work done reversibly at constant temperature and pressure.
6. Relation between Gibbs Free Energy and Electromotive Force

In galvanic cell, electrical energy is produced as a result of spontaneous redox reaction. The redox
reaction occurs spontaneously with the decrease in free energy. The decrease in free energy is
utilized to do useful work. The free energy change and electrical work are related as,
ΔG = – nFE.
Where, n = number of moles of electrons involved in chemical reaction
F = Faraday constant = 96500 coulomb (approximately)
E = Emf of cell
At standard condition, ΔG° = – nFE°
7. Criteria of Spontaneity in Terms of Gibbs Free Energy Change (ΔG)

(Prediction for the feasibility of reaction)
One of the criteria of spontaneity of a process is that entropy change of universe should be positive
which is discussed in the previous unit. To predict the spontaneity of a process in terms of entropy
change of universe, one should know the entropy change of system and that of surrounding but
chemists are more concerned with system rather than surrounding. This necessitates the introduction
of another thermodynamic function so that the spontaneity of a process could be predicted by
knowing the entropy change of system only. That thermodynamic function is Gibbs free energy (G).
We have, G = H – TS. …(i)
Where, H is enthalpy, T is Kelvin temperature and S is entropy. The change in Gibbs free
energy is given as, ΔG = ΔH – T. ΔS …(ii)
Derivation of criteria of spontaneity in terms of ΔG
To come up to the criteria of spontaneity in terms of Gibbs free energy change, we will start
from the criteria of spontaneity in terms of entropy change of universe.
For a process to be spontaneous, ΔSuniv should be positive. The relation is,
ΔSuniv= ΔSsys + ΔSsurr …(i)
Since it is difficult to measure ΔSsurr, it should be omitted from equation (i) by some measurable
terms.
Suppose heat is lost by the surrounding and gained by the system.
ΔH
At constant temperature and pressure, ΔSsurr = – T
Now, Equation (i) becomes,

ΔH
ΔSuniv= ΔSsys – T
or, TΔSuniv = TΔSsys – ΔH

or, TΔSuniv = – (ΔH – TΔSsys)
or, T ΔSuniv= – ΔGsys
For convenience the subscript 'sys' is dropped. Then ΔG = – TΔSuniv …(ii)
For a process to be spontaneous ΔSuniv must be positive. It implies that for the process to be
spontaneous ΔG must be negative.
For the process to be at equilibrium ΔSuniv should be Zero. It shows that when ΔG is zero, the
process attains equilibrium condition. When ΔSuniv is negative, the process is non-spontaneous
in the forward direction. It implies that when ΔG is positive, the process will be non-
spontaneous in the forward direction. It can be understood from the following table.
Value of ΔSuniv ΔG = – T ΔSuniv Process

+ve ΔG = – ve Spontaneous
0 ΔG = 0 Equilibrium
–ve ΔG = +ve Non-spontaneous
Criteria for Spontaneity (Relation among ΔG, ΔH, ΔS and Temperature):

Spontaneity of a process can be explained in terms of entropy change of universe (ΔSuniv) and
Gibbs free energy change (ΔG). Out of these two, Gibbs free energy change (ΔG) is preferred to
entropy change of universe (ΔSsniv) because prediction of spontaneity in terms of ΔG involves
the entropy change of system only where as prediction of spontaneity in terms of ΔSuniv involves
the entropy change of system and surrounding.
The Gibbs Helm-Holtz equation is ΔG = ΔH – TΔS. This equation includes both energy factor
(ΔH) and entropy factor (ΔS). The interplay of energy factor and entropy factor for the
prediction of spontaneity of a process is given below.
S.No. ΔH ΔS ΔG= ΔH – T. ΔS Fate of the process
1. – ve + ve –ve Spontaneous
2. – ve – ve i. if |ΔH| > |T.ΔS|, ΔG = –ve Spontaneous
ii. if |ΔH| < |T.ΔS|, ΔG = +ve Non spontaneous
iii. if |ΔH| = |T.ΔS|, ΔG = 0 Equilibrium
3. +ve – ve + ve Non spontaneous
4. + ve + ve i. if |ΔH| < |T.ΔS|, ΔG = –ve Spontaneous
ii. if |ΔH| > |T.ΔS|, ΔG = +ve Non spontaneous
iii. if |ΔH| = |T.ΔS|, ΔG = 0 Equilibrium
Here, |ΔH| means modulus value (magnitude only) of enthalpy change or value of enthalpy change ignoring sign.
From the above table it is concluded that

i. If the reaction is exothermic (ΔH = – ve) and entropy change of system is positive, the change in
Gibbs free energy is always negative and reaction occurs spontaneously at all temperature.
ii. If the reaction is exothermic (ΔH = – ve) but the entropy change of the system is negative then
different cases arise.
Case I : Most likely at low temperature: The magnitude of T.ΔS will be less than the magnitude of
ΔH. So Gibbs free energy change becomes negative. Then the process is spontaneous.
Case II: Mostly likely at high temperature: The magnitude of T.ΔS will be higher than the
magnitude of ΔH. So Gibbs free energy change becomes positive. Then the process is non-
spontaneous.
Case III: At a certain temperature, the magnitude of TΔS becomes equal to the magnitude of ΔH. So
Gibbs free energy change becomes zero. Then the process is at equilibrium.
iii. For endothermic reaction if the entropy change of reaction is negative the change in Gibbs free
energy always becomes positive irrespective of temperature. Then the process is non-
spontaneous.
iv. If reaction is endothermic and entropy change of system is positive, different case arises.
[Explain yourself as in (ii) above]
Solved Questions
1. What is the physical concept of entropy?
¬ Entropy is the measurement of randomness or disorder of a system. Higher the randomness or disorder of a
system, greater the entropy of the substance. More ordered system has less entropy. Among the three states
of matter the order of entropy is as follows.
Entropy of gas >> entropy liquid > entropy of solid.
2. Define standard free energy of a reaction.
¬ Standard free energy change is defined as the free energy change for a process at 25°C and 1 atmospheric
pressure in which all the reactants in their standard state changes to product in their standard state. i.e.
ΔG° = ΔH° – T . ΔS°.
The standard free energy of formation of an element in its standard state is taken to be zero.
3. What is meant by spontaneous process? Write an example of it.
¬ When a process takes palce itself then the process is called spontaneous process. However the process may
be initiated by some external agency at once. An example of spontaneous process is evaporation of water.
Questions
a. Spontaneous process b. Entropy c. Entropy unit
2. Write short definition
a. Entropy of fusion b. Entropy of vaporization
c. Entropy of sublimation d. Entropy of transition
3. Define second law of thermodynamics and also define thermodynamic efficiency of heat
engine.
4. Define Gibbs free-energy change. Write the mathematical relation to predict the spontaneity.
5. How would you predict the spontaneity using the relation?
T ΔS units = – ΔG sys.
6. Define free energy. Derive an expression to relate Gibbs free energy change with work.
7. Mention the proper conditions of a chemical reaction to become spontaneous, if its ΔH and ΔS
are positive.
8. Distinguish spontaneous and non-spontaneous processes giving one example of each.
9. Give the physical meaning of entropy. Write its unit.
10. Mention two criteria which must be met for a process to be spontaneous, regardless of the
temperature.
1. Discuss the criteria of spontaneity, non spontaneity and equilibrium of exothermic and
endothermic reactions on the basis of free energy and entropy change.
2. "The decrease in enthalpy or increase in entropy." is not a sole criteria for the feasibility of a
process." Explain.
Numerical Problems
1. The latent heat of fusion of ice is 336 Jg–1. Calculate the molar entropy of fusion of ice at its
normal melting point.
–1 –1
Ans: 22.15 Jmol K
2. The standard enthalpy of vaporization of water is 40.75 kJ mol–1 at its normal boiling point
calculate the entropy of vaporization for the process.
Ans: 109.24 Jmol–1
3. Enthalpy of fusion per mol of ice is 6008 J mol-1. Calculate the entropy change in the conversion
of 1 mole of ice at 0°C and 1 atm to liquid at 0°C and 1 atm.
–1 –1
Ans: 22 J mol K
4. For a reaction ΔG = 38.5 kJ mol–1. Calculate the equilibrium constant for the reaction.
-7
Ans: 1.8×10
5. Equilibrium constant for a reaction is 1.8 × 10–7. Calculate ΔG° for the reaction.
–1
Ans: 38.5 kJ mol

1. A chemical reaction will be spontaneous if 5. For a reaction to occur at all possible temperature,
a. activation energy for the reaction is low which of the following condition is required?
b. entropy decreases during a reaction a. ΔH > 0, ΔS > 0 b. ΔH < 0, ΔS > 0
c. free energy decreases c. ΔH = 0, ΔS > 0 d. ΔH < 0, ΔS < 0
d. free energy increases
6. A reaction is not feasible when
2. In spontaneous reactions, in the free energy the a. ΔH = +ve, ΔS = +ve b. ΔH = –ve, ΔS = –ve
system always, c. ΔH = +ve, ΔS = – ve d. ΔH = –ve, ΔS = +ve
a. increases
7. According to the equation ΔG = ΔH – T ΔS.
b. remain unaffected
c. decreases Spontaneous reaction will occur when the value of
d. first increases and then decreases ΔG will be.
3. Decrease in free energy of a reacting system a. Positive b. Negative
c. Zero d. Infinitive
indicates the reaction to be:
a. a reversible reaction b. an endothermic reaction 8. In precipitation reactions entropy of the system
c. a spontaneous reaction d. a primary reaction a. decreases b. increases
c. remains same d. zero
4. A spontaneous reaction is impossible when
a. both ΔH and ΔS are negative 9. Standard enthalpy of graphite is
b. both ΔH and ΔS are positive a. zero b. >0
c. ΔH is negative and ΔS is positive c. <0 d. can't be generalized
d. ΔS is negative and ΔH is positive
1 2 3 4 5 6 7 8 9
c c c d b c b a a
Chemical Kinetics
Positive catalysts help to decrease energy of activation, leading to the increase in the rate of reaction.
7.1 Introduction
There are so many chemical reactions existing in the nature with their own identities and
peculiarities. These reactions can be studied from different point of views. Some chemical reactions
such as reaction of sodium chloride solution with silver nitrate solution are so fast that simple
techniques of measurement for the rate of reaction cannot be applied. On the other hand, the rusting
of iron is slow reaction as it takes some hours to some days for completion. In the light of velocities
for the transformation of reactants into products, chemical reactions may be classified into fast
reactions and slow reactions. The task of the chemists lies within two extremities; at one end
reactions are to be studied on a femto second (10–15 second) or shorter time scale and at another end
reactions are to be studied on geological time scale. This is the domain of chemical kinetics. Chemical
kinetics is the branch of chemistry which deals about rate of chemical reaction, factors affecting it
and mechanism of chemical reaction. The rate of reaction is determined by knowing a series of
intermediate steps or mechanism of the reaction. Knowing the mechanism of a chemical reaction is
the first step toward the understanding of reaction and hence it helps to monitor the chemical
reaction. In this level, we will deal about the basic concept on rate of reaction, way of measurement
of rate of those chemical reactions which are neither too fast nor too slow.
7.2 Rate of Chemical Reaction

Rate of reaction accounts how fast the reactants transform into products.
Let us consider a reaction, A → B
During chemical reaction, reactant A is gradually converts into B. Concentration of A goes on
decreasing while that of B goes on increasing. Disappearance of reactant A or appearance of product
B is the indication of the chemical transformation. Change in concentration is the difference between
final concentration and initial concentration. Therefore, the value of change in concentration of
reactant comes to be negative and rate of reaction appears to be negative. But the rate of reaction is
never negative. Due to this reason negative sign is introduced to express the rate of reaction in terms
of reactant. Rate of reaction or velocity of reaction is defined as the change in concentration of
reactants or products per unit time.
Change in concentration
Rate of reaction = Change in time
If rate of reaction is expressed in terms of reactants, negative sign is introduced and if rate of reaction
is expressed in terms of products, positive sign is introduced.
For above reaction
Δ[A]
Rate of reaction = – (in terms of reactant)
Δt
Δ[B]
or Rate of reaction = (in terms of product)
Δt
The rate of reaction or velocity of reaction can be classified into following types:
1. Average rate of reaction
2. Instantaneous rate of reaction
Chemical Kinetics Unit 7 193
1. Average rate of reaction

Average rate of reaction may be defined as the change of concentration of reactants or products
Δx
per unit time interval (where the time interval is measurable). It is denote by . Here, Δx and Δt
Δt
are finite change in concentration and time, respectively.
Change in concentration Δx
Average rate of reaction= =
Change in time Δt
Here, changes in concentration = Final concentration – Initial concentration.
For reactants, the change in concentration is negative while that for product it is positive. For the
Δx
above reaction, if rate of reaction is expressed in terms of reactant A, the rate of reaction =– . If the
Δt
rate of reaction is studied in terms of product, the change in concentration is found to be positive.
Δx
Therefore, Rate of reaction = +
Δt
Product
Δx
Δt
Concentration
Concentration
Δx
Δt
Reactant
Time Time
Fig. 7.1: Determination of average rate of reaction in terms of reactant and product
2. Instantaneous rate of reaction

One of the implications in the measurements of average velocity of chemical reaction is that the
concentration of reactants decreases with time and so does the rate of reaction. But calculation shows
constant rate of reaction for the particular interval of time. Besides this, the rate of reaction at a
particular instant of time cannot be measured by average rate method. Therefore, to know the rate of
reaction at a particular instant of time during the course of time, the term instantaneous rate of
reaction is introduced. Instantaneous rate of reaction may be defined as the rate of change of
dx
concentration of reactants or products at a particular moment of time. It is denoted by dt .
Where dx is infinitesimal change in concentration of reactants or products and dt is infinitesimal

change in time.
dt Product
dx
Concentration
Concentration
dx Reactant
dt
Time Time
Fig. 7.2: Diagram to show the instantaneous rate of reaction
Instantaneous rate of reaction is determined by measuring the slope of a tangent plotted at a

concentration-time graph corresponding to a particular instant of time.
As the time interval of average rate of reaction Δt decreases and tends to be zero then the average
rate of reaction becomes instantaneous rate of reaction. Mathematically, average rate of reaction and
lim Δx dx
instantaneous rate of reactions are related as = .
Δt → 0 Δt dt
Let us take an examples to study the rate of chemical reaction.
N2(g) +O2(g) 2NO (g)
In this reaction, one mole of nitrogen and one mole of oxygen disappear to produce two moles of
nitric oxide. It means, for the appearance of two moles of NO, each mole of reactant is consumed.
d[N2]
Rate of reaction in terms of N2 (r) = – dt
d[O2]
Rate of reaction in terms of O2 (r) = – dt
d[NO] d[NO]
Rate of reaction in terms of NO (2r) = dt or r = 2 dt
These expressions show that, the rate of reaction depends upon the chemical species chosen from the
balanced chemical equation.
To express the rate of chemical reaction irrespective of the choice of chemical species, it is customary
to express the rate of reaction for each mole of chemical species involved in the balanced chemical
equation. For this purpose, rate expression of each chemical species is divided by stoichiometric
coefficient of the balanced chemical equation. This is often called equivalence rate of reaction.
Hence equivalence rate of reaction is defined as the change in concentration of each mole of
reactants or products per unit time interval. This type of chemical reaction is irrespective of the
choice of chemical species involved to express the rate of reaction. If above reaction is to be
expressed in terms of equivalence rate of reaction, it is written as,
d[N2] d[O2] 1 d[NO]
– dt = – dt = + 2 dt
Self Test
7.1 What is chemical kinetics?
7.2 What are average rate of reaction and instantaneous rate of reaction? How are they related?
7.3 How is instantaneous rate of reaction superior to average rate of reaction in the determination
of rate of chemical reaction?
7.3 Concept of Activation Energy and Threshold Energy

Reactants react to give products only under the given set of conditions. Whether the reaction is
exothermic or endothermic, energy of reactant is insufficient to give product. Hence, energy must be
added so that the reactants can surmount the energy barrier to give product. The concept of different
types of energy for reaction system is clearly understood from figure 7.3 which is called energy
profile diagram. In this diagram AB represents the energy associated with reactant.
C
Potential energy
Ea
D Product
B
Reactant
A
Progress of reaction
Fig. 7.3: A plot for energy versus progress of reactions
The minimum amount of energy that must be supplied to the reactants via collisions to cross the
energy barrier for giving products is called activation energy. In the energy profile diagram , energy
equivalent to BC represents the activation energy.
The minimum amount of energy that must be associated with the reactant molecules to cross the
energy barrier for giving product is called threshold energy. In the above diagram energy equivalent
to AC represents the threshold energy.
Threshold energy = Energy of reactant + Activation energy.
7.4 Theory of Chemical Reaction

There are different theories about the rate of reaction. Out of these, two important theories of rate of
reaction are:
1. Collision theory of reaction
2. Activated complex formation theory
1. Collision theory of reaction

According to this theory, a chemical reaction can only take place when reactant molecules collide
with each other. Chemical reaction results by breaking of pre-existing some or all bonds followed by
formation of new bonds. The breaking of bonds takes place by the collision of molecules. The
number of collisions that takes place per second in given volume of the reacting system is called
collision frequency. It is denoted by Z. Greater the collision frequency, greater the rate of reaction. If
all the collisions would be effective chemical reactions would be completed in fractions of seconds. It
shows that all the collisions are not effective. The impact of collision frequency on the rate of reaction
can be explained on the basis of the following factors. These factors also affect the rate of chemical
reaction.
i. Energy factors: All the collisions are not effective. Only those collisions are effective which
occur with sufficient amount of energy. For a reaction to take place, reactant molecules should
have at least certain minimum amount of energy. The minimum quantity of energy that must
be associated with reactant molecules to give products by crossing the energy barrier is called
threshold energy. Those molecules which lack the threshold energy can't give products
although these have good agreement of collision frequency.
According to kinetic theory of gas, the fraction of molecules having energy more than threshold
energy at temperature T is, f = e–Ea/RT
Where, f = fraction of molecules having sufficient quantity of energy.
Ea = activation energy
R = universal gas constant
T = temperature
ii. Orientation factors (p): High degree of collision and sufficient quantity of energy possessed by
reactant molecules still are not the sufficient criteria for the reactions to yield products because
all the collisions may not be fruitful products. Some of the collisions, although possess sufficient
quantity of energy, may become futile. The most important factor is orientation factor. When
molecules collide with each other in proper alignment or with proper orientation then only
reactants can give the products. All the collisions are not effective. Only those collisions which
occur with proper orientation with sufficient quantity of energy can give the products. Such
types of collisions are called effective collisions. Orientation factor is also called steric factor or
probability factor because effective collision of molecules is the consequence of probability.
When molecules are properly oriented, rearrangement of atoms in a chemical reaction takes
place with minimum expenditure of time and energy. For a hypothetical reaction,
A—A + B—B 2 A—B
Improper collision
Ⓐ–Ⓐ Ⓑ–Ⓑ ⒶⒶ + ⒷⒷ ⒶⒷ Proper collision
ⒶⒷ + ⒶⒷ
ⒶⒷ
According to this theory,

Rate of reaction = Collision frequency (Z) × Fraction of molecules having sufficient energy (f)
Rate of reaction is directly proportional to rate constant (k).
Therefore, above relation can be expressed as,
k=Z×f
or, k = Z. e–Ea/RT . . . (i)
Here, Ea represents molecules achieving activation energy so that they have attained threshold
energy. When orientation factor is introduced, the above relation becomes.
k = P.Z.e–Ea/RT . . . (ii)
Here P is orientation factor or steric factor.
Simply, equation (ii) can be expressed as, Rate of reaction = P.Z.f . . . (iii)
This theory is quite satisfactory for gaseous reactions. However, this theory does not tell us about
the intermediate product formation. There are so many chemical reactions which proceed by the
formation of intermediate product.
2. Activated complex formation theory

Collision theory is inadequate to explain the rate of reaction involving complex molecules. In 1935,
Henry Eyring and Polyani gave a new theory to explain the dependence of reaction rate on
concentration, temperature and other various factors in which activated complex or transition state is
formed during transformation of reactant into product. This theory is called activated complex
formation theory or transition state theory or theory of absolute reaction rate.
The main postulates of this theory are as follows:
i. The reactant molecules are transformed into high energy containing intermediate complex
before changing into product and such intermediate complex associated with high energy is
called activated complex or transition state.
ii. The activated complex is in equilibrium with reactant and it has transient existence.
Reactants Activated complex.
iii. The activated complex decomposes into products.
Activated complex product
iv. The rate of reaction is given by the rate of decomposition of the activated complex to products.
dx
Rate of reaction dt = [activated complex] × rate of dissociation of activated complex
Above points may be summarized by the following reaction and energy profile diagram
(fig. 7.4).
A+B AB* Product
Reactant Activated complex
AB* (Activated complex)

Potential energy
Ea
Reactant (A + B)
Product
Fig. 7.4: Schematic diagram for transformation of reactants into products by forming activated complex in
exothermic reaction
Self Test
7.4 Draw the energy profile diagram of an endothermic reaction.
7.5 Factors Affecting the Rate of Chemical Reaction

All the molecules present in reacting vessels may not yield product. There may be only some
molecules which have sufficient energy to react. The rate of product formation is affected by the
number of collisions of each reacting molecules at a specified time. All the collisions are not effective.
Only those collisions are effective which collide in proper orientation with sufficient energy. There
are following factors which affect the rate of reactions.
1. Nature of reactant or product: Ionic compounds are previously ionized so the rates of reaction
are usually faster than that of covalent compounds. Ionic reactions occur in electrovalent
compound while molecular reactions occur in covalent compounds. Oxidation of nitric oxide is
faster than the oxidation of CO under similar conditions. This is because different amount of
energy is required to break a bond and different amount of energy is released in the formation
of a new bond.
2CO + O2 2CO2 (slow)
2NO + O2 2NO2 (fast)
2. Temperature: Rate of chemical reaction depends upon temperature. When temperature is
increased kinetic energy of molecules is increased and it increases the degree of collision.
Besides this, due to increase in kinetic energy, the fraction of molecules having sufficient
quantity of energy increases which increases the rate of reaction. Increase in temperature
increases the rate of reaction.
Fraction of molecules
T2 > T1
T1
T2
c
b
a
Energy of molecules
Fig. 7.5: A graph of fraction of molecules versus energy of molecules
In figure7.5, molecules lying right side from line ab have sufficient quantity of energy at
temperature T1. When temperature is increased to T2, molecules lying right side from line ac
have sufficient quantity of energy. This shows that with increase in temperature, the fraction of
molecules having sufficient energy increases. Due to increase in energy of chemical species
degree of collisions increases and it increases the rate of chemical reaction.
For each 10° rise in temperature, the rate of chemical reaction is increased by 2 to 3 fold. This is
often expressed in terms of temperature coefficient (Tα). Temperature coefficient is defined as
the ratio of rate constants for a chemical reaction at two different temperatures different by
10°C.
If Kt be the rate constant for a reaction at t°C and K(t + 10) be the rate constant for a reaction at
(t + 10)°C.
Kt + 10
Then temperature coefficient (Tα) = Kt
Generally, temperature chosen are 25°C and 35°C,

K35
Tα = K
25
Where, K35 = Rate constant for a reaction at 35°C and K25 = Rate constant for a reaction at 25°C .
The effect of temperature on the rate of reaction can be explained in terms of Arrhenius equation.
–Ea
Arrhenius equation is K = A e RT
Here, K is rate constant, A is pre-exponential factor or Arrhenius factors, Ea is activation energy,
R is universal gas constant and T is absolute temperature.
A
K= Ea
e RT
Ea
Increase the value of T decreases the value of e RT and it increases the value of K. Grater value of
K signifies the high rate of reaction. In the oxidation of NO to NO2 rate of reaction decreases
slightly on increasing the temperature.
2 NO + O2 2 NO2
In enzyme catalysed biochemical reactions, the rate of reaction is high at a certain temperature,
called optimum temperature. Below and above this temperature the rate of reaction is low.
In explosive type of reaction, the rate of reaction increases abruptly on increasing the
temperature. The natures of graph for different reactions are given below.
Rate
Rate
Rate
Temperature Temperature Temperature
a. Ordinary reaction b. Oxidation of NO to NO2 c. Explosive reaction

Rate
Rate
Optimum
Temperature
Temperature Temperature
d. Enzymatic reaction e. Oxidation of carbon
Fig. 7.6: Rate vs temperature plots for different reactions

3. Concentration: Rate of chemical reaction is appreciably affected by concentration. High

concentration of reactants possesses more numbers of chemical species per unit volume. Due to
increase in molecular density, the degree of collisions increases and thus the rate of reaction
increases. Increase in concentration increases the rate of reaction. If a burning splinter is
introduced into a gas jar filled with oxygen it glows more brightly. This is due to more
concentration of oxygen. The effect of concentration on the rate of reaction was initially studied
by Guldberg and Waage in 1867 and put forward a law which is called law of mass action. The
law of mass action states that the rate at which a chemical substance reacts is directly
proportional to its active mass or molar concentration and the rate of chemical reaction is
directly proportional to the product of active masses of reactants, where each concentration
term raised to power equal to stoichiometric coefficient present in balanced chemical equation.
For a general reaction, aA + bB products
According to the law of mass action,
Rate ∝ [A]a [B]b
or Rate = k[A]a [B]b
The effect of concentration on the rate of reaction can be expressed graphically as in figure 7.7.
Product
Concentration
Reactant
Time
Fig. 7.7: A graph concentration versus progress of reaction
Initially, concentration of reactant is more and rate of reaction is also high. As the time passes,
the concentration of reactant goes on decreasing and rate of reaction also goes on decreasing.
4. Catalyst: Catalysts are those chemical substances which increase or decrease the rate of
chemical reaction by providing the alternative path for the reaction. Catalysts are specific in
nature and catalyse a particular reaction. Catalyst takes part in chemical reaction without
changing in its mass and composition. A positive catalyst increases the rate of reaction by
decreasing the activation energy or threshold energy. Potassium chlorate should be heated upto
360°C in absence of catalyst to liberate oxygen gas. If MnO2 is used as catalyst, potassium
chlorate decomposes by the temperature of 240°C to 260°C. Here, MnO2 acts as positive catalyst.
MnO2
2 KClO3 240°C 2 KCl + 3 O2
Glycerol acts as negative catalyst in the decomposition of H2O2.

Glycerol
2 H2O2 (–ve catalyst)
2 H2O + O2
Activated complex
Reaction without catalyst
Reaction with catalyst

Ea
Ea'
Energy
Reactant ΔH
Product
Fig. 7.8: Energy profile diagram showing the effect of catalyst
The effect of catalyst on the rate of reaction can also be understood with the help of Arrhenius
equation k = A e- Ea/RT.
A
or, k = eEa/RT
1
Hence, rate of reaction ∝ activation energy
When activation energy is decreased, rate of reaction is increased. This is possible by the use of
positive catalyst. A negative catalyst increases the activation energy or threshold energy for a
reaction and it creates the alternative path having higher energy. This decreases the rate of
chemical reaction.
Self Test
7.4 Draw the energy profile diagram to show the effect of catalyst for endothermic reaction.
5. Radiation or light: Radiations may initiate some chemical reactions which are otherwise not
possible. Radiation consists of photon. Photon consists energy as shown by the relation E = hυ.
Some reactions are explosive in presence of light.
Photosynthesis occurs only in presence of sunlight. Chemistry of vision also involves light. H2
and Cl2 react on the surface of water in presence of sunlight to produce HCl as:
H2 + Cl2
hυ 2 HCl
The chemical reaction which occurs by the absorption of light is called photochemical reaction.
Unlike chemical reaction, photochemical reaction depends upon intensity of light. The rate of
photochemical reaction depends upon the wavelength of light. Rates of photochemical reactions
are not affected by temperature.
6. Surface area: Increase in surface area increases the number of molecules undergoing chemical
reaction per unit time which increases the rate of chemical reaction. For example, the rate of
production of H2 gas is more when granulated zinc is reacted with dil. HCl instead of big lumps
of zinc.
Self Test
7.5 Calculate the surface area of cube of a zinc piece having edge length 1cm.
7.6 Zinc piece having edge length 1 cm in cubic structured is transformed into 1000 smaller cubes.
Calculate
i. Surface area of one small cube.
ii. Surface area of all cubes.
iii. Change in surface area when 1 cube is changed to 1000 smaller cubes.
7. Pressure: If the reactants are present in gaseous phase the rate of chemical reaction depends
upon the pressure. Increase in pressure generally increases the number of collisions among the
molecules, causing the increase in the rate of reaction.
450°C, 200 atm
N2 (g) + 3 H2 (g) 2 NH3(g) + heat
Promoted iron
7.6 Types of Reaction Based upon Mechanism

There are different ways of classification of reactions. Depending upon the number of steps involved
in the transformation of reactants into products, chemical reactions are classified into simple and
complex reactions.
1. Simple or elementary reaction: Those chemical reactions which are supposed to take place in
single step to form products are called simple or elementary reactions. Some simple or
elementary reactions are given below.
Δ
PCl5 PCl3 + Cl2
Δ
2 HI H2 + I2
2. Complex reaction: Those chemical reactions, which are supposed to take place in more than
one elementary steps to give products are called complex chemical reactions. Complex chemical
reactions are assumed to be composed of many elementary steps. For example decomposition
of N2O5 is supposed to proceed in following steps.
Step -1 N2O5 NO2 + NO3 ] × 2 (slowest step (RDS))
Step -2 NO2 + NO3 NO2 + NO + O2
Step -3 NO + NO3 2 NO2
Overall reaction 2 N2O5 4 NO2 + O2
7.7 Concept of Rate Determining Step

Elementary reaction completes in single step. Therefore the rate of reaction means, the rate of the
elementary step. However, there are some complications to determine the rate, where complex
reaction takes place.
Let us take an example of decomposition of N2O5, mentioned in section 7.6
The decomposition of N2O5 takes place in three different steps where each step has its own velocity
or rate. Which step would determine the rate of overall reaction? Obviously, the slowest step. It is
because the rate of reaction can not be faster than the rate of slowest step. Hence, the slowest step is
the rate determining step (RDS). The slowest step or rate determining step is obtained
experimentally. A chemical reaction can not proceed faster than its slowest step.
Self Test
7.7 A motor cycle company can manufacture 20 sets of wheels, 4 sets of engines, 10 sets of rems
and 1 set of body part in a day. How many motor-cycles are manufactured by the company in
one day?
7.8 Molecularity of Reaction

Each reaction has its own stoichiometry giving the number of molecules talking part in the chemical
reaction. It is a common practice to express a chemical reaction in terms of molecularity. In the
elementary reaction, molecularity of a reaction is defined as the number of reactant species (atoms,
ions or molecules) reacting in an elementary step. In an elementary reaction, the total number of
reactant molecules present in a balanced equation gives the molecularity of the reaction.
In the reaction,
Br2 2Br
One bromine molecule undergoes decomposition to give two bromine atoms. Therefore, this is
unimolecular reaction. In case of complex reaction, the number of reactant molecules of a slowest
step is regarded as molecularity.
If only one reactant molecule undergoes decomposition or rearrangement in a chemical reaction, it is
called unimolecular reaction. Some examples are given below.
PCl5 (g) PCl3 (g)+ Cl2 (g)
O2F2 (g) O2 (g)+ F2 (g)
If two reactant molecules or atoms or ions undergo simultaneous collisions to give the product, the
reaction is called bimolecular reaction. Some examples are given below.
2 HI (g) H2 (g) + I2 (g)
CH3COOC2H5 + H2O CH3COOH + C2H5OH
NO (g) + O3 (g) NO2 (g) + O2 (g)
If three reactant molecules or atoms or ions undergo simultaneous collision to give product, the
reaction is called termolecular or trimolecualr reaction. Some examples are given below.
2 NO + O2 2 NO2
2 NO + Cl2 2NOCl
If we consider a complex chemical reaction, all atoms, ions or molecules in the balanced chemical
equation do not undergo simultaneous collision. Thus total number of molecules present in the
balanced chemical equation has no meaning to find out molecularity. In complex reaction, the
complete reaction is considered to take place through different steps. Out of these different steps, one
step is the slowest step. The number of reactant molecules which undergo simultaneous collision in
the slowest step is the molecularity of given reaction.
Higher molecularity of reaction is rare. This can be explained on the basis of kinetic theory. For a
chemical reaction to take place, reactant molecules must undergo simultaneous collision. However
the chances of simultaneous collisions go on decreasing for higher molecularity. For example, the
simultaneous collisions among three molecules are less probable than the simultaneous collision
between two molecules.
7.9 Law of Mass Action and the Rate Law Equation

The effect of concentration on the rate of reaction was studied by Guldberg and Waage in 1867 and
they gave a law which is called law of mass action. The law of mass action states, the rate of reaction
is directly proportional to the product of molar concentration of reactants where each concentration
term raised to power equal to stoichiometric coefficient present in the balanced chemical equation.
For a general reaction,
aA+bB cC+dD
According to law of mass action, Rate of reaction (r1) ∝ [A]a [B]b . . . (i)
From equation (i) it is revealed that the rate of reaction depends upon 'a' concentration term of A and
'b' concentration term of B. The rate of overall reaction depends upon (a+b) concentration term.
If the reaction is studied experimentally, the rate of reaction may or may not depend upon the
concentration terms present in balanced chemical equation. In the above example, the rate of reaction
may or may not depend upon 'a' concentration term of A and 'b' concentration term of B. Let the rate
of reaction depends upon 'p' concentration term of A and 'q' concentration tem of B. Here, the values
of p and q may or may not equal to a and b, respectively.
On the basis of this assumption, the rate of reaction is expressed as,
Rate ∝ [A]p [B]q
Rate = k[A]p [B]q . . . (ii)
Where k is proportionality constant and is called rate constant p and q are actual concentration terms
on which rate of reaction depends. The value of p and q are determined experimentally. Their values
may be zero, negative, positive or fractional. The equation (ii) is called rate law equation.
Rate law equation is a mathematical expression which shows the actual dependence of concentration
term on the rate of reaction. Rate law equation is determined experimentally.
To make the concept clear between law of mass action and rate law equation let us take a specific
example of decomposition of N2O5
2 N2O5 4 NO2 + O2
According to law of mass action, Rate ∝ [N2O5]2 . . . (iii)
The law of mass action, reveals that the rate of reaction depends upon two concentration terms of
N2O5. If the mechanism of the chemical reaction is studied, the following reaction pattern for the
gaseous phase decomposition of energized N2O5 is obtained experimentally.
Step -1
N2O5 NO2 + NO3 ]× 2 (lowest step (RDS))
Step -2 NO2 + NO3 NO2 + NO + O2
Step -3 NO + NO3 2 NO2
Overall step 2 N2O5 4 NO2 + O2
Out of these three different steps, the first step is the slowest step and it is rate determining step. The
overall rate of reaction depends upon slowest step. Here, the slowest step consists only one reactant
term.
According to the experimental finding,
Rate ∝ [N2O5]
Rate = k[N2O5] . . . (iv)
The actual concentration term on which the rate of reaction depends is one. Therefore, equation (iv)
is rate law equation.
Rate constant
Let us consider a general reaction
aA+bB cC+dD
According to the law of mass action the rate of reaction is expressed as, Rate ∝ [A]a [B]b . . . (i)
But, if the mechanism of the reaction is observed experimentally, the rate law equation may be same
or different from what is expected from law of mass action. The mathematical expression showing
the actual dependence of concentration term on the rate of reaction is rate law equation. For the
above case, let the rate law equation is
Rate ∝ [A]p [B]q
Rate = k[A]p [B]q . . . (ii)
Here, p and q are actual concentration term on which the rate of reaction depends. Equation (ii) is
rate law equation where k is proportionality constant and is called rate constant or velocity constant
or specific rate of reaction.
From equation (ii), when molar concentration of A and B are unity then Rate = k.
Hence rate constant is defined as the rate of reaction when concentrations of all the reactant terms
are unity. It is also called specific rate of reaction.
Characteristics of rate constant
Some important characteristics of rate constant are given below.
i. Rate constant is the measure of rate of reaction. Larger the value of rate constant, greater will be
the rate of reaction.
ii. Rate constant is independent of the concentration of reactants.
iii. Rate constant is the characteristics value of each reaction. Different reactions have different
values of rate constants at a particular temperature.
iv. Rate constant depends upon temperature. On changing the temperature, the value of rate
constant is also changed.
v. The unit of rate constant depends upon the order of reaction.
7.10 Order of Reaction

Order of reaction assigns the number of reactant molecules on which the rate of chemical reaction
depends. Order of reaction with respect to one of the reactants is the power of concentration term of
the reactant in the rate law equation. The over all order of reaction is the sum of the powers
(exponents) of the concentration terms of reactants present in the rate law equation. As we have
discussed earlier, molecularity of a reaction is a theoretical concept. Unlike molecularity of a reaction,
the order of reaction is experimental value. Order of reaction is determined on the basis of rate law
equation.
For a general reaction, a A + b B Product
dx
Let, the rate law equation be, Rate ⎛ dt⎞ = k [A]p [B]q
⎝ ⎠
The order of reaction with respect to A = p

The order of reaction with respect to B = q
Overall order of reaction = p + q
From this, it is clear that order of a reaction is determined with respect to each kind of individual
reactant as well as with respect to all the participating reactants. Overall order of reaction may also
be defined as the sum of the powers of each concentration terms present in the rate law equation.
Since order of reaction is determined experimentally, it may be zero, positive, negative or fractional.
If reaction environment for a chemical reaction is altered, the order of reaction is also changed. To
understand the order of reaction let us take given example.
2NO2 + F2 2NO2F
the most likely mechanism is,
k1
Step – 1 2NO2 + F2 2NO2 + 2 F (slow)
k2
Step – 2 2NO2 + 2 F 2NO2F (fast)
Overall reaction k3
2NO2 + F2 2NO2F
Apparently, both steps are trimolecular. Experiment shows that the first step is slowest step and it is
dx
rate determining step. The rate ⎛ dt⎞ of the reaction can be expressed as,
⎝ ⎠
dx
dt = k1[NO2] [F2]
This shows that, the rate of reaction depends upon the concentration of NO2 and F2 both.
The order of reaction with respect to NO2= 1
The order of reaction with respect to F2 = 1
The overall order of reaction = 1 + 1 = 2.
Units of Rate Constant

Different the order of reactions, different will be the unit of rate constant. The units of rate constant
are given below.
Let us consider a reaction, A Product
Let the order of reaction be n. It means the rate of reaction depends upon 'n' concentration term of A.
Rate ∝ [A]n
dx
or, dt = k[A]n , where k is proportionality constant and is called rate constant
dx/dt mol lit–1 time–1

or, k = [A]n = (mol lit-1 )n = mol1 – n Ln – 1 time–1
For zero order reaction, n = 0 unit of k = mol L–1 time–1

For first order reaction, n = 1 unit of k = time–1
For second order reaction, n = 2 unit of k = mol–1 L time–1
For third order reaction, n = 3 unit of k = mol–2 L2 time–1
Self Test
7.8 The reaction between NO2 and CO takes place as follows.
a. At lower temperature the reaction mechanism is
Step – 1 NO2 + NO2 NO3 + NO (slow)
Step – 2 NO3 + CO NO2 + CO2 (fast)
Overall reaction NO2 + CO NO + CO2

b. Above 500K temperature, the reaction mechanism is
slow O O O
NO2 + CO
N C
O O O (fast)
NO + CO2
N C
Overall reaction NO2 + CO NO + CO2

7.8 Express the rate law equation for reaction of NO2 and CO below approximate 500 K
temperature. What is the order of reaction?
dx 2
Ans: = K[NO2] (second order reaction)
dt
7.9 Express the rate law equation for the reaction of NO2 and CO above approximate 500 K
temperature. What is the order of reaction?
dx
Ans: = k[NO2] [CO] (second order reaction)
dt
7.10 For a particular reaction, under different conditions, having same order, is it necessary to have
same rate law equation?
Ans: No
Difference between molecularity and order of reaction

For some reactions, the molecularity and order are same, but it is not true for all the cases. The
differences between molecularity and order of reaction are given below.
Molecularity Order
1. It is the number of atoms or ions or 1. It is the sum of the powers which are raised in
molecules which involve in elementary each concentration term in a rate law equation.
step of reaction so as to give product in a
chemical reaction.
2. It is always a natural number (whole 2. It may be zero, negative, positive or fractional.
number except zero). For e.g.,
hυ
H2(g) + Cl2 (g) 2HCl (g) is (Zero order)
2N2O5(g) 4NO2 (g) + O2 is (1st order)
Δ
CH3CHO (g) CH4 (g)+CO (g) (1.5 order)
3O3 (g) 3O2 (g) (–1 order w.r. to O2)
3. It is determined theoretically. 3. It is always determined experimentally.
4. It is invariant. It means on changing the 4. It is variant. On changing the condition, the

condition, the molecularity of reaction order of reaction may change. For example,
does not change. hydrolysis of ethylacetate in acidic medium is of
first order while hydrolysis in alkaline medium
is of second order.
5. For simple reaction, the molecularity can 5. Even for simple reaction, the order of reaction
be determined from balanced can not be determined from balanced
stoichiometric equation. It means, for stoichiometric elementary reaction. The order of
elementary reaction, the molecularity is reaction may not be equal to the number of
equal to the number of reactant reactant molecules present. e.g., For a reaction
molecules present e.g. on the surface of water.
hυ hυ
H2 (g) + Cl2 (g) 2 HCl (g) H2 (g) + Cl2 (g) 2HCl (g)
The molecularity is 2. The order of reaction is zero.
7.10.1 Zero-Order Reaction

The chemical reaction, in which rate of reaction does not depend upon the change in concentration of
reactant is called zero-order reaction. In other words, zero-order reaction is independent to
concentration of reactant. The rate of product formation depends upon the amount of reactant
change.
Some examples of zero-order reaction are given below.
1. Formation of HCl gas from H2 and Cl2 gas in presence of sunlight on the surface of water.
hυ
H2(g) + Cl2(g) 2 HCl (g)
At time = 0 a mole b mole 0
At time = t (a – x) mole (b – x) mole 2x
H2
and
Cl2
Fig.7.9: Reaction of hydrogen and chlorine in presence of radiation on the surface of water.
When light is passed, H2 and Cl2 combine to give HCl gas. Two volumes of reactants give two
volumes of products. So there is no change in volume. As soon as HCl gas is formed it dissolves
in water and water rushes up. Let V1 be the volume of reactant and V2 be the volume of
product.
Number of mole of Before reaction After reaction Result

a a–x a a–x
a
V1 V2 V1 = V2
b b–x b b–x
b
V1 V2 V1 = V2
Due to chemical reaction, the amount of reactants change but the concentration of reactant does
not change because the proportion of decreases in number of moles of reactant to volume in
each step is same. In this case rate of reaction depends upon intensity of light. During chemical
reaction, the amount of reactant changes but concentration of reactant does not change. The rate
of reaction neither depends upon the concentration of H2 nor the concentration of Cl2.
Order of reaction with respect to H2= 0
Order of reaction with respect to Cl2 = 0
Overall order of reaction is zero.
2. Catalytic decomposition of ammonia gas: When decomposition of ammonia is carried out on
the surface of molybdenum or tungsten,
Mo or W
2 NH3 (g) N2 (g) + 3H2 (g)
the rate of reaction does not depend upon the concentration of NH3. To carry out the chemical
reaction the gas molecules should be desorbed on the catalyst surface. When catalyst surface is
limited and concentration of NH3 is high, rate of product formation depends upon the surface
area of catalyst rather than the concentration of ammonia.
The rate law equation for the above reaction is
dx
dt = k[NH3]
0
In this case, the rate of reaction is zero-order with respect to ammonia.

3. Enzyme catalysed reaction: In enzyme catalysed reaction, the rate of reaction depends upon the
concentration of enzyme but not upon the concentration of substrate. So the reaction is first
order reaction with respect to enzyme and zero-order reaction with respect to the substrate.
Enzyme
Substrate Product.
Rate = k [Enzyme]1 [Substrate]0
Kinetics of Zero-Order Reaction

Let us consider a reaction in which reactant A changes into product. Let 'a' be the initial
concentration of reactant A. After certain time t, x mole of reactant changes into product.
A product
At time = 0 a 0
At time = t (a–x) x
For zero order reaction, rate of reaction depends upon zero concentration term of reactant.
Rate ∝ [A]0
dx
or, dt = k0(a–x) , where k0 is proportionality constant and is called rate constant or velocity
0
constant for zero order reaction

dx
or, dt = k0 . . . (i)
Equation (i) is differential rate equation for zero order reaction.

or dx = k0dt
Integrating equation (i), we get

∫dx = k0∫dt
or x = k0t + C . . . (ii)
where C is integration constant.
When t = 0, x = 0 then putting the value of t and x in equation (ii), we get C = 0. Now equation
(ii) changes to
x = k0t
x
or k0 = t . . . (iii)
Equation (iii) is integrated rate equation for zero order reaction.

When amount of reactant changes from x = 0 to x = x with in time t = 0 to t = t, integrating the
equation dx = k0dt, we get
x t
⌠ dx = k ⌠ dt
⌡ ⌡
0
0 0
x t
or, [x]0 = k0 [t]0
or, (x – 0) = k0(t – 0)
or, x = k0t
x
or, k0 = t
Characteristics of zero-order reaction: Unit, Half life and Kinetic Plot

a. Unit of rate constant
x concentration mol. lit–1
k0 = t = time = time = mol L–1 time–1
b. Half life period (t1/2): The time at which the concentration of reactant decreases to half of its
initial value is called half life period. It is denoted by t1/2. At half life period, time t = t1/2 and
a
x= 2.
a/2
Now the rate law equation becomes k0 = t
1/2
a
or t1/2 = 2k . . . (iv)
0
or t1/2∝ a.
For zero order reaction, half life period is directly proportional to the initial concentration of
reactant.
c. Kinetic plots: For zero-order reaction,
x
k0 = t
or, x = k0t
Concentration
Time
Fig. 7.10: A graph of concentration versus time for zero-order reaction.
This equation is in the form of y = mx equation. Therefore, if a graph of concentration (x) versus
time is plotted, a strength line passing through the origin is obtained (fig. 7.10). This verifies the
validity of zero-order reaction.
Self Test
7.10 Plot a logarithmic graph for zero-order reaction.
Hints, x = kot, logx = log ko + logt
7.10.2 First Order Reaction

The chemical reaction in which rate of reaction depends upon only one concentration term is called
first order reaction.
Some examples of first order reaction are given below.
i. Decomposition of H2O2
dx
2 H2O2 H2O + O2, dt = K1 [H2O2]
1
ii. Decomposition of N2O5

dx
2N2O5 4NO2 + O2, dt = K1 [N2O5]
1
iii. Decomposition of NH4NO2

dx
NH4NO2 N2 + 2 H2O, dt = K1 [NH4NO2]
1
iv. Decomposition of SO2Cl2

dx
SO2Cl2 SO2 + Cl2, dt = K1 [SO2Cl2]
1
v. Hydrolysis of ethyl acetate in acidic medium

H+ dx
dt = K1[CH3COOC2H5]
1
CH3COOC2H5 + H2O CH3COOH + C2H5OH,
vi. All radioactive disintegration reactions

Kinetics of first order reaction: Differential and Integrated Rate Equation

Let us consider a general first order reaction in which reactant A changes to product. Let 'a' mol L–1
be the initial concentration of reactant. After certain time t, x mol of reactant changes into product.
Then concentration of reactant at time t is (a – x) mol L–1.
A Product
At time = 0 a 0
For first order reaction, the rate of reaction depends upon only one concentration term.
Rate ∝ [A]1
dx
or, dt = (a – x)
dx
or, dt = k1(a – x) . . . (i)
Where, k1 is proportionality constant and is called rate constant or velocity constant or specific rate of
reaction. Equation (i) is the differential rate equation for the first order reaction.
dx = k1 (a – x)dt
dx
or, (a – x) = k1dt
Integrating the equation, we get
dx
⌠
⌡ (a – x) = ⌠
⌡
k1dt
ln(a – x) dx ln(ax + b)
or, (–1) = k1 t + C [∵ ⌡
⌠ (ax + b) = a +C]
Where C is integration constant

or, – ln(a – x) = k1t + C . . . (ii)
when time t = 0, x = 0, then equation (ii) changes to –ln(a – 0) = k1 × 0 + C
or, – ln a = C
Putting the value of C in equation (ii), we get
or, – ln (a – x) = k1 t – lna
or, ln a – ln (a – x) = k1t
a a
or, ln (a – x) = k1t [∵ ln a – ln b = ln b ]
1 a
or, k1 = t ln (a – x) . . . (iii)
2.303 a
or, k1 = t log (a – x) [∵ ln a = 2.303 log a] . . . (iv)
Equation (iii) and (iv) are different forms of integrated rate equation for first order reaction.
Characteristics of first order reaction: Unit, Half-Life and the Kinetic Plot
a. Unit of rate constant
1 a 1
k1 = t ln (a – x) = time = time–1
b. Half-life period (t1/2): Half life period is defined as the time in which concentration of reactant
decreases to half of its initial value. It is denoted by t1/2.
a
At half life period, time t = t1/2 and reactant changed into product x = 2 .
Now, the expression becomes,

1 a
k1 = t ln
1/2
⎛a – a ⎞
⎝ 2⎠
1 a 1
t1/2 = k ln a/2 = k ln2
1 1
0.693
∴ t1/2 = k1 . . . (v)
For first order reaction half life period is independent to initial concentration.
c. Kinetic plot: The rate constant for first order reaction is
1 a
k1 = t ln a – x
a
or ln a – x = k1t . . . (vi)
a
The equation (vi) is in the form of y = mx. If a graph of ln a – x versus time is plotted, a straight
line passing through the origin is obtained.
a
ln (a –x)
Slop = k1
time (t) →
a
Fig.7.11: A graph of ln versus time for first order reaction.
(a – x)
Equation (vi) can be expressed as,

ln a – ln (a – x) = k1 t
or ln (a – x) = – k1t + ln a . . . (vii)
Equation (vii) is in the form of y = – mx + c. If a graph of ln(a – x) versus time is plotted a
straight line with negative slop is obtained.
↑
ln (a – x)
Slop = – k
∴ k1 = (–) × slope
time (t) →
Fig.7.12: A graph of ln(a – x) versus time for first order reaction.
The natures of graphs mentioned above justify the validity of first order reaction.
7.10.3 Pseudo-Order Reaction

The chemical reaction which seems to be of higher order kinetics but actually follows the lower order
kinetics when one of the reactants is present in large excess is called pseudo-order reaction or
apparent order of reaction.
Let us take some examples of pseudo-order reaction.
i. Hydrolysis of ethyl acetate in acidic medium
H+
CH3COOC2H5 + H2O CH3COOH + C2H5OH
Ethyal acetate Excess Acetic acid
The rate of chemical reaction depends upon concentration of both ethyl acetate and water. The
rate law equation can be expressed as,
Rate ∝ [H2O] [CH3COOC2H5]
Rate = k' [H2O] [CH3COOC2H5] . . . (i)
Where k' is proportionality constant and is called rate constant. Since water is present in large
excess, its concentration remains constant. Therefore, equation (i) can be expressed as,
Rate = k [CH3COOC2H5] . . . (ii)
Where, k = k' [H2O]
Although rate of reaction depends upon the concentration of water as well as ethyl acetate, the
rate of reaction is practically determined by the concentration of ethyl acetate. Therefore,
although the reaction seems to be second order, it actually follows the first order kinetics. This
reaction is also called Pseudo-first order reaction.
ii. Hydrolysis of cane sugar
H+
C12 H22O11 + H2O C6H12O6 + C6H12O6
For the hydrolysis of cane sugar excess of water is used. During chemical reaction, the
concentration of water is almost constant. So rate of chemical reaction practically depends upon
the concentration of cane sugar. Hence this is an example of Pseudo first order reaction.
Rate = k [C12H22O11]
7.10.4 Second Order Reaction

The chemical reaction in which rate of reaction depends upon two concentration terms of reactant is
called second order reaction.
Some examples of second order reactions are given below.

i. Hydrolysis of ethyl acetate in alkaline medium
CH3COOC2H5 + NaOH CH3COONa + C2H5OH
(1 : 1 ratio)
dx
The rate law equation is, dt = k [CH3COOC2H5] [NaOH]
ii. Dissociation of HI
2 HI H2 + I2
dx
The rate law equation is, dt = k[HI]2
iii. Reaction between potassium persulphate and potassium iodide

K2S2O8 + 2 KI 2 K2SO4+ I2
dx
The rate law equation is, dt = k [K2S2O8] [KI]
iv. Hydrogenation of ethylene

CH2 = CH2 + H2 CH3CH3
dx
The rate law equation is, dt =k[C2H4] [H2]
v. Thermal decomposition of N2O

Δ
2 N2O 2 N2 + O2
dx
The rate law equation is, dt = k [N2O]2
Kinetics of second order reaction

In second order reaction, the rate of reaction depends upon either two concentration terms of the
same reactant or each concentration term of two different reactants. If rate of reaction depends upon
each concentration term of different reactants with same initial concentration, the kinetics is similar
to the rate involving two concentration terms of the same reactant.
Case I: Second order reaction in which rate of reaction depends upon two concentration terms of
the same reactant.
Let us take a general example of second order reaction.
Let us consider a general second order reaction in which reactant A changes to product. Let a mol L–1
be the initial concentration of reactant. Then concentration of reactant at time t is (a – x) mol L–1.
A Product
At time = 0 a 0
For second order reaction, the rate of reaction depends upon only one concentration term.
Rate ∝ [A]2
dx
or, dt = (a – x)
2
dx
or, dt = k2(a – x)
2 . . . (i)
Here, k2 is proportionality constant and is called rate constant for second order reaction. Equation (i)
is the differential rate law equation for the second order reaction. Now equation (i) can be expressed
as
dx
or, (a – x)2 = k2dt
Integrating the equation, we get
dx
⌠ = k2⌠ dt
⌡ (a – x)2 ⌡
or, ⌠ (a–x) –2dx = k2⌠ dt
⌡ ⌡
(a–x)–2+1
or, (–2 + 1) (–1) = k2t + C
1
or, (a –x) = k2t + C . . . (ii)
When t = 0, x = 0. Now equation (ii) becomes

1
or, (a–0) = k2× 0 + C
1
or, C =a
Now putting the value of c in equation (ii), we get

1 1
or, (a – x) – a = k2t
a–(a–x)
or, a(a–x) = k2t
a–a+x
or, a(a–x) = k2t
x
or, a(a–x) = k2t
1 x
∴ k2 = t a(a – x) . . . (iii)
Equation (iii) is the integrated rate equation for second order reaction in which rate of reaction
depends upon two concentration terms of the same reactant.
Case II: Second order reaction in which rate of reaction depends upon two different reactants with
different initial concentration.
Let us consider a reaction.
A + B Product
At time = 0 a b 0
At time = t (a–x) (b–x) 0
Let, initial concentration of reactants A and B are a mol L–1 and b mol L–1 respectively. After certain
time, x moles of reactants change into products. The concentrations of reactants A and B at time t are
(a–x) mol L–1 and (b – x) mol L–1, respectively.
For second order reaction,
Rate ∝ [A] [B]
dx
or, dt = (a – x) (b – x)
dx
or, dt = k2(a – x)(b – x) . . . (i)
Here, k2 is proportionality constant and is called rate constant for second order reaction. Equation
(i) is the differential rate law equation for the second order reaction in which rate of reaction depends
upon concentration terms of two different reactants with different initial concentrations.
The integrated rate law equation for such reactions is,
1 b(a–x)
k2 = t(a–b) ln a(b–x) . . . (ii)
7.10.5 Third Order Reaction

The chemical reaction in which rate of reaction depends upon three concentration terms of reactant is
called third order reaction.
Some examples of third order reactions are given below.
i. Combination of NO and O2
2 NO + O2 2 NO2
dx
The rate law equation is dt = k[NO]2 [O2]
ii. The combination of NO and Br2

2 NO + Br2 2 NOBr
dx
The rate law equation is dt = k[NO]2 [Br2]
iii. Combination of NO and Cl2

2 NO + Cl2 2 NOCl
dx
The rate law equation is, dt = k[NO]2 [Cl2]
iv. Reaction between FeCl3 and SnCl2

2 FeCl3 + SnCl2 2FeCl2 + SnCl4
dx
The rate law equation is, dt =k[FeCl3]2 [SnCl2]
7.11 Methods of Determination of Order of Reaction

Order of reaction can be determined by any of the following methods.
1. Initial concentration measurement method 2. Graphical method
3. Half-life period measurement method 4. Integration method
1. Initial concentration method: When concentration of reactant is changed, it may change the
rate of reaction. The extent of change in rate of reaction by changing the concentration of
reactant is different for different order of reaction. This method is illustrated here.
For a reaction, A Product
i. For zero order reaction,
Rate = k0 [A]0
When concentration is increased or decreased, there is no change in rate of reaction.
ii. For first order reaction,
Initial Rate = k1 [A]
New rate = k1 [nA] = n k1A
New rate = n × initial rate
When concentration is increased or decreased by n times the rate or reaction is also increased or
decreased by n times correspondingly
iii. For second order reaction,
Initial rate = k2[A]2
If the concentration of A is increased or decreased by n times
New rate = k2 [nA]2 = n2 × k2[A]2 = n2 × initial rate
When concentration is increased or decreased by n times the rate of reaction is also increased or
decreased by n2 times
iv. For third order reaction,
Initial rate = k3 [A]3
If the concentration is increased or decreased by n times
New rate = k3 [nA]3 = n3 × k3[A]3 = n3 × initial rate
When the concentration is increased or decreased by n times the rate of reaction is also
increased or decreased by n3 times.
If concentration is Rate of reaction is increased by

increased by st nd rd
Zero order reaction 1 order reaction 2 order reaction 3 order reaction
1 2 3
2 times 2° = 1 2 =2 2 =4 2 =8
0 1 2 3
3 times 3 =1 3 =3 3 =9 3 = 27
0 1 2 3
4 times 4 =1 4 =4 4 = 16 4 = 64
2. Graphical method: Different nature of graphs verify the order of reactions. These are described
already.
3. Half-life period method: To determine the order of reaction, the co-relations between initial
concentration of reactant and half life period are studied. For example, half-life period is
directly proportional to initial concentration of reactant for zero-order reaction. Half-life period
is independent to initial concentration of reactant for first order reaction. For nth order of
reaction, t1/2 ∝ a1–n. If two reactions are progress with different initial concentration a1 and a2
(t1/2)1 a1 1–n
with respective half-lives (t1/2)1 and (t1/2)2 then (t ) = ⎛a ⎞ .
1/2 2 ⎝ 2⎠
4. Integration method: In this method, the value of rate constant is calculated by using integrated
rate equation. For different experimental data carried out under similar conditions, the value of
K is found to be almost same. The rate constants for different order of reactions.
Order or Differential rate Integrated rate

Half life period Kinetic plot
reaction equation equation
Concentration
dx x a
0
dt = k0 k0 = t t1/2 = 2k
0
Time
a
ln (a –x)
dx 1 a 0.693 ln (a – x)
1
dt = k1 (a – x) K1 = t ln (a – x) t1/2 = k
1
Time (t) →
Time (t) →
1
(a –x)
dx 2 1 x 1
dt = k2 (a – x) K2 = t a(a – x) t1/2 = ak
2
Time (t) →
1 (a–x)
Different initial
dx 1 b(a – x) concentration (a –b) ln (b–x)
dt = k2(a–x) (b–x) K2= t(a–b) ln a(b – x) corresponds to
different half life period
Time (t) →
Some Solved Numerical Problems

Example 5.1: Hydrogen and nitrogen oxide react according to the following equation.
2NO + 2H2 → H2O (g) + N2(g)
Experiments were performed at 800°C in order to determine the order of reaction and the
following results were obtained.
Initial concentration of Initial concentration of Initial rate of production of
-1 -1 -1
nitrogen oxide (mole litre ) hydrogen (mole litre) nitrogen (mole litre sec )
-3 -3 -3
i. 6 × 10 1 × 10 3 × 10
-3 -3 -3
ii. 6 × 10 2 × 10 6 × 10
-3 -3 -3
iii. 6 × 10 3 × 10 9 × 10
-3 -3 -3
iv. 1 × 10 6 × 10 0.5 × 10
-3 -3 -3
v. 2 × 10 6 × 10 2.0 × 10
-3 -3 -3
vi. 3 × 10 6 × 10 4.5 × 10
a. What is the order of this reaction with respect to (i) nitrogen oxide (ii) hydrogen?
b. Write the rate equation for the reaction of nitrogen oxide with hydrogen.
c. What is the unit of rate constant, K?
d. Why are chemists interested in obtaining order of reaction and rate equations?
Solution
Let rate law equation be
Rate = K[NO]x [H2]y ... (i)
(a) (i) To find the order of reaction with respect to nitrogen oxide.
Let us take the case where concentration of hydrogen is constant.
Rate = K[NO]x
From (iv)
0.5×10-3 = K (1 × 10-3)x
0.5 × 10-3
∴ K = (1 × 10-3)x ... (1)
From (v)
2 × 10-3 = K (2 × 10-3)x
2 × 10-3
∴ K = (2 × 10-3)x ... (2)
From equation (1) and (2),

0.5 × 10-3 2 × 10-3
(1 × 10-3)x = (2 × 10-3)x
( )
x
2 × 10-3 2 × 10-3
(2 × 10-3)x = (2 × 10-3)x
2x = 4
2x = 22
x=2
∴ Order of reaction with respect to NO is 2.
(ii)To find the order of reaction with respect to hydrogen. Let us take the cases where concentration of NO is
constant.
Rate = K[H2]y
From (i)
3 × 10-3 = K (1 × 10-3)y
3 × 10-3
∴ K = (1 × 10-3)y ... (1)
From (ii)
6 × 10-3 = K (2 × 10-3)y
6 × 10-3
∴ K = (2 × 10-3)y ... (2)
From equation (1) and (2),

3 × 10-3 6 × 10-3
(1 × 10-3)y = (2 × 10-3)y
( )
y
2 × 10-3 6 × 10-3
1 × 10-3 = 3 × 10-3
2y = 2
2y = (2)1
∴ y = 1.
Hence, the reaction is 1st order with respect to H2.
(b) Rate equation from equation (i) is

Rate = K [NO]x [H2]y
Putting the value of x and y
Rate = K [NO]2 [H2]
(c) Unit of rate constant K is mole-2 lit2 sec-1
(d) Rate equation shows the actual dependence of concentration on the rate of equation. But actual dependence
of concentration can't be found out by balanced chemical equation. The order of chemical reaction shows
the actual dependence of concentration to the rate equations. The relation of initial concentration and half
life also can be found out from order of reaction. Therefore, chemists are interested in obtaining order of
reaction and rate equation.
Example 5.2: For a hypothetical reaction, 2M + N → product
The following data are given.
-1 -1 -1 -1
Expt. No. Initial conc of M (mol L ) Initial conc of N (mol L ) Initial rate (mol L sec )
2
I 0.10 0.20 3 × 10
3
II 0.30 0.40 3.6 × 10
4
III 0.30 0.80 1.44 × 10
IV 0.30 1.60 A
V 0.60 0.80 B
VI 0.10 0.40 C
From the above data:
i. Find the overall order of the reaction.
ii. Calculate the value of A, B and C.
Solution
Reaction, 2M + N Products
dx
Let the rate law equation be dt = K[M]x [N]y
From expt. no. I, 3 × 102 = K (0.10)x. (0.20)y …(1)

From expt. no. II, 3.6 × 103= K (0.30)x. (0.40)y …(2)
From expt. no. III, 1.44 × 104= K (0.30)x . (0.80)y …(3)
Now, equation (3) is divided by equation (2)
1.44 × 104 K (0.30)x. (0.80)y
3.6 × 103 = K (0.30)x. (0.40)y
( )
0.80 y
or 4 = 0.40
or 4 = 2y
or 22 = 2y
∴ y =2
Now equation (2) is divided by equation (1), we get
3.6 × 103 K(0.30)x. (0.40)y
3 × 102 = K(0.10)x (0.20)y
( )( )
0.30 0.40
x x
12 = 0.10 0.20
12 = 3x . 2y
or 12 = 3x . 22
or 12 = 3x . 4
or 3x =3
∴ x =1
dx
Now, putting the value of x and y in rate law equation dt = K[M]1 [N]2
i. The order of reaction w.r to M = 1

The order of reaction w.r to N = 2
Overall order of reaction = 1 + 2 = 3
ii. Calculation of value of A, B and C.
Calculating the value of K,
From experiment no (1)
3 × 102 = K (0.10)1 . (0.20)2
3 × 102
K = (0.10) (0.20)2 = 75000 = 7.5 × 104 mol–2 lit2 sec–1
From experiment no (iv)

dx
dt = K(0.30) (1.60)
1 2
= 7.5 × 104 × 0.30 × (1.60)2

A = 5.76 × 104 mol lit–1 sec–1
From experiment no (v)
dx
dt = K(0.60) (0.80)
2
= 7.5 × 104 × 0.60 × (0.80)2

B = 2.88 × 104 mol lit–1 sec–1
From experiment no. (vi)
dx
dt = K(0.10) (0.40)
1 2
C = 7.5 × 104 × 0.10 × (0.40)2 = 1.2 × 103 mol. lit–1sec–1
Solved Questions
1. Give a chemical reaction which follows the first order kinetics.
¬ Decomposition of PCl5 into PCl3 and Cl2 is an example of 1st order chemical reaction.
PCl5 PCl3 + Cl2
It is first order reaction because the rate of chemical reaction depends upon only one concentration of PCl5. It
can be written as
Rate ∝ [PCl5]1
dx
dt = K1 [PCl5]
2. What is activation energy?
¬ The minimum amount of energy that must be supplied to the reactant to cross the energy barrier so as to
give the product is called activation energy.
3. If 75% of a first order reaction is completed in 32 minutes, when will be 50% of the
reaction completed?
¬ Integrated rate equation for first order reaction is
2.303 a
t = K log a – x
Using the equation for both situations, we get
2.303 a
32 = K log 75
a – 100a
2.303
or, 32 = K log 4 ... (i)
2.303 a
and t = K log 50a
a – 100
2.303
or, t = K log 2 ... (ii)
Dividing equation (i) by (ii), we get
32 log 4
t = log 2
∴ t = 16 minutes
4. A first order reaction has half-life period of 69.3 seconds. What will be the rate of
reaction when the concentration of the reactant is 0.1 mol/L?
¬ For first order reaction:
0.693
K= t
1/2
0.693
So, K = 69.3 sec–1 = 10-2 sec–1.
Putting the value of K in first order rate equation, Rate = K[A]
Rate = 10–2 × 0.1 = 10–3 Mol lit–1 sec–1.
5. The reaction X + Y products is a second order reaction. Write three
different rate law expressions which may be true to the above reaction.
¬ Order of reaction is the sum of the powers in the rate law equation. To be, x + y product, a second
order reaction the following expressions can be written which may be true.
i. Rate = k2 [x]2 [Y]0 order of reaction = 2 + 0 = 2
ii. Rate = k2 [x]0 [Y]2 order of reaction = 0 + 2 = 2
iii. Rare = k2 [x] [Y] order of reaction = 1 + 1 = 2.
6. What is meant by order of a reaction? State the order of reaction having rate
constant 2×10-2 mol L-1S-1.
¬ The sum of the power of concentration in the rate law equation is called order of chemical reaction.
Given rate constant = 2 × 10-2 mol lit-1 sec-1
Unit of K for nth order reaction = (mol)1-n litn - 1 time-1.
or (mol)1 - n litn - 1 time-1 = mol lit-1 sec-1
or 1 - n = 1.
∴ n = 0.
Hence the given reaction is of zero order reaction.
7. Define the half life of a reaction.
¬ Half-life period is the time required for reactant to change into half of its initial amount. It is denoted by t1/2
Questions
a. Rate of reaction b. Average rate of reaction
c. Instantaneous rate of reaction d. Equivalence rate of reaction
e. Effective collision f. Proper orientation
g. Rate law equation h. Pseudo-order reaction
i. First order reaction j. Half-life period
k. Activation energy l . Threshold energy
2. Draw the energy profile diagram to show the effect of catalyst on the rate of reaction. Justify.
3. What is the order of reaction whose rate constant has same unit as the rate of reaction?
4. Define the half-life period of a reaction. The half-life periods of two reactions A and B are
3.21×102 min. and 569 min respectively. Which of these undergoes nuclear reaction faster? is a
faster reaction?
5. Write the difference between molecularity and order of reaction.
6. Identify the order of reaction, if unit of rate constant are (a) min–1 (b) mol L–1.
7. If the rate of reaction is doubled when concentration of A is doubled but there is no effect in rate
with change in concentration of B. (a) Write rate law equation (b) Find out the unit of rate
constant.
8. Write all possible rate law expression for the reaction:
M+N Products, if the order of the reaction is 3.
9. What are the effects of collision frequency, energy of activation and orientation factor in the rate
of reaction?
10. Write the rate expression for the reaction:
2N2O5 4NO2 + O2
11. Distinguish rate and rate constant of a reaction.
1. Explain the factors which affect the rate of reaction.
2. Show your acquaintance with collision theory of reaction.
3. What do you mean by rate of a reaction? How do the following factor affect rate of reactions:
(a) Surface area (b) temperature (c) catalyst.
4. Write short notes on (a) Half life period (b) First order reaction (c) Collision theory of reactions
Numerical Problems
1. The rate of reaction for, A = B increases by two times when its concentration is increased by 4
times. What is rate law? (Rate = [A]1/2).
Ans: Rate = [A]1/2
2. The rate constant of a reaction is 2.4 × 10-4 L mole−1s−1. What is the order of reaction?
Ans: 2nd
3. Find the three-fourth life of a first order reaction with rate constant 7.4 × 10−5 s−1.
Ans: 1.87 × 104 s
4. Calculate the half-life period of a first order reaction when the rate constant is 5 year–1.
Ans: 0.1386 years.
5. Suppose that the rate law for the reaction A → B has been found to be of the form
Rate = k[A]m.
From the following data, determine the overall order of the reaction and the order with respect
to A.
Initial Concentration of A (M) Initial Rate (M/Sec)
-5
0.05 3 × 10
-5
0.10 12 × 10
-5
0.20 48 × 10
Ans: Order of reaction with respect to A is 2 and the over all order of the reaction is also 2
6. For the reaction Cl2 (g) + 2NO (g) = 2NOCl(g), the obtained data was
Initial concentration of Initial concentration of Initial rate of production of NOCl
Cl2 (mole litre-1) NO (mole litre−1) (mole litre-1 sec-1)
0.02 0.01 2.4 × 10−4
0.02 0.03 2.1 × 10−3
0.04 0.03 2.32 × 10−3
What is order of reaction with respect to (i) Cl2 and (ii) NO, (iii) rate law and rate constant?
Ans: (i) 2 (ii) 1 (iii) 1.2 × 10−2
7. For the gaseous reaction,
A(g) + B(g) → C(g) + D(g)
It is found that, rate = K[A]2 [B]1
How many times does the rate of reaction increase or decrease if (a) the partial pressures of both
A and B are doubled, (b) the partial pressure of A doubles but that of B remains constant. (c) the
volume of reacting vessel is doubled (d) an inert gas is added which doubles the overall
pressure while the partial pressure of A and B remains constant. (e) the temperature rises by
30°C.
Ans: (a) Rate increases by 8 folds (b) rate increases by 4 folds (c) rate decreases by 4 folds (d) no change in the rate of
reaction (e) rate increases by 8 to 27 folds.
8. The half life period of first order reaction is 3 hours. Find the time required to complete 87.5% of
the reaction.
Ans: t = 9.002 hours
9. Compare the rate of reaction of all the components of the following reaction:
2N2O5 (g) → 4NO2 (g) + O2 (g)
Find the rate of each component in mol s–1, when 2.24 litre of O2 at NTP are produced in 30
minutes.
Ans: Rate of disappearance of N2O5 = 1.11 × 10–4 mol s–1
Rate of formation of NO2 = 2.22 × 10–4 mol s–1 Rate of formation of O2 = 5.55 × 10–5 mol s–1
10. For a hypothetical reaction
2M + N → product; The following data are given.
-1 -1 -1 -1
Expt. No. Initial conc of M (mol L ) Initial conc of N (mol L ) Initial rate (mol L sec )
2
I 0.10 0.20 3 × 10
3
II 0.30 0.40 3.6 × 10
4
III 0.30 0.80 1.44 × 10
IV 0.30 1.60 A
V 0.60 0.80 B
VI 0.10 0.40 C
From the above data:
i. Find the overall order of the reaction.
ii. Calculate the value of A, B and C.
iii. Determine the unit of rate constant
11. For a first order reaction, it takes 4 minute for initial concentration of 0.8 mol/L to become 0.2
mol/L. What time will it take to become the concentration to be 0.04 mol/L?
Ans: 8.64 min
12. A first order reaction takes 100 minutes to complete 60% of the reactants into products. What
time will take to complete 90% of the reactant into product?
Ans: 251.31 min

1. A catalyst increases the rate of a chemical reaction a. zero b. one
c. two d. Three
by
a. decreasing the free energy 6. The rate constant of a chemical reaction is changed
b. decreasing the heat of reaction if,
c. decreasing the activation energy a. the reaction temperature is changed
d. increasing the average speed of the reacting molecules. b. the reaction particles size is changed
2. A catalyst speed up a chemical reaction by c. the initial concentration of reactant is changed
a. increasing the activation energy d. the product concentration is increased
b. providing an alternative reaction path of lower 7. The order of the reaction is
activation energy a. Sum of stoichiometric coefficient of all reactants
c. shifting the equilibrium towards the side the product (s). b. Sum of stoichiometric coefficient of all reactants on
d. increasing the reaction enthalpy which rate depends
3. In the reaction, A + B C + D c. Sum of power of concentration of the reactants on
which rate depends
D[A] d[B] Rate constant
–3 d. Sum of power of concentration of all the reactant
0.1 0.1 1.5 × 10 8. The rate of reaction depends upon
–3
0.1 0.2 1.5 × 10 a. initial concentration of reactants
–3
0.2 0.2 3 × 10 b. temperature
The order of reaction is c. pressure
a. 1st order with respect to A d. volume
b. 2nd order with respect to A 9. The factor which does not influence the rate of
c. 1st order with respect to B reaction is
d. 1st order with respect to A and B both a. natural of reactants b. concentration
4. The average minimum energy that must be c. temperature d. molecularity
associated with the reactant molecules in order to 10. 75% of a first order reaction was completed in 32
be capable of forming products: min, when was 50% of the reaction completed?
a. activation energy b. collision energy a. 24 min b. 16 min
c. threshold energy d. transition energy c. 8 min d. 4 min
–3 –1 –1
5. The rate of a reaction is 5.4 × 10 mol L S then
order of reaction is
1 2 3 4 5 6 7 8 9 10
c b a c a a c b d b
Aromatic
Hydrocarbons
H H
C C
H C C H
C C
H H
Benzene molecule: π electron clouds above

and below the plane of the ring.
Benzene is the simplest and the important member of aromatic hydrocarbons (arenes). It is mainly used as a
precursor to other industrially important compounds like polystyrene, nylon, resins, adhesives, rubbers,
lubricants, dyes, detergents, drugs, explosives and pesticides.
8.1 Introduction
The term aromatic is derived from Greek word aroma meaning pleasant odour or fragrance.
Originally, the term aromatic was used to represent a group of organic compounds obtained from
natural sources which had pleasant odour and the term aliphatic is used to represent to distinguish
them from aliphatic compounds usually lack such odour (Greek: aliphos= fat).
Later, it was found that almost such compounds contained benzene or derivatives of benzene. Hence
aromatic compounds are benzene and compounds that resemble benzene in chemical behaviour.
Today's classification is, however, based on molecular structure and chemical behavior of
compounds rather than in the sense of aroma. Aliphatic compounds represent all open chain
compounds and those cyclic compounds which are similar to open chain compounds in chemical
behavior. Aromatic compounds represent only cyclic organic compounds which are planar with
cyclic cloud of pi electrons and quite stable towards addition reaction though unsaturated.
CHO It is a popular flavoring agent in foods,
beverages, and pharmaceuticals which
is obtained naturally from seeds of
OCH3 vanilla (an orchid).
OH
Vanilin
It is used for coloring textiles,
N=N OH foodstuffs, etc.
p–Hydroxyazobenzene
(an azo dye)
NHCOCH3 It is used to lower the body temperature

in high fever (antipyretic).
OH
Paracetamol
Aromatic compounds play key roles in biochemistry of all living beings. They serve as basic
building-blocks of proteins. All five bases in DNA and RNA are aromatic compounds. Aromatic
compounds have high commercial value since they are indispensable part of our society providing
drugs, dyes pesticides, polymers, etc.
Aromatic hydrocarbons are called arenes. Arenes have general formula CnH2n– 6y, where, n = number
of carbons and y = number of rings. Some examples are;
Benzene Napthalene Anthracene Phenanthrene Pyrene
H
CH3
CH3 CH2CH3 CH3 CH=CH2
CH3—C—CH3
CH3
CH3 CH3
Toluene Ethyl benzene o-xylene Mesitylene
Isopropylbenzene Styrene
(Cumene)
Aromatic Hydrocarbons Unit 8 229
8.2 Characteristics of Aromatic Compounds

1. They are cyclic organic compounds having planar ring (usually having 5 or 6 carbon atoms per
molecule) and cyclic cloud of pi electrons.
2. Although unsaturated, they do not give addition reactions easily. They show apparent
unsaturation.
3. They give electrophilic substitution reactions regardless of functional group.
4. They have high proportion of carbon as compared to its aliphatic analog. Hence, they burn with
sooty flame. Aliphatic compounds burn with non sooty flame.
5. They follow Huckel's 4n + 2 rule.
8.3 Nomenclature of Benzene Derivatives

Nomenclature of monosubstituted derivatives of benzene
Many monosubstituted benzene are named by taking name of substituent as prefix of the word -
benzene
F NO2 CH2CH3
Cl Br I
Fluorobenzene Chlorobenzene Bromobenzene Iodobenzene Nitrobenzene Ethylbenzene
Some have special name without any significance of substituent in name.
CH3 NH2 OH COOH SO3H CHO
Toluene Aniline Phenol Benzoic acid Benzenesulfonic acid Benzaldehyde

(Methylbenzene) (Aminobenzene) (Hydroxybenzene)
Nomenclature of di-substituted derivatives of benzene: Concept of ortho, meta and para

If two substituents are present, three positional isomers are possible. The relative positions of
substituents in disubstituted benzene are given by ortho (o-), meta (m-) and para (p-) or by numbers.
Taking the position of substituent as 1, other positions are given:
T
1
Ortho 6 2 Ortho
Meta 5 3 Meta
4
Para
1. Positions 2 and 6 are equivalent and are called ortho or o- with respect to position 1.
2. Positions 3 and 5 are equivalent and are called meta or m- with respect to position 1.
3. Position 4 is called para or p- with respect to position 1.
Br Br Br
1 Br 1 1
6 2 6 2 6 2
3 3
5 3 5 5
4 4 Br 4
Br
1,2-Dibromobenzene 1,3-Dibromobenzene 1,4-Dibromobenzene
(o-Dibromobenzene) (m-Dibromobenzene) (p-Dibromobenzene)
Dimethyl benzene has special name 'xylene'.

CH3 CH3 CH3
CH3
CH3
CH3
1, 2-Dimethylbenzene 1, 3-Dimethylbenzene 1, 4-Dimethylbenzene
(o-xylene) (m-xylene) (p-xylene)
If two substituents are different and one of them gives special name to the molecule, the compound
is named as derivative of that special name.
CH3
CH3 CH3
Cl OH
Cl Cl
Cl
2-Chlorotoluene 3-Chlorotoluene 4-Chlorotoluene m-Chlorophenol
(o-Chlorotoluene) (m-Chlorotoluene) (p-Chlorotoluene)
If two substituents are different and none of them gives special name to the molecule, then
substituents are written in alphabetical order.
I
NO2
Cl Br
m-Chloronitrobenzene 1-Bromo-4-iodobenzene
(p-Bromoiodobenzene)
Nomenclature of polysubstituted derivatives of benzene

Br I CH3
Br Br
Br Br Cl Br
Br
1,3,5-Tribromobenzene 1-Bromo-3-chloro-5-iodobenzene 2,4,6-Tribromotoleune
OH NH2
Br Br Br
NO2 Br
1-Bromo-4-nitrophenol 2,4,6-Tribromoaniline
Some polynuclear hydrocarbons
8 1 α α 8 9 1
7 2 β β 7 2
6 3 β β 6 3
5 4 α α 5 10 4
Napthalene Napthalene Biphenyl or
Anthracene Phenanthrene
Diphenyl
Some aryl groups H

CH3 H—C— —C— O= C—
H—C—

Phenyl-
m-Tolyl- Benzyl- Benzal- Benzo- Benzoyl–
C6H5- or Ph or Ø
8.4 Structure of Benzene

Since aromatic compounds resemble benzene, understanding of structure of benzene is important for
the study of aromatic compounds.
Benzene (phene) was first isolated by Faraday in 1825 from cylinders of compressed illuminating gas
obtained from pyrolysis of whale oil. Hofmann found benzene in coal tar in 1845.
1. Elemental analysis and molecular weight determination indicate that molecular formula of
benzene is C6H6. It has eight hydrogen atoms less than its saturated analog hexane, C6H14. This
indicates that benzene is highly unsaturated. A number of structures can be written for this
formula like:
a. CH3—C ≡ C—C ≡ C—CH3
b. CH2 = CH—C ≡ C—CH = CH2
c. CH ≡ C—CH2—CH2—C ≡ CH
d. = CH2
Kekule (1865) was the first to suggest a ring structure for benzene (I) but did not prove. Dewar
proposed bicyclic structure (D).
H
C
H C C H
H C C H
C
H
Bicyclo[2,2,0]hexadiene
Cyclohexatriene Dewar's formula(1867)
Kekule's formula (1865)
(I) (D)
2. Evidences in support of Kekule's structure of benzene

i. Benzene gives only one monosubstituted product. This indicates that all six hydrogen atoms
are equivalent. This permits the structure (I).
ii. Benzene adds a maximum of six hydrogen atoms on heating in presence of catalyst to give
hexahydrobenzene.
Bayer proved that cyclohexane and hexahydrobenzene were identical hence establishing the
cyclic structure of benzene.
CH2 CH2
Ni
C6H6 + 3 H2 CH2 CH2
200°C
CH2 CH2
iii. Benzene adds a maximum of six chlorine atoms in presence of sunlight.

3. Objections to Kekule's structure of benzene
i. Benzene is quite stable towards addition reaction. If structure I is correct, it should give
addition reaction redially.
Benzene + Bayer's reagent = No reaction
Benzene + Br2/CCl4 = No reaction
Benzene + HX = No reaction
ii. All carbon-carbon bonds in benzene are equal and are intermediate in length between single
and double bonds.
Carbon -carbon single bond is longer (1.50Å in propene) than the carbon- carbon double bond
(1.34 Å). H H
CH3—C = C—H
1.50Å 1.34Å
If Kekule's structure is correct, there should have three long bonds and three short bonds in
benzene. X-ray diffraction studies show that all six carbon-carbon bonds in benzene are equal
and have a length of 1.39Å which is intermediate in length between single and double bonds.
iii. Benzene gives only three disubstituted products. Theoretically, structure (I) should give four
isomeric di-substituted derivatives:
Br Br Br Br
Br Br
Br
Br
(i) (ii) (iii) (iv)
Kekule, later (1872) proposed another structure (II) for benzene and suggested that there is
rapid equilibrium between structure (I) and (II ), each molecule spending half of its time in (I)
and the other half in (II) hence, cannot be separated. Therefore, two 1, 2-disubstituted benzenes
cannot be separated.
I II
Hence, (I) and (II) cannot be distinguished.

iv. Experimental heat of hydrogenation of benzene is found to be 36 kcal mol–1 less than calculated
heat of hydrogenation of hypothetical cyclohexatriene (85.5 kcal mol–1). This indicates that
benzene is 36 kcal mol–1 more stable than hypothetic cyclohexatriene. Such energy of stability of
benzene by 36 kcal mol-1 is known as resonance energy.
4. Resonance theory
According to this theory, benzene is resonance hybrid of I and II.
I II
Resonating structures Resonance hybrid
The resonance hybrid explains the following features of benzene;

i. A resonance hybrid is more stable than the resonating structures. Since, I and II are exactly
equivalent, stabilization due to resonance is high. Hence, benzene is quite stable towards addition
reactions.
ii. Since I and II are exactly equivalent, each structure has equal contribution in resonance hybrid.
Hence, in benzene, all carbon-carbon bonds are identical and are intermediate in length
between single and double bonds.
5. Orbital picture of benzene
Carbon has two half filled orbitals in ground state (1s2, 2s2, 2px1 2py1, 2pz0). It has four half filled
orbitals in excited state since one electron is promoted from 2s to empty 2p orbital during
chemical reaction (1s2, 2s1, 2px1 2py1, 2pz1).
Now, one 2s and two 2p orbitals undergo sp2 hybridization to form three sp2 hybrid orbitals.
Three sp2 orbitals are of equivalent energy and identical shape and size which take trigonal
planar geometry with angle 120º. Unhybridized 2pz half filled orbital remains perpendicular to
the plane of hybrid orbitals.
Unhybridized half filled 2pz orbitals of each carbon atom which are perpendicular to the plane
of the ring, can overlap laterally on either side forming three pi bonds. But, the system is cyclic
and planar, hence pi electrons are not localized but delocalized forming cyclic pi electron clouds
above and below the plane of the molecule. This delocalization stabilizes the molecule. Hence
benzene is a flat molecule (all carbon and hydrogen atoms lie in a plane with bond angle
120º) with delocalized cyclic pi electrons above and below the plane of the molecule.
1s 2s 2px 2py 2pz
C= in ground state
2s 2px 2py 2pz

in exited state
sp2 hybridization
sp2 sp2 sp2 2pz
Three sp2 hybrid orbitals Unhybridized orbital
2pz
sp2
sp2
sp2
1s 1s
sp2 sp2 sp2 sp2
sp2 sp2
sp2 sp2
sp2 sp2
1s 1s
sp2 sp2
sp2 sp2
sp2 sp2 sp2 sp2
1s 1s
H H H H
2pz 2pz
2pz 2pz
H H H H
2pz 2pz
H H H H
H H
C C
` H C C H
C C
H H
Benzene molecule: π electron clouds

above and below the plane of the ring.
8.5 Huckel's (4n+2) Rule for Aromaticity

(Theoretical Criteria for Aromatic Character)
The term aromaticity is related with chemical stability due to resonance. All aromatic compounds
show aromaticity. But some other classes of compounds like heterocyclic compounds also show
aromatic behaviour (aromaticity).
Theoretically, to be aromatic an organic compound must fulfill the following conditions;
1. It must be cyclic and planar.
2. It must have cyclic cloud of delocalized pi electrons above and below the plane of the molecule.
3. π- electron cloud must contain a total of (4n+2) π- electrons, where n is an integer (n=0,1,2,3..)
Hence aromatic compounds are cyclic planar molecules having cyclic cloud of 2 (n=0), 6 (n=1), 10
(n=2), 14 (n=3), 18 (n=4), π- electrons. This is called Huckel rule or 4n+2 rule for aromaticity.
Some examples:
Huckel number (4n

Value of n The compounds showing aromaticity
+2)π electrons
+
(4n + 2) π
0 =4×0+2
O
= 2π electrons Cyclopropenyl cation Cyclopropenone
(4n + 2) π
=4×1+2 S N N
O
= 6 π electrons Thiophene Furan H Pyridine
Pyrrole
1 +
–
Cyclopentadienyl anion Benzene Tropylium cation
(cycloheptatrienyl cation)
(4n + 2) π
2 =4×2+2 N
= 10 π electrons Napthalene Quinoline Azulene
(4n + 2) π
3 =4×3+2
Anthracene
= 14 π electrons Phenanthrene
The Huckel number six is most common in aromatic system and hence the term aromatic sextet is
commonly used for 6π electrons.
Example 8.1 Predict the aromaticity of the following species applying Huckel's rule.
a. Benzene b. Cycloheptatriene c. Napthalene
d. Cyclopropenyl cation e. Cycloheptatrienyl cation
Solution
a. Benzene
Benzene
i. The compound is cyclic and planar since all six ring carbon atoms are sp2 hybridized.
ii. pi electrons = 6: 4n + 2 = 6 , where n = 1
Planar structure permits the delocalization of pi electrons in a ring. Hence it is aromatic.
b. Cycloheptatriene
sp3 hybridised
The compound is cyclic but nonplanar since one ring carbon atom is sp3 hybridized.
pi electrons = 6 : 4n + 2 = 6 , where n = 1
Nonplanar structure does not permit delocalization of pi electrons in a ring. Hence it is not
aromatic.
c. Napthalene
i. The compound is cyclic and planar since all ring carbon atoms are sp2 hybridized.
ii. pi electrons = 10 : 4n + 2 = 10 , where n = 2
d. Cyclopropenyl cation
+
Cyclopropenyl cation
e. Cycloheptatrienyl cation
+
Cycloheptatrienyl cation
Hence, an aromatic compound may be defined as a cyclic planar molecule which has cyclic
cloud of delocalized 4n+2 pi electrons and has unusual stability towards addition reaction
due to delocalization of pi electrons.
Benzenoid and non-benzenoid aromatic compounds
Aromatic compounds having benzene ring are called benzenoid aromatic compounds.
Examples:
Benzene Napthalene Anthracene

Aromatic compounds having no benzene ring are called non-benzenoid aromatic compounds.
Examples:

N O S N
Thiophene Pyridine
Azulene H
Furan
Pyrrole
Concept of Antiaromaticity (Breslow, 1967)

There are some cyclic unsaturated organic compounds having 4n π electrons which are less stable
than acyclic analog. Such organic compounds are called antiaromatic and characteristics shown by
them are called antiaromaticity. For example, 1, 3- cyclobutadiene
CH2 = CH—CH = CH2

1, 3-Butadiene
Although, it has two resonating structures, it is less stable than acyclic compound, 1, 3-butadiene.
Here, resonance instead of stabilization, destabilizes.
Some anti-aromatic species are:
–
+
Cyclopropenyl cation Cyclooctatetraene
Cyclopentadienyl cation
4π electrons 8π electrons
4π electrons
Aromatic, Non-aromatic and Anti-aromatic compounds

Aromatic compounds: Cyclic organic compound which is more stable than its open chain analog
Non-aromatic compounds: Cyclic organic compound which has equal stability to its open chain
analog
Anti-aromatic compounds: Cyclic organic compound which is less stable than its open chain
analog
8.6 Isomerism in Benzene Derivatives

1. Mono-substituted derivative of benzene: All six hydrogen atoms in benzene are equivalent.
Hence, replacement of any of six hydrogen atom gives only one mono-substituted benzene.
2. Di-substituted derivatives of benzene: Three positional isomers are possible.
CH3 CH3
CH3
CH3
CH3
CH3
1, 2-Dimethyl benzene
1, 3-Dimethyl benzene 1, 4-Dimethyl benzene
(o-xylene)
(m-xylene) (p-xylene)
3. Tri-substituted derivatives of benzene: The number of isomers depends upon nature of

substituents:
i. If the three substituents are identical, then three isomers are possible. (Concept of vicinal,
asymmetrical and symmetrical)
NO2 NO2
NO2 NO2
NO2
NO2 NO2
NO2 O2N
vic- trinitrobenzene asy- trinitrobenzene sym- trinitrobenzene
(1,2,3- Trinitrobenzene) (1, 2, 4 - Trinitrobenzene) (1,3,5- Trinitrobenzene)
ii. If two substituents are identical and the third is different, then six isomers are possible.
iii. If all three substituent are different, then ten isomers are possible.
8.7 Commercial Source of Benzene

Before 1950s, benzene was mainly obtained from coal tar. It was obtained as a byproduct of coke
production in steel industries. But, demand of benzene increased especially due to the growing
polymer industry. Today, benzene is mostly produced from petroleum.
1. From coal tar: Coal after destructive distillation gives coal-tar as one of the fractions. The coal
tar contains more than 70 different aromatic compounds like benzene, phenol, naphthalene,
anthracene, etc. The coal tar is subjected to fractional distillation to get aromatic compounds,
separately, where benzene is obtained from light oil fraction of the coal tar distillation.
Coal
1000-1400°C, in absence of air
(carbonization or destructive distillation)
Coke
(solid residue)
Coal tar Coal gas
(black viscous oily liquid) (low mol. wt. alkanes and alkenes)
Coal tar is rich in aromatic compounds. It is subjected to fractional distillation to different fractions.
Main fractions of coal tar
SN Fraction Temperature range % Chief constituents
1 Light oil or Crude upto 170°C 7-8 CH3 CH3

naptha
CH3
Benzene
Toluene o-,m-,p-xylenes
2 Middle oil or 170-230°C 8-10

OH
Carbolic oil
Napthalene
Phenol
3 Heavy oil or 230-270°C 8-10 OH

Creosote oil
CH3
Cresols Napthalene
4 Green oil or 270-360°C 16-20

Anthracene oil
Anthracene Phenanthrene
5 Pitch residue 50-60 90-95% carbon
2. From petroleum: n-alkanes generally with C6–C8 on cyclization followed by aromatization give
arenes.
Cr2O3-Al2O3,500°C, 15 atm
CH3CH2CH2CH2CH2CH3 + 4H2
Hexane Benzene
CH3
Cr2O3-Al2O3,500°C, 15 atm
CH3CH2CH2CH2CH2CH2CH3 + 4H2
Heptane Toluene
8.8 Preparation of Benzene

1. From acetylene: When acetylene is passed through a copper tube heated to about 600°C,
benzene is formed. Benzene was prepared for the first time by Berthelot (1870) by this method.
The process is called trimerization or polymerization or aromatization.
H H
C C
H C C H Red hot Cu tube H C C H
+ 600° C
H C C H H C C H
C C
H H
Ethyne Benzene
2. From sodium benzoate: When sodium benzoate is heated with sodalime, benzene is formed.
The reaction is called sodalime decarboxylation reaction.
NaOH+CaO
COONa + NaO H + Na2CO3
Δ
Sodium benzoate
This reaction is used as laboratory method for the preparation of benzene.

3. From phenol: When phenol is distilled with zinc dust, benzene is formed.
OH
Δ
+ Zn + ZnO
4. From chlorobenzene Benzene
i. When chlorobenzene is treated with Mg metal followed by hydrolysis, benzene is

obtained.
Cl MgCl
Mg H2O
+ Mg(OH)Cl
Chlorobenzene Phenyl magnesium chloride Benzene
ii. When chlorobenzene is reduced with Ni-Al alloy in presence of NaOH, benzene is
obtained.
Cl
Ni – Al Alloy
+ 2[H] NaOH + HCl
Chlorobenzene Benzene
5. From diazonium salt: When diazonium salt is mixed with aqueous hypophosphorous acid,
benzene is formed.
+
N2Cl – H
+ H3PO2 + H2O + H3PO3 + N2 + HCl
Hypophosphorous acid Phosphorous acid
Note:
Benzene diazonium salt is obtained by diazotization reaction of aniline (see in Aromatic Amine).
8.9 Physical Properties

1. Benzene is a colourless liquid with aromatic odour.
2. It is insoluble in water but soluble in organic solvents.
3. The boiling point of benzene is 80.4°C and melting point is 5.5°C.
4. The vapour of benzene is highly inflammable, toxic and burns with sooty flame.
5. It is a very good solvent for fats, resins, sulphur, iodine, etc.
8.10 Chemical Properties

Benzene, a typical aromatic compound, undergoes mainly three categories of reactions:
A. Electrophilic aromatic substitution reactions
B. Addition reactions
C. Combustion
A. Electrophilic aromatic substitution reactions: Typical reaction of aromatic
compounds
Benzene serves as a source of electron due to delocalized cyclic pi electron cloud above and below
the plane of the molecule. So, electrophile attacks benzene ring to give substitution reactions. A
substitution reaction initiated by an electrophile is called electrophilic substitution reaction. This is
the typical reactions of benzene and all aromatic compounds.
Mechanism of electrophilic aromatic substitution reaction
Cl
Fe or FeCl3
+ Cl2 + HCl
dark
Chlorobenzene
Generation of electrophile: Catalyst reacts with the reagent to generate electrophile.
Cl—Cl + FeCl3 Cl+ + FeCl4¯

Lewis acid Chloronium ion
Step I: Electrophile is attracted toward π electron cloud of benzene ring to form arenium ion as intermediate. This step is slow
since aromatic character is destroyed.
Cl H Cl H Cl H Cl H
Slow + +
+ Cl+ (rds)
+
+
Resonance hybrid
(Arenium ion or σ-complex or Benzenonium
ion or Wheland intermediate)
Step II: Abstraction of proton by nucleophile to give product. This step is fast since aromatic character is restored.
Cl
Cl H
+ Fast
+ FeCl4¯ + HCl + FeCl3
TS1
TS2 Here,
Potential Energy→
TS = transition state
Ea Ea' Ea = activation energy
Cl H
Cl
+
+ Cl+ + H+
Progress of reaction →
Energy profile diagram for electrophilic aromatic substitution
1. Halogenation: Benzene reacts with limited amount of Cl2 or Br2 at ordinary temperature (not at
high temperature and in presence of sunlight) and in presence of Lewis acid like FeCl3, AlCl3,
FeBr3 to give corresponding halobenzene. Iron is most commonly used since it is converted to
FeCl3 or FeBr3.
Cl
Fe or FeCl3
+ Cl2 + HCl
dark
Chlorobenzene
Br
FeBr3
+ Br2 + HBr
Bromobenzene
Simplified mechanism:
Cl—Cl + FeCl3 Cl+ + FeCl4¯

Lewis acid Chloronium ion
Cl H
Slow
Step I + Cl+ +
Electrophile
Cl
Cl H
Fast
Step II + + FeCl4¯ + FeCl3 + HCl
2. Nitration: When benzene is heated with a mixture of concentrated nitric acid and concentrated
sulphuric acid (nitrating mixture) at about 50°C – 60°C, nitrobenzene is obtained.
H NO2
H2 SO4 (conc.)
+ HNO3 (conc.) + H2O
(50ºC – 60°)
Benzene Nitrobenzene
When benzene is heated with a mixture of conc. HNO3 and conc. H2SO4 at about 80–100°C, m-
dinitrobenzene is obtained.
NO2
conc. H2SO4
+ HNO3 80-100°C + H2O
NO2
conc.
m-dinitrobenzene
When benzene is heated with a mixture of fuming HNO3 and conc. H2SO4, 1,3,5-trinitrobenzene
is obtained.
NO2
conc. H2SO4
+ HNO3 100°C + H2O
O2N NO2
3. Sulphonation: When benzene is heated with concentrated or fuming sulphuric acid or oleum or
pyrosulphuric acid (sulphuric acid containing SO3), benzenesulphonic acid is obtained. The
reaction is called sulphonation reaction.
SO3H
Δ
+ H2SO4 + H2O
Benzenesulphonic acid
+
2 H2SO4 SO3 + H3O + HSO−4
Oleum Sulphur trioxide
(electrophile)
H SO3¯
Slow
Step I + SO3 +
Electrophile
H SO3¯
SO3¯
Fast
+ + HSO4¯ + H2SO4
Step II
SO3¯ SO3H
+ H3O+ + H2O
4. Friedel-Crafts alkylation: When benzene reacts with alkyl halide (R –X) in presence of
anhydrous AlCl3, BF3 or FeCl3 etc., alkyl group replaces the hydrogen of benzene nucleus to
give alkyl benzene. The reaction is called Friedel-Crafts alkylation.
H R
AlCl3, Δ + HX
+ R—X dry ether
Alkyl benzene
H CH3
AlCl3, Δ
+ CH3—Cl dry ether
+ HCl
Benzene Methylbenzene (Toluene)

Electrophile = CH3+ (Methyl carbocation)
H CH2CH3
AlCl3, Δ
+ CH3CH2—Cl + HCl
dry ether
Benzene Ethylbenzene
Electrophile = CH3CH2+ (Ethyl carbocation)

R—Cl + AlCl3 R+ + AlCl4¯

Lewis acid Carbocation
R H
Slow
Step I + R+ +
Electrophile
R
R H
Fast
Step II + + AlCl4¯ + AlCl3 + HCl
Benzene reacts with n-propyl chloride to give isopropylbenzene as major product rather than n-propylbenzene.
H CH3—CH—CH3 CH2CH2CH3
AlCl3, Δ + HCl
+ CH3CH2CH2Cl +
dry ether
Benzene n-propyl chloride Isopropylbenzene n-propylbenzene

(cumene)
Major product
This is because initially formed primary carbocation undergoes rearrangement to form more stable secondary carbocation.
rearrangement
CH3CH2CH2 Cl + AlCl3 CH3CH2CH2+ CH2 CH CH3
+
1° carbocation 2° carbocation
(less stable) (more stable)
5. Friedel-Crafts acylation: When benzene, reacts with acyl halide RCOCl or anhydride in
presence of anhydrous AlCl3, BF3, or FeCl3 etc. Lewis acid, acyl group replaces the hydrogen of
benzene nucleus to give aromatic ketone (acylbenzene). The reaction is called as Friedel-Crafts
acylation.
O O
AlCl3, Δ
H + X—C— R dry ether
C—R + HX
Acyl chloride Aromatic ketone

Benzene
O O
AlCl3, Δ
H + Cl—C—CH3 C—CH3 + HCl
dry ether
Ethanoyl chloride Acetophenone

Benzene
(Acetyl chloride) (Methylphenyl ketone)
O O
AlCl3, Δ
H + Cl—C—CH2CH3 C—CH2CH3 + HCl
dry ether
Propanoyl chloride Ethylphenyl ketone

Benzene
O O
AlCl3, Δ
H + Cl—C C + HCl
dry ether
Benzene Benzoyl chloride Benzophenone

(Diphenyl ketone)
O O
R—C—Cl + AlCl3 R—C⊕ + AlCl4¯
(Acylium ion)
O O O
AlCl3, Δ
H + CH3 C O C CH3 dry ether
C—CH3 + CH3COOH
Or
Benzene Acetophenone
(CH3CO)2O (Methylphenyl ketone)
Ethanoic anhydride
(Acetic anhydride)
O
H C—R
O
+ R—C⊕ +
O
O
H C—R
C—R
+ + AlCl4¯ + HCl + AlCl3
B. Addition reactions
Benzene and all aromatic compounds are stabilized due to delocalization of pi electrons.
Addition reactions destroy their aromatic character. Hence all aromatic compounds are quite
stable towards addition reactions. However, benzene gives addition reactions under drastic
conditions.
1. Addition of hydrogen (hydrogenation): Benzene reacts with hydrogen in presence of
nickel as catalyst on heating to give cyclohexane.
H H H
C H C H
H C C H C
H2/Ni C
+ 3H2 H H
200°C H H
H C C H C C
C H C H
H H H
Benzene Cyclohexane
2. Addition of chlorine: Benzene reacts with Cl2 in presence of sunlight to give BHC which is
an insecticide.
H
H Cl
C H C
H C C H H
Sunlight C C
+ 3Cl2 Cl Cl
H C C H H C C H
C Cl Cl
C
H H Cl
Benzene 1,2,3,4,5,6- Hexachlorocyclohexane
(BHC)
3. Addition of ozone followed by hydrolysis (Ozonolysis): Benzene reacts with ozone to

form triozonide which on hydrolysis in presence of Zn dust gives glyoxal.
O O
H2O/Zn
+ 3 O3 3 H—C—C—H + H2O2
Ethanedial
Benzene (Glyoxal)
Triozonide
C. Combustion/Oxidation
1. On complete combustion, benzene gives CO2 and water.
C6H6 + 15 O2 12 CO2 + 6H2O + Energy
2. Benzene is partially oxidized in presence of V2O5 to give maleic anhydride.
O
V2O5, 450°C
+ 9 O2 O + 4 CO2 + 4 H2O
O
Maleic anhydride
8.11 Uses of Benzene

Today, more than half of the benzene produced
is converted to ethylbenzene which is converted
World Consumption of Benzene in 2010
then to styrene for polystyrene. The next largest
use of benzene is in the preparation of cumene Other
which is then converted to phenol for resins and
Nitrobenzene
adhesives. The next use is to prepare
cyclohexane which is used in the manufacture of
nylon. Other uses including, the preparation
of aniline (for dyes) and dodecylbenzene (for Cyclohexane
Ethylbenzene
detergents). Benzene is aslo used to make some
types of rubbers, lubricants, detergents, drugs,
explosives, and pesticides. Benzene was used as
solvent in dry cleaning but in these days it was Cumene
discouraged because of its carcinogenic effect.
8.12 Electrophilic Aromatic Substitution Reactions in

Substituted Benzene
Activating group
Reactivity
Deactivating group
Substituent Ortho-para director
Orientation
Meta director
A substituent present in benzene governs the reactivity and orientation of the benzene ring.
Effect on reactivity
A substituent makes the benzene ring either more reactive or less reactive as compared to benzene in
electrophilic aromatic substitution reaction. A substituent which makes the benzene ring more
reactive than benzene in electrophilic aromatic substitution is called activating group. For example,
methyl benzene undergoes nitration about 25 times faster than benzene. Hence -CH3 is an activating
group.
CH3
NO2 CH3
HNO3 (conc.) NO2

H2SO4 H2SO4
1 molecule 25 molecules
Similarly, a substituent which makes the benzene ring less reactive than benzene in electrophilic
aromatic substitution is called deactivating group. For example, chlorobenzene undergoes nitration
about 30 times slower than benzene. Hence -Cl is deactivating group.
Cl
NO2 Cl
HNO3 (conc.) NO2

H2SO4 H2SO4
30 molecules 1 molecule
Effects of substituent on electrophilic aromatic substitution reactions is given below.
Activating group and ortho, para director Deactivating groups

Strongly activating Meta directors
—NH2 (-NHR, —NR2) —NO2
—OH —NH3+
Moderately activating —CN
—OCH3 (—OC2H5 etc.) —COOH (—COOR)
—NHCOCH3 —SO3H
Weakly activating —CHO, —COR
—C6H5 Ortho and para directors
—CH3 (—C2H5, etc.) —F, —Cl, —Br, —I
Effect on orientation
A substituent which directs the incoming group chiefly at ortho and para to it in electrophilic
aromatic substitution reaction is called ortho- para director. For example,
CH3 CH3 CH3

Cl2, FeCl3 Cl
+
Toluene Cl
o-Chlorotoluene p-Chlorotoluene
Hence -CH3 is called ortho- para director.
A substituent which directs the incoming group chiefly at meta to it in electrophilic aromatic
substitution is called meta director. For example,
NO2 NO2
Cl2, FeCl3
Cl
m- Chloronitrobenzene
Hence –NO2 is called meta director.
Note (for Orientation and reactivity of substituted benzene)
The group attached in the benzene ring can be +M group or –M group (M = mesomeric):
1. +M groups: Groups like –Cl , –Br , –I , –OH –NH2 –OR –NR2 –CH3 ,etc. make ortho and para
position electron rich. (see resonance in chlorobenzene, phenol etc.) So, electrophile is likely to
attack in these positions. Thus, these groups are ortho and para directors for electrophilic
substitution reactions. As they create make the ring electron rich, they are activators of the ring
(except halo group, as halo groups are strongly electron withdrawing (–I) groups. In halo
groups their –I effect is more powerful that +M effect).
O O O O
2. –M groups: Groups like –N , –C– , –C–H , –C–OH etc. make the ortho and para positions
O
electron deficient (see resonance in nitrobenzene, benzaldehyde etc.). Thus, electrophile does
not attack in these positions. Only the position left for electrophilic attack is meta. So, these
groups are meta directors. As they make the ring electron deficient, they are the deactivator of
ring.
Explanations in details are given in respective units.

Solved Questions
1. Define aromatic compound. What are benzenoid aromatic compounds and
nonbenzenoid aromatic compounds?
¬ An aromatic compound may be defined as a cyclic planar molecule which has cyclic cloud of delocalized
4n+2 pi electrons and has unusual stability towards addition reaction due to delocalization of pi electrons
though unsaturated.
Aromatic compounds can be divided into benzenoid and nonbenzeoid aromatic compounds on the basis of
benzene ring which is the most common structure in aromatic compounds.
Aromatic compounds having benzene ring are called benzenoid aromatic compounds. For example,
Benzene Napthalene
Aromatic compounds having no benzene ring are called non-benzenoid aromatic compounds. For example,
N
Azulene Pyridine
2. Identify A and B giving complete reactions.

Red hot tube, 600°C Cl2, hv
Acetylene A B
¬
Red hot tube, 600°C Cl2, hv
Acetylene Benzene BHC
H H
C C
H C C H Red hot Cu tube H C C H
+ 600° C
H C C H H C C H
C C
H H
Acetylene Benzene
H
H Cl
C H C
H C C H H
Sunlight C C
+ 3Cl2 Cl Cl
H C C H H C C H
C Cl Cl
C
H H Cl
Benzene 1,2,3,4,5,6- Hexachlorocyclohexane
(BHC)
Questions
1. How do aromatic compounds differ from aliphatic compounds?
2. Define the following with examples:
a. Friedel-Crafts alkylation b. Friedel-Crafts acylation
c. Nitration of benzene d. Chlorination of benzene
3. Why does benzene not decolorize pink color of Baeyer's reagent?
4. How can you convert acetylene into toluene?
1. What is Huckel’s rule for aromaticity? Predict the aromaticity of the following species;
a. Tropyllium cation b. Cycloheptatriene
c. Cyclopentadienyl cation d. Anthracene
e. Pyrrole f. Pyridine
g. Azulene h. Cyclopropenyl cation
i. Cycloctatetraene
2. Identify A and B
NaOH+CaO, Δ H2/ Ni, 200°C
i. Sodium benzenesulphonate A B
Al2O3-Cr2O3, 500°C, 15 atm Br2, FeBr3, dark

ii. Hexane A B
Pt, 500°C, 10-20 atm CH3COCl, AlCl3, Δ

iii. Hexane A B
Zn dust, Δ CH3CH2Cl, AlCl3, Δ

Phenol A B
iv.
O3 H2O, Zn dust, Δ
v. Benzene A B
aq.H3PO2, Δ CH3CH2CH2Cl, AlCl3,Δ

vi. Benzene diazonium chloride A B
3. What happens when:

a. Sodium benzoate is heated with sodalime?
b. Phenol is heated with zinc dust?
c. Benzene is heated with acetic anhydride in presence of anhydrous AlCl3?
d. Benzene is reduced?
e. Benzene is ozonolysed?

1. Benzene was discovered by a. Light oil b. Heavy oil
a. Faraday b. Dalton c. Middle oil d. Vegetable oil
c. Hofmann d. Kekule 4. Which of the followings is the major source of
2. Coal tar is the main source of benzene?
a. Aliphatic compounds b. Aromatic compounds a. Light oil b. Green oil
c. Heterocyclic compounds d. Organic compounds c. Carbolic oil d. Coal tar
3. Which is impossible to obtain from the fractionation 5. Typical reaction of aromatic compounds is
of coal tar? a. Electrophilic addition b. Nucleophilic addition
c. Free radical addition d. Electrophilic substitution
6. Benzene when reacts with hydrogen in presence of 11. Friedel‐Crafts reaction is given by

nickel at high temperature to give cyclohexane, the a. Aliphatic compounds b. Aromatic compounds
reaction is c. Alicyclic compounds d Benzene only
a. addition b. reduction 12. In Friedel‐Crafts acylation, electrophile is
c. oxidation d. substitution a. Carbonium ion b. Carbanion
7. Benzene when reacts with ozone followed by c. Acyl chloride d. Acylium ion
hydrolysis in presence of zinc dust to give 13. Nitration takes place faster in
a. Ethanedial b. Oxalic acd a. Toluene b. Phenol
c. Acetaldehyde d. Glyxol c. Benzene d. Nitrobenzene
8. The electrophile in sulphonation of benzene is 14. Benzene is more stable than alkene due to
a. SO3+ b. SO3 a. Electron losing tendency of ring
c. HSO3 d. HSO4- b. Electron gaining tendency of ring
9. Benzene reacts with the n‐propyl chloride in c. Resonance of ring
presence of anhydrous AlCl3 to give ... as major d. Electromeric effect
product. 15. Structure of benzene is
a. n-propyl benzene b. Isopropyl benzene a. Planar b. Chair form
c. Xylene d. Mesytylele c. Trigonal bipyramidal d. Tetrahedral
10. Friedel‐Crafts reaction is given by 16. If n is number of carbons and y is number of benzene
a. Nitrobenzene b. Aniline ring then the general formula of arene is
c. Benzene d All the three a. CnH2n-2y b. CnH2n-3y
c. CnH2n+2y d. CnH2n-6y
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
a b d a d a a b b c b d b c a d
Haloalkanes and
Haloarenes
CH3CH2– Cl
Ethyl chloride
Ethyl chloride is a haloalkane. It acts as a topical anesthetic by its chilling effect when sprayed on
skin, such as in minor surgical procedures, in minor sports injuries etc.
9.1 Haloalkanes
9.1.1 Introduction
Organic compounds derived from hydrocarbons (alkanes, alkenes, alkynes, cycloalkanes and arenes)
by replacement of one or more hydrogen atoms with equal number of halogen atoms are called
halogen derivatives of hydrocarbons.
Examples:
H
H H
H—C—Cl H—C = C—Cl CH2 = CH—CH2Cl
H 3-Chloropropene
Chloroethene (Allyl chloride)
Chloromethane
(Methyl chloride) (Vinyl chloride)
Cl
HC ≡ C—CH2Cl Cl
3-Chloropropyne Chlorocyclohexane Chlorobenzene

(Propargyl chloride) (Cyclohexyl chloride) (Phenyl chloride)
Halogen derivatives of alkanes, alkenes and alkynes are called haloalkanes, haloalkenes and
haloalkynes, respectively. Halo group (—Cl, —Br, —I) is the functional group of halogen derivatives
of hydrocarbons since it determines their characteristic chemical properties as well as physical
properties.
When one or more hydrogen atoms in alkanes are replaced by halogen atoms, the resulting organic
compounds are called halogen derivatives of alkanes or halogenoalkanes or simply haloalkanes.
H H Cl Cl Cl
H—C—H H—C—Cl H—C—Cl H—C—Cl Cl—C—Cl
H H H Cl Cl
Methane Chloromethane Dichloromethane Trichloromethane Tetrachloromethane
(Alkane)
Depending upon number of halogen atoms per molecule, haloalkanes can be classified into
monohaloalkanes, dihaloalkanes, trihaloalkanes and so on.
9.1.2 Monohaloalkanes (Alkyl halides)

9.1.2.1 Introduction
When one of the hydrogen atoms in alkanes is replaced by a halogen atom, the resulting organic
compounds are called monohaloalkanes or alkyl halides.
Examples:
H H H
H—C—I CH3—C—Br CH3CH2—C—Cl
H H H
Haloalkanes and Haloarenes Unit 9 255
Alkyl halides have general molecular formula CnH2n+1X. Its general structural formula is R-X where
X represents Cl, Br or I.
9.1.2.2 Classification
Depending upon type of carbon to which halogen atom is bonded, monohaloalkanes are classified
into three different classes; primary alkyl halides, secondary alkyl halides and tertiary alkyl halides.
1. Primary (1°) alkyl halides (RCH2X): If halogen atom is bonded to primary carbon, the alkyl
halide is called primary alkyl halide or primary haloalkane.
Examples:
H H H CH3
R—C—X CH3—C—Br CH3CH2—C—Br CH3—C—CH2—Br
H H H CH3
2. Secondary (2°) alkyl halides (R2CHX): If halogen atom is bonded to secondary carbon, the alkyl
halide is called secondary alkyl halide or secondary haloalkane.
Examples:
R H CH3
R—C—X CH3—C—CH3 CH3CH2—C—Br
H Br H
3. Tertiary (3°) alkyl halides (R3CX): If halogen atom is bonded to tertiary carbon, the alkyl halide
is called tertiary alkyl halide or tertiary haloalkane.
Examples:
R CH3 CH3
R—C—X CH3—C—Br CH3CH2—C—Br
R CH3 CH3
9.1.2.3 Nomenclature
The functional group of haloalkanes is halo group because the properties of haloalkanes are
governed by halogen atom. However, during writing IUPAC name, it is not taken as functional
group and treated as substituent. Alkyl halides are named taking Halo- as substituent's name.
Formula IUPAC name Common name
CH3Cl Chloromethane Methyl chloride
CH3CH2Cl Chloroethane Ethyl chloride
CH3CH2CH2Cl 1- Chloropropane n-Propyl chloride

CH3—CH—CH3 2- Chloropropane Isopropyl chloride
Cl
CH3CH2CH2CH2Cl 1-Chlorobutane n-Butyl chloride

CH3CH2—CH—CH3 2-Chlorobutane sec-Butyl chloride
Cl
1-Chloro-2-methylpropane Isobutyl chloride

CH3—CH—CH2—Cl
CH3
CH3
2-Chloro-2-methylpropane tert-Butyl chloride
CH3—C—Cl
CH3
9.1.2.4 Isomerism
Alkyl halides can show following types of structural isomerism.
1. Chain isomerism: Isomers that differ only in chain length are called chain isomers.
Example: CH3CH2—CH—CH3 CH3—CH—CH2—Cl
Cl CH3
2- Chlorobutane 1- Chloro-2-methylpropane
2. Positional isomerism: Isomers having same chain length but differ in the position of functional
group or substituents are called positional isomers.
Example: CH3CH2CH2Br CH3—CH—CH3
1-Bromopropane Br
2-Bromopropane
Molecular formula CH3X C2H5X C3H7X C4H9X C5H11X
Number of structural isomers - - 2 4 8
Self Test
9.1 What are haloalkanes? Write the isomers and give their IUPAC name.
a) C3H7Cl b) C2H4Cl2 c) C3H6Cl2 d) C3H5Cl3
9.2 Write the structural isomers of C4H9Br and give their IUPAC name, common name and classify
them as primary, secondary and tertiary alkyl halide.
9.3 Write the structural isomers of C5H11Cl, give their IUPAC name and indicate them as primary,
secondary and tertiary alkyl halide. Hint: 8 isomers
9.4 Draw the structure and give IUPAC name of;
a) n-Pentyl chloride b) neo Pentyl chloride
c) tert- Butyl chloride d) tert- Pentyl chloride
e) Isobutyl bromide f) Isopentyl bromide
g) Isohexyl bromide h) sec-Butyl bromide
9.1.2.5 General Methods of Preparation

Alkyl halides are prepared as follows;
1. From alkanes 2. From alkenes
3. From alcohols 4. By halide exchange method
5. From silver carboxylate
1. From alkanes: Direct halogenation: Alkane reacts with limited amount of halogen (Cl2 or Br2)
in presence of sunlight or heat to form alkyl halide.
uv or 250-400°C
R—H + X2 R—X + HX
H H
diffused sunlight
H—C—H + Cl2 H—C—Cl + HCl
H (Limited) H
Chloromethane
uv, 25°C
CH3CH3 + Cl2 CH3CH2Cl + HCl
Chloroethane
400°C
CH3CH3 + Cl2 CH3CH2Cl + HCl
Chloroethane
uv, 127°C
CH3CH3 + Br2 CH3CH2Br + HBr
Bromoethane
Generally, this is not a good method for the preparation of haloalkanes due to following
reasons:
i. Excess X2( Cl2 or Br2) leads to formation of a mixture of polyhaloalkanes.
Cl2, uv Cl2, uv Cl2, uv Cl2, uv

CH4 CH3Cl CH2Cl2 CHCl3 CCl4
–HCl –HCl –HCl –HCl
Chloromethane Dichloromethane Trichloromethane Tetrachloromethane

(Methyl chloride) (Methylene chloride) (Chloroform) (Carbon tetrachloride)
ii. Higher alkanes give a mixture of all possible isomeric alkyl halides which are difficult to
separate. Hence, halogenation of alkanes is not suitable method for the laboratory preparation
of alkyl halides.
Cl
Cl2, uv, 25°C
CH3CH2CH3 CH3CH2CH2Cl + CH3CHCH3
n-Propyl chloride Isopropyl chloride
45% 55%
Cl
Cl2, uv, 25°C
CH3 CH2CH2CH3 CH3CH2CH2CH2Cl + CH3CH2CHCH3
n-Butyl chloride Isobutyl chloride
28% 72%
Br
Br2, uv, 127°C
CH3CH2CH3 CH3CH2CH2Br + CH3CHCH3
n-Propyl bromide Isopropyl bromide
3% 97%
Reactivity of hydrogen atom towards halogenation is 3° > 2° > 1° > CH4.

Reactivity of halogen towards halogenation is F2 > Cl2 > Br2 > I2
Iodination is reversible (as HI is powerful reducing agent), hence, it is carried out in presence of
oxidizing agents like HIO3, HNO3, HgO etc which oxidizes HI and equilibrium is shifted
towards forward direction.
HIO3
CH4 + I2 CH3I + HI
2HNO3 + 2HI 2H2O + I2 + 2NO2

conc.
HIO3 + 5HI 3H2O + 3I2
1. F2 is the most reactive of all halogens. It reacts with alkanes explosively producing large
amount of heat and a complex mixture. For example, methane reacts with F2 as:
CH4 + F2 CH3F+ CH2F2+ CHF3+ CF4+ C2F6+ C3F8
Monofluoroalkanes, however, can be obtained by diluting F2 with inert gas like N2 to make the
reaction less vigorous and carrying out the reaction in an apparatus which carry out the heat
produced.
2. Cl2 reacts with alkanes in bright sunlight explosively. Hence, reaction is carried out in diffused
sunlight.
Bright sunlight
CH4 + 2 Cl2 C + 4 HCl
3. Br2 reacts with alkanes in sunlight slowly. Hence heat is also needed in addition to sunlight.
Mechanism of halogenation of alkanes: Free radical substitution

The halogenation of alkanes proceeds through free radical substitution. It involves the following
steps.
i. Chain initiation step:
uv or Δ
X X X + X
Homolytic cleavage
ii. Chain propagation step:
X + R—H R + HX
R + X2 RX + X
iii. Chain termination step:

X + X X2
Or,
R + R R—R
Or
R + X R—X
Direct chlorination of alkanes can also be carried out using sulphuryl chloride (SO2Cl2) in
presence of light and traces of an organic peroxide.
light, organic peroxide
RH + SO2Cl2 RCl +SO2 + HCl
2. From alkenes: Hydrohalogenation: Alkene reacts with hydrogen halide (HX= HCl, HBr, HI) to
give respective alkyl halide. The reaction is frequently carried out by passing the dry gaseous
hydrogen halide directly into alkene. Aqueous solution of hydrogen halide is not used to avoid
chance of hydrolysis of alkyl halide.
—C = C— + HX —C—C—
H X
Alkene Alkyl halide
H H H H
H—C = C—H + HI H—C— C—H
H I
Ethene Iodoethane
CH3—CH = CH—CH3 + HCl CH3—CH—CH—CH3
But-2-ene H Cl
2-Cholorobutane
Addition of hydrogen halide onto unsymmetrical alkene: Markovnikov's addition (1869)
According to Markonikov's rule, when an unsymmetrical reagent is added to unsymmetrical
unsaturated organic compound, negative part of the reagent adds to the unsaturated carbon having less
number of hydrogen.
H H H H
CH3—C = C—H + HBr CH3—C—C—H
Propene Br H
2-Bromopropane
CH3 H CH3 H
CH3—C = C—H + HI CH3—C—C—H
I H
2-Methylpropene 2-Iodo-2-methylpropane
Mechanism of Markovnikov's addition: Electrophilic addition: Addition of hydrogen halide onto

unsymmetrical alkene follows Markonikov's rule and the reaction proceeds through electrophilic
addition as follows.
HBr H + + Br –
Step (i): Addition of electrophile (H+) onto carbon to carbon double bond of alkene to form more
stable carbocation. H H
CH3—C—C—H
+
H
H H 1° carbocation
CH3—C = C—H + H + (Less stable)
H H
CH3—C—C—H
+
H
2° carbocation
(More stable)
Step (ii): Addition of Br¯ on carbocation to form Markovnikov's addition product.
H H H H
CH3—C—C—H + Br¯ CH3—C—C—H
+
H Br H
2-Bromopropane

Addition of hydrogen bromide onto unsymmetrical alkene in presence of organic peroxide:

Anti-Markovnikov's addition/ peroxide effect/ Kharasch effect (1933)
According to anti-Markonikov's rule, when HBr is added to unsymmetrical unsaturated organic
compound in presence of traces of organic peroxide, bromine adds to the unsaturated carbon having more
number of hydrogen.
H H H H
Organic peroxide
CH3—C = C—H + HBr CH3—C—C—H
Propene H Br
1-Bromopropane
Mechanism of anti-Markovnikov's addition: Free radical addition

Addition of hydrogen bromide onto unsymmetrical alkene in presence of organic peroxide follows
anti Markonikov's rule and the reaction proceeds through free radical addition as follow:
Step (i): Chain initiation steps: Generation of bromine free radical.
RO—OR 2RO
RO + H Br ROH + Br
Step (ii): Chain propagation steps: Addition of bromine free radical onto carbon to carbon double
bond of alkene to form more stable free radical followed by addition of stable free radical to new
bromine atom to form anti Markonikov's product. H H
CH3—C—C—H
HH Br
1° Free radical
CH3—C = C—H + Br (Less stable)
H H
CH3—C—C—H
Br
2° Free radical
(More stable)
H H H H
CH3—C—C—H + H Br CH3—C—C—H + Br
Br H Br
Step (iii): Chain termination steps: The reactive particles combine with one another or is captured
by the wall of the reaction vessel, and a chain is terminated.
Only HBr in presence of traces of organic peroxide follows anti Markonikov's rule. Other reagents
like HCl, HI do not follow this rule. This can be explained as follows.
H–Cl is highly polar hence does not undergo homolysis easily. HI undergo homolysis to give iodine
free radicals which instantly combine to give I2.
H—X H +X Homolytic bond dissociation energy(kcal mol-1)
H—Cl H + Cl
103 kcal mol-1
H—Br H +
Br 88 kcal mol-1
H—I H +
I 71 kcal mol-1
Self Test
9.5 Identify A and B
Cl2, uv, 25°C
Isobutane A + B
9.6 Convert propene into
a. 1-Chloropropane b. 2-Chloropropane
3. From alcohol: Alkyl halides are almost always prepared from corresponding alcohols. Alcohol
reacts with halogen acid, phosphorous halides or thionyl chloride to give alkyl halide.
a. Reaction with halogen acid (HX): Alcohol reacts halogen acid (HCl, HBr, HI) to give
corresponding alkyl halide.
R-OH + HX R-X + H2O
Alcohol Alkyl halide
The reaction is carried out by passing the dry hydrogen halide gas into the alcohol or by heating
alcohol with the concentrated aqueous acid. The conditions of reaction depends on both the
nature of alcohol and the halogen acid.
Reactivity of alcohol: 3° > 2° > 1°
With HCl Reactivity of HX: HI > HBr > HCl
HCl is the least reactive of halogen acid. Hence HCl requires anhydrous ZnCl2 to react with
primary and secondary alcohol to give chloroalkane. The reaction of primary and secondary
alcohol with HCl in presence of anhydrous ZnCl2 to give chloroalkane is called Grooves'
process. A mixture of conc. HCl and anhydrous ZnCl2 is called Lucas reagent.
anhydrous ZnCl2
CH3CH2OH + HCl(g) CH3CH2Cl + H2O
anhydrous ZnCl2
CH3CH2CH2OH + HCl(g) CH3CH2CH2Cl + H2O
Propan-1-ol 1-Chloropropane
Tertiary alcohol being more reactive does not need any catalyst even at room temperature.
CH3 CH3
room temp
CH3—C—OH + HCl (conc) CH3—C—Cl + H2O
CH3 CH3
2-Methylpropan-2-ol 2-Chloro-2-methylpropane
With HBr
HBr is more reactive than HCl. Concentrated HBr is used to prepare alkyl bromides. Primary
alcohol requires little concentrated H2SO4 but secondary and tertiary alcohol do not need any
catalyst. CH CH OH + HBr (48%) CH3CH2Br+ H2O
3 2
The reaction can be carried out by heating alcohol with NaBr or KBr in concentrated
H2SO4.
KBr + Conc H2SO4 KHSO4 + HBr
KBr + H2SO4, Δ
CH3CH2CH2OH + HBr CH3CH2CH2Br + H2O
n-Propyl alcohol n-Propyl bromide
HI is the most reactive of all HX. Concentrated HI is used to prepare alkyl iodides. No catalyst
is required.
KI + H3PO4
CH3CH2OH + HI (57%) CH3CH2I+ H2O
The reaction can be carried out by heating alcohol with NaI or KI in 95% H3PO4.
CH3CH2OH + KI + H3PO4 (57%) CH3CH2I+ KH2PO4 +H2O
b. Reaction with phosphorous halide (PX3 or PCl5): When alcohol is refluxed with phosphorous
trihalide or phosphorous pentahalide, corresponding alkyl halide is formed.
reflux
3 CH3CH2OH + PCl3 3 CH3CH2Cl + 3 H3PO3
reflux CH3CH2Cl + POCl3 + HCl

CH3CH2OH + PCl5
PBr3, PI3 are unstable hence a mixture of red phosphorous and Br2 or I2 is used.
P4 + 6 Br2 4 PBr3
P4 + 6 I2 4 PI3
Red P + Br2
3 CH3CH2OH + PBr3 3 CH3CH2Br + 3 H3PO3
CH3 CH3
Red P + Br2
3 CH3—CH—CH2—OH + PBr3 3 CH3—CH—CH2—Br + H3PO3
2-Methylpropan-1-ol 1-Bromo-2-methylpropane
Red P + I2
3 CH3CH2OH + PI3 3 CH3CH2 I + 3 H3PO3
Δ
Red P + I2
3 CH3(CH2)14CH2OH + PI3 3 CH3(CH2)14CH2 I + 3 H3PO3
145-150ºC
c. Reaction with thionyl chloride (SOCl2): Alcohol reacts with thionyl chloride in presence or
absence of pyridine to give alkyl chloride. This is called Darzens procedure (1911).
reflux
ROH + SOCl2 RCl +SO2 + HCl
pyridine
CH3 CH3
reflux
CH—OH + SOCl2 CH—Cl + SO2 + HCl
α-Phenylethanol α-Phenylethyl chloride

Advantages of this method

i. The product is obtained in pure form since the side products are acidic gases, which can be
removed by heating them or by absorbing them by pyridine.
ii. Any excess SOCl2 can be removed by distillation easily due to its low boiling point
(b.pt. 76°C).
4. By halide exchange method: Alkyl iodides can be prepared by treating corresponding alkyl
chlorides or bromides with NaI in presence of acetone or methyl alcohol. This reaction is called
Finkelstein or Conant-Finkelstein reaction.
Acetone or methanol
RCl + NaBr RBr + NaCl
Acetone or methanol
RCl + NaI RI + NaCl
Acetone or methanol
RBr+ NaI RI + NaBr
Fluoroalkanes can be obtained indirectly by using inorganic fluorides like AgF, Hg2F2 etc.
CH3CH2Cl + AgF CH3CH2F + AgCl
This method was used by Swarts (1898) and called Swarts Reaction.
5. From silver salt of carboxylic acid: Hunsdiecker or Borodine-Hunsdiecker reaction(1935)

Silver salt of carboxylic acid reacts with chlorine or bromine in carbon tetrachloride as solvent
to form corresponding alkyl halide. This is called Hunsdiecker or Borodine-Hunsdiecker
reaction.
RCOOAg+ Cl2 RCl +CO2 + AgCl
RCOOAg+ Br2 RBr +CO2 + AgBr
i. This reaction follows free raidcal mechanism

ii. Iodine, however, forms ester with silver salt of carboxylic acid. This is called Birnbaum-Simonini reaction (1892).
2 RCOOAg+ I2 RCOOR + CO2 + 2 AgI

ester
9.1.2.6 Physical Properties

1. CH3Cl, CH3Br, and C2H5Cl are colourless gases, some higher members (upto C18) are sweet
smelling liquids and higher members are odourless solids.
2. Alkyl halides are insoluble in water but soluble in organic solvents like benzene, ether,
chloroform etc. Although alkyl halides are polar compounds, their polarity is not sufficient to
form intermolecular H-bond with water.
3. They burn with green edged flame.
4. Alkyl bromides and iodides are heavier than water whereas alkyl chlorides are lighter than
water. (Generally organic compounds are lighter than water. To be heavier than water, the
organic compounds must have heavier atom like Br, I or more atoms like Cl).
5.
a. For same halogen atom, the boiling points of alkyl halides increase with increase in carbon
number.
RCl < RCH2Cl < RCH2CH2Cl
b. For same alkyl group, the boiling points of alkyl halides
RCl < RBr < RI
This is because of the fact that, with the increase in size and mass of the molecule, the
magnitude of Vander Waals' forces of attraction increases. For example,
δ– H δ+ δ– H
H δ+
C C I
C Cl Br H
H H
H H
H
CH3—Cl CH3—Br CH3—I
b.pt = -24°C b.pt = 5°C b.pt = 43°C
c. In isomeric alkyl halides, boiling point decreases with increase in branching. This is because
with branching, the shape of molecule tends to be spherical i.e. surface area of molecule
decreases due to which intermolecular force of attraction (magnitude of Vander Waals' forces of
attraction) decreases. For example,
CH3
CH3CH2CH2CH2Cl CH3—CH—CH2—Cl
CH3 CH3—C—Cl
n-Butyl chloride CH3
Isobutyl chloride
b. pt. 78°C tert-Butyl chloride
b. pt. 68°C b.pt. 51°C
Self Test
9.7 Explain
a. 1-Chloropropane is not soluble in water
b n-Propyl chloride is liquid (b. pt.= 47ºC ) but n-Butane is gas(b. pt.= 0ºC )
c. Ethyl chloride is gas but ethyl iodide is liquid
d. tert-Butyl chloride has lower boiling point than n-Butyl chloride
9.8 Write all possible monobromoderivatives of propane and arrange them in the decreasing order
of their boiling point.
9.1.2.7 Chemical Properties

Alkyl halides are a highly reactive class of aliphatic compounds which undergo a wide range of
chemical reactions forming a large variety of other organic compounds. Hence they are extremely
important in organic synthesis. The high reactivity of alkyl halides is due to polar nature of carbon to
halogen bond.
δ+ δ–
C X
Element Electronegativity (Pauling scale)

C 2.4
F 4.0
Cl 3.0
Br 2.8
I 2.5
In general, for a given alkyl group, the reactivity is in the order

R—Cl < R—Br < R—I
This can be explained on the fact that C-X bond dissociation energy decreases in the order C-Cl >
C-Br > C-I. For example, heterolytic bond dissociation energy for methyl halides are:
CH3—Cl CH3—Br CH3—I

227 kcal/mol 219 kcal/mol 212 kcal/mol
H δ+ δ– H
H δ+ δ–
C Cl C Br C I
H H
H
H H H
The chemical properties of alkyl halides can be categorized as follows;
i. Nucleophilic substitution reaction ii. Elimination reaction
iii. Reaction with metals iv. Reduction
v. Rearrangement reaction
A. Nucleophilic substitution reaction
In alkyl halides, carbon to halogen bond is polar since halogen is more electronegative than
carbon. Therefore, nucleophile attacks the carbon bearing the halogen atom to give substitution
reaction. A substitution reaction initiated by a nucleophile is called nucleophilic substitution
reaction.
δ+ δ– solvent
–
–
R—X + OH R—OH + X
Product Leaving group
Substrate Nucleophile
[
Depending upon nature of substrate, nature of nucleophile and nature of solvent, nucleophilic substitution reaction occurs
by two different mechanisms;
SN2 reaction and SN1 reaction.
SN2 reaction: SN2 stands for bimolecular nucleophilic substitution reaction. Here, rate of reaction depends upon
concentration of substrate and concentration of nucleophile.
Rate=k[RX] [nucleophile]
Generally, primary alkyl halides follow with this type of mechanism. Here, nucleophile attacks the substrate from backside
(rear side, opposite side) of the leaving group. Nucleophilic attack from front side (from the side of the leaving group) is
difficult since nucleophile and leaving group both are electron rich.
Front side attack H

H H H
δ+ δ– δ– δ–
C X + OH¯ HO C X HO C + X¯
H
H Leaving group
H H H
Transition state
Backside attack
SN2 reaction mechanism: Complete inversion of configuration from substrate to product.
As the nucleophile starts to form bond with the substrate, leaving group also starts to break the bond with the
substrate and finally leaving group leaves to give the product. This means the reaction takes place in a single
step without any intermediate. Due to backside attack of nucleophile, the product is obtained with complete
inversion of configuration like inversion of an umbrella inside out in a strong gale. This is called Walden
inversion.
SN1 reaction: SN1 stands for unimolecular nucleophilic substitution reaction. Here, rate of reaction depends upon
concentration of substrate only but not upon concentration of nucleophile.
Rate=k[RX]
Tertiary alkyl halides follow with this type of mechanism. The reaction occurs in two different steps;
Step I: Substrate undergoes heterolysis slowly to form carbocation
Nucleophilic attack from front side (from the side of the leaving group) is difficult since nucleophile and leaving group both
are electron rich. Nucleophilic attack from backside (rear side, opposite side) of the leaving group is also difficult due to
bulky alkyl groups.(steric hinderance). Hence, nucleophile cannot attack the substrate directly. Here, substrate undergoes
heterolysis slowly to form carbocation.
Front side attack
R R R
OH¯ +
Slow step: rds
δ+ δ– C X¯
C X +
R
Leaving group
R
R
Carbocation
Backside attack Trigonal planar
Step II: Nucleophile attacks the carbocation to give product.

Since carbocation is planner, nucleophile attacks from either side to give products with retention of configuration and
inversion of configuration. However, just formed carbocation is not totally free. For certain time, it remains associated with
the leaving group. For that time period, nucleophilic attack from the side of the leaving group is hindered. Hence in SN1
reaction, the product is obatined with inversoin of configuration and retention of configuration but the former always
exceeds the latter.
R R
+
C
Backside attack R Front side attack
+
OH¯
R R
HO C C OH
R R
R R
Inversion of configuration Retention of configuration
1. Action of aqueous caustic alkali (Substitution by OH¯): Formation of alcohol: Alkyl halide
reacts with aqueous solution of caustic alkali ( NaOH or KOH) to give alcohol.
δ+ δ– + –
R—X + NaOH(aq) R—OH + NaX
H
δ+ δ– + –
CH3 C Br + NaOH (aq) CH3CH2—OH + NaBr
H Ethanol
Bromoethane
2. Action of alcoholic potassium bisulphide (Substitution by SH¯): Formation of thioalcohol:

Alkyl halide reacts with alcoholic solution of KSH to give thioalcohol.
δ+ δ– + –
R—X + KSH R—SH + KX
Thioalcohol
H
δ+ + –
CH3 C Br δ– + KSH CH3CH2—SH + NaBr
H Ethyl thioalcohol
Bromoethane
Water must be avoided as it causes hydrolysis of haloalkanes.

3. Action of alcoholic sodium alkoxide (Substitution by RO¯): Formation of ether (Williamson's
synthesis): When alkyl halide is heated with sodium or potassium alkoxide, ether is obtained.
This method is called Williamson's synthesis. This is a nucleophilic substitution reaction and
alkoxide ion (RO¯) acts as a nucleophile.
δ δ– Δ
R—X + R'O¯Na+ R—O—R' + NaX
Alkyl halide Sodium alkoxide Ether
H
δ+ Δ
CH3 C Br δ– + CH3O¯Na+ CH3CH2—O—CH3 + NaBr
H
Methoxyethane
Bromoethane Sodium methoxide (Mixed ether)
H
δ+ Δ
CH3 C Br δ– + CH3CH2 O¯Na+ CH3CH2—O—CH2CH3 + NaBr
H Ethoxyethane
Sodium ethoxide (Simple ether)
Bromoethane
The importance of this method lies on its versatility; simple as well as mixed ethers can be
obtained by this method.
Self Test
9.9 Convert ethyl alcohol into ethyl methyl ether.
–
4. Action of alcoholic potassium cyanide and alcoholic silver cyanide (Substitution by CN )
a. Action of alcoholic NaCN or KCN: Formation of alkane nitrile: When alkyl halide is
heated with ethanolic potassium cyanide, alkane nitrile (cyanide) is obtained (little isocyanide is
also obtained).
R—X + KCN (alc.) R—CN + KX
Alkane Nitrile
CH3CH2—Br + KCN (alc.) CH3CH2—CN + KBr

Propane nitrile
(Ethyl cyanide)
Nitrile gives different classes of organic compounds with different reagents.

i. Formation of carboxylic acid (Complete hydrolysis): When nitrile is treated with dilute HCl,
carboxylic acid is obtained.
O
dil. HCl
R—CN+ 2H2O R—C—OH + NH3
Δ
Carboxylic acid
dil. HCl
O
CH3CH2—CN+ 2H2O CH3CH2—C—OH + NH3
Δ
Propane nitrile Propanoic acid
ii. Formation of amide (Partial hydrolysis): When nitrile is treated with concentrated HCl,
amide is obtained.
conc. HCl O
R—CN+ H2O R—C—NH2
Amide
conc. HCl O
CH3CH2—CN+ H2O CH3CH2—C—NH2
Propane nitrile Propanamide
iii. Formation of primary amine (Reduction): When nitrile is reduced with H2/Ni, LiAlH4 or
C2H5OH/Na, primary amine is obtained.
H2/Ni or LiAlH4 or
RCN Na/C2H5OH R—CH2NH2
Nitrile
1° amine
Na/C2H5OH
CH3CH2CN + 4[H] CH3CH2CH2NH2
Propane nitrile 1-Aminopropane
Reduction of nitrile into primary amine with Na/C2H5OH is called Mendius reaction.
iv. Formation of aldehyde (Stephen's reduction): When nitrile is treated with SnCl2 and
concentrated HCl followed by hydrolysis, aldehyde is obtained.
i) SnCl2/HCl
O
ii) H2O/H+
R—CN R—C—H
Aldehyde
Advantage of nitrile synthesis
Nitrile synthesis has advantage of increasing carbon chain length by one carbon atom.
Example: O
dil. HCl
CH3CH2—C—OH
Complete hydrolysis
Propanoic acid
conc. HCl
O
CH3CH2—C—NH2
Partial hydrolysis
Propanamide
alc. KCN
CH3CH2Br CH3CH2CN
Propane nitrile H2/Ni or LiAlH4 or
C2H5OH/Na
CH3CH2CH2NH2
Reduction
1-Aminopropane
i) SnCl2/HCl
ii) H2O/H+ O
CH3CH2—C—H
Stephen reduction
Propanal
Self Test
9.10 Starting from ethanol, outline the formation of propanoic acid.
9.11 Convert ethyl alcohol into n-propyl amine.
b. Reaction with alcoholic AgCN: Formation of isonitrile: When alkyl halide is heated with
ethanolic silver cyanide, isonitrile (isocyanide) is obtained (little nitrile is also obtained).
R—X + AgCN (alc.) R—NC + AgX
Isonitrile
CH3CH2—Br + AgCN (alc.) CH3CH2—NC + AgBr

Ethyl carbylamine
(Ethyl isocyanide or Ethyl isonitrile)
Isonitrile gives different classes of organic compounds with different reagents.

i. Formation of primary amine (hydrolysis): Isonitrile is hydrolyzed to primary amine
and formic acid.
H2O/H+
R−N C + 2H2O R—NH2 + HCOOH
1° Amine
H2O/H+
CH3—N C + 2H2O CH3NH2 + HCOOH
ii. Formation of secondary amine (Reduction): Isonitrile is reduced to secondary amine by

H2/Ni or LiAlH4.
H2/Ni or
LiAlH4 or
Na/C2H5OH
RNC R—N—CH3
Isonitrile
H
2° amine
Na/C2H5OH
CH3CH2NC + 4[H] CH3CH2—N—CH3
Ethyl carbylamine H
(Ethyl isonitrile)
(Ethyl isocyanide) N–Methylehanamine
iii. Formation of nitrile (rearrangement): When isonitrile is heated for a long time, nitrile is
obtained.
Δ
R—NC R—CN
Alkyl isocyanide Alkyl cyanide
In AgCN, silver to carbon bond has covalent character, hence nitrogen atom with its lone pair of electron acts as
nucleophilic site and the product is chiefly isocyanide.
H
δ+ δ–
Ag C ≡ N + CH3 C Br CH3CH2 NC + AgBr
Ethyl isocyanide
H
KCN is ionic compound. Here, carbon atom has negative charge and acts as nucleophilic site and the product is chiefly
cyanide.
H
δ+ δ–
+ – + CH3 C Br CH3CH2 CN + KBr
K C≡N
H Ethyl cyanide
A nucleophile in which more than one atom can act as nucleophilic site is called ambident nucleophile. NO2-, CN- etc. are
ambident nucleophile.
Self Test
9.12 Identify A and B in the following reaction sequence
SOCl2, pyridine alc. NaCN Na/C2H5OH
A1 A2 A3
(i) CH3CH2OH
reflux
red P+I2, reflux alc. AgCN Na/C2H5OH

B1 B2 B3
(ii) CH3CH2OH
5. Action of KNO2 or AgNO2

a. Action of alcoholic KNO2: Formation of nitrite: When a primary alkyl halide (especially
bromides and iodides) is heated with ethanolic solution of potassium nitrite, alkyl nitrite is
obtained along with little nitroalkane.
CH3CH2Br +KNO2 Δ CH3CH2 O N O + KBr
Bromoethane Ethyl nitrite
b. Action of alcoholic AgNO2: Formation of nitro compound: When a primary alkyl halide
(especially bromides and iodides) is heated with aqueous ethanolic solution of silver nitrite,
nitroalkane is obtained along with little alkyl nitrite.
O
CH3CH2Br +AgNO2 Δ +
+ AgBr
CH3CH2 N
O¯
Bromoethane Nitroethane
+ -
K O N O
H CH3CH2 O N O + KBr
δ+ δ– Ethyl nitrite
CH3 C Br
O
H +
+ AgBr
CH3CH2 N
Ag O N O O¯
Nitroethane
KNO2 is ionic compound. Here, oxygen atom has negative charge and acts as nucleophilic site and the product is chiefly
alkyl nitrite. In AgNO2, silver to oxygen bond has covalent character, hence nitrogen atom with its lone pair of electron
acts as nucleophilic site and the product is chiefly nitroalkane. (an atom with negative charge is more nucleophilic than the
atom having lone pair of electron).
A nucleophile in which more than one atom can act as nucleophilic site is called ambident nucleophile. NO2-, CN- etc. are
ambident nucleophile.
6. Action of Ammonia: Formation of amine (Hofmann's ammonolysis): When an alkyl halide is

heated with aqueous or alcoholic solution of ammonia at 100°C in a sealed tube or allowed to
stand at room temperature, amine is formed. By varying the proportions of ammonia and alkyl
halide, particular class of amine can be obtained in large proportion. The process of cleavage of
the C-X bond by ammonia molecule is called ammonolysis.
i. If ammonia is excess, primary amine is obtained.
δ+ δ–
H N H + R X R N H + HX
H H
H
δ+
H N H + CH3 C Brδ– CH3CH2 N H + HBr
H H H
Ethylamine
(1°)
ii. If alkyl halide is excess, a mixture of primary, secondary and tertiary amines and
quaternary ammonium salt is obtained.
δ+ δ–
H N H+R X R N H + HX
H H
1° amine
δ+ δ–
R N H+R X R N R + HX
H H
2° amine
δ+ δ–
R N R+R X R N R + HX
H R
3° amine
+
R
δ+ δ– –
R N R+R X R N R X
R R
Quaternary ammonium salt

For example, when ammonia is heated with excess ethyl bromide,

H
δ+
H N H + CH3 C Brδ– CH3CH2 N H + HBr
H H H
Ethylamine
(1°)
H
δ+
CH3CH2 N H + CH3 C Brδ– CH3CH2 N CH2CH3 + HBr
H H H
Diethylamine
H (2°)
δ+
CH3CH2 N H + CH3 C Brδ– CH3CH2 N CH2CH3 + HBr
CH2CH3 H CH2CH3
Triethylamine
(3°)
+
(CH3CH2)3N + CH3CH2Br (CH3CH2 )4N Br-
Tetraethylammonium bromide
(Quaternary ammonium salt)
Or,
NH3 CH3CH2Br CH3CH2Br
CH3CH2Br CH3CH2NH2 (CH3CH2 )2NH (CH3CH2 )3N
Ethyl bromide Ethyl amine Diethyl amine
Triethyl amine
CH3CH2Br
(CH3CH2 )4N Br -
+
Tetraethyl ammonium bromide
Note:
i. The order of reactivity of halides with amines is RI > R Br> RCl
ii. This is nucleophilic substitution reaction. Here, ammonia, primary and secondary amine acts as nucleophile. Primary alkyl
halide gives good yield but tertiary alkyl halide gives elimination reaction.
CH3 CH3
CH3 C Br + NH3 CH3 C CH2 + NH4Br
CH3
2-Methylpropone
3°alkyl halide
Self Test
9.13 Identify A in the following reaction sequence:
NH3 CH3I CH3I CH3I
CH3I A1 A2 A3 A4
7. Action of alcoholic silver salt of carboxylic acid: Formation of ester: When alkyl halide is
refluxed with alcoholic solution of silver salt of carboxylic acid, ester is formed.
O O
δ+ δ–
R—X + R'—C—O¯Ag+(alc.) R' C—OR + AgX
—
Silver carboxylate Alkyl alkanoate
(Ester)
O O
CH3CH2—Br + CH3—C—OAg(alc.) CH3 C—OCH2CH3 + AgBr
—
Silver ethanoate Ethyl ethanoate
(Ethyl acetate)
B. Elimination reaction: Dehydrohalogenation

When alkyl halide is boiled with alcoholic solution of caustic alkali, elimination of elements of
hydrogen halide takes place to give alkene. This is an elimination reaction and called
dehydrohalogenation. This reaction belongs to 1,2 elimination since eliminating groups are
removed from adjacent carbons and also called β- elimination since β- hydrogen is removed.
H H H H
β α Boil
H—C—C—H + KOH (alc.) H—C = C—H + KI + H2O
H I Ethene
Iodoethane
H H H H H
β α β Boil
H—C—C—C—H + KOH (alc.) CH3—C = C—H + KI + H2O
H Br H Propene
2-Bromopropane
In dehydrohalogenation (also in dehydration), if there is possibility of forming two different

alkenes, the more substituted alkene is formed as major product. This is called Saytzeff rule.
Example:
H H
CH3CH2—C = C—H
But-1- ene
H H H H 19%
KOH (alc.)
β α β
H—C—C—C—C—H
H H Br H
H H
2-Bromobutane
CH3—C = C— CH3
But-2- ene
81%
(Major product)
1,2-Elimination: Dehydrohalogenation
β α – Boil –
—C C— + OH —C = C— + H2O + X
base
protonated base
X
alkene leaving group
substrate
In deydrohalogenation, –OH (from alcoholic KOH) acts as a base (not nucleophile) and abstracts
H+ from β carbon.
Reactivity of alkyl halides towards dehydrohalogenation is 3º > 2º >1º
Self Test
9.14 Write the structure of all alkenes obtained on heating following alkyl halides with alcoholic
potassium hydroxide.
a. 1-Chloropentane b. 2-Chloropentane
c. 3-Chloropentane d. 2-Chloro-2-methylbutane
9.15 Convert 1-Bromopropane into 2-Bromopropane and vice versa.
9.16 Convert 1-Chloropropane into 2-Chloropropane and vice versa.
C. Reaction with Metals

a. Reaction with sodium: Wurtz reaction: When alkyl halide is heated with sodium metal in dry
ether as solvent, two molecules of alkyl halide combine to give higher alkane. This reaction is
called Wurtz reaction.
Dry ether, Δ
R—X + 2Na + X—R R—R + 2NaX
Dry ether, Δ
CH3CH2—Br + 2Na + Br—CH2CH3 CH3CH2CH2CH3 + 2NaBr
CH3 CH3 CH3 CH3
Dry ether, Δ
H—C—Br + 2Na + Br—C—H H C — C—H
— + 2NaBr
CH3 CH3 CH3 CH3
2-Bromopropane 2,3-Dimethylbutane
This method is suitable for the preparation of symmetrical alkanes (alkanes having even
number of carbon atoms) of higher carbon number.
Limitations of Wurtz reaction
i. This method is not suitable for the preparation of unsymmetrical alkanes and alkanes having
odd number of carbon atoms. To prepare unsymmetrical alkanes, two different alkyl halides
have to be used which gives a mixture of three different alkanes. For example, when a mixture
of methyl iodide and ethyl iodide is heated with sodium metal in anhydrous ether, a mixture of
ethane, propane and butane is formed.
Dry ether, Δ
CH3—I + 2Na + I—CH3 CH3CH3 + 2NaI
Dry ether, Δ
CH3—I + 2Na + I—CH2CH3 CH3CH2CH3 + CH3CH3 + CH3CH2CH2CH3 + 2NaI
Dry ether, Δ
CH3CH2—Br + 2Na + Br—CH2CH3 CH3CH2CH2CH3 + 2NaBr
ii. Methane can not be prepared by this method.

iii. Only primary and secondary alkyl halides give Wurtz reaction. 3º alkyl halide gives alkene.
b. Reaction with magnesium: Formation of Grignard reagent: Alkyl halide reacts with
magnesium metal in anhydrous ether to form alkylmagnesium halide which is commonly
called Grignard reagent1.
Dry ether
RX + Mg RMgX
Inert atmosphere Alkyl magnesium halide (Grignard reagent)
where, R= Alkyl group

X= Cl, Br or I
Examples,
Dry ether
CH3I + Mg CH3MgI
Inert atmosphere
Methyl magnesium iodide
Dry ether
CH3CH2Br + Mg CH3CH2MgBr
Inert atmosphere
Ethyl magnesium bromide
Dry ether
CH3CH2CH2Cl + Mg CH3CH2CH2MgCl
Inert atmosphere
n-Propylmagnesium bromide
Dry ether
CH3—CH— CH3 + Mg CH3—CH— CH3
Inert atmosphere
Cl MgCl
Isopropyl chloride Isopropylmagnesium chloride
1. Victor Grignard discovered and developed the use of Grignard reagent in 1900, so he was awarded Nobel prize for chemistry in 1912.
To vaccum
RX in dry ether
Inert gas
To vaccum
Mg metal in dry ether
Ice bath
Fig. 9.1: Preparation of Grignard reagent
It is an organometallic compound2. It is extremely valuable and versatile reagent from which

various classes and varieties of organic compounds can be synthesized like alkanes, alcohols,
carboxylic acids etc.
Rate of formation of Grignard reagent
R—I > R—Br > R—Cl
CH3X > C2H5X > C3H7X ......
Precautions for the preparation of Grignard reagent

i. The apparatus, solvent and the reactants must be dry. If water is present, it reacts with Grignard
reagent to form alkane.
RMgX + HOH RH + Mg(OH)X
ii. The reaction must be carried out in inert atmosphere. Otherwise oxygen of air reacts with
Grignard reagent to form hydroperoxide.
RMgX + O2 R—O—OMgX
c. Reaction with lead: Ethyl chloride reacts with lead sodium alloy to form tetraethyl lead (TEL)
which is used as anti-knocking additive to petrol.
4 CH3CH2Cl + 4 Na-Pb (CH3CH2)4Pb +3Pb +4 NaCl

Tetraethyl lead
2 Organometallic compounds are those compounds in which metal atom is directly bonded to carbon.
C-M, where M= Li, Mg, Al, Zn, Cd, Hg, Sn, Pb, Cu etc. For example,
RLi (Alkyl lithium), Al(C2H5)3 (Triethyl aluminium), (C2H5)4Pb (Tetraethyl lead), R2CuLi (Lithium dialkyl copper) etc.
D. Reduction
Alkyl halide can be reduced to alkane by different ways using different reagents.
a. Catalytic hydrogenolysis: Alkyl halides (alkyl iodides, bromides and chlorides) are reduced
into alkanes by hydrogen in presence of catalyst like Ni, Pt or Pd.
R—X H2/Ni
R—H + HX
Alkyl halide Δ Alkane
H2/Ni
CH3CH2I + H2 CH3CH3 + HI
Δ
b. Reduction with metal hydride
i. Reduction with LiAlH4 (Lithium aluminium hydride): Primary and secondary alkyl
halides (not tertiary alkyl halides) are reduced into alkanes by LiAlH4.
ii. Reduction with NaBH4 (Sodium borohydride): Secondary and tertiary alkyl halides (not
Primary) are reduced into alkanes by NaBH4.
c. Reduction with dissolving metals: Alkyl halides are reduced into alkanes by Zn/CH3COOH,
Zn/HCl, Zn/NaOH, zinc-copper couple and ethanol, etc.
Zn-Cu/C2H5OH
CH3CH2I CH3CH3
e; H+
The reaction occurs due to transfer of electron from metal to organic molecule being reduced followed by
transfer of proton from solvent. Nascent hydrogen is not responsible.
E. Rearrangement reaction
Alkyl halides on heating with aluminium chloride undergo rearrangement reaction.
AlCl3, 300°C
CH3CH2CH2Cl CH3-CH-CH3
1-Chloropropane Cl
2-Chloropropane
CH3 CH3
AlCl3, 300°C
CH3—C—CH2—Cl CH3—C—CH2—CH3
CH3 Cl
1-Chloro-2,2,-dimethylpropane 1-Chloro-2-methylbutane
AlBr3, Δ
CH3CH2CH2Br CH3—CH—CH3
1-Bromopropane Br
2-Bromopropane
9.1.3 Dihaloalkanes
When any two of the hydrogen atoms in alkanes are replaced by halogen atoms, the resulting
organic compounds are called dihaloalkanes. They have general formula CnH2nX2.
There are following types of dihaloalkanes.
i. 1, 1-Dihalides (geminal dehalide or gem-dihalide) or alkylidene dihalide: two halogen atoms

on the same carbon atom Br H
H—C—C—H
Br H
1, 1 Dibromoethane
(Ethylidene bromide)
ii. 1, 2-Dihalides (vicinal dihalide or vic-dihalide) or alkylene halide: two halogen atoms on the
adjacent carbon atoms H H
H—C—C—H
Br Br
1, 2- Dibromoethane
(Ethylene bromide)
iii. Polymethylene dihalides (α,ω-dihalides) two halogen atoms on the terminal carbon atoms of
the chain ClCH2CH2CH2CH2CH2Cl
1,5-Dichloropentane
iv. Dihalogen compounds having two halogen atoms other than mentioned above
Some Reactions
1. Dehydrohalogenation: When 1, 1-dihalide or 1,2-dihalide is boiled with alcoholic solution of
caustic alkali, elimination of elements of hydrogen halide takes place to give alkyne. This is an
elimination reaction and called dehydrohalogenation.
H H
Δ
H—C—C—H + 2KOH (alc.) H—C ≡ C—H + 2 KBr + 2 H2O
Br Br
1, 2 Dibromoethane
(Ethylene bromide)
H Br
Δ
H—C—C—H + 2KOH (alc.) H—C ≡ C—H + 2KBr + 2 H2O
H Br
1, 1- Dibromoethane
(Ethylidene bromide)
Alternatively, sodamide in liquid ammonia can be used for the better yield of alkyne.
H H
Δ
H—C—C—H + 2NaNH2 H—C ≡ C—H + 2 NaBr + 2 NH3
Br Br
2. Dehalogenation: When 1, 2-dihalide is heated with zinc dust, dehalogenation takes place to
give alkene.
H H H H
Δ
H—C—C—H + Zn H—C = C—H + ZnBr2
Br Br
1, 2 Dibromoethane
Self Test
9.17 Convert ethane into ethyne.
9.18 Write the structural isomers of C2H4Br2 and give their IUPAC as well as common name.
Convert one isomer into another and vice versa.
9.19 Write the structure and give IUPAC name of
i. Methylene chloride ii. Ethylidene bromide
iii. Ethylene bromide iv. Propylidene chloride
9.1.4 Trihaloalkales: Chloroform

Some important trihalogen derivatives of alkanes are as follows;
Formula IUPAC name Common name Medicinal value
CHCl3 Trichloromethane Chloroform Anaesthetic
CHBr3 Tribromomethane Bromoform Medicine for whooping cough
CHI3 Triiodomethane Iodoform Antiseptic
9.1.4.1 Laboratory Preparation of Chloroform

H
Cl Cl
Cl
geometry of CHCl3
μ = ⎯↓
Theory
Chloroform is prepared in laboratory by distilling ethyl alcohol or acetone with aqueous paste of
bleaching powder. In the reaction, aqueous bleaching powder acts as oxidizing agent, chlorinating
agent as well as hydrolyzing agent.
Preparation of chloroform involves following steps of reactions
Bleaching powder reacts with water
CaOCl2 + H2O Ca(OH)2 + Cl2
1. Preparation from Ethyl Alcohol

a. Oxidation of ethyl alcohol into acetaldehyde: The liberated chlorine gas acting as an oxidizing
agent, oxidizes ethyl alcohol to acetaldehyde.
H O
oxidation
CH3—C—OH + Cl2 CH3—C—H + 2 HCl
Δ
H
Ethanal
Ethanol
b. Chlorination of acetaldehyde into trichloroaceatldehyde (Chloral): The excess of liberated
chlorine acting as the chlorinating agent, chlorinates acetaldehyde into chloral.
O Cl O
chlorination
CH3—C—H + 3 Cl2 Cl—C—C—H + 3 HCl
Δ
Cl
Trichloroethanal
(Chloral)
c. Hydrolysis of chloral into chloroform: The calcium hydroxide obtained from hydrolysis of
bleaching powder, hydrolyzes chloral to chloroform.
Cl O hydrolysis Cl O
Ca(OH)2 + 2Cl—C—C—H 2 H—C—Cl + H—C—O 2 Ca
Cl Cl
Chloroform Calcium formate
2. Preparation from acetone
a. Chlorination of acetone into trichloroacetone: The liberated chlorine gas from bleaching
powder acting as the chlorinating agent, which chlorinates acetone into trichloroacetone.
O Cl O
chlorination
CH3—C—CH3 + 3 Cl2 Cl— C—C—CH3 + 3 HCl
Propanone Cl
1,1,1-Trichloropropanone
b. Hydrolysis of trichloroacetone into chloroform: The calcium hydroxide obtained from

hydrolysis of bleaching powder, hydrolyzes trichloroacetone to chloroform.
Cl O Cl O
hydrolysis
Ca(OH)2 + 2Cl—C—C—CH3 2 H—C—Cl + H3C—C—O 2 Ca
Cl Cl
Chloroform Calcium acetate
Water out
Ethyl alcohol or Water condenser

acetone + paste of
bleaching powder in
water
Water bath
Cold water in
To sink
Cold water
Chloroform
Fig. 9.2: Laboratory preparation of chloroform

Procedure
A paste of bleaching powder in water is prepared by
mixing 100 g of bleaching powder in 200 ml water and
transferred into one liter round bottom flask. 25 ml of ethyl Aqueous layer
alcohol or acetone is added into the flask. The flask is Chloroform
fitted with water condenser provided with receiver then
heated gently on a water bath. Chloroform formed distills
over which is collected in the water cooled receiver. It is
transferred into a separating funnel, where chloroform
forms the lower layer and such layer is separated.
Fig. 9.3: Separating funnel, separation
Purification of chloroform from reaction mixture
The main impurities in chloroform are acids and water. To remove these impurities following
steps are applied:
1. Chloroform is treated with dilute NaOH in a separating funnel to dissolve acidic
impurities and aqueous layer is rejected.
2. Chloroform is washed with water 2-3 times to remove water soluble impurities and
aqueous layer is again rejected.
3. Chloroform is dried with anhydrous CaCl2.
4. Finally, chloroform is redistilled at about 60 to 65°C to get pure and dry chloroform.
In this way, chloroform is prepared in laboratory in pure and dry state.
Industrial Preparation
i. Manufacture from carbon tetrachloride
Chloroform can be prepared on a large scale by partial reduction of carbon tetrachloride using iron fillings and water.
Fe/H2O
CCl4 + 2 [H] CHCl3 + HCl
Limitation of the method: Chloroform manufactured by this method is used as a solvent only as it is not enough pure for
its use as an anesthetic agent.
ii. Manufacture from methane
Chloroform can also be prepared by the chlorination of methane with calculated quantity of chlorine in the presence of
sunlight.
Cl2, uv Cl2, uv Cl2, uv
CH4 CH3Cl CH2Cl2 CHCl3
–HCl –HCl –HCl
Chloromethane Dichloromethane Trichloromethane
(Methyl chloride) (Methylene chloride) (Chloroform)
In the reaction, a mixture of methyl chloride, methylene chloride, chloroform and carbon tetrachloride is obtained, from
which chloroform is separated by fractional distillation.
9.1.4.2 Physical Properties of Chloroform

1. It is colorless sweet smelling liquid.
2. It boils at 61ºC and its freezing point is –63ºC.
3. It is heavier than water (sp. gr.= 1.485 at 25°C)
4. The vapor of chloroform induces unconsciousness therefore it can be used as an anesthetic
agent.
5. It acts as solvent, which dissolves substances like oils, fats, waxes etc.
9.1.4.3 Chemical properties of chloroform

1. Reaction with air: Chloroform reacts with air in presence of sunlight slowly forming carbonyl
chloride which is commonly called phosgene. Phosgene is a highly poisonous gas which attacks
to the central nervous system and may cause death.
Cl
Sunlight Cl
2 H—C—Cl + O2 2 C=O + 2 HCl
Cl
(air)
Cl Carbonyl chloride
(Phosgene)
How to store chloroform?
To prevent the formation of poisonous phosgene gas, chloroform is stored in the following
ways for the given reasons:
i. It is always kept in dark coloured bottles so that it could be protected from exposure to
sunlight.
ii. It is filled well up to the stopper so that no air be left inside the bottles.
iii. A small amount of ethanol (1%) is added to the chloroform while filling the bottle. Ethanol
converts phosgene gas, if formed, into non-poisonous diethyl carbonate.
C2H5O H Cl C2H5O
+ C=O C=O + 2 HCl
Cl C2H5O
C2H5O H
Diethyl carbonate
(C2H5)2CO3
Test for the purity of anesthetic chloroform
Impure chloroform containing phosgene (due to the oxidation of chloroform in air) produces
–
white precipitate with aqueous AgNO3 due to Cl formed (from HCl) during the phosgene
formation.
Cl¯ + AgNO3 AgCl + NO3¯
white ppt
2. Reaction with acetone: Chloroform undergoes condensation with acetone in presence of caustic
alkali to form chloretone (colorless crystalline solid, m.pt. 97ºC). Chloretone is a hypnotic drug
(used as a sleep-inducing agent).
O Cl OH Cl
KOH
CH3—C + H—C—Cl CH3 — C — C — Cl
CH3 Cl CH3 Cl
Propanone 1, 1, 1 – Trichloro-2-methylpropan-2-ol
(Acetone) (Chloretone)
3. Reaction with aqueous caustic alkali: Hydrolysis: When chloroform is boiled with aqueous
solution of alkali like NaOH or KOH followed by acidification, formic acid is obtained.
Cl OH O O
Δ KOH (excess)
H—C Cl + 3 KOH –3 KCl H—C OH H—C—OH H—C—OK
–H2O –H2O
Cl OH Potassium formate
HCl (dil.)
Acidification
O
H—C—OH + KCl
Formic acid
4. Reaction with chlorine: Chloroform reacts with chlorine in presence of sunlight to form
carbontetrachloride.
Cl Cl
hν
Cl—C—H + Cl2 Cl—C—Cl + HCl
Cl Cl
Tetrachloromethane
(Carbontetrachloride)
5. Reaction with HNO3: When chloroform is heated with concentrated nitric acid,
nitrochloroform or chloropicrin is formed which is used as an insecticide and has been used as a
war gas or tear gas.
Cl Cl
Δ
Cl—C—H + HO—NO2 Cl—C—NO2 + H2O
Conc. Cl
Cl
Trichloronitromethane
(Chloropicrin, nitrochloroform)
6. Reaction with Phenol: Reimer-Tiemann Reaction: When chloroform is refluxed with phenol in
presence of aqueous solution of caustic alkali followed by acidification, salicyaldehyde is
obtained as major product. The reaction is called Reimer-Tiemann reaction.
OH OH O OH
60-70°C C—H
2 +2CHCl3 + 6KOH (aq.) + + 6KCl + 4H2O
Phenol o-Hydroxybenzaldehyde C=O

(Salicyaldehyde)
Major product H
p-Hydroxybenzaldehyde
See phenol for mechanism

7. Reaction with primary amine: Carbylamine Reaction: When chloroform is warmed with a
primary amine (aliphatic or aromatic amine) in presence of alcoholic KOH solution, isocyanide
(carbylamine) is formed which gives an unpungent smell like that of rotten onion. This reaction
is known as carbylamine reaction.
H Cl H warm
+ C + 3KOH (alc) R—N C + 3KCl + 3H2O
R—N
Carbylamine/ isocyanide/ isonitrile
H Cl Cl
(offensive smell)
Primary amine Chloroform
H Cl H
+ C Δ
CH3 CH2 – N + 3KOH (alc) CH3CH2— N C + 3KCl + 3H2O
H Cl Cl Ethyl carbylamine
Ethyl amine (Ethyl isocyanide)
H Cl H
Δ
N + C + 3KOH (alc) N C + 3KCl + 3H2O
H Cl Cl
Phenyl carbylamine
Aniline (Phenyl isocyanide)
This reaction serves as the test for both chloroform and primary amines under the name
carbylamine test or isocyanide test.
8. Reduction: Chloroform undergoes reduction with Zn/HCl (acidic reducing agent) in presence
of ethyl alcohol to give methylene chloride.
Zn/HCl
CHCl3 + 2[H] CH2Cl2 + HCl
Methylene chloride
Chloroform on reduction with Zn/H2O (neutral reducing agent) gives methane.

Zn/H2O
CHCl3 + 6 [H] CH4 + 3 HCl
9. Reaction with silver: When chloroform is heated with metallic silver powder, acetylene gas is
evolved.
Cl Cl
Δ
H—C Cl + 6 Ag + Cl C—H HC ≡ CH + 6 AgCl
Cl Cl Acetylene
9.1.4.4 Uses of chloroform
Chloroform is used
1. as a solvent in organic reactions and in industry for fats, waxes, resins, rubber, etc.
2. as laboratory reagent for testing primary amines (Carbylamine test)
3. for the preparation of chloretone and chloropicrin.
4. as an anesthetic: Chloroform was a popular anaesthesia from the mid 1800s to around 1900. Sir
James Young Simpson, and Scottish Obestrician, introduced the medical use of chloroform as
an anesthetic in 1847 in Scotland specially for childbirth.
9.1.5.5 Trihaloalkane: Iodoform

Preparation
1. From ethyl alcohol: When ethyl alcohol is warmed with I2 and NaOH or Na2CO3, pale yellow
precipate of iodoform is obtained.
2 NaOH + I2 NaOI + NaI + H2O ] × 4
H O
Δ CH3—C—H + NaI + H2O
CH3—C—OH + NaOI oxidation
H Ethanal
Ethanol
O I O
Δ
CH3—C—H + 3 NaOI I—C—C—H + 3 NaOH
iodination
I
Tri-iodoethanal
I O I
Δ
NaOH + I—C—C—H H—C—I + HCOONa
hydrolysis
I I
Iodoform Sodium formate
The overall reaction is
CH3CH2OH + 4I2 + 6 NaOH CHI3 +5NaI + 5H2O + HCOONa
Δ
2. From acetone: When acetone is warmed with I2 and NaOH or Na2CO3, pale yellow precipate of
iodoform is obtained.

iodination
CH3COCH3 + 3 NaOI CI3COCH3 + 3 NaOH
Δ
hydrolysis
CI3COCH3 + 3 NaOH CHI3 + CH3COONa
Δ

Δ
CH3COCH3 + 3I2 + 4NaOH CHI3 +3NaI + CH3COONa + 3H2O
When sodium carbonate is used instead of NaOH, the reactions are

Δ
CH3CH2OH + 4I2 + 3 Na2CO3 CHI3 +5NaI + 2H2O + HCOONa + 3CO2
Δ
CH3COCH3 + 4I2 + 3Na2CO3 CHI3 +5NaI + CH3COONa+ 3CO2 + 2H2O
Physical Properties
1. Iodoform is pale yellow crystalline solid with characteristic odour.
2. Its melting point is 119ºC.
3. It is insoluble in water but readily soluble in ethyl alcohol and ether.
Chemical properties
Chemically, iodoform resembles chloroform.
1. Reaction with aqueous caustic alkali: Hydrolysis: When iodoform is boiled with aqueous
solution of alkali like NaOH or KOH followed by acidification, formic acid is obtained.
I OH O O
Δ KOH (excess)
H—C I + 3 KOH H—C OH H—C—OH H—C—OK
–3K I –H2O –H2O
I OH
Dil HCl
O
H C—OH + KCl
—
Methanoic acid
2. Reaction with primary amine: Carbylamine Reaction: When iodoform is warmed with a
primary amine (aliphatic or aromatic amine) in presence of alcoholic KOH solution, isocyanide
(carbylamine or isonitrile) is formed which gives a pungent smell like that of rotten onion. This
reaction is known as carbylamine reaction.
H I H
warm
R—N + C + 3KOH (alc) R—N C + 3KI + 3H2O
H I I Carbylamine
Primary amine Iodoform (offensive smell)
3. Reaction with silver: When iodoform is heated with metallic silver powder, acetylene gas is
evolved.
I I
Δ
H—C I + 6 Ag + I C—H HC ≡ CH + 6 AgI
I I Acetylene
Uses of Iodoform
It is used as an antiseptic, its antiseptic property is not due to itself but due to the liberated I2.
Iodoform Test
1. For alcohols
OH
Alcohols having CH3—CH— structure on heating with excess I2 and aqueous alkali (NaOH)
give yellow crystalline precipitate of iodoform. This test is called iodoform test.

oxidation
CH3CH(OH)R + NaOI CH3COR + NaI + H2O
iodination
CH3COR + 3 NaOI CI3COR + 3 NaOH
hydrolysis
CI3COR + 3 NaOH CHI3 + RCOONa
Δ
CH3COR + 4 I2 + 6 NaOH CHI3 ↓ + 5 NaI + RCOONa + 5 H2O
Iodoform
(Yellow ppt)
2. For aldehydes and ketones O
Aldehydes or ketones having CH3—C— structure on heating with excess I2 and aqueous
alkali (NaOH) give yellow crystalline precipitate of iodoform. This test is called iodoform test.

iodination
hydrolysis

Δ
CH3COR + 3I2 + 4NaOH CHI3 ↓ +3 NaI + RCOONa + 3 H2O
Iodoform
(Yellow ppt)
Carbonyl compounds like HCHO, CH3CH2COCH2CH3, C6H5CHO (benzaldehyde) etc. do not

contain CH3— groups in α positon. So they do not give iodoform test. The compounds like
CH3CHO, CH3COCH3, CH3COCH2CH3 etc. contain CH3CO— group. So they give positive
iodoform test.
9.1.6 Tetrahaloalkane: Carbon tetrachloride

Tetrachloromethane (Carbon tetrachloride): It is a colorless liquid with boiling point 77ºC. It is
insoluble in water but soluble in organic solvent.
Cl
Cl Cl
Cl
Tetrahedral geometry of CCl4
μ=0
It is prepared industrially by different ways:
1. By the action of Cl2 on CS2
AlCl3
CS2 + 3Cl2 CCl4+ S2Cl2
2. By the action of Cl2 on CH4
uv
CH4 + 2Cl2 CCl4+ 4HCl
Carbon tetrachloride is nonpolar, aprotic solvent. It is used industrially as solvent for fats, oils,
resins, etc. It is also used as a fire extinguisher under the name of Pyrene.
1,1,2,2-Tetrachloroethane (Westron): It is used noninflammable liquid with boiling point 146ºC
and used as solvent for fats, oils, paints, varnishes, rubber etc.
Cl Cl
HC ≡ CH + 2 Cl2 H—C—C—H
Cl Cl
1, 1, 2,2 – Tetrachloroethane
(Westron)
9.2 Haloarenes (Aryl halides)

9.2.1 Introduction
Halogen derivatives of arenes where halo group is direcetly bonded to aromatic ring are called
haloarenes or aryl halides. It may be represented by Ar-X; where Ar is any aryl group and X is F, Cl,
Br or I.
F Cl Br I
Fluorobenzene Chlorobenzene Bromobenzene Iodobenzene
Br Br Br
Br
Br
Br
1,2-Dibromobenzene 1,3-Dibromobenzene 1,4-Dibromobenzene
(o-Dibromobenzene) (m-Dibromobenzene) (p-Dibromobenzene)
CH3 CH3 CH3

Cl
Cl
Cl
2-Chlorotoluene 3-Chlorotoluene 4-Chlorotoluene
(o-Chlorotoluene) (m-Chlorotoluene) (p-Chlorotoluene)
Br I CH3
Br Br
Br Br Cl Br
Br
1,3,5-Tribromobenzene 1-Bromo-3-chloro-5-iodobenzene 2,4,6-Tribromotoleune
If halogen atom is not directly bonded to aromatic ring e.g. ArCH2X ,they are called aryl substituted
alkyl halide or arylalkyl halide since they behave very much like alkyl halides. They are not aryl
halides. For example, Benzyl Chloride
CH2Cl
Benzyl Chloride
Triiodothyronine (T3)
Thyroxine (T4)
Organic compounds in which halogen atom is directly bonded to aromatic ring are also found in
human beings. For example, thyroid hormones, triiodothyronine (T3) and thyroxine (T4). In both
hormones, iodine atoms are directly bonded to aromatic ring. They are produced by the thyroid
gland that are primarily responsible for regulation of metabolism. Iodine is necessary for the production
of T3 and T4. A deficiency of iodine leads to decreased production of T3 and T4, enlarges the thyroid
tissue and will cause the disease known as goitre.
(i) List all the functional groups present in T3 and T4 and arrange them in the priority order .
9.2.2 General Methods of Preparation

1. From aromatic hydrocarbons
Aromatic hydrocarbon reacts with limited amount of Cl2 or Br2 at ordinary temperature in dark
and in presence of Lewis acid like FeCl3, AlCl3 to give corresponding aryl halide. Iron is most
commonly used since it is converted to FeCl3 .
Cl
FeCl3 or Fe
+ Cl2 dark
+ HCl
Chlorobenzene
Br
FeBr3
+ Br2 + HBr
dark
Bromobenzene
Direct iodination is carried out in presence of oxidizing agent like nitric acid, mercuric oxide etc.
oxidizing agents are used to remove powerful reducting agent HI.
I
conc. HNO3
+ I2 + HI
Iodobenzene
2HNO3 + 2HI 2H2O + I2 + 2NO2

conc.
2. From diazonium salts

Primary aromatic amine reacts with nitrous acid in ice cold solution to form diazonium salt.
The reaction is called diazotization. (See also Amines)
NaNO2 + HCl HNO2 + NaCl
H N H N+2 Cl¯
Ice cold
+ HNO2 + HCl + 2 H2O
(0°-10°C)
Benzene diazonium chloride

Diazonium salts are very important synthetic reagents for the preparation of a wide range of
valuable aromatic compounds. Haloarenes are prepared as follows;
i. Preparation of fluorobenzene: Schiemann reaction (1927): When fluoroboric acid is added to a
diazonium salt solution, precipitate of diazonium fluoroborate is obtained which on gentle
heating gives fluorobenzene.
N2Cl N2BF4
+ HBF4 + HCl
Benzene diazonium fluoroborate (precipitate)
N2BF4 F
Δ + N2 + BF3
ii. Preparation of Chlorobenzene and Bromobenzene: Sandmeyer reaction (1884): When

diazonium salt solution is mixed with cuprous chloride or cuprous bromide dissolved in the
corresponding halogen acid at room temperature or sometimes on warming, diazo group is
replaced by -Cl and -Br respectively. This reaction is called Sandmeyer reaction.
N2Cl Cl
HCl
+ Cu2Cl2 + N2 + Cu2Cl2
Chlorobenzene
N2Cl Br
HBr
+ Cu2Br2 + N2 + Cu2Cl2
Bromobenzene
This reaction can be carried out by warming daizonium salt solution with copper powder in
place of cuprous halide. The process is called Gattermann reaction (1890).
N2Cl Cl
HCl
+ Cu + N2 + Cu2Cl2
Chlorobenzene
N2Cl Br
HBr
+ Cu + N2 + Cu2Cl2
Bromobenzene
iii. Preparation of Iodobenzene: When diazonium salt solution is boiled with aqueous potassium
iodide, diazo group is replaced by -I.
N2Cl I
boil
+ aq. KI + N2 + KCl
Iodobenzene
i. HBF4
F
ii. heat
Fluorobenzene
Cl
CuCl/ HCl
NH2 N2Cl
Chlorobenzene
NaNO2 + HCl
0-10ºC Br
Aniline Diazonium salt CuBr/HBr
Bromobenzene
I
KI, warm
Iodobenzene
When a mixture of benzene vapour, hydrogen chloride and air is passed over heated copper chloride, chlorobenzene is
formed. The process is called Raschig process. Chlorobenzene is commercially prepared by this method.
Cl
1 + H2O
+ HCl + 2 O2
Self Test
9.20 How do you prepare chlorobenzene form (i) benzene (ii) aniline
9.2.3 Physical Properties

1. They are colourless oily liquids or crystalline solids.
2. Chlorobenzene is colourless liquid having aromatic odour.
3. They are insoluble in water but soluble in organic solvents.
Cl Cl Cl
Cl
Cl
Cl
o-Dichlorobenzene m-Dichlorobenzene p-Dichlorobenzene
m.pt. - 17ºC m. pt. - 24ºC m. pt. 52ºC
b. pt 180ºC b. pt. 173ºC b. pt. 175ºC
In isomeric dihalobenzenes, there is only slight variation in the boiling point and the order is:
ortho > para > meta. However, there is considerable variation in their melting point. Para isomer
has considerably high melting point. This is because para isomer is symmetrical to fit better in
the crystal lattice.
9.2.4 Chemical Properties

Chemical properties of chlorobenzene can be categorised as follows;
1. Electrophilic aromatic substituion reaction
2. Nucleophilic substitution reaction
3. Reduction
4. Reaction with metals
4. Other reactions
1. Electrophilic aromatic substitution reaction
Halogen atom (-X) present in benzene governs the reactivity and orientation in electrophilic
aromatic substitution reaction.
Deactivating group
X
Ortho-para director
Chlorine atom (-Cl) withdraws electron from benzene ring due to electron withdrawing
inductive effect (-I effect) of Cl since chlorine is more electronegative than carbon.
Chlorine atom releases electron to benzene ring due to resonance effect (+M effect).
+ + + δ+
Cl Cl Cl
Cl Cl Cl
–
– δ– δ–
– δ–
I II III IV V
Resonating/canonical structures of chlorobenzene Resonance hybrid
Here, inductive effect is stronger than resonance effect and causes net electron withdrawal from
benzene ring.
Hence, chlorine atom (Cl) decreases the electron density in benzene ring of chlorobenzene as
compared to that in benzene. Hence chlorobenzene is less reactive than benzene in electrophilic
aromatic substitution reaction (each position of chlorobenzene is less reactive than
corresponding position in benzene). A substituent that makes the benzene ring less reactive
than benzene in electrophilic aromatic substitution reaction is called deactivating group. Chloro
group is deactivating group.
However, due to resonance, Cl releases electrons towards benzene ring not equally to all
positions. It releases electrion more to ortho and para positions than meta positions, so electron
density is relatively higher in ortho and para positions than meta in positions. Hence,
chlorobenzene gives ortho- para substituted products. A substituent that directs the incoming
group chiefly ortho and para to it is called ortho-para director.
Cl Cl
Cl2/FeCl3
Cl
+
Chlorination
Cl
Ortho- Para-
Dichlorobenzene
Cl Cl
HNO3/H2SO4/Δ NO2
+
Nitration
NO2
Cl
Ortho- Para-
Chloronitrobenzene
Cl Cl
Chlorobenzene H2SO4/SO3/Δ SO3H
+
Sulphonation
SO3H
Ortho- Para-
Chlorobenzenesulphonic acid
Cl Cl
CH3Cl/AlCl3 CH3
+
Friedel-Craft alkylation
CH3
Ortho- Para-
Chlorotoluene
Self Test
9.21 Chlorobenzene is less reactive than benzene in electrophilic aromatic substitution reaction,
explain.
9.22 Chlorobenzene gives ortho para substituted products, explain.
2. Nucleophilic substitution reaction

Haloalkanes undergo nucleophilic substitution reaction only with extreme difficulty. The low
reactivity of haloarenes towards nucleophilic substitution reaction can be explained as follows;
a. Carbon to halogen bond in haloarenes are strong: Resonance effect: Haloarene is resonance
hybrid of structures I to V which indicates that carbon to halogen bond on haloarene has a
partial double bond character. A double bond is shorter and stronger than the corresponding
single bond. Hence it is difficult to break down the carbon to halogen bond.
+ + + δ+
Cl Cl Cl
Cl Cl Cl
–
– δ– δ–
– δ–
I II III IV V
Resonating/canonical structures of chlorobenzene Resonance hybrid
b. Carbon to halogen bond in haloarene is less polar: Hybridization effect: In haloarene,

halogen atom is bonded to sp2 carbon whereas in haloalkane halogen atom is bonded to sp3
carbon. An sp2 carbon (33.33% s-character) is more electronegative than sp3 carbon (25% s-
character). Hence carbon to halogen bond in haloarene is less polar than that in haloalkanes.
H H
C C H
1.69Å 1.77Å
CH3 C Cl
H C C Cl
H
C C
H H
sp3 Hybridized carbon
sp2 Hybridized carbon 25% s-character
33.33% s-character μC-Cl = 2.05 D
μC-Cl = 1.73 D
However, aryl halides undergo nucleophilic substitution reaction under vigorous conditions
like high temperature, high pressure, catalyst, etc.
i. Action of NaOH (hydrolysis): When chlorobenzene is heated with caustic soda at 360°C
and 300 atmospheric pressure followed by acidification, phenol is formed. This method
was used by Dow chemical company, USA for the commercial preparation of phenol .
Hence this method is called Dow process.
Cl OH ONa OH
NaOH, 360°C, 300 atm. NaOH (excess) HCl (dil)
– NaCl
+ NaCl
–H2O Acidification
Phenol
or Cl OH
(i) NaOH, 360°C,300 atm
(ii) dil. HCl
Powerful electron withdrawing group ( eg. -NO2, -CN. -COOH etc.) present ortho and para
to halogen atom increases the reactivity of benzene ring towards nucleophilic substitution
reaction.
Cl OH
(i) NaOH, 160°C
(ii) dil. HCl
NO2 NO2
p-Chloronitrobenzene p-Nitrophenol
Cl OH
NO2 (i) NaOH, 100°C NO2
(ii) dil. HCl
NO2 NO2
2,4-Dinitrochlorobenzene 2,4-Dinitrophenol
Cl OH
O2N NO2 (i) H2O, Warm O2N NO2
(ii) dil. HCl
NO2 NO2
2,4,6-Trinitrochlorobenzene 2,4,6-Trinitrophenol
ii. Action of ammonia (Ammonolysis): When chorobenzene is heated with aqueous ammonia
solution under pressure in presence of cuprous oxide, aniline is formed.
Cl NH2
Cu2O, 200°C, 60 atm.
+ NH3 (aq.) + HCl
Aniline
iii. Action of cuprous cyanide: When chorobenzene is heated with cuprous cyanide in DMF as
solvent, phenyl cyanide is formed.
Cl CN
200°C, DMF
+ Cu2(CN)2 + Cu2Cl2
Benzonitrile
(Phenyl cyanide)
Application of nitrile synthesis
Nitrile synthesis has advantage of increasing carbon chain length by one carbon atom.
Example:
O
Dil. HCl
C—OH
Complete hydrolysis
Benzoic acid
Cl CN
O
Cl2, FeCl3 Cu2(CN)2 Conc. HCl
C—NH2
dark 200°C, DMF Partial hydrolysis
Benzonitrile Benzamide
H2/Ni or LiAlH4
or C2H5OH/Na
CH2NH2
Reduction
Benzyl amine
O
C CH3
H N
DMF stands for dimethyl formamide, which is a
CH3 polar aprotic, non aqueous solvent.
Dimethylformamide (DMF)
Self Test
9.22 Convert benzene into (a) Benzoic acid (b) Benzamide (c) Banzyl amine
9.23 Nucleophilic substitution reaction is difficult in haloarene, explain.
9.24 Convert chlorobenzene into bromobenzene.
3. Reaction with metals

a. Reaction with magnesium: Formation of Grignard reagent: Aryl halide reacts with
magnesium metal in dry ether or THF to give Grignard reagent.
Cl MgCl
dry THF, inert atm.
+ Mg + HCl
Phenyl magnesium chloride

(Grignard reagent)
Br MgBr
dry ether, inert atm.
+ Mg + HBr
Phenyl magnesium bromide

(Grignard reagent)
I MgI
dry ether, inert atm.
+ Mg + HI
Phenyl magnesium iodide

(Grignard reagent)
b. Reaction with sodium

i. Fittig reaction (1863): When etheral solution of aryl halide is warmed with sodium metal,
two molecules of aryl halides combine to give biphenyl compounds.
dry ether, Δ
Cl + 2 Na + Cl + 2 NaCl
Chlorobenzene Biphenyl
ii. Wurtz-Fittig reaction (1863): When etheral solution of aryl halide and alkyl halide is
warmed with sodium metal, alkyl benzene is formed.
dry ether, Δ
Cl + 2 Na + Cl—CH3 CH3 + 2 NaCl
Chlorobenzene Chloromethane Toluene
dry ether, Δ
Br + 2 Na + CH3CH2CH2CH2-Br CH2CH2CH2CH3 + 2 NaBr
Bromobenzene n-Butyl bromide n-Butylbenzene
4. Other reactions
a. Reduction: When chlorobenzene is heated with nickel aluminium alloy in presence of caustic
alkali, it is reduced to benzene.
Cl
Ni-Al alloy, NaOH, Δ
+ 2 [H] + HCl
Benzene
b. Reaction with NaNH2: When chlorobenzene is treated with NaNH2 or KNH2 in liquid
ammonia, aniline is obtained. The reaction follows elimination-addition mechanism through
benzyne intermediate.
Cl NH2
Liq. NH3
+ KNH2 + KCl
c. Reaction with Chloral: When chlorobenzene is heated with chloral in presence of concentrated
H2SO4, DDT is formed which is an insecticide. It is a colorless, tasteless crystalline compound.
Cl
H Cl
Cl H Cl
conc. H2SO4, Cl C C H + H2O
Cl C C O +
Cl H Cl Cl
Trichloroethanal Chlorobenzene
(Chloral) (2 molecules) Cl
2,2- Bis (4-chlorophenyl)- 1,1,1 -trichloroethane
DDT (Dichlorodiphenyltrichloroethane)
Insecticidal property of DDT was discovered by the Swiss chemist Paul Hermann
Müller in 1939. In the second half of World war II, it was used with great success
to control malaria and typhus among civilians and troops. After the war, DDT was
made available for use as an agricultural insecticide and extensively used
in agriculture. Müller was awarded the Nobel prize in physiology or medicine
for his discovery of the high efficiency of DDT as a contact poison against several
arthropods in 1948.
DDT is toxic to a wide range of living organisms including human beings. It is
a persistent organic pollutant and bioaccumulate concentrating more chemicals
especially in predatory birds and apex consumers through the food chain. It causes
egg shell thinning in birds of prey. Eggshell thinning lowers the reproductive rate
of certain bird species by causing egg breakage and embryo deaths. It is considered a
major reason for the decline of the bald eagle, peregrine falcon, brown pelican etc.
Because of its hazards in health and environment, the use of DDT as agricultural
insecticide was outlawed in 2004 under Stockholm Convention and restricted to
disease vector control.
9.2.5 Some Commercially Important Halogen Derivatives of Hydrocarbons

1. Polyvinyl chloride (PVC): It is prepared by polymerization of vinyl chloride. (Detail in chapter
Polymers)
2. Polytetrafluroethane (Teflon): It is prepared by polymerization of tetrafluroethene. (Detail in
chapter Polymers)
3. Chlorofluorocarbons (CFCs): Chlorofluorocarbons (CFCs) also known as Freons are
compounds having only carbon, fluorine and chlorine and synthesized for their use in
refrigeration, air conditioning and aerosol propellant. However, CFCs are to be phased out due
to their role ozone layer depletion
CCl3F CF2Cl2
Trichlorofluromethane Dichlorodifluromethane
Freon 11 (CFC 11) Freon 12 (CFC 12)
4. DDT and BHC are insecticides. Detail in chapter 16

Alkyl halides undergo a wide range of chemical reactions hence provide useful routes to form a large
variety of other organic compounds. Hence they are extremely important in organic synthesis.
aq. KOH
R-OH
alc. KSH
R-SH
Thioether/ Mercaptan H2O/H+
R-COOH
R'ONa
R-O-R' Carboxylic acid
Ether
alc. KCN conc HCl
R-CN R-CONH2
Nitrile
Amide
alc. AgCN H2/Ni or LiAlH4
R-NC Na/C2H5OH
Isonitrile R-CH2NH2
1º Amine
alc. KNO2 R-NO2 i. SnCl2/HCl
Nitroalkane ii. dil HCl
R-CHO
alc. AgNO2 Aldehyde
R-O-N=O
Alkyl nitrite
HX, NH3
RNH2
PX3 or PX5 or
SOCl2 1º Amine
.
R-OH R-X
RNH2
R2NH
2º Amine
R2NH R3N
3º Amine
R'COOAg O
R'-C-OR
Ester
alc.KOH
alkene
Na, dry ether,Δ

R-R
Higher alkane
Mg, dry ether

RMgX
Grignard reagent
H2/Pd RH
Alkane
Solved Questions
1. Convert ethane into ethyne.
¬ H H H Br Br Br NaNH2 in
Br2,hν alc. KOH Br2/CCl4 liquid NH3
H—C—C—H H—C—C—H H—C = C—H H—C—C—H HC ≡ CH
Δ Δ
H H H H H H H H
Ethane 1,2-Dibromoethane Ethyne
Bromoethane Ethene
2. Convert ethane into propanoic acid.

¬
Cl2, νυ alc. KCN, Δ H2O/H+
CH3CH3 CH3CH2Cl CH3CH2CN CH3CH2COOH
Ethane Chloroethane Propane nitrile Propanoic acid
3. Convert 1–Bromopropane into 2–Bromopropane and vice-versa.

¬ Conversion 1-Bromopropane into 2-Bromopropane
H H H H H H H H H
alc. KOH, Δ HBr
H—C—C—C—H H—C—C=C—H H—C—C—C—H
H H Br H H Br H
1–Bromopropane Propene 2–Bromopropane
Conversion 2-Bromopropane into 1-Bromopropane

H H H H H H H H H
alc. KOH, Δ HBr, benzoyl peroxide
H—C—C—C—H H—C—C=C—H H—C—C—C—H
H Br H H H H Br
2–Bromopropane Propene 1–Bromopropane
4. Write down the IUPAC name of major products P and Q in the following reaction
sequence.
HBr Na/ether, Δ
Propene P Q
¬
Br
HBr Na/ether CH3 CH3
CH3CH = CH2 CH3—CH—CH3 CH—CH
Δ CH3 CH3
2-Bromopropane
(P) 2,3-Dimethylbutane
(Q)
5. What would you do to distinguish chloroform from carbontretrachloride?
¬ Carbylamine test (isocyanide test) is carried out.
When chloroform is warmed with aliphatic or aromatic primary amine in presence of alcoholic KOH,
offensive smell of isocyanide is obtained. CCl4 does not give this test.
Example
H Cl H
+ C Δ
6. How do you get benzoic acid from chlorobenzene?

¬ Cl CH3 COOH
CH3Cl,
Na/ether KMnO4/OH–
Δ Δ
Chlorobenzene Toluene Benzoic acid
or,
Cl CN COOH
Cu2(CN)2 H2O/H+
200°C
Chlorobenzene Benzonitrile Benzoic acid
Questions
1. Identify A and B Cl2,uv, 25°C
Butane A +B
Br2,uv, 125°C
2. Identify T and M Butane T +M
3. Identify T and M and indicate the major product giving reason.

KOH(alc.), boil
2-Bromobutane T+ M
4. Write all steps when excess ethyl bromide reacts with alcoholic ammonia.
5. Identify A, B, C, D, E and F
Na, C2H5OH
C
alc. KCN
A
H2O/H+
D
Ethyl bromide
Na, C2H5OH
E
alc. AgCN
B
H2O/H+
F
6. Identify X and Y:
Mg, dry ether C2H5OH
Methyl iodide X Y
7. Why is chloroform stored in dark coloured bottles with little ethanol?

8. Give an example of
a. Carbylamine reaction b. Dehydrohalogenation c. Grooves process
d. Hofmann ammonolysis e. Hydrogenolysis f. Hydrohalogenation
g. Reimer-Tiemann reaction h. Williamson synthesis i. Wurtz reaction
9. Give an example of
a. Diazotization b. Fittig reaction c. Wurtz-Fittig reaction
d. Sandmayer reaction e. Gattermann reaction f. Schiemann reaction
g. Benzene into benzoic acid.
10. A primary haloalkane (X) if allowed to react with KCN yields a compound (Y), which on acidic
hydrolysis gives propanoic acid. Identify X and Y.
11. Why does chloroform not give white precipitate with aqueous silver nitrate?
12. How is Grignard reagent prepared? What precautions should be taken for its preparation?
13. Write the action of trichloromethane with monohydroxy benzene in presence of alcoholic
NaOH.
14. Why does chlorobenzene give ortho-para substituted products?
1. Identify P and Q
PCl5, reflux Na, dry ether, Δ
i. Isobutyl alcohol P Q
(P4+I2), reflux C2H5ONa

ii. Ethanol P Q
Br2, light, 127°C aq. KOH

iii. Ethane P Q
SOCl2, reflux moist Ag2O

iv. Ethanol P Q
HCl(g),anhd.ZnCl2 Dry Ag2O

v. Ethanol P Q
2. Starting from iodoethane, how do you get

a. Ethane b. Ethene c. Ethyne
d. Butane e. Bromoethane f. Methoxyethane
g. Ethoxyethane h. Ethylethanoate i. Ethyl thioalcohol
j. Nitroethane k. Ethyl nitrite l. Ethyl carbylamine
m. Propanoic acid n. Propanamide o. 1-Aminopropane
3. How is chloroform prepared in laboratory in pure and dry state? How does chloroform
react when heated with
i. Aqueous KOH
ii. Phenol in presence of aqueous KOH
iii. Ethanamine in presence of alcoholic KOH
iv. Acetone in presence of alcoholic KOH
v. Conc. HNO3
4. Give any two methods for the preparation of chlorobenzene.Why is nucleophilic
substitution reaction is difficult in chlorobenzene as compared to chloroethane? Convert
chlorobenzene into DDT.
5. How can you convert
a. 1– Bromopropane into 2– Bromo propane and vice-versa
b. Methane into ethane c. Ethane into butane d. Ethane into Ethene
e. Ethane into Ethanol g. Chlorobenzene into Toluene
a. Chloroethane is hydrolized?
b. 2– Chlorobutane is heated with alcoholic KOH?
c. Chlorobenzene is treated with chloral in acidic medium?
d. Chlorobenzene is heated with Ni-Al in alkaline medium?
7. Write any three methods of preparation of iodoethene. What happens when iodoethane is
heated with (i) sodium in presence of dry ether? (ii) alcoholic caustic soda.
8. Starting form trichloromethane, how would you prepare
a. Ethyne b. Methane c. Chloropicrin
d. Carbonyl chloride e. Chloretone

1. The number of primary alkyl halide having molecular a. Groove’s method
formula C4H9X is b. Dorzen’s method
a. 1 b. 2 c. Finkelstein method
c. 4 d. 3 d. Borodine Hunsdickner reaction
2. For the reaction ,C2H5OH +HX → C2H5X +H2O ,the 13. When But‐1‐ene reacts with HBr gives 1‐
order of reactivity is: bromobutane in presence of Peroxide, it follows
a. HCl > HBr> HI b. HI > HCl> HBr a. Markonikov's rule b. Anti-Markonikoff’s rule
c. HI > HBr> HCl d. HBr> HI > HCl c. Saytzeff rule d. None of above
3. When propylene reacts with HCl in presence of 14. Alkyl halide burns with
a. Green edged flame b. Smoky flame
traces of organic peroxide, it follows
c. Yellow flame d. Blue flame
a. Markonikov's rule b. Anti-Markonikov's rule
c. Free radical addition d. Chain reaction 15. Chloroform when reacts with Zn dust and water and
4. When Chloroform is boiled with aqueous KOH and Zn dust and HCl respectively forms
a. CH4 and CH2Cl2 b. CH2Cl2 and CH4
followed by acidification, it forms
c. CCl4 and CH4 d. CH4 and CCl4
a. Salicyaldehyde b. Methanoic acid
c. Methoxymethane d. Methanal 16. When Chloroform is boiled with KOH and followed
5. Alkyl halide reacts with alcoholic AgCN to give by acidification, it forms
a. Alkyl cyanide b. Alkyl iscyanide a. Methanol b. Methanoic acid
c. Alkyl iscyanate d. Nitrile c. Methoxy methane d. Methanal
6. Tear gas is 17. Isocyanide test can not be used to distinguish
a. Chloretone b. Ethyl carbonate a. CHCl3 and CCl4
c. Chloropicrin d. Methylene chloride b. 1° and 2° amine
c. Ethyl amine and trimethyl amine
7. Which of the following is wrong statement? d. Ethyl amine and aniline
a. CHCl3 is used in surgery as an anesthetic
18. Which of the following is used as refrigerant?
b. CHCl3 is prepared from chlorination of chloral
c. CHCl3 on exposure to sunlight and air gives phosgene a. CH2Cl2 b. CF2Cl2
d. Chloropicrin is an insecticide prepared from nitration c. CCl4 d. CF4
of chloroform 19. Which of the following is used as a War gas?
8. Which of the following is gem‐halide? a. CCl3NO2 b. CH2Cl2
a. CH3CH2BrCH2Br b. CH3CHBr2 c. CHCl3 d. COCl2
c. CH3CHBr CH2CH2Br d. BrCH2CH2Br 20. Acetone is warmed with iodine and dil. alkali gives
9. The most common reaction that alkyl halide shows a. CHI3 b. CH2I2
c. CH3I d. CI3COCH3
is
a. Electrophilic addition 21. CHCl3 on oxidation with air gives
b. Nucleophilic substitution a. Phosgene b. Formic acid
c. Free radical addition c. Chloropicrin d. CCl4
d. Electrophilic substitution 22. Chlorobenzene is prepared commercially by
10. The order of methyl halide to the formation of a. Dow process b. Down process
Grignard reagent is c. Darzens procedure d. Groove's process
a. CH3Br> CH3Cl > CH3I b. CH3I> CH3Br > CH3Cl 23. When benzene diazonium chloride is heated with
c. CH3Cl > CH3I > CH3Br. d. CH3Br> CH3I> CH3Cl the cuprous chloride in corresponding halogen acid,,
11. Out of the following compound which is not an chlorobenzene is formed. The reaction is
organometallic compound? a. Sandmeyer reaction b. Gattermann reaction
a. CH3MgI b. (CH3)2Li c. Scheimann reaction d. Fitttig reaction
c. C2H5ONa d. TEL 24. Which of the following compound is non polar?
12. Which out of the following is the best method to a. CH3Cl b. CH2Cl2
prepare chloroalkane? c. CHCl3 d. CCl4
1 2 3 4 5 6 7 8 9 10 11 12
b c a b b c b b b b c b
13 14 15 16 17 18 19 20 21 22 23 24
b a a b d b a a a a a d
Alcohols and Phenols
Power alcohol is being used nowadays as the source of fuel (which is used to save petrol).
10.1 Alcohols
10.1.1 Introduction
Aliphatic alcohols: Hydroxy derivatives of aliphatic hydrocarbons are aliphatic alcohols. Their
general representation is ROH, where R— is alkyl group.
–H
R—H R—OH
+ OH
Alkane Alcohol
Examples: OH
CH3CH2OH
CH3CHCH3
Ethanol
Propan-2-ol
Aliphatic alcohols are also regarded as alkyl derivatives of water.

–H
H—O—H R—O—H
+R
Water Alcohol
Aromatic alcohols: Hydroxy derivatives of arenes where the —OH group is attached to the side
chain of the aromatic ring are called aromatic alcohols.
–H
Ar—CH3 Ar—CH2OH
+ OH
Arene Aromatic alcohol
Examples:
CH2OH CH2CH2OH
Benzyl alcohol 2-Phenylethanol

(Phenylmethanol)
10.1.2 Classification of Aliphatic Alcohols

A. Classification based upon number of –OH groups per molecule
Aliphatic Alcohols are classified into different classes according to the number of –OH groups
contained in their molecules.
1. Monohydric (Monohydroxy) alcohols: Alcohols containing only one –OH group per molecule
are called monohydric alcohols. The common name of monohydric alcohol is alkyl alcohol and
their IUPAC name is alkanol. The general structural formula of it is R–OH and molecular formula
is (CnH2n+1OH).
Examples: CH3OH, CH3CH2OH, etc.
2. Dihydric (Dihydroxy) alcohols: Alcohols containing two –OH groups per molecule are called
dihydric alcohols. The general molecular formula is CnH2n(OH)2.
Examples: OH OH
OH OH
CH2—CH2 CH3—CH—CH2
Ethane -1,2-diol Propane- 1,2-diol
(Ethylene glycol)
Alcohols and Phenols Unit 10 305
3. Trihydric (Trihydroxy) alcohols: Alcohols containing three –OH groups per molecule are called
trihydric alcohols. The general molecular formula is CnH2n – 1 (OH)3.
Example: OH OH OH
CH2—CH—CH2
Propane- 1,2,3-triol
(Glycerol)
Alcohol with two or more –OH groups attached to the same carbon atom of the carbon chain of the molecule becomes
unstable and hence it is decomposed to aldehyde, ketone or carboxylic acid.
Examples:
OH O
CH3—C—O H CH3—C—H + H2O
H Ethanal
Ethane-1,1-diol
OH O
CH3—C—O H CH3—C—OH + H2O
OH Ethanoic acid
Ethane-1,1,1-triol
OH OH O OH
CH3 — C — CH2 CH3—C—CH2 + H2O
OH 1-Hydroxypropanone
1,2,2-Trihydroxy propane
4. Polyhydric alcohols: Alcohols containing four or more –OH groups per molecule are called
polyhydric alcohols.
B. Classification of monohydric alcohols (based upon type of carbon, in which
the hydroxy group is attached)
Monohydric alcohols are further classified as primary (1o), secondary (2o) and tertiary (3o) alcohols
according to the type of carbon in which the hydroxyl (—OH) group is attached.
1. Primary alcohols: Alcohols in which the —OH group is attached to a primary carbon atom are
called primary alcohols. Primary alcohols are characterized by the presence of a structural unit of
—CH2OH group, hence they are represented by general formula RCH2OH.
Examples:
CH3
CH3—CH2—OH CH3—CH2—CH2—OH
CH3—CH—CH2—OH
Ethanol Propan-1-ol
(Ethyl alcohol) (n-Propyl alcohol) 2-Methylpropan-1-ol
(isobutyl alcohol)
2. Secondary alcohol: Alcohols containing –OH group attached to a secondary carbon atom of the
molecule are called secondary alcohols. Secondary alcohols are characterized by the presence of
structural unit of >CHOH and hence they are represented by general formula R2CHOH.
Examples:
OH
CH3—CH—OH
CH3—CH—CH2—CH3
CH3
Propan-2-ol butan-2-ol
(Isopropyl alcohol) (sec-butyl alcohol)
3. Tertiary alcohol: Alcohols containing –OH group attached to a tertiary carbon atom are called
tertiary alcohols. Tertiary alcohols are represented by general formula R3C—OH, which are
characterized by the presence of a characteristic structural unit of —C—OH
Example: CH3
CH3—C—OH
CH3
2-Methylpropan -2-ol
(tert- Butyl alcohol)

10.1.3 Nomenclature
1. The common naming system: In the common naming system, the monohydric alcohols are
named as alkyl alcohols. They are named by writing the name of alkyl group followed by the word
'alcohol' .
Examples:
CH3 OH
CH3—CH2—CH2OH CH3—CH—CH2OH CH3—CH2—CH—CH3
n-Propyl alcohol Isobutyl alcohol sec-Butyl alcohol
CH3 CH3
CH3—C—OH CH3—C—CH2OH
CH3 CH3
tert- Butyl alcohol Neopentyl alcohol
2. Carbinol system of naming: CH3 – OH is a first member of alcohol called carbinol and all other
members of alcohol are considered as substituted products of carbinol.
Examples: CH3
CH3—CH2OH
CH3—CH—OH
Methyl carbinol
Dimethyl carbinol
Other examples of alcohols which are famous for their common name are:
CH2 = CH—CH2OH HC ≡ C—CH2OH CH2 = CH—OH
Allyl alcohol Propargyl alcohol Vinyl alcohol
3. The IUPAC system: In the IUPAC system, the monohydric alcohols are named as alkanols. The
numbering of parent is done so as to give the lowest number to the carbon atom carrying the
–OH group.
CH3 CH3
Examples
OH CH3—C—CH2OH CH3—CH—CH2—OH
CH3—CH2—CH2—OH CH3—CH—CH3 CH3
2-methylpropan-1-ol
Propan-1-ol Propan-2-ol 2,2-dimethylpropan-1-ol
10.1.4 Isomerism in Monohydric Alcohols

Alcohols show the following types of structural isomerisms.
1. Chain isomerism: Alcohols having same molecular formula but different carbon skeleton gives
rise chain isomerism in alcohols.
Example: CH3
CH3—CH2—CH2—CH2—OH and CH3—CH—CH2—OH

2-methylpropan-1-ol
Butan-1-ol
2. Positional isomerism: Different alcohols having same molecular formula but different structure
due to the difference in the position of the –OH group in the identical carbon chain gives rise to
positional isomerism.
Example: OH
CH3—CH2—CH2OH and CH3—CH—CH3
Propan-1-ol Propan-2-ol
3. Functional isomerism: Alcohols show functional isomerism with ethers. Alcohols and ethers are
functional isomers each other as they have same general molecular formula of CnH2n +2O.
Examples:
a. C2H6O has two functional isomers.
CH3—CH2OH CH3—O—CH3
Ethanol Methoxymethane
(Ethyl alcohol) (Dimethyl ether)
b. C3H8O has three isomers, out of them two compounds viz. 1-propanol or 2-propanol and
methoxyethane are functional isomers.
Alcohols: OH
CH3—CH2—CH2OH CH3—CH—CH2
propan-1-ol propan-2-ol
Ether: CH3CH2—O—CH3
Methoxyethane
Self Test
10. 1 Write the possible isomers of molecular formula C4H10O with their IUPAC names.
10.1.5 General Methods of Preparation of Monohydric Alcohols

Monohydric alcohols are generally prepared from:
1. Haloalkanes
2. Aldehydes and ketones
3. Esters
4. Primary amines
1. Preparation of alcohols from haloalkanes: (Nucleophilic Substitution Reaction of Haloalkanes).

a. By hydrolysis of haloalkanes: Haloalkanes undergo hydrolysis into alcohols by boiling
with aqueous solution of alkali like NaOH or KOH.
i.e. Δ
R—X + KOH (aq.) R—OH + KX
Alcohol
Examples:
Δ
CH3—CH2—I + KOH (aq.) CH3—CH2—OH + KI
Ethanol
(Ethyl alcohol)
i. Primary alkyl halides give good yield of alcohols. However, tertiary alkyl halides in this reaction give mainly alkene due to
dehydrohalogenation.
ii. Secondary alkyl halides give a mixture of alcohol and alkene.
iii. This method is not very useful commercially for preparing aliphatic alcohols because alkyl halides are themselves obtained
from alcohols. However, this method is utilized in the preparation of aromatic alcohols.
b. By action of moist silver oxide on haloalkanes: Haloalkanes give corresponding alcohols

upon heating with moist silver oxide. (Suspension of Ag2O is moist ether).
Ag2O + H2O 2 AgOH
Moist
CH3CH2I + AgOH CH3CH2OH + AgI
Ag2O
Iodoethane Ethanol
2. Preparation of alcohols from aldehydes and ketones

a. By reduction of aldehydes and ketones: Aldehydes and ketones are easily reduced to the
corresponding alcohols by the action of reducing agents like H2/Ni or Na/C2H5OH or
LiAlH4 or NaBH4 etc.
i. Aldehydes are reduced to primary (1°) alcohols.
O H2/ Ni, Δ OH
2 [H], Na/C2H5OH
R—C—H R—C—H
LiAlH4 or NaBH4
Aldelyde H
1° alcohol
Examples:
O
Ni
H—C—H + H2 CH3OH
Δ
Methanal Methanol
O
Ni
CH3—C—H + H2 CH3CH2OH
Δ
Ethanal Ethanol
O
LiAlH4
CH3—C—H + 2 [H] CH3CH2OH
or NaBH4
Ethanal or Na/C2H5OH Ethanol
ii. Ketones are reduced to secondary (2°) alcohols.
O H2/ Ni, Δ OH
2[H], Na/C2H5OH
R—C—R R—C—R
LiAlH4 or NaBH4
Ketone H
2° alcohol
Example:
O OH
LiAlH4
CH3—C—CH3 + 2 [H] CH3—CH—CH2
or NaBH4
Acetone or C2H5OH + Na propan-2-ol
b. By Grignard synthesis of alcohols: Grignard reagent (RMgX) undergoes nucleophilic addition

reaction to the carbonyl (>C=O) group of aldehydes or ketones form an intermediate addition
product adduct, which on acidic hydrolysis with dilute HCl yields different types of alcohols.
According to the nature of aldehydes and ketones used in the Grignard synthesis, different
classes of alcohols (1°, 2° and 3°) are obtained.
– +
O δ– OMgBr OH
Dry ether, H2O/H+
δ+
—C— + R—MgX —C— —C— + Mg(OH)X
Inert atm.
Carbonyl Grignard R R
Compound reagent Adduct Alcohol
Examples:
i. Synthesis of primary alcohols: Addition of Grignard reagent to formaldehyde followed
by the hydrolysis of adduct gives primary alcohol.
– +
δ–
O OMgI OH
δ+ Dry ether, H2O/H+
H—C—H + CH3—MgI H—C—H H—C—H + Mg(OH)I
Inert atm. Δ
CH3 CH3
Methanal Methyl magnesium Adduct Ethanol
iodide
ii. Synthesis of secondary alcohols: Addition of Grignard reagent to aldehydes other than
formaldehyde, followed by hydrolysis of adduct yields secondary alcohols.
δ– – +
O OMgBr OH
CH3—C—H + CH3—MgBr CH3—C—H CH3—C—H + Mg(OH)Br
Inert atm. Δ
Ethanal Methyl magnesium
CH3 CH3
bromide Adduct
Propan-2-ol
iii. Synthesis of tertiary alcohols: Addition of Grignard reagent to ketones followed by

hydrolysis of adduct yields tertiary alcohols.
δ– – +
O OMgBr OH
CH3—C—CH3 + CH3—MgBr CH3—C—CH3 CH3—C—CH3 + Mg(OH)Br
Inert atm. Δ
Propanone Methyl magnesium
CH3 CH3
bromide Adduct
tert-Butyl alcohol
3. Preparation of alcohols from esters:

a. By reduction of esters: Esters are easily reduced with different reducing agents like
Na/C2H5OH or LiAlH4 into alcohols.
O
Na/C2H5OH
R—C—OR' + 4[H] RCH2OH + R'OH
or LiAlH4
Ester 1° alcohol
Example:
O
Na/C2H5OH
CH3—C—OC2H5 + 4[H] CH3CH2OH + C2H5OH
LiAlH4
Ethyl acetate Ethanol Ethanol
b. By acidic hydrolysis of esters: When esters are subjected to acidic hydrolysis by boiling
with dilute H2SO4, a mixture of alcohol and carboxylic acid is formed. Alcohol is obtained
from the alcohol (R'O—) group of ester (RCOOR') while the carboxylic acid is obtained
from acyl (R—CO—) group of ester (RCOOR').
O O
H+
R—C—OR' + H—OH R—C—OH + R'OH
Carboxylic acid Alcohol
Example:
O
H+
CH3—C—OC2H5 + H—OH CH3COOH + C2H5OH
Ethanoic acid Ethanol
c. By alkaline hydrolysis of esters: When esters are subjected to alkaline hydrolysis by

boiling with dilute aqueous solution of alkali (NaOH or KOH), a mixture of alcohol and
salt of carboxylic acid (carboxylate salt) is formed. Alcohol is obtained from the alkoxy
(R'O—) group and the carboxylate salt is obtained from acyl (R—CO—) group of ester
(RCOOR').
O O
dil. NaOH R—C—ONa + R'OH
R—C—OR' + NaOH (aq.)
Δ
1° Alcohol
Example:
O O
dil. NaOH
CH3—C—OC2H5 + HO—H CH3—C—ONa + C2H5OH
Δ
Ethyl acetate Sodium ethanoate Ethyl alcohol
4. Preparation of alcohols from carboxylic acids:

Carboxylic acids can be reduced to primary alcohols by using the reducing agents like
H2/copper chromite, LiAlH4 etc.
O
LiAlH4 RCH2OH + H2O
R—C—OH + 4 [H]
Example: 1° alcohol
LiAlH4 CH3CH2OH + H2O
CH3COOH + 4 [H]
Ethanol
5. Preparation of alcohols from aliphatic primary amines:

Aliphatic primary amines react with cold solution of nitrous acid (mixture of cold and aqueous
solution of NaNO2 and conc. HCl) at about 0o–5°C to form an unstable alkyl diazonium salts
(alkyl diazomium chloride, R-N=N-Cl). The salts at once decompose to liberate nitrogen gas
and form primary alcohols.
(NaNO2 + conc. HCl)
R—NH2 + HNO2 R—OH + N2 + H2O
(0–5°C)
(NaNO2 + conc. HCl) CH3—CH2OH + N2 + H2O

CH3—CH2—NH2 + HNO2
(0–5°C)
Ethanamine Ethanol
Note:
Preparation of methyl alcohol using this method is not suitable as it gives mixture of other compounds also
(NaNO2 + conc. HCl) CH3OH + CH3OCH3 + CH3ONO
CH3—NH2 + HNO2
(0–5°C)
Methanamine
10.1.6 Industrial Method of Preparation of Alcohols

Alcohols are commercially prepared from:
1. Alkenes
2. Carbohydrates by fermentation
1. From alkenes: In commercial scale, alkenes are obtained from the thermal cracking or pyrolysis
of petroleum products, and hence these alkenes are widely used for various synthetic purposes.
Among them commercial preparation of alcohols is the most important.
a. By hydration of alkenes: Hydration of alkene means addition of water molecule onto the
C=C double of the alkene molecule to yield alcohol.
Hydration of alkene is carried out by passing the alkene gas through cold and concentrated
H2SO4 or H3PO4 under pressure, where H2SO4 is added to the C= C double bond of alkene to
form an addition product of alkyl hydrogen sulphate. Alkyl hydrogen sulphate thus formed
on subsequent hydrolysis by boiling it with water yields alcohol.
0°C
CH2 = CH2 + H2SO4 CH3—CH2—OSO3H
Ethyl hydrogen sulphate
Distill
CH3—CH2—OSO3H + H2O CH3—CH2—OH + H2SO4
Ethyl alcohol
The addition of H2SO4 to unsymmetrical alkenes takes place according to Markownikov's

rule and hence there is overall Markownikov's addition of water onto the C=C double bond
of unsymmetrical alkenes.
OSO3H OH
Conc. H2SO4, 0°C CH3—CH—CH3 H2O CH3—CH—CH3
CH3—CH = CH2
Isopropyl sulphate Propan-2-ol (2°)
Direct hydration of alkene can also be carried out under high temperature and high pressure
in presence of phosphoric acid (H3PO4) catalyst.
CH3 CH3
CH3—CH = CH2 + H2O H3PO4
CH3—C—CH3
240°C
2-methylpropene OH
2-methylprepan-2-ol
[
b. By Oxo-Process: Hydroformylation of alkene: Alkenes react with carbon monoxide and

hydrogen in the presence of oxo-catalyst (octacarbonyl/dicobalt), Co2(CO)8, at high
temperature and pressure to yield aldehydes. Catalytic hydrogenation of aldehydes with
H2/Ni gives primary alcohol having one more carbon atom than that of its parent alkene.
Oxo-process is hydroformylation reaction which means addition of hydrogen and formyl
(–CHO) group onto the C=C double of alkene molecule in presence of oxo-catalyst.
CO2(CO)8 H2/Ni
CH2 = CH2 + [CO + H2] CH3—CH2—CHO CH3—CH2—CH2OH
Δ Reduction
pressure Propan-1-ol
c. By Hydroboration-oxidation of alkene: The indirect addition of water to alkenes can be

performed through Hydroboration-oxidation reaction. In this method alkene is treated
with diborane followed by treatment with alkaline H2O2 yields primary alcohol.
Hydroboration is a reduction process, which is carried out by treating alkene with
diborane, (BH3)2 to give alkayl dialkyl trialkyl borane which upon oxidation with alkaline
solution of H2O2 gives primary alcohol.
BH3
3 CH3—CH = CH2 (CH3—CH2—CH2)3B
Tri n-propylborane
3H2O2/OH¯ –
(CH3CH2CH2)3B 3 CH3—CH2—CH2—OH + B(OH)3
Propan-1-ol
Each step the reaction here follows Markowikov's rule. But the product formed here is
antimarkownikov product.
By Oxymercuration-demercuration:
The indirect addition of water to alkenes can also be performed through oxymercuration-demercuration reaction. In this
method alkene is treated with mercuric acetate in THF-water solution followed by treatment with NaBH4 yields alcohol.
This is carried out by treating alkene with aqueous solution of mercuric acetate in dry THF, where alkene is oxidized
organo-mercuric compound, which on subsequent reduction or demercuration with NaBH4 yields alcohol.
OH HgOCOCH3 OH
Dry THF NaBH4
CH3—CH = CH2 + (CH3COO)2Hg + H2O CH3—CH—CH2 CH3—CH—CH3
oxidation reduction
2-Propanol
Over all oxymercuration-demercuration is a hydration of alkene, in which addition of water occurs in Markownikov's way
in the C=C double bond of alkene.
2. From Carbohydrates by fermentation: Many chemical reactions like petrification of meat,

conversion of fruit juices and sugars into alcohol and vinegar are brought about by the
enzymatic action of the living organisms. In all these reactions, the complex organic compounds
are decomposed into simpler substances. Such process of slow decomposition of complex
organic compound into simpler ones by the agency of microorganisms (Ferments) is known as
Fermentation (Latin, ferver = to boil). Fermentation is an exothermic process.

In the modern sense, fermentation is the process of slow decomposition of complex organic
substances into its simpler form of organic compounds in the presence of complex nitrogeneous
substances secreted by the cells of microorganisms (e.g. yeast, bacteria) known as Enzymes. The
enzymes act as a catalyst in all these reactions and are generally referred to as biocatalysts.
The Yeast containing various enzymes like invertase, zymase etc., which are used for the
fermentation of carbohydrates like cane sugar juice, molasses, grapes, apples etc. into ethyl
alcohol.
i. Manufacture of ethyl alcohol from sugar or molasses: Molasses is a mother liquor left during
the crystallization of sugar. It is a dark coloured viscous liquid which contains 30% sucrose and
32% invert sugar i.e. mixture of glucose and fructose.
Fermentation of sugar or molasses is carried out by adding quantitative amount of yeast to the
solution of sugar or molasses at low concentration in presence of ammonium phosphate,
(NH4)3PO4 as a food for yeast. The mixture is left under warm condition at about 30oC for few
days, when fermentation takes place with the slow effervescence of CO2 gas with the boiling
appearance.
C12H22O11 + H2O Invertase
C6H12O6 + C6H12O6
(Sucrose) Glucose Fructose
C6H12O6 Zymase
2C2H5OH + 2CO2
Glucose or fructose Ethyl alcohol
ii. Manufacture of ethyl alcohol from starch (Weizmann method): Fermentation of starch rich
substances likes rice, wheat, barley, potatoes, maize etc. into ethanol is carried out in usual
manner as that has been used for fermentation of sugar or molasses. But in this process the
starch containing materials are first cooked with water so as to release the granules of starch.
The resulting mass is called "Mash". The Mash is then mixed with "Malt" and the mixture is
left under warm condition at about 30oC for few days, when fermentation takes place.
Malt is especially germinated barley. Diastase enzyme from malt converts starch into maltose (a
disaccharide). Maltase by enzymatic action of yeast gives ethanol.
2(C6H10O5)n + nH2O Diastase

n(C12H22O11)
Starch Maltose sugar
C12H22O11 + H2O Maltase

2 C6H12O6
Maltose Glucose
C6H12O6 Zymase
2 C2H5OH + 2CO2
Glucose Ethyl alcohol
The fermented liquor obtained from fermentation vessel is called "Wash", which is filtered and
the filtrate on distillation gives a distillate. The distillate contains about 90% ethyl alcohol along
with impurities of acetaldehyde and fusel fuel (fusel fuel mainly contains amyl alcohol,
C5H11OH). The fractional distillation of distillate gives a major fraction of about 95% ethyl
alcohol and a minor fraction of acetaldehyde and fusel fuel. These two fractions are separately
collected. The major fraction of ethyl alcohol is called Rectified spirit. The exact composition of
rectified spirit is 95.87% ethyl alcohol and 4.13% water. The fermentation can be retarded by
+
NH4 salts.
10.1.7 Physical Properties of Alcohols

The —OH group of alcohol gives the characteristics physical and chemical properties whereas alkyl
group (R–) depending upon its shape and size modifies their properties.
The –OH group of alcohol is quite polar and contains H-atom bonded to the highly electronegative
oxygen.
1. State: The lower members are usually colorless liquids with the characteristic hospital odour,
whereas higher members are usually colourless and odourless solids.
2. Solubility:
i. The solubility of alcohols is higher than that of the solubility of corresponding aliphatic
hydrocarbons (alkanes), alkyl halides (haloalkanes) and ethers of comparable molecular
masses.
Reasons: The high solubility of alcohols in water is due to ability of forming hydrogen bonding
between water and polar O –H group of alcohol molecules. Such hydrogen bonding is absent in alkanes
and alkyl halides. δ+ δ+
H H R R
R—O H—O H—O H—O
δ– δ+ δ– δ+ δ– δ+ δ–
Intermolecular H-bonding
ii. There is gradual decrease in the solubility of alcohols in its homologous series with increase in
their molecular masses.
Reasons: The gradual increase in the molecular mass in the homologous series of alcohols is due to
increase in the molecular mass of the non-polar lipophilic or hydrophobic alkyl group of the alcohols
becomes predominant and masks the effect of polar –OH group and hence solubility goes on decreasing
gradually from lower alcohols to higher alcohols.
iii. The solubility of isomeric alcohols increases with branching of carbon chain in the molecules.
It means that the solubility of isomeric alcohols increase in the order as 1o< 2o< 3o alcohols.
Reason: The branching in the non-polar alkyl group of alcohol causes the decrease in available surface
area of the molecule and hence enhancing the solubility. The argument is well supported by solubility
data of isomeric alcohols with molecular formula C4H9OH:
Alcohols Solubility: gm/100gm of water

n-Butyl alcohol 7.9
Isobutyl alcohol 10.0
sec-Butyl alcohol 12.5
tert-Butyl alcohol > 12.5
3. Boiling point and melting point:
i. The boiling points of alcohols are higher than that of the boiling points of corresponding
aliphatic hydrocarbons (alkanes), alkyl halides (haloalkanes) and ethers of comparable
molecular masses.
The given data illustrate the higher boiling point of alcohols with respect to other
compounds.
o
Compounds Molecular wt. B. pt. ( C)
Propane (CH3.CH2.CH3) 44 - 65
Ethyl alcohol (CH3.CH2OH) 46 78
Dimethyl ether (CH3.O.CH3) 46 - 25
Reasons: Alcohols molecules are closely and strongly associated together by strong intermolecular
force of attraction of hydrogen bonding. Such hydrogen bonding is absent in alkanes, alkyl halides
and ether. The presence of hydrogen bonding in alcohols requires an additional amount of energy to
overcome the hydrogen bonding so the alcohols molecules boil at high temperature.
ii. There is gradual increase in the boiling points of alcohols in its homologous series with the
increase in their molecular masses.
Reason: The gradual increase in the molecular mass in the homologous series of alcohols also
increases the magnitude of van der Waals' force, which causes the increase in the boiling points of
alcohols.
O—H O—H O—H
R R R
iii. The boiling points of isomeric alcohols decrease with branching of carbon chain in the
molecules. It means that the boiling points of isomeric alcohols decrease in the order as 1o>
2o> 3o alcohols.
Reason: The gradual decreases in the boiling points of the isomeric alcohols are due to the regular
decrease in the available surface area occupied by more branched alcohols molecules.
10.1.8 Important Terms Used in Alcohol Industries

1. Alcoholate: Lower alcohols especially methyl alcohol and ethyl alcohol interact with anhydrous
CaCl2 or MgCl2 to form the solid crystalline derivatives known as alcoholates. Like water
molecules are closely associated in the hydrated crystalline inorganic salts as 'water of
crystallization', similarly, alcohol molecules are also closely associated in the crystalline
alcoholates as 'alcohol of crystallization'. It is the reason for that alcohol cannot be dried over
anhydrous CaCl2 or MgCl2.
Example: CaCl2.3C2H5OH MgCl2.6C2H5OH
2. Wood spirit (wood alcohol): Methyl alcohol also called carbinol is commonly known as wood
spirit because of one time it was obtained by destructive distillation of wood. It is highly
poisonous that drinking of it causes blindness as well as nervous unconscious. A dose of 15 to
20 mL of CH3OH is sufficient to cause death of a person.
3. Rectified spirit and absolute alcohol: Ethyl alcohol obtained by the fractional distillation of
distillate from wash of fermentation as a major fraction containing concentration about 95% is
called Rectified spirit, it includes 95.87% ethyl alcohol and 4.13% water is called azeotrope or
constant boiling mixture which can not be purified by simple distillation.
The pure and anhydrous ethyl alcohol (100%) is called absolute alcohol. The absolute alcohol is
obtained from rectified spirit by following methods:
i. By distilling the rectified spirit over quicklime (CaO), followed by re-distillation over
calculated amount of sodium metal in anhydrous condition.
ii. By azeotropic distillation: Rectified spirit is mixed with a very small amount of benzene
make ternary azoetrope which distillation gives 100% alcohol.
4. Power alcohol: A mixture of absolute ethyl alcohol and gasoline (petrol) in the approximate
proportion of about 20:80 in a co-solvent like benzene or ether is known as 'power alcohol'. It is
called power alcohol because it can be used to generate the power in internal combustion engines.
The calorific value of alcohol is low but it has good antiknocking properties. Its octane number is
90. Alcohols thus help to increase octane number of fuel. It is also important to reduce
dependency on petroleum import.
5. Methylated spirit (Denatured alcohol): Ethyl alcohol is made available only for industrial
purpose by addition of some poisonous substances likes methyl alcohol, acetone, pyridine or
colouring matter, and hence it becomes unfit for drinking.
It has been found that some times urea is illegally added to ethyl alcohol to improve its alcoholic
action, which is also unfit for drinking.
Such undrinkable ethyl alcohol containing poisonous substances especially methyl alcohol is
called denatured alcohol or methylated spirit. The process of making methylated spirit is known
as denaturing. Methylated alcohol is very important and excellent solvent in industries. It is much
cheaper than that of ethyl alcohol, and hence it has been illegally sold for drinking and it causes
serious physiological hazard to the human health including blindness. This alcohol is not taxable
as it is to be used for industrial purposes only.
6. Alcoholic beverages: They are liquors for drinking purpose. They contain ethanol, water,
colouring material and flavouring material. They may be distilled (e.g. Vodka, Gin, Whiskey,
brandy etc.) or undistilled (e.g. Beer, Wine, etc.)
10.1.9 Chemical Properties of Alcohols

The chemical properties of alcohols can be studied under the following heads.
A. Reactions involving the cleavage of O—H bond (Oxygen-Hydrogen bond) in alcohols: Reaction
due to –H atom of alcohols:
B. Reactions involving the cleavage of C—O bond (Carbon-Oxygen bond) in alcohols: Reaction due
to –OH group of alcohols:
A. Reaction involving the cleavage of O—H (Oxygen-hydrogen) bond in

alcohols: Reaction due to —H atom of alcohols:
1. Reaction of alcohols with active metals: Acidic nature of alcohols: When alcohols are
treated with active metals like Na, K, Mg etc., these liberate hydrogen with the formation
of metal alkoxides (alkali alcoholate).
– +
2 C2H5O—H + 2 Na 2 C2H5O Na + H2 ↑
Sodium ethoxide
CH3 CH3
– +
2 CH3—C—OH + 2 K 2 CH3—C —O K + H2 ↑
CH3 CH3
tert- Butyl alcohol Potassium tert-butoxide
The active metals displace hydrogen from the –OH group of alcohol in the form of H2 gas.
This shows the acidic nature of alcohols.
i. However, alcohols are very weak acids (Ka=10–16–10–18) even weaker than water
(Ka=10–14) that they neither turn litmus paper nor neutralize even strong alkali like NaOH.
Alcohols do not react with aqueous alkali solution.
ii. The weak acidic nature of alcohols than that of water is also explained on the basis of
electron releasing inductive effect (+I effect) of alkyl (R–) group attached to –OH group in
alcohols. The electron releasing tendency of alkyl group increases the electron density
around the oxygen atom due to which the polarity of the O–H bond decreases and causes
the breaking of O–H bond comparatively difficult in alcohols than that of water. In
addition, the alkoxide (RO–) ion formed is also destabilized due to high concentration of
negative charge on oxygen atom by electron releasing inductive effect of alkyl group.
Thus, the release of H+ ion is difficult. This explains the weak acidic character of alcohols
and hence makes alcohols weak acidic than water.
Order of acidity: H—OH > CH3–OH > RCH2 –OH (1o alcohol) > R2CH–OH (2o alcohol) >
R3C–OH (3o alcohol) > NH3 > CH4
2. Reaction with metal hydrides: Alcohols react with metal hydrides to form salts along with
evolution of hydrogen gas.
– +
CH2OH CH2O Na
+ NaH + H2
Benzyl alcohol Sodium phenyl methoxide
3. Reaction with Grignard's reagent: Alcohol contains active hydrogen atom so, it reacts with
Grignard reagent to form alkane. In this reaction, the alkane is obtained from the alkyl part of
the Grignard's reagent. This reaction is used for the estimation of alcoholic group under the
name of Zerewitnoff reaction.
C2H5OH + CH3MgBr CH4 + Mg(OC2H5)Br

Methane Ethoxy magnesium bromide
4. Formation of esters: Esterification reaction

a. Reaction of alcohols with carboxylic acids: Basic nature of alcohol: When a mixture of
alcohol and carboxylic acid is heated in presence of calculated amount of conc. H2SO4, an ester
is formed, which gives a characteristic pleasant fruity smell.This reaction is called esterification
test.
Conc. H2SO4
RCO OH + H OR' RCOOR' + H2O
Carboxylic acid Alcohol Δ Ester
The function of conc. H2SO4 is to act as a dehydrating agent since the reaction is reversible in
nature and the equilibrium can be shift to the right by removing water as soon as it is formed.
This reaction has an important application for the detection of both alcoholic and carboxylic
acid functional groups under the name of esterification test since the ester gives the
characteristics fruity smell.
b. Reaction of alcohols with acid chlorides and acid anhydrides: Acylation: When an alcohol is
heated either with acid chloride or with acid anhydride in the presence of pyridine as catalyst,
an ester is formed. Through this reaction, an acyl group (R–CO–) is introduced in the alcohol
molecule by replacing hydrogen atom of the –OH group and hence the reaction is termed as
'acylation' of alcohols.
O O
Pyridine
CH3—C—Cl + H OCH2CH3 CH3—C—OCH2CH3 + HCl
Δ
Ethanoyl chloride Ethanol Ethyl ethanoate
(Acid chloride)
O O O
Δ
CH3—C—O—C + CH3 + H OCH2CH3 CH3—C—OCH2CH3 + CHCOOH
Ethanoic anhydride Ethanol Ethyl ethanoate
(Acetic anhydride)
B. Reaction involving the cleavage of C—O (Carbon-oxygen) bond in alcohols:

Reaction due to —OH group of alcohols: Nucleophilic substitution reaction:
1. Reaction of alcohols with ammonia: Ammonolysis of alcohols: Like ammonolysis of alkyl
halides, alcohols can also undergo ammonolysis when the vapor of alcohols mixed with
ammonia is passed over heated alumina (Al2O3) or thoria (ThO3) at about 400oC. The reaction
results a mixture of amines (1°, 2° and 3°).
The 1o amine would be a major product, when large excess of ammonia gas is used as compared
to alcohol.
δ+ δ– Al2O3
H N H + R OH Δ R N H + H2O
H H
Example:
H
δ+ δ–
H N H + CH3 C OH CH3CH2 N H + H2O
H H H
Ethylamine
(1°)
However, if the alcohol is in excess, the 1o amine formed at first stage of reaction as given above
further reacts with excess of alcohol to form 2o amine then 3o amine and finally 4o quaternary
ammonium hydroxide.
H N H+R OH R N H + H2O
H H
1° amine
R N H+R OH R N R + H2O
H H
2° amine
R N R+R OH R N R + H2O
H R
3° amine
R +
R N R+R OH R N R OH¯
R R
Quaternary ammonium hydroxide
Tetralkyl ammonium hydroxide
Examples: H
Al2O3
H N H + CH3 C OH CH3CH2 N H + H2O
Δ
H H H
Ethylamine
(1°)
H
CH3CH2 N H + CH3 C OH CH3CH2 N CH2CH3 + H2O
H H H
Diethylamine
H (2°)
CH3CH2 N H + CH3 C OH CH3CH2 N CH2CH3 + H2O

CH2CH3 H CH2CH3
Triethylamine
(3°)
+
(CH3CH2)3N + CH3CH2OH (CH3CH2 )4N OH¯
Tetraethylammonium hydroxide
2. Reaction of alcohols with hydrogen halides (HX): Alcohols react readily with hydrogen
halides to yield alkyl halides and water.
R—OH + H X R—X + H2O
The reaction is carried out either by passing dry hydrogen halide gas into the heated alcohol or
by heating the alcohol with the concentrated aqueous solution of hydrogen halide. In some
reactions the use of catalyst may be needed.
Sometime hydrogen bromide is generated in situ by reaction between sulphuric acid and
sodium bromide in presence of alcohol. Similarly hydrogen iodide is generated in the same
manner by reaction between sulphuric acid and sodium iodide.
NaBr + H2SO4 HBr + NaHSO4
NaI + H2SO4 HI + NaHSO4
The order of reactivity of various alcohols for given hydrogen halide follows the sequence of: 3o alcohols >
2o alcohols > 1o alcohols > methyl alcohol
On the other hand, the order of reactivity of various hydrogen halides for a given alcohol follow the
sequence of: HI >HBr > HCl
Examples:
a. On this background, the least reactive hydrogen halides like hydrogen chloride, generally
requires the presence of anhydrous ZnCl2 for reaction with 1o and 2o alcohols. The mixture
of hydrogen chloride and anhydrous ZnCl2 is called Lucas reagent. On the other hand, the
very reactive tert-butyl alcohol reacts with conc. HCl by simply shaken at room
temperature.
anh. ZnCl2/Δ
CH3CH2OH + HCl CH3CH2Cl + H2O
Ethyl alcohol Ethyl chloride
(1°) (1°)
OH Cl
anh. ZnCl2
CH3—CH—CH3 + HCl CH3—CH—CH3 + H2O
Isopropyl alcohol Isopropyl chloride
(2°) (2°)
CH3 CH3
room temperature
CH3—C—OH + HCl CH3—C—Cl + H2O
CH3 CH3
tert-Butyl alcohol tert-Butyl chloride
(3°) (3°)
b. Primary alcohol when reacts with hydrogen bromide in presence of conc. H2SO4 gives
corresponding alkyl bromide. For secondary and tertiary alcohols reacts with hydrogen
bromide even in absence of conc. H2SO4.
conc. H2SO4
CH3CH2OH + HBr CH3CH2Br + H2O
Ethyl alcohol 48% Ethyl bromide
OH Br
room temperature
CH3—CH—CH3 + HBr CH3—CH—CH3 + H2O
Isopropyl alcohol 48% Isopropyl bromide
c. Hydrogen iodide is highly reactive so it reacts with alcohols even in room temperature
when shaken together.
room temperature
CH3CH2OH + HI CH3CH2I + H2O
Ethyl alcohol Ethyl iodide
The order of reactivity of various alcohols for a hydrogen halide can be explained on the
basis of electron releasing inductive (+I) effect of alkyl (R-) groups present in alcohols. The
alkyl groups by their electron releasing effect tend to increase the electron displacement
towards oxygen. In other words, the polarity of C–O bond increases and this makes the
breaking of the bond between carbon and oxygen easier. Therefore, the alcohols with
greater number of alkyl groups attached to carbon will be more reactive. This justifies the
above sequence of reactivity of alcohols in this type of reactions.
3. Reaction of alcohols with phosphorus halides: Alcohols are readily converted to the
corresponding alkyl halides by reaction with phosphorus halides (PCl5 or PX3).
3 R—OH + PX3 3 R—X + H3PO3
R—OH + PCl5 R—Cl + POCl3 + HCl
PBr3 and PI3 are generally prepared in situ from the reaction of red phosphorus with bromine
and iodine respectively.
3 R—OH + PCl3 3 R—Cl + H3PO3
3 R—OH + PBr3 red P + Br2/Δ 3 R—Br + H3PO3
3 R—OH + PI3 red P + I2/Δ 3 R—I + H3PO3

4. Reaction of alcohols with thionyl chloride: Alcohols react with thionyl chloride in presence of
pyridine, to give chloroalkane.
pyridine
R—OH + SOCl2 R—Cl + SO2 + HCl
The order of reactivity of various alcohols towards this reaction follows the same sequence of:
3o alcohols > 2o alcohols > 1o alcohols > methyl alcohol
C. Other Reaction:
1. Oxidation of alcohols
a. Oxidation using KMnO4/H+ or K2Cr2O7/H+
Oxidation of primary (1o) alcohols: Primary alcohols are oxidized first to aldehydes,
which on further oxidation give carboxylic acids with the same number of carbon atoms as
that of the parent alcohols.
Examples:
KMnO4/H+ or KMnO4/H+ or O
OH O
K2Cr2O7/ H+ K2Cr2O7/ H+
CH3—C—H + [O] CH3—C—H CH3 C—OH
—
–H2O [O]
H Ethanal Ethanoic acid
Ethanol
Oxidation of secondary (2o) alcohols: Secondary alcohols are oxidized to ketones with the
same number of carbon atoms as that of the parent alcohols.
OH O
K2Cr2O7/H2SO4/Δ
R—C—H + [O] R—C—R
–H2O
R Ketone
2° Alcohol
Examples:
OH O
K2Cr2O7/H2SO4/Δ
CH3—C—CH3 + [O] CH3—C—CH3
–H2O
H Propanone
2-Propanol
Note:
Unlike aldehydes, ketones are quite resistant to further oxidation under ordinary and mild conditions with these oxidizing
agents. But upon prolonged treatment with strong oxidizing agent at high temperature, ketones are oxidized to carboxylic acids
with lesser number of carbon atoms than that of the parent secondary alcohols. The reaction is called "oxidative degradation"
of alcohols.
O O
Drastic conditions
CH3—C—CH3 + 4 [O] CH3—C—OH + H2O + CO2
Oxidative degradation
Propanone Ethanoic acid
Oxidation of tertiary (3o) alcohols: Tertiary alcohols are quite resistant for oxidation with
mild oxidizing agents in aqueous, alkaline or neutral conditions.
However, when oxidation is carried out under drastic acidic conditions with strong
oxidizing agent like KMnO4 conc. H2SO4, tertiary alcohols first undergo dehydration into
alkenes. The alkene formed is then oxidized to ketone, which is finally oxidized to
carboxylic acid with lesser number of carbon atoms than that of the parent alcohol.
OH [O] O
KMnO4/H2SO4/Δ 4[O]
CH3—C—CH3 CH3—C = CH2 CH3—C—CH3
–H2O
−H2O
CH3 CH3 Propanone
−CO2
2-Methyl-2-propanol 2-Methyl propane
Oxidative degradation
O
CH3—C—OH + H2O + CO2
Ethanoic acid
Oxidation using PCC

Pyridinium chlorochromate: PCC is obtained by treading CrO3 with pyridine and HCl. This reagent is used non-polar
solvent like CH2Cl2. It does not hydrate aldehyde. So, no further oxidation of aldehydes takes place here. PCC can oxidize 1°
alcohol into aldehyde and 2° alcohol into ketons.
b. Catalytic dehydrogenation of alcohols: (Oxidation):

When vapour of alcohol is passed over heated copper at 300°C, different nature of
products are formed depending upon the nature of alcohol used in the reaction.
i. Methyl alcohol forms formaldehyde upon catalytic dehydrogenation by passing its vapor
over reduced copper at 300°C.
Cu, 300°C
CH3—OH HCHO + H2 ↑
Δ
Methanol Methanal
ii. Primary alcohols form aldehydes upon catalytic dehydrogenation by passing their vapors
Cu, 300°C
R—CH2—OH R—CHO + H2 ↑
Δ
1° alcohol Cu, 300°C Aldehyde
CH3—CH2—OH CH3—CHO + H2 ↑
Δ
Ethanol Ethanal
iii. Secondary alcohols form ketones upon catalytic dehydrogenation by passing their vapors
R Cu, 300°C R
CH—OH C=O + H2 ↑
Δ
R R
2° Alcohol Ketone
Examples:
OH O
Cu, 300°C
CH3—CH—CH3 CH3—C—CH3 + H2 ↑
Δ
2-Propanol Propanone
Note:
Tertiary alcohols are resistant towards dehydrogenation due to absence of α-hydrogen. However, upon passing their vapors
over reduced copper at 300°C, they get dehydrated into alkenes rather than dehydrogenation.
OH CH3
Cu, 300°C
CH3—C—CH3 CH2 = C—CH3 + H2O
Δ
CH3 2- Methyl propene
2- Methyl-2-propanol
(3° alcohol)
2. Dehydration of alcohols: Alcohols undergo dehydration reaction into different products

depending upon the conditions of reaction and nature of dehydrating agents used in the
reaction.
a. Dehydration of alcohols into ethers with catalytic amount of conc. H2SO4 at 140oC:
Intermolecular dehydration of alcohols: Preparation of Ether: When excess of ethyl
alcohol is heated with catalytic amount of conc. H2SO4 as a dehydrating agent at about
140oC, ethyl alcohol undergoes intermolecular dehydration to give diethyl ether.
Conc.H2SO4, Δ
2R—OH R—O—R + H2O
Example:
Conc.H2SO4
2CH3CH2OH CH3CH2—O—CH2CH3 + H2O
140°C
The reaction takes place in two steps: In first step, ethyl alcohol reacts with H2SO4 at 100oC
to form ethyl hydrogen sulphate. In second step, ethyl hydrogen sulphate further reacts
with excess of ethyl alcohol at 140oC to produce diethyl ether with the regeneration of
H2SO4. The regenerated H2SO4 can further reused to dehydrate addition amount of ethyl
alcohol into diethyl ether and hence the method is known as 'Williamson's Continuous
Etherification'.
100°C
C2H5—OH + H O—SO3H C2H5OSO3H + H2O
Ethyl hydrogen sulphate
140°C
C2H5 OSO3H + H —OC2H5 C2H5—O—C2H5 + H2SO4
140°C
2C2H5OH conc. H2SO4 C2H5—O—C2H5 + H2O
Ethanol Ethoxyethane
b. Dehydration of alcohols into alkenes with excess of conc. H2SO4 at 170oC:

Intramolecular dehydration of alcohols: Preparation of Alkenes: When calculated
amount of ethyl alcohol is heated with excess of conc. H2SO4 as a dehydrating agent at
about 170oC, ethyl alcohol undergoes intarmolecular dehydration to ethene.
The reaction takes place in two steps: In first step, ethyl alcohol reacts with H2SO4 at 100oC
to form ethyl hydrogen sulphate. In second step, ethyl hydrogen sulphate decomposes at
about 170°C to produce ethene.
Conc. H2SO4
C2H5OH + HO SO3H C2H5OSO3H + H2O
100°C
C2H5OSO3H CH2 = CH2 + H2SO4

170°C
Dehydration of alcohols into alkenes can also be carried out by heating alcohol with
phosphoric acid or boric acid at high temperature.
c. Catalytic dehydration of alcohols with alumina (Al2O3):
i. Passing the vapor of ethyl alcohol over heated alumina to the temperature less than 300°C
can undergo intermolecular dehydration of alcohol into diethyl ether.
Al2O3, 250°C
2CH3CH2OH CH3CH2—O—CH2CH3 + H2O
ii. On the other hand, passing the vapor of ethyl alcohol over heated alumina as a catalyst to
the temperature above than 300°C can undergo intramolecular dehydration of alcohol into
ethene.
Al2O3, 350°C
CH3CH2OH CH2 = CH2 + H2O
3. Reduction of Alcohols
Alcohols can be reduced using reducing agents like HI/P4 to get corresponding alkanes.
Example:
CH3CH2OH + 2 HI P4 CH3CH3 + H2O + I2
Δ Ethane
Ethanol
4. Iodoform Test
OH
Alcohols having CH3—CH— structure on heating with excess I2 and aq. alkali (NaOH) give
yellow crystalline precipitate of iodoform. This test is called iodoform test.

oxidation
CH3CH(OH)R + NaOI CH3COR + NaI + H2O
iodination
hydrolysis

Δ
CH3CH(OH)R + 4 I2 + 6 NaOH CHI3 ↓ + 5 NaI + RCOONa + 5 H2O
Iodoform
(Yellow ppt)
10.1.10 Distinction of Primary, Secondary and Tertiary Alcohols

There are several methods used to distinguish primary, secondary and tertiary alcohols. These
methods are:
1. Victor Meyer test: Given alcohol is treated with PI3 (red P4 + I2) to get corresponding iodoalkane.
The iodoalkane thus obtained is treated with alc. AgNO2 to get corresponding nitroalkane. The
nitroalkane thus obtained is treated with nitrous acid (NaNO2 + HCl) and then with aqueous
alkali
Colour of the solution observed:
♦ If blood red colouration is obtained, the alcohol is primary (1°)
♦ If blue colouration obtained the alcohol is secondary (2°) alcohol.
♦ Colourless solution indicates presence of tertiary (3°) alcohol.
RCH2OH (1° alcohol) R2CHOH (2° alcohol) R3COH (3° alcohol)
Δ Red P4 + I2
Δ Red P4 + I2 Δ Red P4 + I2
R R
R—CH2—I CH—I R—C—I
R
R
1° Iodoalkane 2° Iodoalkane 3° Iodoalkane
alc. AgNO2 alc. AgNO2 alc. AgNO2
R R
R—C H2 —NO2 R—C—NO2 R—C—NO2
1° Nitroalkane H 2° Nitroalkane R
3° Nitroalkane
O = N—OH OH—N = O
HNO2
R—C—NO2
R
N—OH
Nitrolic acid R—C—NO2
No reaction
N=O
aq. NaOH Pseudonitrol
aq. NaOH
aq. NaOH
R—C—NO2
N—O¯Na+
Blue colouration Colourless solution
Sodium nitrolate
(Blood red colouration)
Self Test
10. 2 How would you distinguish propan-1-ol, propan-2-ol and 2-methylpropan-2-ol?
2. Lucas test: In this method, the given alcohol is treated with Lucas reagent (mixture of anhydrous
ZnCl2 dissolved in conc. HCl) at room temperature, where an appearance of cloudiness in the
reaction mixture shows the formation of alkyl chloride.
ZnCl2
R—Cl + HCl (aq.) R—Cl + H2O
cloudyness
Since the order of reactivity of alcohols is 3o> 2o> 1o:

a. A 3o alcohol reacts immediately with Lucas reagent and shows cloudiness immediately.
b. A 2o alcohol reacts steadily with Lucas reagent and shows cloudiness after few minutes.
c. A 1o alcohol does not react appreciably with Lucas reagent at ordinary condition of temperature
and does not show cloudiness. However the cloudyness appears only after heating the solution.
Note:
Iodoform test is given by alcohols with CH3—CH(OH)– structure and aldehyde or ketone with CH3—CO— structure.
10.1.11 Laboratory Test for Ethanol (Already discussed )

1. Esterification test (Refer section 10.1.9A)
2. Iodoform test (for the compounds having CH3 –CH(OH)–structure. Refer section 10.1.9C)
3. Dichromate test and permanganate test (Refer section 10.1.9C)
10.1.12 Dihydric Alcohols

Alcohols containing two —OH groups attached per molecule are called Dihydric alcohols. The
common name of it is Alkylene glycol and its IUPAC name is alkanediol. The general molecular
formula of it is CnH2n(OH)2.
Examples:
OH OH
OH OH
CH2—CH2
CH3—CH2—CH2
Ethane -1,2-diol Propane- 1,2-diol
(Ethylene glycol)
Preparation of Dihydric alcohols:

1. By hydroxylation of alkenes: Hydroxylation of alkenes means addition of –OH (hydroxy)
groups onto the C=C double bond of alkene into diols. Hydroxylation of alkenes into diols is a
redox reaction, which is carried out by the action of cold and alkaline solution of KMnO4 known
as Baeyer's reagent. Baeyer's reagent acts as an oxidizing agent, where it oxidizes alkenes into
diols and itself get reduced to colourless product of MnO2. Hence this reaction has great
importance in organic analysis to detect the presence of unsaturation center (multiple bonds:
double or triple bonds) in organic compounds.
Ethylene glycol is prepared in the laboratory by hydroxylation of ethylene,when the ethylene
gas is bubbled through a cold dilute alkaline solution of KMnO4(Baeyer's reagent). Ethylene is
oxidized to ethylene glycol and the purple color of Baeyer's reagent is discharged.
CH2 = CH2 + 2 KMnO4 + 2 KOH 2 K2MnO4 + CH2—OH
Ethene Pink CH2—OH
Colourless Ethylene glycol
2. By hydrolysis of ethylene chlorohydrin: Ethylene glycol can also be obtained by the hydrolysis
of ethylene chlorohydrin.
aq. Na2CO3
CH2—CH2 CH2 —CH2
OH Cl OH OH
3. By hydrolysis of Epoxy-ethane: Industrial preparation of Ethylene glycol: Ethylene glycol is

commercially prepared by oxidation of ethylene. Ethylene on heating with air in silver as a
catalyst at about 250°C forms epoxyethane (ethylene epoxide), which upon hydrolysis with super
heated steam yields ethylene glycol.
O
Ag H2O
CH2 = CH2 + O2 CH2 CH2 CH2—CH2
Δ, 250°C Super heated steam
OH OH
Physical Properties of ethylene glycol:
i. It is a colorless and viscous liquid with sweet taste.
ii. It boils at 197°C.
iii. It is highly soluble in both water and ethyl alcohol.

Its viscous nature and high boiling point is due to the intermolecular hydrogen bonding. Its
high solubility in water and alcohols is also due to the formation of hydrogen bonding between
molecules of water and alcohol.
Uses of Ethylene Glycol

i. It is used as a solvent.
ii. It is used as a coolant for aeroplane engines.
iii. It is used as an anti-freeze agent in the radiators of automobiles.
iv. It is used in the preparation of explosive.
v. It is also used in the preparation of solvents like dioxane, polymethylene glycol, etc.
vi. It is also used in the preparation of polymer Dacron (Terylene).
10.1.13 Trihydric Alcohols

Alcohols containing three –OH groups attached per molecule are called trihydric alcohols. The
common name of it is glycerols and its IUPAC name is alkanetriol. The general molecular formula of
it is CnH2n-1(OH)3. It can be purified by vacuum distillation as it decompose at its normal boiling
point.
Example: OH OH OH
CH2—CH—CH2
Propane- 1,2,3-triol
Glycerol
Oils and fats are triesters of glycerol with long chain of higher fatty acids. These higher fatty acids
may be palmitic acid (C15H31COOH), stearic acid (C17H35COOH), oleic acid (C17H33COOH) etc. The
triesters of glycerol are also known as Triglycerides. A glyceride may be represented by general
formula as given below, where R, R' and R" may be same or different alkyl groups.
Preparation
1) From oils and fats: By saponification:
Glycerol is prepared in soap industries during the manufacture of soap by heating oils or fats
(triglycerides) with caustic soda solution. Thus, the alkaline hydrolysis of triglycerides with
NaOH solution into soap and glycerol is called saponification. Glycerol is the byproduct of
saponification and the major product is soap. Soap is the sodium salt of higher fatty acid.
Reaction:
HO H
H—C—O—C—R' H—C—OH +
R' COO Na
O
H—C—O—C—R" H—C—OH +
+ 3NaOH (aq) + R'' COO Na
O
H—C—O—C—R'" H—C—OH +
R'" COO Na
H H
A triacylglycerol Glycerol Mixture of sodium salt of
(Triglyceride) fatty acids (Soap)
Fat
Glycerol can also be prepared as follows;

Cl2 H2O, OH¯
CH3—CH = CH2 Cl—CH2—CH = CH2 OH—CH2—CH = CH2
400-450°C
HOCl
aq. Na2CO3
CH2—CH—CH2 CH2—CH—CH2
OH OH OH OH OH Cl
Glycerol
Uses of Glycerol
i. It is used as lubricant.
ii. It is used to prepare nitroglycerine, which is used in making dynamite.
iii. It is used as soothing agent.
iv. It is used in the manufacture of cosmetics and transparent soaps.
v. It is used as moistening agent for skin in winter in the name of glycerine.
vi. It is also used as a sweetening agent for sugar free sweet, confectionaries and beverages.
vii. It is used as a humectant in non-drying printing inks, stamp pad inks etc.
viii. It is used as an anti-freeze agent in the radiators of automobiles.
ix. Glyceryltrinitrate is used as medicine to low the blood pressure.
Self Test
10.3 What are primary, secondary and tertiary alcohols? Starting from Grignard reagent, how would
you obtain each of them? State what happens when the three types of alcohols are oxidized?
Some Solved Questions

1. How can you convert propan-1-ol into propan-2-ol?
Br OH
¬ aq. KOH
Excess HBr CH3CHCH3
CH3CH2CH2OH CH3CH = CH2 CH3CHCH3
conc. H2SO4,Δ Δ
2-bromopropane Propan-2-ol
Propan-1-ol Propene
2. How can you convert propan-2-ol into propan-1-ol?

¬
OH
Excess HBr aq. KOH
CH3CHCH3 CH3CH = CH2 CH3CH2CH2Br CH3CH2CH2OH
conc. H2SO4,Δ Peroxide Δ
Propene Propan-1-ol
Propan-2-ol
3. Outline the synthesis of t-butyl alcohol from acetone.

¬
O OMgBr OH
Ether H2O/H+
CH3—C—CH3 + CH3—MgBr CH3—C—CH3 CH3—C—CH3
Δ
CH3 CH3
Addition product t-Butyl alcohol
4. How can you distinguish methanol and ethanol?

¬ Methanol (CH3OH) does not have CH3CH(OH)— structure. So it does not give iodoform test. Where as
ethanol (CH3CH2OH) has CH3CH(OH)—structure. So, it gives iodoform test.
Δ
CH3CH2OH + 4 I2 + 6 NaOH CHI3 ↓ + 5 NaI + HCOONa + 5 H2O
Iodoform
(Yellow ppt)
Questions
1. Describe Victor Meyer method of distinguishing 1°, 2° and 3° alcohols.
2. Alcohols are not dehydrated by CaCl2. Why?
3. Why are higher alcohols practically insoluble in water?
4. What happens when an alcohol is dehydrated?
5. Write structure of the tertiary alcohol having a molecular formula C4H10O and write its IUPAC
and common name.
6. Write any two laboratory tests of ethanol.
7. What is meant by esterification? Give an example.
8. How can you distinguish propan–1–ol and propan–2–ol?
9. Why is phenol more acidic than ethanol?
10. What happens when propan–2–ol is treated with I2 in presence of aqueous NaOH?
11. Identify A, B, C and D in the following reaction writing the related reactions.
PCl3 Alc.KOH 1. O3/CCl4
(CH3)2CHOH A B C+D
Δ Δ 2. H2O2/OH–
12. What is meant by fermentation? Write an example.

1. How can you distinguish:
a. Ethanol and methanol
b. Propan-1-ol and propan-2-ol by Victor Meyer method
c. t-butyl alcohol and sec-butyl alcohol d. chloromethane and ethanol
2. Outline the synthesis of the following alcohols using Grignard synthesis
a. Propan-2-ol b. 2-methylpropan-2-ol
c. Isobutyl alcohol d. n-propyl alcohol
3. Write shrot notes on:
a. Lucas test b. Victor Meyer test
c. Fermentation d. Uses of ethanol
e. Oxo process
4. A dihydric alcohol C2H6O2 (A) undergoes stepwise oxidation with K2Cr2O7/H⊕ to give a
dicarboxylic acid C2H2O4 (B), as final product. Identify A and B writing related reaction with
their IUPAC names.
5. How can you convert:
a. Ethanol into ethanoic acid b. Ethanol into propanoic acid
c. Ethanol into acetylene d. Ethanol into benzene
e. Methane into ethanoic acid f. Ethanol into methanol
g. propan–1–ol into propan–2–ol
a. Ethanol is dehydrated b. Propan-2-ol is reacted with PCl5
c. Ethanol is treated with acetic acid in presence of conc. H2SO4
d. Propan-2-ol is treated with sodium. e. Sucrose is fermented.
7. Write down the isomers of C3H8O with their IUPAC and common names which one of them
gives iodoform test. Why? Write the reactions involved.
8. An organic compound A reacts with PBr3 to give B. Compound B produces C when heated with
alcoholic KOH. The compound C undergoes ozonolysis to give ethanal and methanal. The
compound A responds iodoform test. Identify A, B and C writing related reactions.

1. Formation of alcohol and carboxylic acid for ester is 6. The boiling point order of alcohols is
an example of a. 1°> 2°> 3° b. 1°>3 °> 2°
a. Esterification b. Trans-esterification c. 3°> 2°>1° d. 2°>3°>1°
c. Ester-hydorlysis d. Oxidation 7. The most suitable reagent to convert Alcohol into
2. Grignard reagent reacts with alcohols to form aldehyde is
a. Alkanes b. Alkenes a. KMnO4 b. K2Cr2O7
c. Alkynes d. All c. PCC (pyridine chlochromate)
3. The reaction of alcohol and carboxylic acid is d. CrO3
8. Drinking of which alcohol may cause blindness
a. Esterification b. Hydrolysis
c. Saponification d. Hydrogenation a. Wood spirit b. Ethanol
c. absolute alcohol d. Rectified spirit
4. Which of the following compound does not give
Iodoform test? 9. The grain alcohol refers to
a. C2H5OH b. CH3CHO a. Amyl alcohol b. Methyl alcohol
c. CH3COCH3 d. HCHO c. Ethyl alcohol d. Isopropyl alcohol
5. Which has the highest boiling point? 10. The amine is changed into corresponding alcohol by
a. Propan-1-ol b. Propane a. acidified KMnO4 b. HNO2
c. Chloropropane d. Diethyl ether c. Br2/KOH d. HNO3
1 2 3 4 5 6 7 8 9 10
c a a d a a d a c b
10.2 Phenols
OH
OCH3
CH2—CH = CH2
2-Methoxy-4 (prop-2-enyl) phenol
(Eugenol)
Clove oil
Phenols occur widely in nature. Eugenol (b.pt. 254°C) is oily liquid found in many essential oils and
it is also a main constituent of clove oil, which is responsible for aroma of cloves. It is used in
perfumeries, flavorings, essential oils and in medicines as dental antiseptic and anesthetic
10.1.1 Introduction
Phenols are a class of organic compounds of the general formula Ar—OH, where Ar is phenyl
(C6H5—) or substituted phenyl (R—C6H4—), or some other aryl group like naphthyl (C10H7—), etc. In
phenols the hydroxyl group (–OH) is directly attached to the aromatic ring. The most important
member of phenols is phenol, where aromatic ring is benzene.
Both phenols (ArOH) and alcohols (ROH), contain the —OH OH
group, and as a result these two families resemble each other to a
limited extent. In most of their properties and in their preperations,
phenols and alcohols differ so greatly that they are classified as Phenol
different families. Phenols differ from alcohols in having the —OH (Monohydroxybenzene)
group attached directly to an aromatic ring whereas in alcohols the or C6H5OH or PHOH or φOH
—OH group is attached to an alkyl group.

Definition
Hydroxy derivatives of arenes, where the —OH group is directly attached to the aromatic ring are
called phenols.
i.e. Ar—H
Ar—H + OH
Ar—OH
Arene Phenol
Phenol is colorless crystalline solid with melting point 43ºC and boiling point 182ºC. It is moderately soluble
in water (solubility 9.3) but readily soluble in organic solvents. Phenol with 5% water is commonly called
carbolic acid.
10.2.2 Classification
Like alcohols, phenols are classified as mono-, di- and trihydric phenols according to the number of
—OH groups contained in their molecules. When four or more —OH gourps are present, they are
called polyhydric phenols. Some examples of mono, di- and trihydric phenols are as follows:
a. Monohydric phenols: OH
OH OH OH
Br
Br Br
Phenol 2-Bromophenol 3-Bromophenol 4-Bromophenol
(Monohydroxybenzene) (o-Bromophenol) (m-Bromophenol) (p-Bromophenol)
Methyl phenols are called cresols.
OH OH
OH
CH3
CH3
m-Cresol
CH3
o-Cresol
(3-Methylphenol) P-Cresol
(2-Methylphenol)
(4-Methylphenol)
OH OH
O2N NO2
OH
α OH
CH3 CH3 β
NO2
Cl
2,4,6-Trinitrophenol 4-Chloro-3,5-dimethylphenol 1-Napthol 2-Napthol
(Picric acid) (Chloroxylenol) (α-napthol) (β-napthol)
b. Dihydric phenols:
OH
OH
OH
OH
OH OH
1,2-Dihydroxybenzene 1,3-Dihydroxybenzene 1,4-Dihydroxybenzene
(Catechol) (Resorcinol) (Hydroquinone or quinol)
c. Trihydric phenols:
OH
OH OH
OH
OH
OH HO OH
OH
1,2,3-Trihydroxybenzene 1,2,4-Trihydroxybenzene 1,3,5-Trihydroxybenzene
(Pyrogallol) (Hydroquinol) (Phloroglucinol)
Note:
It may be noted that the aromatic compounds in which —OH group is not directly attacted to benzene ring are not phenols but
they are called aromatic alcohols. These may be regarded as aryl alkyl alcohols since they behave very much like alcohols.
Examples:
CH2OH CH2CH2OH
Phenylmethanol 2-Phenylethanol
(Benzyl alcohol)
Self Test
10.4 What are phenols? Draw the possible isomers of molecular formula C7H8O having benzene
ring and indicate the phenols.
10.2.3 Methods of Preparation

1. From coal tar: Middle oil fraction of coal tar contains phenols and cresols.
2. From chlorobenzene (Dow Process): When chlorobenzene is heated with aqueous NaOH at
high temperature (350°C) and pressure (300 atm.) in presence of copper catalyst followed by
acidification, phenol is obtained. It is an industrial method of preparation.
Cl OH ONa OH
NaOH, 350°C, 300 atm. NaOH (excess) dil. HCl
– NaCl + NaCl
–H2O acidification
Sodium phenoxide Phenol
This method was first used by 'Dow chemical company' of USA in 1928 for the manufacture of
phenol. Hence, this process is known as Dows process.
3. From cumene (Isopropyl benzene): Cumene reacts with air to from cumene hydroperoxide
which on treatment with dilute acid gives phenol along with acetone.
H O—OH
CH3—C—CH3 CH3—C—CH3 OH
O
O2 (air) H2O/H+
+ CH3—C—CH3
Cumene Acetone
Cumene hydroperoxide Phenol
This is the most important commercial method because the raw materials are easily available
from petroleum and the byproduct of the reaction is acetone, which is a valuable chemical.
4. From sodium aryl sulphonate (alkali fusion of sulphonate): When sodium benzene
sulphonate is fused with NaOH at high temperature (300°C) followed by acidification, phenol is
formed.
SO3Na ONa
Fuse, 300°C
+ 2 NaOH + 2 Na2SO3 + H2O
Sodium benzenesulphonate Sodium phenolate
ONa OH
Acidification
+ HCl + NaCl
Note:
i. Sodium benzene sulphonate is obtained from benzene by sulphonation with fuming H2SO4 followed by action of aq. NaOH on
benzene sulphonic acid.
ii. Conversion of benzene into phenol
SO3H SO3Na ONa OH

Fuming H2SO4 NaOH NaOH, 300°C HCl (dil)
Acidification
Benzene sulfonic acid Phenol
5. From benzene diazonium salt: When aqueous solution of benzene diazonium salt is boiled in
presence of little dilute sulphuric acid, where diazo group (N≡N+—) is replaced by —OH group,
phenol is formed. This is laboratory method of preparation.
Boil
N ≡ N Cl + H—OH OH + N2 + HCl
Benzenediazonium chloride
6. By decarboxylation of salt of salicylic acid: Phenol can also be obtained by the decarboxylation
of salt of salicylic acid with soda lime.
OH OH
COO Na CaO
+ NaOH + Na2CO3
Δ
Salicylic acid
Self Test
10.5 Outline the preparation of phenol from
a. Aniline b. Benzene sulfonic acid c. Chlorobenzene d. Cumene

1. The simplest phenols are colourless liquids or low melting solids.
2. They have characteristic phenolic odour.
3. They have quite high boiling point due to intermolecular hydrogen bonding in them.
4. Phenol itself is somewhat soluble in water (9 g/100 g water) because of hydrogen bonding with
the water while most other phenols are insoluble in water but soluble in organic solvents.
5. The physical properties of isomeric nitrophenols: ortho-nitrophenol has a much lower boiling
point and much lower solubility in water than its other isomers (para-nitrophenol and meta-
nitrophenols). Therefore, o-nitrophenol is steam-distillable.
In p-nitrophenol the relative positions of —OH and —NO2 groups permit them to form
intermolecular hydrogen bonding between their molecules and hence has a high melting point
(114°C) and boiling point than that of its other isomers.
δ+ δ– δ– δ–
H O O δ+ O
N
Intermolecular p-Nitrophenol is non volatile in steam distillation, its solubility is
hydrogen bonding 1.69 g /100 g water at 25ºC and its m.pt. 114°C
δ+
N
O– O H O–
δ δ– δ+ δ
The high solubility of p-nitrophenol in water (1.69 g/100 g H2O at 25°C) than its other isomers is
because of hydrogen bonding with water molecules.
δ– δ– δ+ δ–
O δ+ O H—O
N
Hδ+
H δ+
H O– O– — H+
δ+ δ δ δ
Intermolecular hydrogen bonding
In o-nitrophenol the relative positions of —OH and —NO2 groups permit them to form
intramolecular hydrogen bonding within a single molecule, therefore o-nitrophenol has low
melting point (45°C) and boiling point than that of its other isomers.
δ+
H
δ– O
Intramolecular hydrogen bonding
O δ–
N
δ+ O o-Nitrophenol is steam volatile and its solubility is 0.2 g /100 g
δ–
water at 25°C and its m.pt. 45°C
The low solubility of o-nitrophenol in water (0.2 g/100 g H2O at 25°C) than its other isomers is
because of lack of hydrogen bonding with water molecules.
Note:
o-Nitrophenol can be separated from p-Nitrophenol by steam distillation.
Self Test
10.6 How do you account for the fact that o-Nitrophenol has lower boiling point and lower solubility
in water as compard to its p-isomer?
10.7 Both phenol and ethanol have –OH functional group. Why is ethanol completely soluble in
water, while phenol is slightly soluble?

1. Acidic Nature: Salt formation: (Reaction due to H- atom of phenolic —OH
group)
Phenols are fairly acidic compounds which can be shown as follows;
i. Reaction with active metals: Phenol reacts with active metals such as sodium or
potassium to form phenolate salt and hydrogen gas is liberated.
OH ONa
2 + 2 Na 2 + H2
Sodium phenolate
(Sodium phenoxide)
ii. Reaction with caustic alkalies (NaOH, KOH): Phenol is soluble in solution of caustic
alkali to form phenolate salt and water.
OH ONa
+ NaOH + H2O
Sodium phenolate or sodium phenoxide
iii. Reaction with sodium carbonate and bicarbonate: Phenol is weak acid hence it does not
react with weak bases like sodium carbonate and bicarbonates. This reaction can be used to
distinguish phenols from carboxylic acids since, acids react to give them with
effervescence of CO2.
OH
+ NaHCO3 No Reaction
RCOOH + NaHCO3 RCOONa + CO2 + H2O
iv. Litmus test: Phenol behaves as acid because of the presence of polar O—H group,
which ionizes in aqueous solution to give H3O+ ions and that turns moist blue litmus
into faint red. –
OH O
+
+ H2O + H3O
Phenol Phenoxide ion
Self Test
10.8 Phenol and formic acid are given to you separately, how would you chemically distinguish
them?
Explanation for acidic nature of phenol
Phenol in aqueous solution ionizes as;
–
OH O
+
+ H2O + H3O
Phenol Phenoxide ion
Phenol is resonance hybrid of structures I to V, similarly, phenoxide ion is also resonance

hybrid of structures VI to X.
+ + +
O—H O—H O—H O—H O—H
– –
–
I II III IV V
Phenol
Relatively less stable: each has negative and positive charge
Resonating structures of phenol (I – V)

–
O O O
–
O O
– –
–
VI VII VIII X
IX
Phenoxide
Resonating structures of phenoxide ion (VI-X)
Resonance in phenoxide ion is more important than the resonance of phenol. The phenoxide ion
(which is the conjugate base of phenol) is stabilized by resonance. Therefore, its corresponding
acid (phenol) is fairly acidic in nature. Note that, more the stability of a conjugate base, stronger
will be the corresponding acid.
+
R—O—H R—O¯ + H
Alcohol Alkoxide ion
Alcohol and alkoxide ion have no resonating structures (highly unstable ion). Hence
equilibrium does not shift towards ionization as in alcohol. Hence phenol is more acidic than
alcohol.
Self Test
10.9 Why is phenol more acidic than alcohol though both involve cleavage of O–H bond?
Effect of substituent(s) on acidity of phenol
Any factor that stabilizes phenoxide ion increases the acidity of phenol. Electron donating
substituent intensifies the negative charge in phenoxide ion and hence destabilizes the
phenoxide ion to decrease acidity of phenol.
–
OH O
Electron donating group
+ G = —NH2
+ H2O + H3O —OH
—OCH3
—NHCOCH3
G Phenol G — C6H5
Phenoxide ion — CH3
G = donates electron (electron-donating group)

destabilizes phenoxide ion: stability decreases
decreases acidity of phenol : acidity decreases
Electron withdrawing substituent acts in opposite way.
–
OH O Electron withdrawing groups
G = —NO2
+ —CN
+ H2O + H3O
—SO3H
—COOH
G G — CHO
Phenol
— COR
Phenoxide ion —X
G = withdraws electron (electron-withdrawing groups)
Stabilizes phenoxide ion: stability = increases
Increases acidity of phenol: acidity = increases
Sequencial order of acidity of phenols
OH OH OH OH OH OH OH
O2N NO2 NO2
> > > > > >
NO2 NO2 NO2 Cl CH3 OCH3

2,4,6-Trinitrophenol 2,4-Dinitrophenol p-Nitrophenol p-Chlorophenol Phenol p-Cresol p-Methoxyphenol
Ka = 1000000x10-10 Ka = 690x10-10 Ka = 6.3x10-10 Ka = 1.1x10-10 Ka = 0.67x10-10
Self Test
10.10 How do you account for the fact that 2,4,6-trinitrophenol reacts with aqueous sodium
bicarbonate but phenol does not?
2. Reaction with acid chlorides and anhydrides: Acylation: Reaction due to

H-atom of phenolic —OH group: Formation of phenyl ester
Phenol reacts with acid chlorides in presence of pyridine or with acid anhydrides in presence of
base or sodium acetate to form phenyl ester.
O
RCOCl
R—C—O + HCl
OH
O
RCOOCOR
R—C—O + RCOOH
Examples:
OH
O O
Pyridine
+ CH3—C—Cl CH3—C—O + HCl
Ethanoyl chloride Phenylethanoate
OH
O O O
CH3COONa
+ CH3—C CH3—C—O + CH3—C—OH
O
CH3—C Phenylethanoate
O
Ethanoic anhydride
(Acetic anhydride)
Fries rearrangement: When ester of phenol is heated with anhydrous aluminium chloride in presence of CS2 as solvent,
acyl group (CH3CO—) migrates from phenolic oxygen to ortho- and para- position of the ring, thus forming
hydroxyketone. This reaction is called Fries rearrangement.
O OH
O—C—CH3 OH O
anh. AlCl3 C
CH3
CS2 +
C
O CH3
o-Hydroxyacetophenone
p-Hydroxyacetophenone
3. Benzoylation: Schotten-Baumann reaction

Phenol reacts with benzoyl chloride in presence of aqueous NaOH to form phenyl benzoate.
This reaction is known as Schotten-Baumann reacton.
OH
O O
aq. NaOH
+ C—Cl C—O + HCl
Benzoyl chloride Phenyl benzoate
4. Reaction with alkyl halides: Alkylation: Formation of aryl ether:

Williamson's synthesis
When sodium phenoxide is heated with alkyl halide in presence of aqueous NaOH, aryl ether is
formed. This is an example of Williamson's etherification.
R—X + NaO R—O + NaX

Examples:
aq. NaOH
CH3—I + NaO CH3—O + NaI
Δ
Methyl iodide Sodium phenoxide Methoxybenzene
(Anisole)
aq. NaOH
CH3CH2—Br + NaO CH3CH2—O + NaBr
Δ
Ethyl bromide Ethoxybenzene
(Phenetole)
Self Test
10.11 Convert phenol into (a) Methoxybenzene (b) Ethoxybenzene
5. Reaction due to phenolic —OH group

a. Reaction with zinc dust: When phenol is distilled with zinc dust, it gets reduced to benzene.
OH
Distill
+ Zn + ZnO
Phenol
b. Reaction with ammonia: Phenol reacts with ammonia at high temperature in presence of
anhydrous ZnCl2 to give aniline.
OH NH2
anhy. ZnCl2
+ NH3 + H2O
400°C
Phenol Aniline
c. Reaction with PCl5: Phenol reacts with phosphorous pentachloride to give only a small amount
of chlorobenzene, along with the major product of triphenyl phosphate.
OH Cl
+ PCl5 + POCl3 + HCl
Phenol Chlorobenzene
Self Test
10.12 Convert phenol into:
a. Benzene b. Aniline c. Chlorobenzene
6. Reaction due to benzene ring: Ring substitution: Electrophilic aromatic

substitution reaction
In phenol, –OH group is a srongly activating group, which activates the benzene ring towards
electrophilic substitution reactions and direct the substitution at ortho- and para- positions.
Strongly activating group

OH
ortho- and para- director
Phenol
a. Halogenation: Bromination: Test of phenol: Phenol reacts with aqueous solution of bromine
immediately to form a white precipitate of 2,4,6-tribromophenol. This reaction can be used to
test phenol as well as quantitative estimation of phenol.
OH OH
Br Br
+ 3 Br2 (aq.) + 3HBr
Br
2, 4, 6 – Tribromophenol
(White ppt)
Due to strong activating effect of —OH, reactivity of benzene ring in phenol is very high, so
polyhalogenation of phenol occurs even in absence of catalyst.
Monobromophenol is obtained by reacting phenol with bromine in presence of less polar
solvents like CS2 or CCl4 at low temperature.
OH OH OH
0°C Br
+ Br2 + + HBr
solution in CS2
Br
o- Bromophenol p- Bromophenol
(Trace amount) (Major product)
b. Nitration: Phenol reacts with concentrated nitric acid to form 2,4,6-trinitrophenol.

OH OH
O2N NO2
+ 3 HNO3 (conc.) + 3H2O
NO2
2, 4, 6 – Trinitrophenol
(Picric acid)
Due to strong activating effect of –OH, reactivity of benzene ring in phenol is very high, so
polynitration of phenol occurs even in absence of catalyst.
To obtain mononitrophenol, it is necessary to carry out the reaction at low temperature with
dilute nitric acid.
OH OH OH
20°C NO2
+ dil. HNO3 + NO2 + H2O
NO2
o- Nitrophenol p- Nitrophenol
(major) (minor)
c. Sulphonation: Phenol on sulphonation gives different product depending upon the

temperature of reaction. Sulphonation takes place manily at ortho- position at low temperature
and at para- position at high temperature.
OH
20°C SO3H
– H2O o- hydroxybenzenesulphonic acid
OH
H2SO4 (conc.) 100°C
OH
Phenol
100°C
p- hydroxybenzenesulphonic acid
– H2O
SO3H
d. Friedel-Crafts Alkylation and Acylation: Phenol undergoes Friedel-Crafts alkylation and
acylation but the yield is often poor since -OH of phenol competes with the benzene ring.
OH OH OH
anhd. AlCl3 CH3
+ CH3Cl + NO2 + HCl
Phenol o- Cresol CH3

(minor) p- cresol
(major)
OH OH O
anhd. AlCl3 C—CH3
+ CH3COCl + HCl
o-Hydroxyacetophenone
e. Reimer-Tiemann reaction: Formation of hydroxy aldehyde: When phenol is refluxed with

choloroform in presence of aqueous solution of caustic alkali, salicyaldehyde is obtained as
major product. The reaction is called Reimer-Tiemann reaction.
OH OH O OH
70°C
C—H
+ CHCl3 + KOH (aq.) + + KCl + H2O
o-Hydroxybenzaldehyde C=O
(Salicyldehyde)
Major product H
p-Hydroxybenzaldehyde
If CCl4 is used instead of CHCl3, salicyclic acid is obtained.
Mechanism
OH O
+ OH¯ + H2O
Cl
Cl C—H + OH¯ H2O + CCl3¯
Cl
CCl3¯ Cl¯ + CCl2

Dichlorocarbene
OH
O O O O
CCl2 CHCl2 CH OH
NaOH
+ CCl2 H
– 2 NaCl
– H2O
O
OH O
C H
CHO
H2O
f. Kolbe's reaction: Carbonation: When sodium or potassium salt of phenol is heated with
carbondioxide under pressure, salicylate salt is obtained, whch upon acidification gives
salicylic acid as major product. This reaction is called Kolbe's carbonation reaction.
ONa OH O OH O
125°C, 4-7 atm
C—ONa C—OH
dil. HCl
+O=C=O + NaCl
Sodium Salicylate o-Hydroxybenzoic acid

(Salicylic acid)
Major product
Note:
i. Salicylic acid is a starting materials for the manufacture of a well known analgesic (pain killer) "aspirin". Aspirin is obtatined
when salicylic acid reacts with acetic anhydride in the presence of sodium acetate.
O
OH O—C—CH3
COOH COOH
CH3COONa
+ (CH3CO)2O + CH3COOH
Acylation
2- Acetoxybenzoic acid
(Aspirin)
ii. Salicylic acid can be used to prepared salol an intestinal antiseptic by heating it with phenol is presence of POCl3.
OH OH
COOH COOC6H5
POCl3
+ C6H5OH + H2O
Esterification
Phenyl salicyalate
(salol)
iii. Methyl salicylate is prepared from salicylic acid, is used used as a pleasant smelling liquid also called "oil of wintergreen" in
perfumery.
OH OH
COOH COOCH3
HCl/reflux
+ CH3OH + H2O
Esterification
Methyl salicyalate
(oil of wintergreen)
Self Test
10.13 Convert phenol into aspirin.
g. Reaction with benzenediazonium chloride (coupling reaction): Phenol reacts with diazonium
salt solution in slightly alkaline medium at low temperature to form p-Hydroxyazobenzene
which appears as orange red compound called azo dye.
+ pH = 9-10
N ≡ N Cl¯ + H OH N=N OH + HCl
Phenol p–Hydroxyazobenzene
orange red azo dye
h. Nitrosation: Phenol reacts with ice cold solution of nitrous acid to form p- nitrosophenol.
Though, +NO (nitrosonium ion) is weak electrophile, the reaction occurs due to high reactivity
of phenol. The p-nitrosophenol can be further oxidized with dilute HNO3 to p- nitrophenol.
OH OH OH
NaNO2 + H2SO4, 7 – 8°C dil. HNO3
+ HNO2
Phenol
N=O NO2
p-Nitrosophenol p-Nitrophenol
80% yield
i. Gattermann -koch aldehyde synthesis: When phenol is treated with a mixture of CO and HCl
in presence of AlCl3 followed by hydrolysis, salicyaldehyde is obtained.
OH OH
CHO
CO + HCl
AlCl3
o-Hydroxybenzaldehyde
(Salicyldehyde)
j. Reaction with formaldehyde: Lederer-Manasse reaction: Phenol condenses with formaldehyde

in presence of dilute acid or alkali especially at low temperature to form p- hydroxybenzyl
alcohol with little o-isomer. This is known as the Lederer-Manasse reaction (1894).
OH OH OH
O
H+ or OH¯ CH2OH
+ H—C—H +
Phenol
CH2OH
p- Hydroxybenzyl alcohol
(Major product)
When the reaction is carried out at elevated temperature, the condensation occurs to form
phenol formaldehyde resin (bakellite) which is thermosetting polymer.
OH OH OH OH
OH CH2
CH2OH CH2
Δ
+
CH2 CH2
CH2OH
CH2 CH2
OH OH OH
Bakellite
(Thermosetting plastic)
Fig. 10.1: Different uses of bakellite
Self Test
10.14 Phenol ranks near the top of the list of synthetic aromatic compounds. Its principal use is in
the manufacture of bakelite, which is a thermo-setting polymer. Outline the reaction involved in
the foratmion of bakellite from phenol and formaldehyde.
7. Condensation reaction: Reaction with phthalic anhydride

When phenol is heated with phthalic anhydride in presence of concentrated sulphuric acid,
phenolphthalein is formed.
O
C Phthalic anhydride O
O C
C O
O H2SO4 (conc.) Δ C
+ H2O
H + H
OH OH
OH OH
Phenolphthalein
Phenol Acid base indicator
Self Test
10.15 Convert benzene into picric acid.
10.16 Convert phenol into 1, 3, 5-tribromobenzene.
10.17 What happen when phenol is treated with phthalic anhydride in the presence of conc.
H2SO4?
8. Catalytic hydrogenation
Phenol on catalytic hydrogenation at 150°C in presence of nickel catalyst gives cyclohexanol.
OH OH
Ni
+ 3 H2
150°C
Phenol Cyclohexanol
(alcohol)
9. Air oxidation
Phenol gets slowly oxidized on exposure to air and turns pink in colour. The oxidation product
is quinone, which forms an addition product with phenol having a pink colour.
OH
+ O2 (air) O O + H2O
p-Benzoquinone
Phenol
δ– δ+ δ– δ– δ+ δ–
2 OH + O O O–H O O H–O
Phenoquinone
(pink colour)
10.3 Tests for Phenols

1. Solubility test: A water insoluble compound soluble in aqueous NaOH but insoluble in
NaHCO3 is most likely a phenol.
2. Ferric chloride test: Reaction with ferric chloride: Phenol reacts with FeCl3 solution to give
green, blue, violet or red coloured water soluble complex. It is a coordination compound in
which iron is hexa covalent.
OH
3–
6 + FeCl3 Fe(C6H5O)6 + 3HCl + 3 H+
Phenol Hexaphenoxide iron (III) ion

(Violet colour)
3. Libermann's test: Many phenols react with nitrous acid (NaNO2 + H2SO4) in presence of conc.
H2SO4 to give brown and red colour which becomes a blue or green on adding NaOH solution.
OH
HNO2
OH O=N OH HO N O
Conc. HCl or 70% H2SO4
p- Nitrosophenol Indophenol
(Brown solid, gives red solution in ethanol)
NaOH
NaO N O
Salt of indophenol
(Blue solution)
Self Test
10.18 Suggest a suitable chemical test to distinguish phenol from: (a) Ethanol (b)
Formaldehyde
10.4 Uses of Phenol

1. Large quantities of phenol are used for the preparation of bakelite.
2. For the manufacture of dyes, drugs, explosives.
3. For the preparation of phenolphthalein.
4. As disinfectant and germicides.
Solved Questions
1. Explain Diazo-coupling test with example.
¬ When benzene diazonium chloride is treated with aromatic compound like phenol, aniline, etc. azo
dyes are obtained. This test is called diazo-coupling test.
Example:
HO¯
N = N—Cl + H OH N=N OH + HCl
p–Hydroxyaobenzene
orange coloured dye
2. How can convert benzene into anisole?

¬ OH
NO2 NH2 N2Cl
HNO3(conc.)+ H2SO4(conc.) [H] NaNO2(aq.)+ HCl (aq) H2O/H+,Δ
60°C Sn/HCl 0-5°C
Benzene Nitrobenzene Aniline Benzenediazonium Phenol
chloride
OCH3 ONa
CH3Cl / AlCl3 NaOH (aq)
Anisole Sod. phenoxide
3. How can you convert benzene into phenol?

¬ NO2 NH2 N2Cl OH
HNO3(conc.)+ H2SO4(conc.) Sn/HCl NaNO2(aq.)+ HCl (aq) H2O, boil
40-60°C 0-10°C
4. How can you convert benzene into m-Bromophenol?

¬ NO2 NO2 NH2 N2Cl OH
HNO3(conc.)+
H2SO4(conc.) Br2, FeBr3 Sn/HCl HNO2 H2O
40-60°C 0-10°C Δ
Br Br Br Br
m-Bromonitrobenzene m-Bromoaniline m-Bromobenzenediazonium m-Bromophenol
chloride
Questions
1. What happens when diazotized solution of aniline is hydrolysed?
2. The colour of phenol changes on standing in air, why?
3. What is Reimer-Tiemann reaction?
4. What happens when diazotized solution of aniline is treated with phenol?
5. Why is —OH group in phenol ortho- and para– directing towards electrophilic substitution
reaction?
a. Phenol is treated with benzenediazonium chloride. b . Phenol is carboxylated.
c. Phenol is treated with methanol in acidic medium. d. Phenol is nitrated.

a. Benzene into phenol? b. Phenol into m-nitrobenzoic acid
c. Phenol into toluene d. Benzene into m-bromophenol
e. Benzene into m-chlorophenol
3. Show your acquantance with:
a. Reimer - Tiemann reaction b. Kolbe reaction
c. Acidic nature of phenol d. Diazo-coupling test
e. Nitration of phenol
4. An aromatic compound A on reduction gives parent hydrocarbon B. B on nitration gives C. C
on reduction in acidic solution gives D. On coupling with diazonium salt D gives diazoamino-
benzene. Identify A, B, C and D writing related reactions.
5. An organic compound A with a molecular formula C6 H6O gives a parent hydrocarbon B. The
compound A responds to FeCl3 test. The compound B can also be obtained by the
polymerisation of acetylene. Identify A and B writing related reactions. Why is compound A
slightly acidic?

1. Phenol and benzoic acid can be distinguished by 6. Oil of wintergreen is
a. AgNO3 b. Baeyer's reagent a. Phenyl saliaylate b. Phenyl benzoate
c. Tollen's reagent d. NaHCO3 c. Benzoic acid d. Methyl salicylate
2. FeCl3 gives violet colour with 7. Reimer‐Tiemann reaction yields
a. Alcohols b. Amines a. Salicyladehyde b. Benzaldehyde
c. Phenol d. Aldehydes c. Benzoic acid d. Aspirin
3. Phenol on heating with Zn gives 8. Carbolic acid is
a. Benzene b. Aniline a. Dil. solution of formaldehyde
c. Benzaldehyde d. Cyclohexane b. Dil. solution of ethanol
4. Picric acid is an example of c. Dil. solution of phenol
a. Azo dye b. Phthalein dye d. Dil. solution of methanol
c. Nitro dye d. Anthracene dye 9. Phenol formaldehyde resin is
5. O‐acetoxybenzoic acid is a. Bakelite b. Thermoplastic
a. Paracetamol b. Aspirin c. Malamine d. PMMA
c. Salol d. Salicylaldehyde 10. Which of the following is most acidic?
a. Phenol b. o-nitrophenol
c. Picric acid d. Dnisole
1 2 3 4 5 6 7 8 9 10
d c a c b d a c a c
Ethers
C2H5 C2H5
Diethyl ether
Diethyl ether, simply known as ether, is a highly volatile and inflammable colourless liquid commonly used as
organic solvent. It was once used as general anesthesia in surgery.
11.1 Aliphatic Ethers

11.1.1 Introduction
Ethers are a class of organic compounds having general structure R-O-R, where R may be alkyl or
aryl group.
R—O—R'
Ether
R and R' = alkyl or aryl group
Ethers are regarded as anhydride of alcohols.
R—O—H + H—O—R R—O—R + H2O

Alcohol Ether
They are also referred as alkoxy derivative of alkane.

–H
R—H R—O—R
+ OR
Ethers may be considered as derivative of water in which both hydrogen atoms have been replaced
by alkyl or aryl groups.
H—O—H R—O—H R—O—R
Water Alcohol Ether
If R and R' are alkyl groups, ethers are called aliphatic ethers.
Examples:
CH3CH2—O—CH3 CH3CH2—O—CH2CH3
Ethyl methyl ether Diethyl ether
Diaryl or aryl alkyl derivatives of water are called aromatic ethers.
Example:
O O—CH3
Diphenyl ether Methylphenyl ether

(methoxybenzene or anisole)
If R=R', ethers are called symmetrical ethers or simple ethers and if R≠R', ethers are called
unsymmetrical ethers or mixed ethers.
CH3CH2—O—CH2CH3 CH3CH2—O—CH3
Simple ether Mixed ether
Petroleum ether is not ether chemically. It is a fraction of petroleum as a mixture of pentane and hexane, which is used as
solvent in dry cleaning.
Ethers Unit 11 351
11.1.2 Nomenclature
CH3—O—CH3 Methoxymethane Dimethyl ether
CH3CH2—O—CH3 Methoxyethane Ethylmethyl ether
CH3CH2—O—CH2CH3 Ethoxyethane Diethyl ether
CH3CH2CH2—O—CH3 1-Methoxypropane Methyl n-propyl ether
CH3—CH—O—CH3 2-Methoxypropane Isopropylmethyl ether
CH3
11.1.3 Isomerism
Ethers can show following types of structural isomerism.
Examples:
CH3CH2—O—CH2CH3 CH3CH2CH2—O—CH3
Ethoxyethane 1-Methoxypropane
group or substituent is called positional isomers.
Examples:
CH3—CH—O—CH3 CH3CH2CH2—O—CH3
CH3 1-Methoxypropane
2-Methoxypropane
3. Functional isomerism: Isomers that differ in their functional group are functional isomers.
Ether shows functional isomerism with alcohol.
Examples:
CH3—O—CH3 CH3CH2—OH
Methoxymethane Ethanol
4. Metamerism: Like ketones and secondary amines, ethers can show metamerism. Isomers
differing in alkyl group present on either side of the functional group are called metamers.
Examples:
CH3—CH—O—CH3
CH3CH2—O—CH2CH3 CH3CH2CH2—O—CH3 CH3
Ethoxyethane 1-Methoxypropane 2-Methoxypropane
Molecular Total isomers Alcohols Ethers
formula
C2H6O 2 1 1
C3H8O 3 2 1
C4H10O 7 4 3
Self Test
11.1 What are ethers? Give two examples of aliphatic as well as aromatic ethers.
11.2 Write the structure of ethers of molecular formula C4H10O and point out the simple and mixed ethers.

Ethers are generally prepared
1. From alkyl halides
2. From alcohols
1. From alkyl halide
a. By Williamson's synthesis: When alkyl halide is heated with sodium or potassium alkoxide,
ether is obtained. This method is called Williamson's synthesis. This is nucleophilic
substitution reaction when alkoxide ion (OR–) acts as nucleophile substitutes the halogen atom
from alkyl halide.
δ
δ–
+
R—X + R'O¯Na+ R—O—R' + NaX

Sodium alkoxide
Examples:
CH3CH2Br + CH3ONa CH3CH2—O—CH3 + NaBr

(alc)
Methoxyethane
Bromoethane Sodium methoxide (Mixed ether)
CH3CH2Br + CH3CH2ONa CH3CH2—O—CH2CH3 + NaBr

(alc)
Ethoxyethane
Sodium ethoxide (Simple ether)
The importance of this method lies on its versatility that simple as well as mixed ethers can be
obtained by this method.
Secondary and tertiary alkyl halides are not used in Williamson's synthesis: Substitutions vs. Elimination
In Williamson's synthesis, for the preparation of unsymmetrical ether, primary alkyl halide and alkoxide of secondary and
tertiary alcohol are used. Secondary and tertiary alkyl halides are not preferred because they undergo elimination reaction to
give alkene in presence of alkoxide ion since alkoxide ions are not only acts as nucleophiles but also acts as strong bases.
CH3 CH3
CH3—C—O¯Na+ + CH3CH2—Br CH3—C—O—CH2CH3 + NaBr
CH3 CH3
Sodium tert-butoxide tert-butyl ethyl ether
(nucleophile)
CH3 CH3
CH3 C Br + CH3CH2O¯Na+ CH3—C=CH2+ CH3CH2OH + NaBr
CH3 (base)
b. By the action of dry silver oxide: When alkyl halide is heated with dry silver oxide, ether is
formed.
2 R—X + Ag2O R—O—R + 2 AgX
2 CH3CH2Br + Ag2O CH3CH2—O—CH2CH3+2 AgBr
This method is only suitable for the preparation of simple ethers.
Ethers Unit 11 353
Self Test
11.3 Outline the preparation of ethyl methyl ether and diethyl ether by Williamson's method.
2. From alcohol
Dehydration of alcohol with concentrated H2SO, alumina or aluminum phosphate under proper
reaction conditions gives ether.
a. By using conc. H2SO4: When excess alcohol is heated with concentrated H2SO4 to proper
temperature, ether is obtained by intermolecular dehydration:
Conc.H2SO4, Δ
2 R—OH R—O—R + H2O
Conc.H2SO4
2 CH3CH2OH 140°C CH3CH2—O—CH2CH3+H2O
If alcohol is not excess and temperature is high, elimination reaction takes place to give alkene
by intra-molecular dehydration.
H H
Conc. H2SO4
H—C—C—H H2C = CH2 + H2O
160 – 170° C
H OH Ethene
Ethyl alcohol
This method is not useful for preparing unsymmetrical ethers because a combination of two
different alcohols give a mixture of three ethers.
R—OH + R' —OH Conc.H2SO4, Δ R—O—R' + R—O—R + R'—O—R'
Self Test
11.4 A mixture of ethyl alcohol and n-propyl alcohol when heated with concentrated H2SO4, gives a
mixture of three different ethers. Identify them.
b. By using alumina: When alcohol vapour is passed over heated alumina at 250ºC, ether is
obtained by intermolecular dehydration.
Al2O3, 250°C
2 CH3CH2OH CH3CH2—O—CH2CH3 + H2O
If temperature is higher, alkene is formed by elimination.
Al2O3, 350°C
CH3CH2OH CH2 = CH2 + H2O
Dimethyl ether (b.pt. -23°C) is prepared industrially by passing methyl alcohol vapour over aluminum phosphate as
catalyst at 350°C to 400°C under pressure of 15 atmosphere.

1. Dimethyl ether and ethylmethyl ether are gases. Other members are colorless volatile liquids
with pleasant odour.
2. In alcohol, there exists intermolecular hydrogen bond due to polar nature of O-H bond. But in
ethers, there does not exist intermolecular hydrogen bond since there is no polar O-H bond.
Hence, ethers have much lower boiling point than alcohol of comparable molecular weight.
R R R R
H—O —
H O H—O H—O
δ+ δ– δ+ δ– δ+ δ- δ+ δ-
3. Like water, ether molecule is angular and has a net dipole moment. For example, in
methoxymethane, bond angle is 111°43' and dipole moment is 1.3D. Hence, ether molecule can
form intermolecular hydrogen bond with water. Hence lower member of ethers are partially
soluble in water.
O
111°43' R H δ+
δ-
CH3 CH3 O H—O δ-
R δ+
Methoxymethane
(μ = 1.3 D) Intermolecular H-bonding
Self Test
11.5 Write the isomers of C2H6O and compare their boiling point.
11.6 How do you account for the fact that, although diethyl ether has a much lower boiling point
than n-butyl alcohol, it has the same solubility (8g per 100g) in water?

Ethers are relatively less reactive class of organic compounds and comparable to hydrocarbons in
their chemical reactivity. They do not react with oxidizing agents, reducing agents, highly reactive
alkali metals, caustic alkalis. Due their low reactivity, ethers are used as solvents in laboratories as
well as in industries. However, ethers react with acids due of presence of lone pair of electron on
oxygen atom which can accept proton from acid. The reactions of ethers can be categorized as
follows;
A. Reactions involving etheral oxygen
B. Reactions involving alkyl group
C. Reactions involving cleavage of C-O bond
A. Reactions involving etheral oxygen
1. Formation of oxonium salt: Due to presence of lone pair of electron on oxygen atom, ether
behaves as Bronsed-Lowry base and accepts H+ from acids. Hence ethers dissolve in cold and
concentrated mineral acids (HCl, H2SO4) to form oxonium salts.
Cold +
CH3CH2—O—CH2CH3 + conc. H2SO4 CH3CH2—O—CH2CH3 HSO4–
H
Diethyloxonium hydrogensulphate
(Oxonium salt)
Cold +
CH3CH2—O—CH2CH3 + conc. HCl CH3CH2—O—CH2CH3 Cl –
H
Diethyloxonium chloride
(Oxonium salt)
Oxonium salts are unstable at high temperature and in dilute solution.
Ethers also form coordination complexes commonly known as etherate with Lewis acids like
BF3, RMgX etc.
R R
O + BF3 O BF3
R R
Etherate
Ethers Unit 11 355
R OR2
2 R2O + R MgX Mg
R2O X
Etherate
Ethers can be distinguished from hydrocarbons from their solubility; ethers are soluble in cold concentrated sulphuric acid due
to formation of oxonium salts but hydrocarbons do not.
2. Reaction with air: Aliphatic ethers react with air slowly in presence of light to form ether
peroxides.
Light
CH3CH2—O—CH2CH3 + O2 (Air) CH3CH2—O—CH—CH3
O—OH
Ether peroxide
Ether peroxide is explosive and thermally unstable. Hence care should be taken during
distillation of old sample of ethers otherwise violent explosion may take place. Addition of
small amount of cuprous compound like Cu2O has been recommended to prevent formation of
ether peroxide.
Detection of ether peroxide
To detect peroxide in ether, ether sample is shaken with little ferrous ammonium sulphate and
potassium thiocyanate. Formation of blood red color indicates presence of peroxide in ether.
peroxide SCN¯
Fe2+ Fe3+ Fe(SCN)3
Blood red
Removal of ether peroxide
To remove ether peroxide
i. Ether is distilled with concentrated sulphuric acid, which oxidizes peroxide.
ii. Ether is washed with ferrous sulphate solution, which reduces peroxide.
B. Reactions involving alkyl group
Halogenation: Ether reacts with Cl2 or Br2 to form halogen substituted ethers. The nature of
substitution products depend upon the conditions of reaction.
Cl2, dark
CH3CH2—O—CH2CH3 CH3—CH—O—CH—CH3
Cl Cl
α α'-Dichlorodiethyl
Cl Cl Cl Cl
Cl2, light
CH3CH2—O—CH2CH3 Cl—C—C—O—C—C—Cl
Cl Cl Cl Cl
Perchlorodiethyl ether
C. Reactions involving cleavage of C-O bond

1. Reaction with HBr and HI: Ethers readily react with concentrated HBr and HI in different
conditions.
In cold R—O—R + HI Cold R—OH + RI
In hot and excess HI R—O—R + HI R—OH + RI

R—OH + HI RI + H2O
R—O—R + 2 HI 2 RI + H2O
Δ
Examples:
CH3CH2—O—CH2CH3 + HI Cold
CH3CH2OH + CH3CH2I
CH3CH2—O—CH2CH3 + 2 HI Hot
2 CH3CH2I + H2O
CH3 CH3 CH3
130–140°C
CH3 —CH—O—CH—CH3 + 2 HBr 2 CH3—CH—Br + H2O
(48%) Isopropyl ether
Diisopropyl ether
Cleavage of unsymmetrical ether:

When unsymmetrical ether is treated with conc. HI, the cleavage in ether takes place in such a
way that oxygen atom remains attached to the larger alkyl group. This is because alkoxide
having the larger alkyl group is bulkier and better leaving group.
Example:
CH3CH2—O—CH3 + HI Cold
CH3CH2OH + CH3I
CH3CH2—O—CH3 + HI CH3CH2I+ CH3OH
But, if 3° alkyl group is present, the bond breakage takes place in such a way that oxygen
remains attached to the smaller alkyl group. This is because, formation of 3° haloalkane is more
feasible due to the high stability of 3° carbocation.
Example:
CH3 CH3
CH3 —C—O—CH3 + HI CH3 —C—I + CH3OH
CH3 CH3
2. Reaction with dilute sulphuric acid: When ether is heated with dilute sulphuric acid under
pressure, corresponding alcohol is obtained by its hydrolysis.
Dilute H2SO4
R—O—R + H2O 2 ROH
Dilute H2SO4
CH3CH2—O—CH2CH3 + H2O 2 CH3CH2OH
Ethers Unit 11 357
When ether is warmed with concentrated sulphuric acid, alcohol and alkyl hydrogen sulphate
are formed.
R—O—R + conc. H2SO4 ROH + RHSO4
When unsymmetrical ether is heated with conc. H2SO4, the bond breakage generally takes place
in such a way that oxygen remains attached to the larger alkyl group.
Example:
CH3 –O – C2H5 + H2SO4 2 C2H5OH + CH3OSO3H
3. Reaction with phosphorous pentachloride: When ether is heated with PCl5, alkyl chloride is
formed.
R—O—R + PCl5 2 RCl + POCl3
Δ
CH3CH2—O—CH2CH3 + PCl5 2 CH3CH2Cl + POCl3
Δ
Self Test
11.7 Give the reaction of diethyl ether with
a. conc. HCl in cold b. conc. HI in cold c. conc. H2SO4 in cold
d. conc H2SO4 in hot e. dil. H2SO4 in hot
11.8 Convert ethoxyethane into methoxyethane and vice versa.
11.1.7 Diethyl Ether

The use of ether as anesthetic was first publicly demonstrated on 16th October, 1846 at Massachusetts General
Hospital, Boston, USA to remove a tumor from neck of a young man. The patient felt no pain during the surgery,
which seemed like a miracle at the time. Citizen of Boston raised funds to construct a monument to commemorate
humankind’s triumph over pain.
Before anesthetics, surgery was a very painful and horrific practice. Surgeons had few options for dulling the
intense pain. The most common techniques were plying the patient with opium or alcohol and then employing
several strong men to hold the patient down to carry out a quick and brutal surgery. Patients would scream with
pain throughout the entire procedure. It wasn't uncommon for people to commit suicide rather than go through
the nightmare of surgery. Ether obviously made surgery a more comfortable experience for patients, and allowed
surgeons to take more time in which they can work more effectively and develop more and more complex and
beneficial surgical techniques. The use of ether as an anesthetic in the mid 19th century opened a new advances in
surgical technology and medical history although it has been replaced by safer anesthetic.
C2H5 C2H5
Ethoxyethane
(μ = 1.18 D)
Ethoxyethane is the most important member of ether. It is commonly called diethyl ether or
sulphuric ether or simply ether.
11.1.8 Laboratory Preparation of Diethyl Ether

Principle: When an excess of ethyl alcohol is heated with concentrated sulphuric acid at 140°C,
diethyl ether is formed. The reaction occurs is two steps.
C2H5—OH + H—OSO3H 100°C

C2H5—OSO3H + H2O
Ethanol conc. Ethyl hydrogen sulphate
140°C
C2H5—OSO3H + H O—C2H5 C2H5—O—C2H5 + H2SO4
Ethanol
Water out
Water condenser
Ethanol +
conc.H2SO4
Sand bath
Cold water in
To sink
Ice cold water

Ethoxyethane
Fig. 11.1: Laboratory preparation of ethoxyethane
Procedure
About 100 ml of ethyl alcohol is taken in a distillation flask in which dropping funnel, thermometer,
water condenser and receiver are fitted as shown in the figure. The rubber tube is attached to the side
tube of receiver to carry away any uncondensed vapour of ether. The whole apparatus is made air
tight because ether is highly inflammable. About 100 ml of concentrated sulphuric acid is added
from dropping funnel and heated to about 140°C on sand bath. Ether so formed distills off and is
collected in ice cooled receiver. As ether starts distilling, a continuous stream of fresh alcohol is
added from the dropping funnel at rate of the formation of ether. In this process, ether can be
obtained continuously, hence the process is called Williamson's continuous etherification.
Purification
The main impurities in diethyl ether are alcohol, water, SO2 and CO2. To remove these impurities
following steps are applied.
i. Ether is treated with dilute NaOH in a separating funnel, which dissolves CO2, SO2 and other
acidic impurities and the aqueous layer is rejected.
Ethers Unit 11 359
ii. Ether is washed with water 2-3 times to remove water soluble impurities and the aqueous layer
is again rejected.
iii. Ether is treated with 50% CaCl2 solution which removes alcohol forming alcoholates.
iv. The ether is dried over anhydrous CaCl2.
v. Finally, ether is redistilled at about 34 to 40°C to get it in pure and dry state.
In this way, diethyl ether is prepared in the laboratory in pure and dry state.

1. Diethyl ether is highly volatile and highly inflammable colourless liquid.
2. Its boiling point is 34.6°C and freezing point is -116°C.
3. It is sparingly soluble in water (8 g per 100 g water) but soluble in organic solvents.

Diethyl ether shows all chemical properties of aliphatic ethers.
11.1.11 Uses
i. The major use of diethyl ether is as solvent. It is used as solvent in industries for fats, oils,
waxes, resins, etc. In laboratories, it is used as solvent in many organic reactions like Wurtz
reaction, Fittig reaction, for the preparation of Grignard reagent and carrying out its reactions,
in solvent extraction for the separation and purification of organic compounds, etc.
ii. It is also used as refrigerant.
iii. It can also be used as general anesthetic during surgery. However, it has been replaced by more
safe anesthetic.
iv. It is used as volatile starting fluid for diesel engines and gasoline engines in cold weather.
11.2 Aromatic Ethers

11.2.1 Nomenclature
Some common examples of aromatic ethers are:
O—CH3 Methoxybenzene Methyl phenyl ether or Anisole
Ethyl phenyl ether

O—CH2CH3 Ethoxybenzene
or phenetole
O Phenoxybenzene Diphenyl ether

11.2.2 Preparation of Methoxybenzene/Anisole

Anisole is the common aromatic ether. Anisole is prepared from methyl halide, when it is treated
with phenoxide salt by using Williamson etherification process.
–+
ONa OCH3
CH3—Br + + NaBr
Methyl bromide Sodium phenoxide Methoxybenzene

(Anisole)
But anisole could not be prepared quantitatively from aryl halide with methoxide salt through the
following pathway.
Br OCH3
–+
+ CH3ONa + NaBr
Methoxybenzene
(Anisole)
In aryl halide, nucleophilic substitution reaction is difficult than alkyl halide due to following
reasons:
i. carbon to halogen bond has partial double bond character due to resonance effect.
ii. carbon to halogen bond is less polar due to hybridization effect.
+ + +
Br Br Br Br Br
– –
–
I II III IV V
Resonating structures of Bromobenzene

The chemical reaction of methoxybenzene can be divided into two categories.
A. Reaction due to clevage of C–O bond
Reaction with HI: When anisole is heated with HI, the products are always phenol and methyl
iodine but never methanol and iodobenzene. i.e.
OH
a
+ CH3I
O—CH3
b Phenol
120-130°C
+ HI
I
57%
Anisole
+ CH3OH
Iodobenzene
Ethers Unit 11 361
This can be explained as follows:

Oxygen to carbon of benzene ring bond (bond b) is stronger: Oxygen to carbon of benzene ring
(bond b) has partial double bond character since anisole is resonance hybrid of structures I-V. Hence
it is stronger than oxygen to carbon of alkyl group (bond a).
+ + +
O—CH3 O—CH3 O—CH3 O—CH3 O—CH3
– –
–
I II III IV V
Resonating structures of anisole
B. Reaction due to benzene ring: Electrophilic substitution reaction
Like other aromatic compounds, anisole undergoes elctrophilic substitution reaction. The –OCH3
(methoxy group) is weakly activating group, which is ortho- and para- director towards electrophilic
substitution reaction. Activating group
OCH3
Ortho- para- director
Methoxybenzene
(Anisole)
Self Test
11.9 Anisole gives ortho- and para- substituted products, explain.
1. Halogenation: When anisole reacts with Br2 in CS2, a mixture of p-Bromoanisole and o–
Bromoanisole is formed.
OCH3 OCH3 OCH3
Br
CS2
+ 2Br2 + + 2HBr
Br
Anisole o–Bromoanisole p–Bromoanisole
2. Nitration: When anisole is heated with a mixture of conc. HNO3 and conc. H2SO4 (nitrating
mixture), a mixture of o–nitroanisole and p–nitroanisole is formed.
OCH3 OCH3 OCH3
NO2
conc.H2SO4
+ HNO3 + + H2O
NO2
Anisole o–Nitroanisole p–Nitroanisole
3. Sulphonation: When anisole is heated with conc. H2SO4, a mixture of
o–Methoxybenzenesulphonic acid and p–Methoxybenzenesulphonic acid is formed.
OCH3 OCH3 OCH3

SO3H
+ conc. H2SO4 + + H2O
o–Methoxybenzenesulphonic acid
SO3H
Anisole p–Methoxybenzenesulphonic acid
Self Test
11.10 Identify A, B and C in the following reaction sequence.
ONa
CH3—Br HI, 130°C
A B + C
Solved Questions
1. Write possible unsymmetrical ethers having molecular formula C4H10O and give their
IUPAC name.
¬ Ethers may be considered as derivative of water in which both hydrogen atoms have been replaced by
alkyl or aryl groups.
R—O—R
Ether
If R=R', ethers are called symmetrical ethers or simple ethers and if R≠R', ethers are called unsymmetrical
ethers or mixed ethers. There are two different ether with molecular formula C4H10O.
CH3-CH-O-CH3
CH3CH2CH2-O-CH3
CH3
1-Methoxypropane 2-Methoxypropane
2. Convert ethoxyethane into methoxyethane.

¬ Δ CH3ONa
CH3CH2—O—CH2CH3 + 2 HI 2 CH3CH2I CH3OCH2CH3
Ethoxyethane Iodoethane
H
δ+
CH3 C I δ– + CH3O¯Na+ CH3CH2—O—CH3 + NaI
H Sodium methoxide Methoxyethane
3. Identify A and B in the following reactions sequence.

¬
Ethanol Conc. H2SO4, Conc. HCl,
A B
Conc. HCl, +
2 CH3CH2OH
Conc. H2SO4, CH3CH2—O—CH2CH3 CH3CH2—O—CH2CH3 Cl –
140°C H
Ethanol Ethoxyethane
Diethyloxonium chloride
(Oxonium salt)
4. Care should be taken during distillation of old sample of ethers, give reason.
¬ Ether, especially diethyl ether which is the most commonly used ether, is volatile and highly inflammable
liquid. Ethers react with air slowly in presence of light to form ether peroxides.
Light
CH3CH2—O—CH2CH3 + O2 CH3CH2—O—CH—CH3
(air)
O—OH
Ether peroxide
Ethers Unit 11 363
Ether peroxide is explosive and thermally unstable. Hence care should be taken during distillation of old
sample of ethers otherwise violent explosion may take place.
Q Questions
1. Write the possible isomers of C3H8O and indicate the isomer which does not decolorize
acidified potassium permanganate solution.
2. Write the alcohols having molecular formula C4H10O with their IUPAC name and indicate the
isomers which do not decolorize acidified potassium permanganate solution.
3. How can you detect presence of organic peroxides in ether? Give any method to remove
peroxides.
4. Outline the preparation of tert-Butyl ethyl ether by Williamson’s synthesis.
5. Anisole is prepared by using sodium phenolate and methyl iodide but not sodium methoxide
and chlorobenzene, why?
6. What is unsymmetrical ether? Write an example with their IUPAC name.
7. Name the isomer of C2H6O which reacts with excess HI to give iodomethane as major product.
Give the reaction involved.
8. Write the chemical equation for the reaction taking place when:
a. Sodium phenoxide reacts with iodomethane.
b. Ethoxyethane is exposed to light and air.
9. An organic compound with a molecular formula C4H10 O does not react with Na and gives only
single haloalkane when heated with excess conc. HI. Identify the organic compound.
1. Identify A and B
NaOH CH3I
(i) Monohydroxybenzene A B
(i) Na (ii) CH3I (i) 57% HI, 120-

(ii) Phenol A B+C
130°C
(iii) Ethanol
(i) Na (ii) CH3I HI, Δ
A B+C
Conc. H2SO4, Conc. HCl, 0°C

(iv) Ethanol A B+C
140°C
Ag2O, ∆ PCl5, ∆
(v) Ethyl chloride A B
2. How is ethoxyethane prepared in laboratory in pure and dry state?

3. An organic liquid ‘A’ has molecular formula C4H10O which is soluble in cold and conc.
sulphuric acid but doesn’t decolorize pink color of acidified potassium permanganate. ‘A’ when
refluxed with phosphorous pentachloride gives C2H5Cl. Identify ‘A’ giving necessary reactions.
How does ‘A’ react with:
i. Cold HI ii. Hot excess HI
4. a. Write all possible isomers of ethers of molecular formula C5H12O and give their IUPAC
names.
b. Convert ethoxyethane into methoxyethane
5. a. What is Williamson synthesis? What is the advantage of this method over dehydration of
alcohol?
b. Write the reaction when anisole is heated with conc. HI.
Q Multiple Choice Questions

1. Diethyl ether is 6. The explosive substance formed when ether is
a. Mixed ether b. Petroleum ether exposed to air for sometime is
c. Sulphuric ether d. Phenetole a. TNT b. Super oxide
2 When ethyl halide reacts with sodium ethoxide, it c. Oxide d. Peroxide
gives diethyl ether. The reaction is 7. When ethyl hydrogen sulphate is heated to 140°C,
a. Williamson’s synthesis b. Wurtz reaction it gives
c. Kolbe’s reaction d. Hoffmann’s reaction a. Ethoxyethane b. Ethanal
3. When tert‐butyl bromide is reacted with sodium c. Ethene d. 1,2-Ethandiol
ethoxide, the major product is 8. With cold and conc. HCl, Diethyl ether forms
a. tert-Butyl methyl ether b. Diethyl ether a. Ethyl alcohol b. Ethyl chloride
c. Ethane d. 2-methyl-1-propene c. Oxonium salt d. Ether peroxide
4. When vapors of ethanol is passed over heated 9. Which of the following does not form dative bond
alumina at 523K, it gives with ether?
a. Ethoxyethane b. Ethanal a. RMgX b. BF3
c. Ethene d. Ethylhydrogen sulphate c. AlCl3 d. NaBH4
5. The number of metamers that is represented by 10. When anisole reacts with HI, it gives,
formula C4H10O is a. Methanol b. Phenol
a. 2 b. 3 c. Iodobenzene d. Iodophenol
c. 4 d. 5
1 2 3 4 5 6 7 8 9 10
c a d c b d a c d b
Aldehydes and Ketones
CH3
Musk deer (Kasturi mriga) 3-Methylcyclopentadecanone

-s:t'/L d[u_ (Muscone)
Aldehydes and ketones are widespread in nature. Muscone is a ketone that is the primary
contributor to the odour of musk. Natural muscone is obtained from musk, a glandular secretion of
the musk deer which has been used in perfumery and medicine for thousands of years. Since
obtaining natural musk requires killing the endangered animal, nearly all muscone used in
perfumery today is synthetic.
12.1 Aliphatic Aldehydes and Ketones

12.1.1 Introduction
The organic compounds containing the carbonyl (>C=O) group in their molecules are called carbonyl
compounds. The carbonyl (>C=O) group may exist in two forms; if it exists in the form of –CHO
group, it is an aldehydic functional group (formyl group) and if it exists as such in the form of –CO–
group, it is a ketonic functional group (oxo or keto group).
The aldehydic (formyl) functional group containing organic compounds are aldehydes, in which the
carbonyl group is linked to an alkyl (R-) or aryl (Ar-) group and a hydrogen atom in the form of R–
CHO or Ar-CHO. On the other hand, ketonic functional group containing compounds are ketones, in
which the carbonyl group is linked to two alkyl or aryl groups in the form of R—CO—R, R—CO—Ar
or Ar—CO—Ar. General molecular formula of aliphatic aldehydes and ketones is CnH2nO.
Definitions
¾ Derivatives of alkanes, where two terminal hydrogen atoms are replaced by divalent oxygen atom are
called aliphatic aldehydes.
i.e. O
– 2H
R—CH3 +O R—C—H
¾ Derivatives of alkanes, where two non-terminal hydrogen atoms are replaced by divalent oxygen atom are
called aliphatic ketones.
O
– 2H
R—CH2—R +O R—C—R
Derivatives of arenes, where two hydrogen atoms from side chain —CH3 are replaced by divalent oxygen atom are called
aromatic aldehydes.
i.e. O
– 2H
Ar—CH3 +O Ar—C—H
Derivatives of arenes, where two hydrogen atoms from side chain —CH2—R or —CH2—Ar are replaced by divalent
oxygen atom are called aromatic ketones.
O O
– 2H – 2H
Ar—CH2—Ar Ar—C—Ar Ar—CH2—R +O Ar—C—R
+O
In other words, both aldehydes and ketones contain the carbonyl (>C=O) group and are often
referred to collectively called as carbonyl compounds. It is the carbonyl group that largely
determines the chemistry of aldehydes and ketones i.e. the presence of the carbonyl group in both
aldehydes and ketones is responsible for their identical chemical properties. However, the presence
of H–atom attached with the –CO– group in aldehydes is more reactive than alkyl group (R—)
attached with the —CO— group in ketones and hence they differ from each other in certain aspects.
Examples:
a. Aliphatic aldehydes and ketones:
O O O
H C—H
— CH3—C—H CH3—C—CH3
Formaldehyde (methanal) Acetaldehyde (ethanal) Acetone (propanone)
Aldehydes and Ketones Unit 12 367
b. Aromatic aldehydes and ketones:

O O O
C—H C—CH3 C
Bezaldehyde Acetophenone Benzophenone
Simple or symmetrical ketones: Those ketones in which the –CO– group is attached with two
identical alkyl or aryl groups.
O O
CH3—C—CH3 —C—
Acetone Benzophenone
(Aliphatic ketone) (Aromatic ketone)
Mixed or unsymmetrical ketones: Those ketones in which the –CO– group is attached with two
different alkyl and aryl groups.
O O
CH3—C—CH2CH3 CH3—C—
Ethyl methyl ketone
Acetophenone
(Butan-2-one)
(Aromatic ketone)
(Aliphatic ketone)
12.1.2 Structures of Carbonyl Group

Both aldehydes and ketones have common carbonyl group. Carbon of the carbonyl σ
σ
group is sp2 hybridized. So, the geometry of the molecule across the carbonyl carbon C π O
σ
is trigonal planar with the bond angle of 120°.
Carbon and oxygen atoms are linked together by a double bond, one of this bond is σ–bond and the
another is π bond. The π bond is weak and polarisable, so the carbonyl compounds are likely to give
addition reactions.
Since the carboxyl carbon atom of carbonyle group is sp2 hybridized which contains singly filled
unhybridized p-orbital that undergoes side ways on overlaps with singly filled p-orbital of oxygen
atoms giving π bonds.
2py 2py
π- bond
π
C O
sp2
C sp2 O
sp2
σ- bond
Fig. 12.1: Orbital overlap picture of the carbonyl group

12.1.3 Nomenclature of Carbonyl Compounds

Nomenclature of Aldehydes
a. Common names: The common names of aldehydes are derived from the names of the
corresponding carboxylic acid, where –ic acid of parent carboxylic acid is replaced by –
aldehyde.
Examples:
O O
O O
CH3—C—OH CH3—C—H
H—C—OH H—C—H
Acetic acid Acetaldehyde
Formic acid Formaldehyde
O O CH3 O CH3 O
CH3CH2—C—OH CH3CH2—C—H CH3—CH2—CH—C—OH CH3—CH2—CH—C—H

Propionic acid Propionaldehyde α-Mehtyl butyric acid α-Mehtyl butyraldehyde
b. IUPAC names: Aldehydes are named by replacing –e of alkane by –al as secondary suffix.
Examples:
O O O CH3 O
H—C—H CH3—C—H CH3CH2—C—H CH3—CH2—CH—C—H

Methanal Ethanal Propanal 2-Methylbutanal
Nomenclature of ketones
a. Common names: Ketones are named by writing the names of alkyl groups attached to the
carbonyl group followed by the word "ketone". First member of ketone (CH3COCH3) is known
as acetone which has been in use for a long time as a solvent, nail-polish remover, etc.
Examples:
O O O
CH3 C—CH3
— CH3CH2 C—CH3
— CH3CH2CH2—C—CH3
Acetone or dimethyl ketone Ethyl methyl ketone Methyl n–propyl ketone
(Simple ketone) (Mixed ketone) (Mixed ketone)
Aromatic ketones
A ketone in which the carbonyl group attracted to a benzene ring is named as a –phenone.
Examples:
O O
O
CH3—C— CH3CH2CH2—C— —C—
n-butyrophenone Benzophenone
Acetophenone (Aromatic ketone) (Aromatic ketone)
(Aromatic ketone)
b. IUPAC names: In longest carbon chain carrying >C=O group is considered as parent chain, and
is named by replacing –e of the corresponding alkane with –one.
The position of various substituents is indicated by numbers, the carbonyl carbon of –CO–
group being given the lowest possible number.
Examples:
O O O
CH3—C—CH3 CH3CH2—C—CH3 CH3CH2CH2—C—CH3
Propanone Butanone Pentan-2-one
Self Test
12.1 Give the structures and IUPAC names of the following:
i. ethyl neo-pentyl ketone ii. phenyl acetaldehyde
iii. vinyl acetone iv. salicylaldehyde
v. acetyl acetone
12.2 Give structures and IUPAC names of carbonyl compounds of molecular formula C4H8O.
12.1.4 Structural Isomerism in Aliphatic Carbonyl Compounds

Aliphatic aldehydes and ketones exhibit the following types of structural isomerisms.
1. Chain isomerism: Aldehydes and ketones exhibit chain isomerism.
Examples:
i. Pentanal, 3-methylbutanal and 2-methylbutanal are chain isomers.
O CH3 O CH3 O
CH3CH2CH2CH2—C—H CH3 CH CH2 C—H
— — — CH3—CH2—CH—C—H
pentanal 3-methylbutanal 2-methylbutanal
ii. Pentan-2-one and 3-methylbutan-2-one are chain isomers.

O CH3 O
CH3CH2CH2—C—CH3 CH3—CH—C—CH3
Pentan-2-one 3–Methyl butan-2-one
2. Positional isomerism: Ketones show positional isomerism when position of >C=O group is
different in the longest carbon chain of compound of same molecular formula. For example,
Pentan-2-one and pentan-3-one are positional isomers and they are also metamers to each other.
O O
CH3—C—CH2CH2CH3 CH3CH2—C—CH2CH3
Pentan-2-one Pentan-3-one
But aliphatic aldehyde doesnot exhibit positional isomerism as the —CHO group remains in the
terminal position and the difference of position of —CHO group gives rise chain isomerism. For
example, butanal and 2- methylpropanal are chain isomers not the positional isomers.
O CHO
CH3—CH2—CH2—C—H CH3—CH—CH3
butanal 2-methylpropanal
3. Functional isomerism: Aldehydes and ketones can be functional isomers of each other because
both of them have same molecular formula of CnH2nO. For example, propanal and propanone
are functional isomers.
O
CH3CH2—CHO CH3—C—CH3
Propanal Propanone
4. Tautomerism
i. Ethanal and ethenol are tautomers, and they undergo keto-enol tautomerism.
O OH
CH3—C—H CH2 C—H

Ethanal Ethenol
(Vinyl alcohol)
O—H O
CH2 C—H CH3—C—H
ii. Propanone and propen-2-ol are tautomers.

O OH
CH3—C—CH3 CH2 C—CH3

Propanone Propene-2-ol
O—H O
CH2 C—CH3 CH3—C—CH3
Note
Tautomers are interconvertible functional isomers.
Self Test
12.3 How many isomeric ketones are possible for 2,2-dimethylpropanal ?
12.1.5 General Methods of Preparation of Aliphatic Aldehydes and Ketones

Some general method for the prepanation of aliphatic aldehydes and ketons are discussed below:
1. From Alcohols
a By catalytic dehydrogenation of alcohols
i. When vapours of primary (1°) alcohol is heated over Cu or MnO at 300°C, an aldehyde is
formed where hydrogen atoms are removed each from -OH group and α-carbon. The
reaction is called as catalytic dehydrogenation.
H H
Cu, 300°C
R—C—O H Δ R—C O + H2 ↑
Aldehyde
H
1° alcohol
Examples: Cu, 300°C

CH3OH HCHO + H2 ↑
Δ
Methanol Methanal
Cu, 300°C
CH3CH2OH CH3CHO + H2 ↑
Δ
Ethanol Ethanal
ii. When vapour of secondary (2°) alcohol is heated over Cu at 300°C, ketone is obtained.
R R
Cu, 300°C
R—C—O H Δ R—C O + H2 ↑
Ketone
H
2° alcohol
Example:
OH O
Cu, 300°C
CH3—CH—CH3 CH3—C—CH3 + H2 ↑
Δ
Propan-2-ol Propanone
Note:
When vapour of tertiary (3°), alcohol is passed over heated Cu at 300ºC, alcohol undergoes dehydration into respective alkene
instead of dehydrogenation into aldehyde or ketone.
OH H
Cu, 300°C
CH3—C—CH2 CH3—C CH2 + H2O
Δ
CH3 CH3
tert-Butyl alcohol 2-Methylpropene
(3° alcohol) (Alkene)
b. By oxidation of alcohols
The oxidation of an alcohol involve the loss of one or more α-hydrogens from the carbon
bearing the –OH group. The nature of product formed depends upon the type of alcohol.
i. Oxidation of primary alcohols: A primary alcohol contains two α–hydrogens, and can
either lose one of them to form an aldehyde or both of them to form a carboxylic acid.
H H
Oxidizing agent
R—C—O H + [O] R—C O + H2O (Loss of one α-hydrogen)
H Aldehyde
1° alcohol
H O
Oxidizing agent
R—C—OH + 2[O] R—C—OH + H2O (Loss of two α-hydrogens)
Carboxylic acid
H
1° alcohol
Oxidation of 1° alcohols to carboxylic acids is usually accomplished by use of acidified

aqeous KMnO4, K2Cr2O7, CrO3 in glacial acetic acid, etc. Oxidation of 1° alcohols yields
aldehydes, and aldehydes are susceptible so they are further oxidized to carboxylic acid.
Example: O
KMnO4/H+
CH3CH2OH + 2 [O] CH3—C—H + H2O
Ethanol Ethanal
O O
KMnO4/H+
CH3—C—H + [O] CH3—C—OH
Ethanoic acid
Therefore, the conversion of 1° alcohols to aldehydes requires special methods. One of the
best and most convenient reagents for this conversion is pyridinium chlorochromate, PCC
(C5H5NH+CrO3Cl¯) or collin's reagent (chromium trioxide pyridine complex) used in non-
aqueous medium like CH2Cl2.
Thus, 1° alcohols are oxidized to aldehydes with PCC or Collin's reagent in CH2Cl2 as a
solvent. This reagent prevents the further oxidation of aldehyes to carboxylic acids.
When primary alcohol is oxidized with pyridinium chlorochromate (PCC) or Collin's
reagent in dichloromethane as a solvent, aldehyde is obtained.
H H
PCC, CH2Cl2
R—C—O H + [O] R—C O + H2O
or
H CrO3/Pyridine Aldehyde
1° alcohol
Example:
PCC, CH2Cl2
CH3CH2OH + [O] or CH3CHO + H2O
Ethanol CrO3/Pyridine Ethanal
+
The pyridinium chlorochromate, C5H5NH CrO3Cl¯ (PCC) is prepared by heating chromic acid with pyridinium chloride.
PCC =
+
N
CrO3 Cl¯
H
Primary alcohols can also be selectively oxidized up to aldehyde using CrO3/pyridine

Example:
CrO3/Pyridine
CH3CH2OH + [O] CH3CHO + H2O
Ethanol Ethanal
ii. Oxidation of secondary alcohols: Oxidation of 2° alcohols can lose its only one α-hydrogen to
form a ketone is generally straight forward.
When secondary alcohol is oxidized by using oxidizing agents like acidified K2Cr2O7 or
acidified KMnO4, ketone is obtained.
R R
K2Cr2O7 + H2SO4
R—C—O H + [O] R—C O + H2O
or KMnO4 + H2SO4
Ketone
H
2° alcohol
Example:
OH O
K2Cr2O7 + H2SO4
CH3—CH—CH3 + [O] CH3—C—CH3 + H2O
or KMnO4 + H2SO4
propan-2-ol Propanone
i. Chromic anhydride in pyridine is called Sarett's reagent.

ii. Aqueous solution of CrO3, acetone and conc. sulphuric acid is called Jone's reagent and oxidation using Jone's reagent is
called Jone's oxidation.
iii. Tertiary alcohols do not contain α–H. So they are not oxidized under ordinary condition. However, in drastic conditions
they are oxidized to ketones having decrease no. of C atoms.
Example:
OH O
Drastic condtions
CH3—C—CH3 + [O] CH3—C—CH3 + H2O + CO2
CH3 Propanone
tert-Butyl alcohol
(3° alcohol)
2 By Ozonolysis of Alkenes
When an alkene is treated with ozone is presence of CCl4 as a solvent, ozonide is obtained. The
ozonide when distilled with water in presence of zinc, gives carbonyl compounds (aldehyde and/or
ketone). The nature of aldehyde and ketone so formed may depend upon the structure of alkene.
Hence, this reaction is used to identify the structure of alkene.
O
O3
C C C C Zn/H2O
C C CCl4
C O+O C + H2O2
O O Δ
Ethene O O
O
Molozonide Ozonide
(Unstable)
Examples: O
H2C CH2 Zn/H2O
O3 2 HCHO + H2O2
CH2 CH2 Δ
Ethene
CCl4 O O Methanal
Ethylene ozonide
O
O3 CH3CH CH2 Zn/H2O
CH3CH CH2 CH3CHO + HCHO + H2O2
CCl4 Δ
O O Ethanal Methanal
Propene
Ozonide
O
O3 CH3CH CHCH3 Zn/H2O
CH3CH CHCH3 2 CH3CHO + H2O2
CCl4 O Δ
But-2-ene O Ethanal
O
H3C H O O
H3C H O3 C C Zn/H2O
C C CH3 CH3—C—H + CH3—C—CH3 + H2O2
CH3 CCl4 H3C Δ
H3C O
O Ethanal Propanone
2-Methylbut-2-ene
Ozonide
O O
H3C CH3 O3 H3C CH3 Zn/H2O
C C C C 2 CH3—C—CH3 + H2O2
H3C CH3 CCl4 H3C CH3 Δ
O O
2,3-Dimethyl-2-butene Propanone
Ozonide
Note:
• Ozonides are generally explosive at high temperaute so, they are not isolated in dry condition.
• Zinc absorbs H2O2 obtained as a side product. If H2O2 is not absorbed, it oxidizes the aldehyde so formed into carboxylic acid.
• Ozonolysis occurs in two steps.
a. Formation of ozonide (ozonation)
b. Decomposition of ozonide thus obtained by water (hydrolysis).
• Unbranched alkene is likely to give aldehydes only.
• Ozonolysis is an important reaction to determine the structure of alkene.
• Zn is used to remove H2O2 as: Zn + H2O2 Zn (OH)2, otherwise, aldehydes get oxidised to carboxylic acids.
Self Test
12.4 Which aldehydes are formed by reductive ozonolysis of 1,3-pentadiene?
a. HCHO b. CHO–CHO c. CH3CHO d. CH3COCH3
3 From Acid Chloride

When acid chlorides are heated with H2 in presence of Pd–BaSO4 poisoned by quinoline, aldehydes
are obtined. This reactiion is called Rosenmund Reduction.
i.e. O O
Pd-BaSO4
R—C—Cl + H2 R—C—H + HCl
Quinoline Aldehyde
Acid chloride
Example:
O O
Pd-BaSO4
CH3 C—Cl + H2
— CH3—C—H + HCl
Quinoline Ethanal
Ethanoyl chloride
(Acetyl chloride)
Note:
LiAlH4 and H2/Ni cannot be used for this reduction as they reduce the aldehyde further in to 1° alcohols.
When acid chlorides are treated with dialkyl cadmium in presence of ether, ketones are obtained.
O O
dry ether
2 R C—Cl + R'2Cd
— 2 R—C—R' + CdCl2
Acid chloride Ketone
Example:
O O
dry ether
2 CH3—C—Cl + (CH3)2Cd 2 CH3—C—CH3 + CdCl2
Acetyl chloride Dimethyl cadmium Acetone
Note:
Ketones cannot be obtained by the reaction of acid chloride with Grignard reagent. It is because the ketone obtained would
further react with Grignard reagent to form tertiary alcohol.
O O OMgCl OH
dry ether CH3 MgCl H2O
CH3—C—Cl + CH3 MgCl – MgCl2 — —
CH3 C CH3 Ether CH3 — C— CH3 CH3 — C—CH3
–Mg(OH)Cl
Acetyl chloride Acetone CH3 CH3
tert-butyl alcohol
4. From geminal dihalides

Geminal dihalides on base promoted hydrolysis (on heating with aqueous KOH) give aldehyes or
ketones.
Examples:
Cl OH O
2 KOH (aq.)
CH3—C—H CH3—C—H CH3—C—H
– 2 KCl –H2O
Ethanal
Cl OH
1,l-dichloroethane Unstable
Cl OH O
2 KOH (aq.)
CH3 C—CH3
—
– 2 KCl CH3—C—CH3 CH3 C—CH3
—
–H2O
Cl Acetone
OH
2,2-Dichloropropane Unstable
5. By the dry distillation of fatty acids

Fatty acids on heating with MnO at 300°C give aldehyes or ketones. General equation:
O O O
MnO, 300°C
R—C—OH + H O—C—R R—C—R + CO2 ↑ + H2O
a. Formaldehyde is obtained by passing the vapours of formic acid over heated MnO catalyst at
300°C.
O O O
MnO, 300°C
H—C—OH + H O—C—H H—C—H + CO2 ↑ + H2O
2 molecules of formic acid Formaldehyde
b. Aldehydes other than formaldehyde are obtained by passing the vapours of a mixture of a
carboxylic acid and formic acid over heated MnO catalyst at 300°C.
O O O
MnO, 300°C
R—C—OH + H O—C—H R—C—H + CO2 ↑ + H2O
Carboxylic acid Formic acid Aldehyde
Example:
O O O
MnO, 300°C
CH3—C—OH + H O—C—H CH3—C—H + CO2 ↑ + H2O
Acetic acid Formic acid Acetaldehyde
c. Simple ketones are obtained by passing the vapours of a carboxylic acid (other than formic acid)
over heated MnO catalyst at 300°C.
O O O
MnO, 300°C
2 molecules of carboxylic acid Ketone
Example:
O O O
MnO, 300°C
CH3—C—OH + H O—C—CH3 CH3—C—CH3 + CO2 ↑ + H2O
2 molecules of acetic acid Acetone
6. By the distillation of calcium salts of fatty acids

Calcium slats of fatty acid on heating (distillation) give carbonyl compounds.
The general equation:
O O O
(R—C—O)2 Ca + Ca (O—C—R)2 2 R—C—R + 2 CaCO3
Δ
a. Dry distillation of calcium formate (calcium salt of formic acid) alone gives formaldehyde.
O O O
Δ
(H—C—O)2 Ca + Ca (O—C—H)2 2 H—C—H + 2 CaCO3
2 molecules of calcium formate Formaldehyde
b. Dry distillation of a mixtures of calcium formate and calcium salt of other acids give aldehydes
other than formaldehyde.
O O O
Δ
(R—C—O)2 Ca + Ca (O—C—H)2 2 R—C—H + 2 CaCO3
Calcium carboxylate Calcium formate Aldehyde
Example:
O O O
Δ
(CH3—C—O)2 Ca + Ca (O—C—H)2 2 CH3—C—H + 2 CaCO3
Calcium acetate Calcium formate Acetaldehyde
c. Dry distillation of calcium carboxylate (calcium salts of carboxylic acid other than formic acid)
alone gives simple ketone.
O O O
Δ
2 molecules of calcium carboxylate Ketone
Example:
O O O
Δ
(CH3—C—O)2 Ca + Ca (O—C—CH3)2 2 CH3—C— CH3 + 2 CaCO3
Calcium acetate Acetone
d. Dry distillation of a mixture of different calcium carboxylates gives mixed ketone. But this
method gives a mixture of ketone.
O O O
Δ
(R—C—O)2 Ca + Ca (O—C—R')2 2 R—C—R' + 2 CaCO3
Different calcium carboxylate Mixed ketone
Example:
O O O
Δ
(CH3—C—O)2 Ca + Ca (O—C—C2H5)2 2 CH3—C— C2H5 + 2 CaCO3
Calcium acetate Calcium propionate Butanone
When calcium salt of dicarboxylic acid is heated, cyclic ketone is obtained.

Self Test
12.5 What happens when calcium salt of dicarboxylic acid is heated?
12.6 Calcium salt of an acid X on dry distillation with calcium formate produces
iso-butyraldehyde as the product. What is X?
7. Catalytic hydration of alkynes

Hydration of alkynes with water in presence of catalyst like dilute solution of H2SO4 and HgSO4 at
60°C give corresponding aldehydes or ketones.
Examples:
i. Acetaldehyde is prepared by catalytic hydration of acetylene. When acetylene gas is heated
with dil. H2SO4 in presence of dil. HgSO4 solution as a catalyst, acetylene adds a molecule of
H2O onto its C≡C triple bond, vinyl alcohol is formed. Vinyl alcohol undergoes tautomerization
into more stable acetaldehyde.
dil. H2SO4
Rearrangement
O
H—C ≡ C—H + H2O CH2 = CH
HgSO4, 60°C CH3—C—H
Acetylene O—H Tautomerisation Acetaldehyde
Vinyl alcohol
ii. Under similar condition higher alkynes other than acetylene give ketone.
O—H O
dil. H2SO4
CH3—C ≡ C—H + H—OH CH3—C = C—H CH3—C—CH3
HgSO4, 60°C
H Acetone
Markownikov's addition
product
Note:
Formaldehyde cannot be prepared by this method.

a. State: Formaldehyde is a gas is room temperature. Aldehydes and kentoes upto C11 are
colouless liquies. Higher members are colourless solids.
b. Odour: Formaldehyde has irritating pungent odour while other lower aldehyes and ketones
have pleasant odour. Many ketones have performatic value.
c. Boiling points: Aldehyes and ketones have fairly polar C=O bond.
The molecules have a very high dipole moment. So, the
δ–O δ+
intermolecular force of attraction in the carbonyl compounds is '''''''''''' C
releatively stronger (dipole-diple interaction). However this force δ+ '''''''''''' O δ–
C
is weaker than that in alcohols (where the intermolecular force is
hydrogen-bonding). So, aldehyes and ketones have boiling point Dipole-dipole interaction
greater than of alkanes and smaller than those of alcohols and
carboxylic acids of neary same molecular mass.
Compound Name Mol. wt. Boiling point

CH3—CH2—CH2—CH2— CH3 Pentane 72 36°C
CH3CH2CH2CHO Butanal 72 76°C
O
CH3—CH2—C—CH3
Butanone 72 80°C
CH3—CH2—CH2—CH2—OH Butan-1-ol 74 118°C
d. Solubility: Lower aldehydes and ketones are fairly O

soluble in water. This is because, the molecules of
O H H
aldehydes and ketones can form hydrogen bonding
with water. Moreover aldehyes and ketones are polar C
Hydrogen bond
compounds and water is also a polar solvent.
But higher aldehydes and ketones are practically insoluble in water. This is because, higher
aldehydes and ketones contain longer hydrophobic part in their molecule which make them
water insoluble.
However, they are soluble in nonpolar solvents (organic solvents).
Self Test
12.7 Arrange the following in order of increasing boiling points:
a. Propanone b. Propanal c. Propane d. Propan-1-ol

Aldehydes and ketones resemble with each other closely in most of their properties due to a
common structural features of a carbonyl (>C=O) group. However, there is a H–atom attached to the
carbonyl group of aldehydes, and there are two alkyl groups attached to the carbonyl group of
ketones.
H R'
Aldehyde: R—C= O Ketone: R—C=O

(H–atom attached to >C=O) (Two alkyl groups R and R' attached to >C=O)
This difference in structure affects their properties in two ways:

a. Aldehydes are quite easily oxidized, whereas ketones are oxidized only with difficulty.
b. Aldehydes are usually more reactive than ketones towards nucleophilic addition.
Main type of reactions given by carbonyl compounds are nucleophilic addition reactions. In this type
of addition reactions, nucleophile is added in the first step (rate determining step). The mechanism of
the reaction is shown below:
O O¯ OE
slow E+
C + Nu– C C
Nu Nu
For these types of reactions aldehydes are more reactive than ketones.
Reasons:
a. Electronic factor: In ketones, carbonyl carbon is attached to two alkyl groups (e– releasing
groups) which make the carbonyl less electropositive and make the carbonyl group less reactive
for nucleophilic attack.
O δ– O δ–
C δ+ C δ+
R R R H
Ketone: Two + I groups Aldehyde: One + I group
decrease +ve charge on carbon
b. Steric factor: In aldehydes carbonyl carbon is attached to one bulky alkyl groups, whereas in
ketones, the carbonyl carbon is attached with two bulky alkyl groups, which cause much steric
hinderance for attack by nucleophile. Thus reactivitly of ketone gets decreased.
O δ– O δ–
C δ+ C δ+
R R R H
Ketone: Two bulky alkyl groups Aldehyde: One bulky alkyl group
Reactions of aliphatic aldehyes and ketones will be discussed under the following heads.
A. Nucleophilic addition reactions
B. Oxidation of aldehydes and ketones
C. Reduction of aldehydes and ketones
D. Other reactions of aldehydes and ketones.
A. Nucleophilic addition reactions of aldehydes and ketones
1. Addition of HCN (hydrogen cyanide): When of HCN (mixture of NaCN + H2SO4) is added
to aldehydes and ketones, cyanohydrins are formed. Aldehydes form aldehyde
cyanohydrins and similarly ketones form ketone cyanohydrins. The reaction is often carried
out by adding mineral acid (H2SO4) to a mixture of carbonyl compound and aqueous NaCN,
when HCN is prepared in situ from NaCN and mineral acid (H2SO4).
2 NaCN + H2SO4 HCN + NaHSO4
CN CN
+
H
CN¯ + C=O C C
–
Trigonal planar
O OH
Cyanohydrin
(Addition product)
O NaCN+ H2SO4
OH
R —C—H + HCN R —C—H
Aldehyde CN
Aldehyde cyanohydrin
O NaCN+ H2SO4
OH
R —C—R + HCN R —C—R
Ketone
CN
Ketone cyanohydrin
Examples:
O OH
NaCN+ H2SO4
CH3 —C—H + HCN CH3—C—H
Acetaldehyde CN
Acetaldehyde cyanohydrin
2-hydroxypropanenitrile
O OH
NaCN+ H2SO4
CH3 —C—CH3 + HCN CH3—C—CH3
Acetone CN
Acetone cyanohydrin
2-hydroxy-2-methylpropanenitrile
Application of cyanohydrins: Cyanohydrins can be hydrolyzed to α-hydroxy carboxylic

acid. The hydroxy acid upon strong heating, is dehydrated to α,β-unsaturated carboxylic
acid.
OH OH
H2O/H2SO4 conc. H2SO4, Δ
CH3 —C—CN CH3—C—COOH CH2 = CH—COOH
–H2O
H H Propenoic acid
(Acrylic acid)
Acetaldehyde cyanohydrin Lactic acid
(α,β-unsaturated acid)
(α-hydroxypropanoic acid)
(2-hydroxypropanoic acid)
2. Addition of NaHSO3 (sodium bisulphite): When aliphatic aldehydes or ketones are

treated with saturated solution of NaHSO3 in presence of ethanol, the crystalline
precipitate of aldehyde or ketone sodium bisulphite is obtained (Test of aldehydes and
ketones)
O OH
R —C—H + NaHSO3 R —C—H
Aldehyde SO3Na
Aldehyde sodium bisulphate
(crystalline ppt.)
O OH
R —C—R + NaHSO3 R —C—R
Ketone SO3Na
Ketone sodium bisulphate
(crystalline ppt.)
Examples:
O OH
CH3 —C—H + NaHSO3 CH3—C—H
Acetaldehyde SO3Na
Acetaldehyde sodium bisulphite
O OH
CH3 —C—CH3 + NaHSO3 CH3—C—CH3
Acetone SO3Na
Acetone sodium bisulphite
Note:
This crystalline precipitate formed is filtered from ethanol solution and can be decomposed by the action of acid or base back to
its parent aldehyde or ketone. Therefore, this reaction is used for separation of carbonyl compounds from a mixture and other
impurities.
OH O
HCl (aq.)
CH3 —C—H CH3—C—H + Na2SO3 + NaCl + H2O
Δ
Acetaldehyde
SO3Na
Acetaldehyde sodium bisulphite
3. Addition of Grignard reagents: Grignard synthesis of alcohols: Nucleophilic addition

reaction of Grignard reagent on aldehydes and ketones.
Grignard reagent (RMgX) undergoes nucleophilic addition reaction to the carbonyl
(>C=O) functional group of aldehydes or ketones to form an addition product called
adduct, which on acidic hydrolysis with dilute HCl yields different types of alcohols.
δ– – +
O OMgBr OH
Dry ether, H2O/H+
δ+
—C— + R—MgX —C— —C— + Mg(OH)X
Inert atm.
Carbonyl Grignard
R R
Compound reagent Adduct Alcohol
According to the structure of aldehydes and ketones used in the Grignard synthesis,
different classes of alcohols (1°, 2° and 3°) are obtained.
Reactions
i. Formaldehyde reacts with Grignard reagent followed by acid hydrolysis always gives
primary (1°) alcohol.
– +
δ– OMgX OH
O Dry ether, H2O/H+
δ+
H—C—H
R—MgX H—C—H H—C—H + Mg(OH)X
Inert atm.
R R
Methanal Alkyl magnesium halide Adduct 1° alcohol
Example:
δ– – +
O OMgI OH
Dry ether, H2O/H+
δ+
H—C—H + CH3—MgI H—C—H H—C—H + Mg(OH)I
Inert atm.
Methanal CH3 CH3
Methyl magnesium Adduct Ethanol (1°)
iodide
ii. Higher aldehydes (other than formaldehyde) react with Grignard reagent followed by acid
hydrolysis give secondary (2°) alcohols.
– +
O OMgX OH
H2O/H+
R —C—H + R—MgX R—C—H R—C—H + Mg(OH)X
Alkyl magnesium R R
Aldehyde
halide Adduct
2° alcohol
Example:
– +
O OMgBr OH
H2O/H+
CH3 —C—H + CH3—MgBr CH3 —C—H CH3—C—H
CH3 CH3
Ethanal Methyl magnesium Adduct Propan-2-ol
bromide (Isopropyl alcohol)
iii. Ketones react with Grignard reagent followed by acid hydrolysis gives tertiary (3°)
alcohols.
– +
O OMgX OH
R —C—R + R—MgX R —C—R H2O/H+
R—C—R + Mg(OH)X
Ketone R
R
Adduct 3° alcohol
Example:
O OMgBr OH
– + H2O/H+
CH3 —C—CH3 + CH3—MgBr CH3 —C—CH3 CH3—C—CH3
CH3 CH3
Acetone
Adduct 2-Methylpropan-2-ol
(tert- Butyl alcohol)
4. Reaction of phosphorus pentachloride (PCl5): Formation of geminal dehalides:

Aldehydes and ketones react with PCl5 to gives gem-dihalides.
Examples: O Cl
CH3 —C—CH3 + PCl5 Δ

CH3 —C—CH3 + POCl3
Acetone Cl
2,2-dichloropropane
O Cl
CH3 —C—H + PCl5 Δ

CH3 —C—H + POCl3
Ethanal Cl
1,1-dichloroethane
5. Addition of alcohols: Formation of acetals:

Aldehyde reacts with alcohols in presene of dry HCl giving hemiacetal. If alcohol is in
excess acetal is obtained. Aliphatic ketones donot form acetals. Dry HCl shifts the
equilibrium towards right hand side.
Example:
O OH OC2H5
dry HCl C2H5OH (excess)
CH3 —C—H + C2H5OH CH3 —C—H CH3 —C—H
dry HCl, H2O
Ethanal OC2H5 OC2H5
1-ethoxyethanol 1,1-diethoxyethane
(Hemi-acetal) (acetal)
6. Addition of ammonia: Formaldehyde reacts with ammonia giving hexamethylene

tetraammine (urotropine).
6 HCHO + 4 NH3 (CH2)6N4 + 6H2O

Urotropine
Structure of Urotropine:
N
CH2 CH2
CH2
N
CH2 CH2
N N
CH2
Urotropine is used as urinary antiseptic drug.

Acetaldehyde reacts with ammonia giving acetaldehyde ammonias.
O OH
CH3 —C—H + NH3 CH3 —CH— NH2

Δ
Ethanal Acetaldehyde ammonia
Acetone reacts with ammonia giving acetone ammonias, which further reacts with excess
of acetone to form ketonic amine.
H O
OH NH2 O
O CH2 —C—CH3
CH3 —C—CH3 + NH3 CH3 —C—CH3 CH3 —C—CH2—C—CH3
–H2O
Acetone NH2 CH3
Acetone ammonia 4-amino-4-methylpentan-2-one
(ketonic amine)
7. Addition of ammonia derivatives followed by loss of water: Nuclephilic addition

followed by elimination of water
Ammonia derivatives are compounds that can be made by replacing one H- atom from
NH3 by a group G. It can be generally represented as NH2–G.
When aldehyde or ketone is treated with ammonia derivative, an organic compound
containing carbon nitrogen (C=N) double bond known as imine is formed.
This reaction is completed in two steps and is represented as:
Step (i) Acid catalyzed nucleophilic addition of ammonia derivative (NH2–G) onto carbonyl
carbon of aldehyde or ketone to give carbinol amine.
H+ NH2—G – H+
C O C OH C OH C OH
Nucleophilic
addition H NH—G H N—G
⊕
Carbinol amine
Step (ii) Elimination of water molecule gives imine.

–H2O
C OH —C = N—G
Imine
H N—G
Carbinolamine
Both steps are summarized as:

–H2O
C O + H2 N—G C N—G
Imine
G Ammonia derivatives (NH2–G) The product

—OH NH2—OH (Hydroxylamine) >C=N—OH (Oxime)
—NH2 NH2—NH2 (Hydrazine) >C=N—NH2 (Hydrazone)
—NH NH2—NH >C=N—NH

(Phenyl hydrazine)
(Phenylhydrazone)
NO2 NO2
NO2
NH2—NH NO2 >C=N—NH NO2
—NH NO2
2,4-Dinitrophenyl hydrazine (2,4–DNP) (2,4-Dinitrophenyl hydrazone)
yellow ppt
—NHCONH2 NH2—NHCONH2 (Semicarbazide) >C=N—NHCONH2
(Semicarbazone)
crystalline ppt
i. Reaction with Hydroxylamine: Formation of Oximes
Aldehydes and ketones react with hydroxylamine giving oximes. Aldehydes form
aldoxines and ketones form ketoximes.
C O + H2 N—OH C N—OH + H2O
Aldehyde or ketone Hydroxylmine Oxime
Examples:
CH3 CH3
H H
Acetaldehyde Acetaldoxime
CH3 CH3
CH3 CH3
Acetone Acetoxime
The Beckmann rearrangement: The oximes obtained above can be transformed to amides on reaction with strong acids like
H2SO4, SOCl2, etc.
ii. Reaction with Hydrazine: Formation of Hydrazone: Aldehyes or ketones react with
hydrazine giving hydrazones.
CH3 CH3
C O + H2 N—NH2 C N—NH2 + H2O
H H
Acetaldehyde Hydrazine Acetaldehyde hydrazone
CH3 CH3
C O + H2 N—NH2 C N—NH2 + H2O
CH3 CH3
Acetone Acetone hydrazone
iii. Reaction with phenylhydrazine: Formation of phenylhydrazone: Aldehydes and ketones

react with phenylhydrazine to give phenylhydrazone.
CH3 CH3
C O + H2 N—NH C N—NH + H2O
H H
Acetaldehyde Phenylhydrazine Acetaldehyde phenylhydrazone
CH3 CH3
C O + H2 N—NH C N—NH + H2O
CH3 CH3
Acetone Phenylhydrazine Acetone phenylhydrazone
iv. Reaction with 2,4-dinitrophenyl hydrazine (2,4-DNP): Formation of 2,4-dinitrophenyl

hydrazone: 2,4-DNP test: When aldehydes and ketones are treated with 2,4-dinitrophenyl
hydrazine (2,4-DNP), yellow or red precipitate of aldehyde/ketone 2,4-diphexylhydrazone
obtained. It is characteristic reaction of carbonyl compounds and is used to distinguish
carbonyl compounds from other classes of organic compounds. Thus reaction serves as a
test for carbonyl compounds.
NO2 NO2
CH3 CH3
C O + H2 N—NH NO2 C N—NH NO2 + H2O
H H
Acetaldehyde 2,4-DNP Acetaldehyde-2,4–dinitrophenyl hydrazone
(Yellow ppt)
NO2 NO2
CH3 CH3
C O + H2 N—NH NO2 C N—NH NO2 + H2O
CH3 CH3
Acetone-2,4–dinitrophenyl hydrazone
Acetone (Yellow ppt)
v. Reaction with semicarbazide: Formation of semicarbazone: Aldehydes and ketones react

with semicarbazide to give crystalline precipitate of semicarbazone.
O O
CH3 CH3
C O + H2 N—NH—C—NH2 C N—NH—C—NH2 + H2O
H H
Acetaldehyde Acetaldehyde semicarbazone
Semicarbazide
(Crystalline ppt.)
O O
CH3 CH3
C O + H2 N—NH—C—NH2 C N—NH—C—NH2 + H2O
CH3 CH3
Acetone Acetone semicarbazone
(Crystalline ppt.)
B. Oxidation
Aldehydes are not only oxidized by strong oxidizing agents like KMnO4, K2Cr2O7, etc. but they are
also oxidized by mild oxidizing agents like Tollen's reagent, Fehling's solution, etc. and they show
reducing properties. Ketones are not oxidized under ordinary conditions.
1. Oxidation with Tollen’s reagent (Silver mirror test): The ammoniacal silver nitrate
solution, [Ag (NH3)2]OH, is called Tollen's reagent. Tollen's reagent contains Ag (NH3)2+
ion in water soluble form.
Reaction involved in the preparation of Tollen’s reagent:
AgNO3 + NaOH Ag(OH) + NaNO3
Δ
2Ag(OH) Ag2O + H2O

Insoluble
Ag2O + 4 NH4OH 2 [Ag(NH3)2]OH + 3H2O
Soluble
Tollen's reagent, diammine Ag(I) hydroxide
When an aldehyde is heated with Tollen’s reagent, aldehyde reduces the Tollen’s reagent
into free metallic silver and aldehyde itself gets oxidized to carboxylic acid. The metallic
silver appears in the form of mirror deposited around the inner wall of the reaction test
tube. Therefore, this reaction is widely known as silver mirror test of aldehyde. Tollen's
reagent oxidizes both aliphatic and aromatic aldehydes.
O
R —C—H + 2 [Ag(NH3)2]OH RCOONH4 + 2 Ag↓ + 3 NH3 + H2O
Aldehyde Tollen's reagent Silver mirror
Examples:
Oxidation of formaldehyde, acetaldehyde, etc. with Tollen's reagent:
O
H—C—H + 2 [Ag(NH3)2]OH HCOONH4 + 2 Ag↓+ 3NH3 + H2O
Δ
Formaldehyde Tollen's reagent Silver mirror
O
CH3 —C—H + 2 [Ag(NH3)2]OH CH3COONH4 + 2Ag↓ + 3NH3 + H2O
Δ
Acetaldehyde Tollen's reagent Silver mirror
Ketones do not respond this reaction; therefore, aldehydes can be distinguished from
ketones by silver mirror test in laboratory.
2. Oxidation with Fehling's solution and Benedict’s solution: Fehling’s and Benedict’s tests)
The alkaline solution of copper sulphate complexed by sodium potassium tartarate
(Rochelle salt) is called Fehling’s solution, whereas alkaline solution of copper sulphate
complexed by sodium citrate is called Benedict's reagent. In Fehling’s solution, the
complexing agent is tartarate ion but in Benedict’s reagent, the complexing agent is citrate
ion.
When an aldehyde is heated with Fehling’s solution, red precipitate of cuprous oxide
(Cu2O) is obtained.
O O
++
R —C—H + [2 Cu + 4 OH¯] R —C—OH + Cu2O↓ + 2 H2O
Δ
Aldehyde Fehling's solution Carboxylic acid Red ppt
(deep blue colour)
Examples:
O O
++
H —C—H + [2 Cu + 4 OH¯] H —C—OH + Cu2O↓ + 2 H2O
Δ
Formaldehyde Fehling's solution Formic acid
(deep blue colour)
O O
CH3 —C—H + 2 Cu(OH)2 CH3—C—OH + Cu2O↓ + 2 H2O
Δ
Acetaldehyde Fehling's solution Acetic acid
C6H12O6 + 2 Cu(OH)2 C6H12O7 + Cu2O↓ + 2 H2O

Δ
Glucose Fehling solution or Gluconic acid
Benedict's reagent
Note:
Aliphatic aldehydes give Fehling’s solution and Benedict's tests, whereas aromatic aldehydes like benzaldehyde does not
response to this reaction; therefore, aliphatic aldehydes can be distinguished from aromatic aldehydes by performing the
Fehling’s solution and Benedict's solution tests in the laboratory. Similarly the Fehling's solution or Benedict's test are also not
given by ketones.
Self Test
12.8 How can you distinguished between:
a. Acetaldehyde and benzaldehyde
b. Acetaldehyde and acetone
3. Oxidation using acidified KMnO4 or acidified K2Cr2O7: These oxidizing agents can
oxidize aldehyes into carboxylic acids. In these reactions, pink colour of KMnO4 discharged
or orange colour K2Cr2O7 is changed to green. These tests are called permanganate test and
dichromate test, respectively.
i.e O O
KMnO4/H+ or
R—C—H + [O] R—C—OH
K2Cr2O7/H+
Example:
O O
KMnO4/H+ or
CH3—C—H + [O] CH3—C—OH
K2Cr2O7/H+ CH3
H2N
4. Action of Schiff's Reagent: Aldehydes give pink C NH2Cl

colour with Schiff's reagent (Rusaniline hydrochloride,
pink colour of which is discharged by SO2) H2N
Rosaniline hydrochloride
Note
Oxidation of ketones under drastic conditions: Ketones are not oxidized under ordinary conditions. However in drastic
conditions, they are oxidized to give smaller carboxylic acids.
eg. O O
Drastic
CH3—C—CH3 + [O] CH3—C—OH + CO2 + H2O
Condition
In case of unsymmetrical ketones cleavage takes place in such a way that smaller alkyl group remains attached to the carbonyl
group (Popoff's rule").
O O
Drastic
CH3—CH2—C—CH3 + [O] 2 CH3—C—OH
Condition
C. Reduction of aldehydes and ketones

1. Reduction to alcohols
Aldehydes are reduced to primary (1°) alcohols, whereas ketones are reduced to secondary
(2°) alcohols either by catalytic hydrogenation (H2/Ni, Δ) or by use of chemical reducing
agents like Na/C2H5OH, lithium aluminum hydride (LiAlH4), sodium borohydride
(NaBH4) etc.
H2 / Ni or C2H5OH +Na
C O —C—OH
or LiAlH4 or NaBH4
H
Aldehyde or ketone
Alcohol
Examples
O
Ni
H—C—H + H2 CH3OH
Δ
Formaldehyde Methyl alcohol
O
Ni
CH3—C—H + H2 CH3 —CH2—OH
Δ
Acetaldehyde Ethyl alcohol (1° alcohol)
O OH
Ni
CH3 —C—CH3 + H2 CH3 —CH—CH3
Δ
Acetone Isopropyl alcohol
(2° alcohol)
O OH
LiAlH4
CH3 —C—CH3 + 2 [H] CH3 —CH—CH3
Acetone propan-2-ol
To reduce a carbonyl group that is conjugated with carbon-carbon double (C=C) bond without reducing the carbon and
carbon double bond requires a chemoselective reducing agent like 9–BBN, (9–borbicyclo[3,3,1]nonane).
H2, Ni, Δ
CH3—CH = CH—CHO CH3—CH2—CH2—CH2OH (Reduction of both C=C
double bond and –CHO)
2-butenal (Crotonaldehyde) n-Butyl alcohol
9-BBN
CH3—CH = CH—CHO CH3—CH = CH—CH2OH (Reduction of only –CHO)
HOCH2CH2NH2
Crotyl alcohol
2-butenal (Crotonaldehyde)
(But-2-en-l-ol)
In fact, the reduction by LiAlH4 takes place in two steps (a) Addition by LiAlH4 to get alkoxide (b) Hydrohysis of the
alkoxide. This concept is beyond the scope of this text.
O O¯ OH
H+ H —OH
—C— —C— —C—
LiAlH4
H H
2. Reduction to alkanes (hydrocarbons): Wolff-Kishner reduction and clemensen

reduction: The conversion of the acyl (R-CO-) group into an alkyl (R-CH2-) group can be
accomplished by the Clemmensen reduction or the Wolff-kishner reduction. In both of
these reduction reactions, the carbonyl (>C=O) group of aldehydes and ketones are
reduced to the methylene (-CH2-) group of hydrocarbons (alkanes).
Clemmensen reduction: Zn (Hg) + conc. HCl or

C O —C—H + H2O
Wolff-kishner reduction: NH2—NH2, KOH+ethylene glycol
H
Hydrocarbon
i. Clemmensen reduction: Aldehydes or ketones are reduced to alkanes by amalgamated

zinc in presence of conc. HCl. The reaction is known as Clemmensen reduction.
O
Zn (Hg)+ conc. HCl
—C— + 4 [H] —CH2— + H2O
Methylene group
Examples:
O
Zn (Hg)+ conc. HCl
CH3—C—H + 4 [H] CH3—CH3 + H2O
Ethanal Ethane
O
Zn (Hg)+ conc. HCl
CH3—C—CH3 + 4 [H] CH3—CH2—CH3 + H2O
Propanone Propane
Clemmensen reduction is useful method for the reduction of the organic compounds
which are base sensitive.
ii. Wolff-Kishner reduction: Aldehydes and ketones are reduced into respective alkanes with
a mixture of hydrazine (NH2–NH2) and alkali (KOH) in ethylene glycol is known as Wolff-
Kishner reduction.
H H
–H2O KOH/Ethylene glycol
CH3—C O + H2 N—NH2 CH3—C N—N H2 CH3—CH3 + N2 ↑
200°C
Ethanal Ethane
Hydrazine Hydrazone
CH3 CH3
–H2O KOH/Ethylene glycol
CH3—C O + H2 N—NH2 CH3—C N—N H2 CH3CH2CH3 + N2 ↑
200°C
Propanone Propane
Hydrazine
Wolff-Kishner reduction is useful method for the reduction of the organic compound
which are acid sensitive.
D. Other reactions O
1. Iodoform test: Aldehydes or ketones having CH3—C—
structure on heating with
excess I2 and aq. alkali (NaOH) give yellow crystalline precipitate of iodoform. This test is
called iodoform test.

iodination
hydrolysis
CI3COR + NaOH CHI3 + RCOONa

Δ
CH3COR + 3I2 + 4NaOH CHI3 ↓ +3 NaI + RCOONa + 3 H2O
Iodoform
(Yellow ppt)
Carbonyl compounds like HCHO, CH3CH2COCH2CH3, C6H5CHO (benzaldehyde) etc. do not

contain CH3— groups in α position do not give iodoform test. Whereas compounds like
CH3CHO, CH3COCH3, CH3COCH2CH3 etc. contain CH3CO— group, give positive iodoform
test.
Self Test
12.9 How can you distinguish formaldehyde and acetaldehyde?
2. Aldol condensation: Aldehydes or ketones having α-hydrogen on treatment with dilute

bases like NaOH or K2CO3, undergo condensation reaction to give β-hydroxy aldehyde or
β-hydroxy ketone. This reaction is called aldol condensation. β-hydroxy aldehyde or β-
hydroxy ketone is also known as aldol since it is a compound containing both aldehyde and
hydroxy functional groups.
Examples:
O O OH O
dil. NaOH
CH3 —C—H + CH3 —C—H CH3 —C— CH2 —C—H
2 molecules of acetaldehyde H
3- Hydroxybutanal or
β-Hydroxy aldehyde (Aldol)
O O OH O
dil. NaOH
CH3 —C—CH3 + CH3 —C—CH3 CH3 —C—CH2—C—CH3
2 molecules of acetone CH3
4-Hydroxy-4-methyl-2-pentanone
β-Hydroxy ketone
Aldol condensation between the molecules of different compounds is called crossed-aldol
condensation.
Example:
O O OH O
CH3 —C—H + C—H CH—CH2—C—H
OH–
Acetaldehyde Benzaldehyde 3-hydroxy-3-phenylpropanal
3. Cannizzaro reaction: Aldehydes that do not have α- hydrogen atoms (like formaldehyde,
benzaldehyde etc.), when treated with concentrated aqueous solution of alkali (for
example 50% aqueous NaOH) at room temperature and left over the reaction over night,
self-oxidation-and-reduction reaction (also known as disproportionation reaction), takes
place giving a mixture of alcohol and a salt of carboxylic acid This reaction is known as
cannizzaro reaction. In the reaction, one molecule of aldehyde is reduced to corresponding
alcohol and another molecule is oxidized to corresponding carboxylic acid, which gives its
sodium carboxylate salt.
Examples:
O O
H—C—H + H—C—H + NaOH CH3OH + HCOONa + H2O
2 molecules of Formaldehyde Methanol Sodium formate
CHO CHO CH2OH COONa
+ + NaOH + + H2O
2 molecules of Benzaldehyde Benzyl alcohol Sodium benzoate
Cannizzaro reaction between molecules of different aldehydes is termed as crossed

Cannizzaro reaction.
O
C—H CH2OH
O
conc. NaOH
+ H—C—H + HCOONa + H2O
Benzyl alcohol Sodium formate
4. Polymerization of formaldehyde: Formaldehyde undergoes polymerization in

various conditions giving various products.
i. Aqueous formaldehyde when allowed to evaporate upto dryness, white crystalline solid of
paraformaldehyde is obtained.
n HCHO(aq.) Evaporation (n = 6 – 50)

(CH2O)n.H2O
Para- formaldehyde
ii. Gaseous formaldehyde when allowed to stand for long time, metaformaldehyde (trioxane)
is formed.
CH2 O
3 HCHO O CH2 or (CH2O)3
CH2 O
Gas
Meta-formaldehyde
(Trioxane)
iii. Formaldehyde upon treatment with weak base like Ca(OH)2 gives formose (hexose sugar).
Ca(OH)2
6 HCHO CH2OH—CHOH—CHOH—CHOH—CHOH—CHO
Formose
12.1.8 Uses of Aldehydes and Ketones

1. Formaldehyde is used in preparation of urotropine and polymers (eg. bakelite).
2. Formaldehyde is used as biological preservative (40% aqueous solution of formaldehyde in the
form of formalin).
3. Aldehydes are used as reducing agent in laboratory.
4. Many ketones are used as solvents. For example: acetone is used as nail polish remover and for
removing stains.
12.2 Aromatic Aldehydes and Ketones

12.2.1 Introduction
Derivatives of arenes, where two hydrogen atoms from side chain —CH3 are replaced by divalent
oxygen atom are called aromatic aldehydes.
O
i.e. – 2H
Ar—CH3 +O Ar—C—H
Examples: CHO
CHO
OH
Benzaldehyde Salicyaldehyde
Derivatives of arenes, where two hydrogen atoms from side chain —CH2—R or —CH2—Ar are
replaced by divalent oxygen atom are called aromatic ketones.
O O
– 2H – 2H
Ar—CH2—Ar +O Ar—C—Ar Ar—CH2—R Ar—C—R
+O
Examples:
O O
C—CH3 C
Acetophenone Benzophenone
(Methyl phenyl ketone) (Diphenyl ketone)
12.2.2 Preparation of Aromatic Aldehyde (Benzaldehyde)

1. By the oxidation of toluene: Toluene can be oxidized to benzaldehyde using the following
methods:
a. When toluene is treated with chromic anhydride and acetic anhydride, benzylidene acetate
is obtained, which on hydrolysis gives benzaldehyde.
O
CH3 CH(O—C—CH3)2 CHO
[O], CrO3 H2O /OH¯
+ 2 CH3COOH
(CH3CO)2O Δ
Benzylidene acetate Benzaldehyde
Note:
Formation of benzylidene acetate prevents further oxidation of benzaldehyde into benzoic acid.
b. Benzaldehye on treatement with chromyl chloride in presence of CCl4 gives brown

coloured complex, which on decomposition by water gives benzaldehyde.
CH3 CH3 CHO
CrO2Cl2 H2O/OH¯
CCl4 . 2 CrO2Cl2
Δ
Addition product Benzaldehyde
c. Oxidation of toluene in air with vanadium pentoxide at high temperature gives

benzaldehyde.
CH3 CHO
V2O5
+ O2 + H2O
350°C
Benzaldehyde
d. Selctive oxidation of toluene into benzaldehyde can be achieved by using active surface
exposed cerium oxide (CeO2) heterogeneous catalyst.
CH3 CHO
O2/ CeO2
+ H2O
35 - 90°C
Benzaldehyde
2. By the hydrolysis of benzal chloride: Benzal chloride on heating with aqueous alkali gives
benzaldehyde.
Cl OH
CH—Cl CHO
CH—OH
2NaOH (aq.) –H2O
–2 NaCl
Benzal chloride Benzaldehyde
Unstable
3. From acid chloride: By Rosenmund’s reduction: When benzoyl chloride is heated with H2 in
presence of palladium catalyst deposited in BaSO4 and poisoned by quinoline, benzaldehyde is
obtained. This reaction is called as Rosenmund's reduction.
O
O
C—Cl
Pd-BaSO4 C—H
+ H2 + HCl
quinoline, Δ
Benzaldehyde
4. By Gattermann-Koch synthesis: Formylation: When benzene is treated with a mixture of CO

and dry HCl gas in presence of anhydrous AlCl3 under pressure, benzaldehyde is formed. The
reaction is called Gattermann-Koch reaction.
CHO
anhyd. AlCl3
+ CO + HCl (g) + HCl
pressure
Benzene Benzaldehyde
12.2.3 Preparation of Aromatic Ketones (Acetophenone)

When benzene is treated with acetyl chloride (CH3COCl) or acetic anhydride (CH3COOCOCH3) in
presence of anhydrous AlCl3 as a lewis acid, acetophenone is formed. This reaction is Friedel-Craft
acylation.
O O
anhyd. AlCl3
CH3—C— Cl + H CH3—C + HCl
Δ
Acetyl chloride
O O O
anhyd. AlCl3
CH3—C— O—C—CH3 + H CH3—C + CH3COOH
Δ
Acetic anhydride Acetophenone
Benzene
Similarly, benzophenone is prepared by heating benzene with benzoyl chloride in presence of
anhydrous AlCl3.
O O
anhyd. AlCl3
C— Cl + H C + HCl
Δ
Benzoyl chloride Benzene Benzophenone
(Diphenyl ketone)
12.2.4 Physical Properties of Benzaldehyde and Acetophenone

Benzaldehye is a colourless liquid. Its boiling point is 179°C. It has an odour of bitter almonds. It is
sparingly soluble in water.
Acetophenone is colourless liquid. Its boiling point is 202°C. It is sparingly soluble in water.
12.2.5 Chemical Properties of Benzaldehyde and Acetophenone

Most of the properties of aromatic aldehydes and ketones are similar to aliphatic aldehydes and
ketones. The chemical reactions in benzaldehyde and acetophenone will be discussed under the
following heads.
A. Nucleophilic addition reactions
B. Oxidation
C. Reduction
D. Electrophilic substitution reactions
E. Other reactions.
A. Nucleophilic addition reaction:

1. Reaction with HCN: Benzaldehyde and acetophenone react with HCN (a mixture of
NaCN + H2SO4) giving cyanohydrins.
O OH
NaCN + H2SO4
C—H + HCN C—H
Benzaldehyde
CN
Benzaldehyde cyanohydrin
O OH
NaCN + H2SO4
C—CH3 + HCN C—CH3
CN
Acetophenone
Acetophenone cyanohydrin
2. Addition of NaHSO3: Benzaldehyde reacts with NaHSO3 solution to give crystalline

precipitate of benzaldehyde sodium bisulphite.
O OH
C—H + NaHSO3 C—H
Benzaldehyde SO3Na
Benzaldehyde sodium bisulphate
(Crystalline ppt.)
3. Addition of Grignard reagent: Nucleophilic addition of Grignard reagent on aromatic

aldehyde followed by hydrolysis gives secondary (2°) alcohol.
Example:
O OMgBr OH
Ether H2O/H+
C—H + CH3MgBr C—H C—H + Mg(OH)Br
Δ
Methyl magnesium CH3 CH3
Benzaldehyde bromide
1-Phenylethanol
(2° alcohol)
Nucleophilic addition of Grignard reagent on aromatic ketone followed by hydrolysis

gives tertiary (3°) alcohol.
Example:
O OMgBr OH
Ether H2O/H+
C—CH3 + CH3MgBr C—CH3 C—CH3 + Mg(OH)Br
Δ
Acetophenone Methyl magnesium CH3 CH3
bromide
2-Phenylpropan-2-ol
(3° alcohol)
4. Addition of ammonia: Benzaldehyde reacts with ammonia giving hydrobenzamide.

H
H
C=O N—H CH
H H
N
O=C HC
H Δ, – 3 H2O N
H CH
C=O N—H
H
Hydrobenzamide
5. Reaction with PCl5: When aldehyde or ketone is treated with PCl5, the carbonyl oxygen is
replaced by two chlorine atoms and germinal- dichloride is formed.
O Cl
C—H + PCl5 C—H + POCl3
Cl
Benzaldehyde
Benzal chloride
O Cl
C—CH3 + PCl5 C—CH3 + POCl3
Cl
Acetophenone
1,1-dichloro-1-phenylethane
6. Reaction of benzaldehyde with amine: When benzaldehyde is treated with primary

aliphatic or aromatic amine (aniline), Schiff's base is formed.
H
C O + H2 N CH=N + H2O
Benzaldehyde Aniline Benzalaniline
(Schiff's base)
7. Reaction with ammonia derivatives: Nucleophilic addition followed by loss of water:

Similar to aliphatic aldehydes and ketones, aromatic aldehydes and ketones also give
reaction with ammonia derivatives.

NH2OH
CH = N—OH + H2O
Hydroxylamine amine
Benzaldoxime
NH2—NH2
CH = N—NH2 + H2O
Hydrazine
Benzaldehyde hydrazone
NH—NH2
CH = N—NH + H2O
O Phenyl hydrazine
C—H Benzaldehyde phenylhydrazone
Benzaldehyde NO2
NH2—NH NO2 NO2

CH = N—NH NO2 + H2O
2,4-DNP
Benzaldehyde-2,4-dinitrophenylhydrazone
(yellow ppt)
O
O
H2N—NH—C—NH2
CH=N—NH—C—NH2 + H2O
Semicarbazide
Benzaldehyde semicarbzone
(crystalline ppt)
CH3
NH2OH
C N—OH + H2O
Acetophenoxime
CH3
NH2—NH2
C N—NH2 + H2O
Acetophenone hydrazone
NH2—NH CH3
C N—NH + H2O
O
Acetophenone phenylhydrazone
C—CH3
NO2
Acetophenone NO2 CH3 NO2
NH2—NH
C N—NH NO2 + H2O
Acetophenone-2,4-dinitrophenylhydrazone
CH3
NH2—NHCONH2
C N—NHCONH2 + H2O
Acetophenone semicarbazone
B. Oxidation
Aromatic aldehydes are also oxidized to the respective acids as in aliphatic aldehydes.
1. Oxidation with Tollen’s reagent: Silver mirror test: Like aliphatic aldehydes, benzaldehyde also
gives silver mirror test.
O O
C—H C—ONH4
+ 2[Ag(NH3)2]OH + 2 Ag ↓ + 3 NH3 + H2O
Tollen's regent
Amononium benzoate
2. Oxidation using KMnO4/H+ or K2Cr2O7/H+: Benzaldehyde is oxidized to benzoic acid.
O O
C—H C—OH
KMnO4/H+ or
+ [O]
K2Cr2O7/H+
Benzoic acid
Note:
Benzaldehyde does not reduce Fehling's solution though it is an aldehyde. Aliphatic aldehydes give Fehling’s solution test,
whereas aromatic aldehydes like benzaldehyde do not respond this reaction. Therefore, aliphatic aldehydes can be distinguished
from aromatic aldehydes by Fehling’s solution test in laboratory.
C. Reduction
Aromatic aldehydes and ketones are reduced to aromatic alcohols or arenes.
1. Reduction to aromatic alcohols: Aromatic aldehydes or ketones are reduced to aromatic
alcohols using LiAlH4.
Examples: O
C—H LiAlH4
CH2OH
+ 2 [H]
Benzyl alcohol
Benzaldehyde
O OH
C—CH3 CH—CH3
LiAlH4
+ 2 [H]
Acetophenone 1-phenylethanol
2. Reduction to aromatic hydrocarbons (arenes):

i. Clemmensen reduction: Aromatic aldehydes or ketones are reduced by zinc-
amalgam and conc. HCl, to give corresponding arenes (aromatic hydrocarbons).
O
Zn (Hg)+ conc. HCl
C—H + 4 [H] CH3 + H2O
Benzaldehyde Toluene
O
Zn (Hg)+ conc. HCl
C—CH3 + 4 [H] CH2CH3 + H2O
Acetophenone Ethylbenzene
ii. Wolff-Kishner reduction: Like aliphatic aldehydes and ketones, aromatic aldehydes
and ketones are also reduced by alkaline solution of hydrazine to give corresponding
by arenes. Reduction of aldehyde or ketone into respective hydrocarbon with basic
solution of hydrazine in presence of ethylene glycol at 200°C is known as Wolff-
Kishner reduction.
H
H2 N—NH2 KOH/ethylene glycol
C=O CH = N—NH2 CH3 + N2↑
(–H2O) 200°C
Benzaldehyde Hydrazone
CH3 CH3
H2 N —NH2
KOH/ethylene glycol
C=O C = N—NH2 CH2CH3 + N2↑
(–H2O) 200°C
Acetophenone Hydrazone Ethylbenzene
D. Reaction given by aromatic benzene ring: Electrophilic aromatic substitution reaction

Benzaldehyde is less reactive than aliphatic aldehydes towards nucleophilic addition reaction. It
can be explained on the basis of electron-releasing resonance effect of benzene ring. The
carbonyl (>C=O) group is electron-withdrawing group, which pull the electron density from
aromatic benzene ring towards the carbonyl oxygen of the >C=O group. As a result of which,
negative charge is developed on carbonyl oxygen and positive charge is developed in the
aromatic benzene ring. Therefore, the electron-withdrawing carbonyl (>C=O) group always
deactivates the benzene ring towards electrophilic substitution reaction.
The positive charge so developed on benzene ring is delocalized in the aromatic benzene ring to
give the resonance hybrid structures. In these resonance structures, the positive charge (δ+) is
appeared in ortho- and para- positions rather than in meta- positions, which makes ortho-, para-
positions less reactive than meta- positions towards electrophilic substitution reaction.
Therefore, aromatic aldehydes and ketones are meta- directing towards electrophilic
substitution reaction and hence the reaction takes place slowly at meta- positions to give meta-
substituted products.
– – δ–
O O O O– O O
C—H C—H C—H C—H C—H C—H
+ + δ+ δ+
+ δ+
Resonating structures of benzaldehyde
Examples:
CHO
Cl2, Anh. FeCl3
+ H2O
Chlorination
(Halogenation) Cl
m–chlorobenzaldehyde
CHO CHO
Fuming H2SO4, Δ + H2O
(Sulphonation)
SO3H
m–formylbenzenesulphonic acid
CHO
conc. HNO3+ conc. H2SO4, Δ + H2O

(Nitration)
NO2
m–nitrobenzaldehyde
E. Other reactions:
1. Perkin reaction: When aromatic aldehyde (e.g. benzaldehyde) is heated with acid
anhydride (e.g. acetic anhydride) in presence of salt of same carboxylic acid as a base, α,β-
unsaturated carboxylic acid is obtained. This reaction is called Perkin reaction.
O
C—H O O CH = CH—COOH
CH3COONa
+ CH3—C—O—C—CH3 + CH3COOH
Δ
Benzaldehyde Acetic anhydride 3-phenylpropenoic acid

(Cinnamic acid)
2. Benzoin condensation: When benzaldehyde is heated with alcoholic solution of KCN,

condensation takes place giving benzoin. This reaction is called as benzoin condensation.
O O O OH
C—H C—H C—CH
KCN, reflux
+
Benzaldehyde Benzoin
12.2.6 Uses of Aromatic Aldehydes and Ketones
Uses of benzaldehyde
1. It is used as flavouring agent in perfumes.
2. It is used to prepare various aromatic compounds like benzion, hydrobenzamide, α, β-
unsaturated acid etc.
3. It is used for the preparation of dyes like malachite green.
Uses of acetophenone
1. It is used as a precursor for the prepration of some resins and fragrances.
2. It is used as a raw material for the synthesis of some drugs like phenylpropanolamine.
Solved Questions
1. How can you distinguish formaldehyde and benzaldehyde?
¬ Benzaldehyde does not reduce Fehling solution, where as formaldehyde reduces it. So, when formaldehyde
is heated with Fehling solution, red precipitate of CH2O is obtained, whereas benzaldehyde does not
O O
H —C—H + 2 CuO Δ
H —C—OH + Cu2O↓
Formaldehyde Fehling's solution Red ppt
2. How can you convert ethanal into methanal?

¬ O O O
[O]
CH3 —C—H CH3 —C—OH CH3 —C—ONa CH4
KMnO4/H+ NaOH (aq.) NaOH/CaO, Δ
Ethanal Ethanoic acid Sod. ethanoate
O aq. KOH, Δ
Cu, 300°C Cl2, hυ
H —C—H CH3OH CH3Cl
Methanal Methanol Chloromethane
Questions
1. How can you distinguish acetaldehyde and actone?
2. For nucleophilic addition reactions, aldehydes are more reactive than ketones, why?
3. Write any two electrophilic addition reactions for banzaldehyde.
4. How can 2, 4-DNP test be utilized to distinguish carbonyl compounds from other campunds?
5. Give an example of:
(a) DNP test (b) Aldol condensation
6. How can you obtain 3-hyrdoxybutanal from ethanal?
7. Write the structure and use of the main product obtained by the reaction of formaldehyde with
ammonia.
8. Identify A, B and C in the following reaction writing related reactions.
I2/NaOH Ag ozonolysis O O
A B C H C C H
Δ Δ
9. Why are aromatic carbonyl compounds less reactive than those of aliphatic ones?
10. Identify an aldehyde, which responds to iodoform test writing justification and related
reactions.
11. Write isomers of C4H3O with their IUPAC names. Which one of them gives iodoform test? Why?
12. What happens when acetophone is:
(a) treated with hydroxylamine.
(b) reduced using Zn. Hg + HCl.

1. Write any five methods for the preparation of aldehydes.
2. Write any five differences between aldehydes and ketones.
3. How can you distinguish?
(a) Methanal and Ethanal (b) Ethanal and Benzaldehyde
(c) Pentan-2-one and Pentan-3-one (d) Benzaldehyde and Phenylethanl
(e) Propanal and Propanone
(a) Methanal into Ethanal (b) Ethanal into Methanal
(c) Ethanal into Propanone (d) Ethanal into propanal
(e) Phenol into benzaldehyde (f) Nitrobenzene into Acetophenone
(g) Propane into 2-hydroxy-2-methyl propanoic acid
5. What happen when:
(a) Methanal reacts with ammonia?
(b) Methanol reacts with Conc. NaOH?
(c) Toluene is treated with chromic anhydride and acetic anhydride and the product is
hydrolyzed?
(d) Propanone is treated with semicarbazide?
(e) Benzaldehyde is treated with alc. KCN?
6. Show your acquaintance on/Write short notes on:
(a) Iodoform test for carbonyl compound
(b) Canizzaro Reaction
(c) Oxidation of aldehydes
(d) Relative reactivities of aldehydes and ketones
7. A carbonyls compound, A, having molecular formula C3H6O is found to decolorise acidified
KMnO4 and responds to 2, 4-DNP test. The compound does not give iodoform test. Identify A,
writing the related reactions. How can the compound A be converted into Ethane?
8. An organic compound 'P' is found to reduce Fehling solutions. 'P' on oxidation using
KMnO4/H+ gives compound 'Q' having same number of C as 'P'. The compound 'Q' responds to
NaHCO3 test and gives as ester 'R' with molecular formula C4H8O2 when reacted with ethanol in
presence of concentrated H2SO4. Identify P, Q and R writing related reactions and write their
IUPAC names.
9. An alkene 'A' on ozonolysis gives two aldehydes 'B' and 'C'. Compound 'B' on clemensen
reduction gives propane while the compound 'C' on treatment with HCN followed by acid
hydrolysis gives 2-hydroxypropanoic acid. Identify A, B and C writing related reactions.
Ans: A = Pent–2–ene, B = Propanal, C = Ethanal)
10. An organic compound 'A' on oxidation using CrO3/Pyridine gives compound 'B'. Both the
compound 'A' and 'B' respond to iodoform test. The compound 'A' is a primary alcohol. Identify
'A' and 'B' writing related reactions. How can the compound A be converted into benzene?
(Ans: A = Ethanol, B = Ethanal)

1. Fehling solution test is not given by 8. When 2‐propanol is heated with Cu at 300 C, gives:
a. Acetaldehyde b. Benzaldehyde a. Acetone b. Acetaldehyde
c. Formaldehyde d. Propanal c. Propene d. Propyne
2. The reagent that is used to detect sugar in urine is: 9. Most reactive carbonyl compound is
a. Bayer’s reagent b. Benedict’s solution a. HCHO b. CH3COCH3
c. AgNO3 d. Tollen’s reagent c. C6H5CHO d. C6H5COCH3
3. The compound having least solubility in water is: 10. A Carbonyl compound is treated with HCN and the
a. Ethanal b. Propanal product is hydrolysed. The final product is
c. Acetophenone d. Methanal a. Cyanohydrin b. carboxylic acid
4. Which of the following reagent reacts with both c. β-hydroxyaldehyde d. α-hydroxy acid
aldehyde and ketone? 11. Active part of benedict reagent is
a. Fehling’s solution b. Grignard’s reagent a. CuO b. Cu
c. Schiff’s reagent d. Tollen’s reagent c. Ag2O d. Ag
5. Clemmenson reduction reaction is carried out by: 12. Methanal and ethanal can be distinguished by
a. H2/Pd b. NH2NH2 + Glycol a. Fehling's solution b. Tollen's reagent
c. LiAlH4/ether d. Zn-Hg/HCl c. I2 + NaOH d. All of the above
6. Calcium acetate on distillation gives: 13. The alkene which gives ethanal only on ozonolysis is
a. Ethane b. Acetone a. 2–methylpropane b. Ethene
c. Acetaldehyde d. Acetic acid c. But-1-ene d. But-2-ene
7. Methanal and ethanal can be distinguished by 14. Which of the following can distinguish
a. KMnO4 b. K2Cr2O7 formaldehyde and benzaldehyde?
c. AgNO3 d. iodoform test a. Fehling's solution b. Tollen's reagent
c. I2+ + NaOH d. NH3
1 2 3 4 5 6 7 8 9 10 11 12 13 14
b b c b d b d a a d a c d a
Carboxylic Acids
and Their Derivatives
OH
HOOC—CH2—C—CH2—COOH
COOH
Citric acid
Citric acid is a carboxylic acid. Naturally, it occurs mainly in citrus fruits like lime, lemon etc. It is a commodity
chemical, and produced in large scale every year by fermentation. It is used as a flavoring and preservative in
food and beverages, especially soft drinks.
13.1 Aliphatic Carboxylic Acids

13.1.1 Introduction
Organic compounds having carboxyl (—COOH) functional group with acidic property are
carboxylic acids.
Example:
COOH OH
CH3—COOH HOOC—CH2—C—CH2—COOH
Acetic acid COOH
Benzoic acid Citric acid
Vinegar is very dilute aqueous solution of acetic acid. Benzoic acid serves as food preservative and
flavouring agent. Citric acid is responsible for sour taste of lemons.
The term carboxyl is a composite word of the term 'carb' derived from carbonyl group (>C=O) and
'oxyl' derived from hydroxyl group (—OH) as:
O O
—C— + —OH —C— OH
Carbonyl Hydroxyl group Carboxyl

δ–
O O O
C C C
O—H O—H O—H
+ δ+
(I) (II) Resonance hybrid

Resonating structures of carboxylic acid
Carboxyl group is resonance hybrid of (I) and (II). Hence, carboxylic acids have their own distinctive
properties and do not show all the properties of carbonyl compounds and alcohols through it seems
to have both carbonyl and hydroxyl part in them.
Carboxylic acids are broadly classified as (i) Aliphatic carboxylic acids and (ii) Aromatic carboxylic
acids, depending upon whether -COOH group is attached to alkyl (R-) chain and aromatic aryl (Ar-)
group respectively.
The aliphatic carboxylic acid may be regarded as derivatives of alkanes in which one or more H-
atoms have been substituted by –COOH group as shown as below:
–H
R—H R—COOH
+ COOH
Alkane Carboxylic acid
The general formula of aliphatic saturated monocarboxylic acids (homologous series) is

CnH2n+1.COOH (exception: Formic acid, HCOOH).
The carboxylic acids, aliphatic as well as aromatic, are further classified as mono-, di-, tri- or poly-
carboxylic acids according to the number of —COOH groups present in a molecule of carboxylic
acid.
Carboxylic Acids and Their Derivaties Unit 13 405
1. Aliphatic monocarboxylic acids: The carboxylic acids containing only one—COOH group per
molecule are called monocarboxylic acids.
Example:
HCOOH CH3—COOH
Formic acid Acetic acid
The open chain aliphatic monocarboxylic acids are also called fatty acids because many higher
members with even number of carbon occur in natural fats and oils as esters in substantial
amount and they can be obtained by their hydrolysis.
The percentages of carboxylic acids in butter.
Saturated carboxylic acids Unsaturated carboxylic acids
Myristic acid (8-13%) Oleic acid (22-29%)

Palmitic acid (25-32%) Linoleic acid (3%)
Stearic acid (8-13%) Linolenic acid (2-10%)
Octadecanoic acid (Stearic acid, C17H35COOH), melting point 70°C

O
17 15 13 11 9 7 5 3 1
OH
18 16 12 10 8 6 4 2
O
15 13 11 9 7 5 3 1
OH
16 14 12 10 8 6 4 2
Hexadecanic acid (Palmitic acid, C15H31COOH), melting point 63°C
O O
9 7 5 3
10
8 6 4 2
1 OH HO
12 11
14 13
Trans -9-Octadecenoic acid
16 15 (Trans-Oleic acid)
17 cis-9-Octadecenoic acid
18
(cis-Oleic acid)
O O
OH OH
CH3
CH3
cis,cis,cis-9,12,15-Octadecatrienoic acid
cis,cis-9,12-Otadecadienoic acid
(Linolenic acid), melting point -11°C
(Linoleic acid), melting point -5°C
2. Aliphatic dicarboxylic acids: The carboxylic acids having two —COOH groups per molecule
are called dicarboxylic acids.
Example:
COOH
COOH
Oxalic acid
(Ethanedioic acid)
3. Aliphatic tricarboxylic acids: The carboxylic acids having three —COOH groups per molecule
are called tricarboxylic acids.
Example:
CH2—COOH
CH—COOH
CH2—COOH
Propane-1,2,3-tricarboxylic acid
13.1.2 Nomenclature
Carboxylic acids are named according to following systems:
1. Common System: Common name of carboxylic acids are given on the basic of the source from
which they are obtained. For example, the name formic acid was given since it was first obtained
by the distillation of red ants (Latin: Formica = ants). Similarly, the name valeric acid is given
since it is naturally found in valerian plant, which is a perennial flowering plant and so on.
Formula IUPAC name Common name Source
HCOOH Methanoic acid Formic acid Ant (Latin: Formica = Red ant)
CH3COOH Ethanoic acid Acetic acid Vinegar (Latin: Acetum = Vinegar )
CH3CH2COOH Propanoic acid Propionic acid Milk (Greek: Protos pion = First fat)
CH3CH2CH2COOH Butanoic acid Butyric acid Butter (Latin: Butyrum = Butter)
CH3 (CH2)3COOH Pentanoic acid Valeric acid Valerian plant
CH3 (CH2)4COOH Hexanoic acid Caproic acid Goat fat ( Latin: Caper = Goat)

The positions of the substituents are indicated by the Greek letters- α, β, γ, δ, etc. The α– carbon
is the one bearing the —COOH group, the next one as β and so on as:
δ γ β α
C—C—C—C—COOH (used in common names)
Example:
CH3 OH
CH3 CH2 CH COOH CH3 CH COOH
α– Methyl butyric acid α–Hydroxy propionic acid
2. Derived system: According to this system, some monocarboxylic acids are named as alkyl
derivatives of acetic acid.
Example: CH3
CH3 CH2 COOH CH3 CH COOH
Methyl acetic acid Dimethyl acetic acid
3. IUPAC system
a. Monocarboxylic acids: The longest chain of carbon atoms including –COOH in monocarboxylic
acid is considered the parent chain, and is named by replacing the –e of the corresponding
parent alkane with –oic acid and hence IUPAC name of monocarboxylic acid is Alkanoic acid.
Carbon is always given as C-1, in numbering the carbon atom in the parent chain as:
5 4 3 2 1 (used in IUPAC names)
C—C—C—C—COOH
The positions of the substituents are indicated by the number before the names of substituents,
where the positions and names are separated by hyphen.
Example:
CH3 Cl
CH3—CH2—CH—COOH CH3—CH—CH2—COOH CH2—CH2—COOH
2–Methylbutanoic acid 3–Chlorobutanoic acid
3-Phenylpropanoic acid
b. Dicarboxylic acids: IUPAC name of dicarboxylic acid is Alkanedioic acid. The suffix –dioic acid
is added to the name of parent alkane containing the same number of carbon atoms.

HOOC-COOH Ethanedioic acid Oxalic acid
HOOC-CH2-COOH Propanedioic acid Malonic acid
HOOC-(CH2)2-COOH Butanedioic acid Succinic acid
HOOC-(CH2)3-COOH Pentanedioic acid Glutaric acid
HOOC-(CH2)4-COOH Hexanedioic acid Adipic acid
HOOC-(CH2)5-COOH Heptanedioic acid Pimelic acid
HOOC-(CH2)6-COOH Octanedioic acid Suberic acid
HOOC-(CH2)7-COOH Nonanedioic acid Azelaic acid
c. Tricarboxylic acids:
i. If more than two carboxyl groups are bonded to unbranched longest carbon chain, carbon
atoms of the carboxyl groups are not included in the parent chain.
COOH
CH2—COOH
CH—COOH HOOC—CH2—CH2—CH—CH2—COOH
CH2—COOH Butane-1,2,4-tricarboxylic acid
Propane–1,2,3–tricarboxylic acid
ii. If all carboxyl groups are not directly bonded to unbranched longest carbon chain, the
longest chain of carbon atoms between two carboxyl groups is selected as parents chain.
Carbon atoms of the two carboxyl groups are included in the parent chain and the
remaining is treated as substituent.
CH2COOH
HOOC—CH2—CH—CH2—CH2—COOH
3-(Carboxymethyl)Hexane-1,6-dioic acid
Self Test
13.1 What are carboxyl acids? Why – COOH is called carboxyl group? Give examples of mono-, di-
and tricarboxylic acids.
13.2 Write the isomers of the compound with formula C2H4O2 and give their IUPAC name.
13.3 Write the isomers of the compound with formula C3H6O2 and give their IUPAC name.
Some Other Examples of Carboxylic acid

O O
H—C—COOH CH3—C—COOH H2C = CH —COOH H—C≡C—COOH
Oxoethanoic acid 2-Oxopropanoic acid Propenoic acid Propynoic acid
(Glyoxalic acid) (Pyruvic acid/acetyl formic acid ) (Acrylic acid) (Propiolic/ propargylic acid
H COOH H COOH
C C
C C
CH3—CH = CH—COOH H COOH HOOC H
2-Butenoic acid cis-Butenedioic trans-Butenedioic
acid (maleic acid) acid (Fumaric acid)
m pt. = 130°C m pt. = 302°C
H H
H HO—C—COOH
HO—C—COOH
CH3—C—COOH
H—C—COOH HO—C—COOH
OH
H H
2-Hydroxypropanoic acid
(Lactic acid) 2-Hydroxybutanedioic acid 2,3- Dihydroxybutanedioic acid
(Malic acid) (Tartaric acid)
13.1.3 General Methods of Preparation of Monocarboxylic Acids

The straight carbon chain aliphatic carboxylic acid upto C6 and those of even carbon number upto
C18 are commercially available. Other carboxylic acids can be prepared by the methods outlined
below.
1. From primary alcohols and aldehydes (By oxidation): Oxidation of primary alcohol or
aldehyde by using oxidizing agents like Na2Cr2O7/H2SO4, K2Cr2O7/H2SO4, KMnO4/H2SO4
gives carboxylic acid of same number of carbon.
K2Cr2O7 (aq.)/H+, Δ [O], K2Cr2O7 (aq.)/H+

RCH2OH + [O] RCHO RCOOH
–H2O Δ
1° alcohol Aldehyde Carboxylic acid
Example:
K2Cr2O7 (aq.)/H+, Δ [O], K2Cr2O7 (aq.)/H+
CH3CH2OH + [O] CH3CHO CH3COOH
–H2O Δ
Ethanol Ethanal Ethanoic acid
2. From nitriles (By hydrolysis): Nitrile synthesis of carboxylic acid: Hydrolysis of nitrile by
boiling with aqueous solution of mineral acid or alkali gives carboxylic acid. The reaction is
popularly known as nitrile synthesis of carboxylic acid.
H+
(acid) R—COOH + NH4+
R—C ≡ N + H2O
OH¯
R—COO¯ + NH3
(base)
(i) Acidic hydrolysis of nitrile:
O O
dil HCl H2O/HCl
R—C ≡ N + H2O R—C—NH2 R—C—OH + NH4Cl
Δ Δ Carboxylic acid
Alkanenitrile Alkanamide
(Alkyl cyanide)
Example:
O O
dil HCl H2O/HCl
CH3—C ≡ N + H2O CH3—C—NH2 CH3—C—OH + NH4Cl
Δ Δ
Ethanamide Ethanoic acid
Ethanenitrile
(Methyl cyanide) (Acetic acid)
(ii) Alkaline hydrolysis of nitrile: If aqueous NaOH is used for the hydrolysis of alkyl nitrile,
the sodium salt of carboxylic acid is formed at first, which upon acidification gives the
corresponding carboxylic acid.
O O O
NaOH H2O/NaOH aq. HCl
R—C ≡ N + H2O R—C—NH2 R—C—ONa R—C—OH + NaCl
Δ –NH3
Alkanenitrile Alkanamide Sodium carboxylate Carboxylic acid
(Alkyl cyanide)
Example:
O O O
NaOH H2O/NaOH aq. HCl
CH3—C ≡ N + H2O CH3—C—NH2 CH3—C—ONa CH3—C—OH + NaCl
Δ –NH3
Ethanenitrile Ethanamide Sodium ethanoate Ethanoic acid
(Methyl cyanide) (Sodium acetate)
The nitrile synthesis of carboxylic acid is a good synthetic method for preparing carboxylic
acids and has an advantage of increasing the length of a carbon chain than that of the parent
alkyl halide as:
Example:
SOCl2 KCN(alc) H2O/H+

CH3CH2OH CH3CH2Cl CH3CH2CN CH3CH2COOH
pyridine, Δ Δ Δ
Ethanol Chloroethane Propanenitrile Propanoic acid
3. From Grignard reagent: Grignard synthesis of carboxylic acid (Carbonation): When carbon
dioxide gas is bubbled through ether solution of the Grignard reagent followed by hydrolysis,
carboxylic acid is obtained. This reaction is also carried out when ether solution of Grignard
reagent is poured over crushed dry ice followed by hydrolysis. Dry ice serves not only as a
source of CO2 but also serves as cooling agent.
O O
δ– δ+ δ– dry ether H2O/H+
RMg X + O=C=O R—C—OMgX R—C—OH + Mg(OH)X
inert atm.
Adduct Carboxylic acid
Grignard reagent
Example:
O O
CH3MgI + O=C=O CH3—C—OMgI CH3—C—OH + Mg(OH)I
inert atm.
Methyl magnesium Ethanoic acid
iodide
Carboxylic acid thus obtained always has one carbon atom more than that of the alkyl group of
parent Grignard reagent and hence has advantage of increasing the length of the carbon chain.
Note:
Preparation of carboxylic acid
KMnO4/H+
CH3COOH
same carbon number
CH3CH2 OH KCN(alc) H2O/H+

CH3CH2CN CH3CH2COOH
one carbon more
SOCl2
CH3CH2Cl
reflux (i) CO2
Mg (ii) H2O/H+
CH3CH2MgCl CH3CH2COOH
dry ether one carbon more
Self Test
13.4 Convert ethanol into:
i. Ethanoic acid ii. Propanoic acid
4. From dicarboxylic acids (Decarboxylation): When a dicarboxylic acid having two carboxyl
groups attached to the same carbon atom is heated strongly, decarboxylation takes place and
monocarboxylic acid is obtained.
COO H
Δ R—CH2—COOH + CO2 ↑
R HC
COOH 160°
Monocarboxylic acid
Dicarboxylic acid
(both COOH are bonded to same carbon)
Examples:
COO H Δ
HCOOH + CO2 ↑
COOH (160°C)
Formic acid
Oxalic acid
COO H Δ
H2C CH3—COOH + CO2 ↑
COOH Acetic acid
Malonic acid
Effect of heat on dicarboxylic acids:

When dicarboxylic acids are heated, different products are obtained. The nature of products formed depends on the number
of carbon atoms intervening two carboxyl groups.
i. Dicarboxylic acids with one or without intervening carbon atom between two –COOH groups on simple heating produce
monocarboxylic acid with elimination of CO2.
COO H Δ
HCOOH + CO2 ↑
COOH (160°C)
Formic acid
Oxalic acid
COO H Δ
H2C CH3—COOH + CO2 ↑
COOH Acetic acid
Malonic acid
ii. Dicarboxylic acids with two or three intervening carbon atoms between two –COOH groups on heating undergo
cyclization with elimination of a molecule water to yield acid anhydrides with five or six membered ring respectively.
O O
C C
CH2 OH CH2
O + H2O
Δ CH2
CH2 OH
C C
O O
Succinic acid Succinic anhydride
iii. Dicarboxylic acids with four or five intervening carbon atoms between two –COOH groups on heating loses a molecule
water and CO2 to yield cyclic ketones with five or six membered ring respectively.
CH2 CH2
CH2 COOH CH2
C = O + CO2 + H2O
Δ CH2
CH2 COOH
CH2 CH2
Cyclopentanone
Adipic acid
iv. Dicarboxylic acids with more than five intervening carbon atoms between two –COOH groups undergo intermolecular
dehydration to give linear polymer.
O O O O
Δ
HO—C—(CH2)6—C—O H + HO—C—(CH2)6—C—OH –H2O
O O O O
Suberic acid
HO—C—(CH2)6—C—O—C—(CH2)6—C—OH
5. From sodium alkoxide (alkali alcoholates): When pure and dry carbon monoxide is passed
through sodium alkoxide (alkali alcoholate) under pressure, sodium carboxylate is obtained,
which on acidification with mineral acid gives monocarboxylic acid.
pressure aq. HCl
RONa + CO RCOONa RCOOH + NaCl
Δ
Sodium alkoxide Carboxylic acid
Example:
pressure aq. HCl

CH3O Na + CO CH3COONa CH3COOH + NaCl
Δ
Sodium methoxide Ethanoic acid
6. From trihaloalkanes: Hydrolysis of trihaloalkane containing three halogen atoms at the same
carbon atom with hot and aqueous solution of caustic alkali (NaOH or KOH) followed by
acidulation gives corresponding carboxylic acid.
X K OH OH O
R C X + K OH R C R C OH
– 3 KX OH – H2O
X K OH OH
Trihaloalkane 3 molecules – H2O excess KOH
Unstable
O O
dil. HCl
KCl + R C OH R C OK
acidification
Carboxylic acid
Example:
Cl K OH OH O
H C Cl + K OH H C H C OH
– 3 KCl OH – H2O
Cl K OH OH
Chloroform – H2O excess KOH
O O
dil. HCl
KCl + H C OH H C OK
acidification
Formic acid
Cl K OH OH O
CH3 C Cl + K OH CH3 C CH3 C OH
– 3 KCl OH – H2O
Cl K OH OH
1,1,1-Trichloroethane – H2O excess KOH
O O
dil. HCl
KCl + CH3 C OH CH3 C OK
acidification
Acetic acid
Hydrolysis of fat gives a mixture of monocarboxylic acids which can be fractionally distilled to get in a purity of over 90%
straight chain monocarboxylic acid with 6 – 18 carbon atoms of even number of carbon atoms.
This is the most important commercial source of aliphatic monocarboxylic acid.
13.1.4 Physical Properties of Monocarboxylic Acids

1. Physical state: The first three members (C1, C2, C3) of aliphatic monocarboxylic acids are
colourless liquids with pungent smell. The next three members (C4, C5, C6) are oily liquids with
unpleasant odour of rancid butter and higher members are colourless waxy solids and do not
have distinct odour because of their low volatility.
2. Solubility: Carboxylic acids are polar and form intermolecular hydrogen bonds with water. The
first four members of carboxylic acids (C1 to C4) are miscible with water due to formation of
effective hydrogen bonding between the carboxylic acid and water.
δ+
H
δ- δ+ δ-
O '''''''''''''''''' H O
δ+
R C δ- δ+ δ- δ+
O H O H
''''''''''''''''''''
δ+
H
The carboxylic acid up to five carbon atoms are partially soluble, and the higher acids are
insoluble in water. Solubility of the carboxylic acid decreases rapidly with increase in the size of
water insoluble hydrophobic alkyl part of the acid.
3. Boiling Point: The boiling points of lower member of carboxylic acids are higher than that of
alcohols of comparable molecular masses. This is due to the fact that a pair of carboxylic acid
molecules are held together by two intermoleular hydrogen bonds and, it is stronger (due to
formation of special two point hydrogen bond) than those in alcohols. These two carboxylic
acids exist as cyclic dimers. Also, O–H bond of carboxylic acid is more polar than O–H bond of
alcohol due to electron withdrawing effect of carbonyl group (>C = O) in carboxylic acid.
δ+ δ-
δ-
O '''''''''''''''''' H O δ+
δ– δ+ δ–
δ+
δ-
C R R O ''''''''''''''''''''''' H O
R C δ- δ+
O
O H ''''''''''''''''''''
H R
Intermolecular H-bonding between a δ+
pair of acid (stronger than alcohols)

Cyclic dimer of carboxylic acids between a pair of alcohols
Self Test
13.5 Saturated monocarboxylic acid have higher melting point as compare to their unsaturated
analog. Explain.
13.6 Account for the fact that propanoic acid has higher boiling point (b. pt. 141°C) than that of the
alcohol of comparable molecular masses, n–butyl alcohol (b. pt. 118°C).
13.7 The boiling point of methanoic acid is higher than ethanol though they have same molecular
mass. Explain.
13.1.5 Chemical Properties of Monocarboxylic Acids

The chemical properties of monocarboxylic acids can be discussed under following heading:
A. Reaction due to H- atom of the —COOH group: Acidic Nature:
Carboxylic acids are the most acidic of all organic compounds. Carboxylic acids undergo
ionization when dissolved in water and produce H3O+ ions, which is responsible for their acidic
behaviour. In aqueous solution, there exists a measurable equilibrium between acid and H3O+.
RCOOH + H2O RCOO + H3O+

Carboxylate ion Hydronium ion
According to law of mass action,

[RCOO–] [H3O+]
Keq = [RCOOH] [H O]
2
In very dilute solution,

[RCOO–] [H3O+]
Keq [H2O] = Ka = [RCOOH]
Here, Ka is ionization constant of the acid. Greater the value of Ka, more acidic is the acid. Hence,
acidic strength can be expressed in terms of Ka or pKa of the acid, pKa = -log Ka
The following reactions prove the acidic nature of carboxylic acids.
1. Litmus test: Aqueous carboxylic acid turns blue litmus red. This is due to the presence of H3O+
ion in aqueous solution.
Carboxylate ion Hydronium ion
2.. Reaction with active metals: Carboxylic acid reacts with active metals like Na, K, Zn, Mg, etc.
to liberate hydrogen gas.
2 RCOOH + 2 Na 2 RCOONa + H2↑
Carboxylic acid Sodium carboxylate
Example:
2 CH3COOH + 2Na 2CH3COONa + H2↑
Ethanoic acid Sodium ethanoate
(Sodium acetate)
2 CH3COOH + Zn (CH3COO)2Zn + H2↑

Zinc acetate
3. Reaction with metal oxides: Carboxylic acid reacts with metal oxides to give corresponding
salts of carboxylic acid (carboxylate) and water.
2 RCOOH + Na2O 2 RCOONa + H2O
Sodium oxide
2 CH3COOH + Na2O 2 CH3COONa + H2O

Ethanoic acid Sodium oxide
2 CH3COOH + CaO (CH3COO)2Ca + H2O

Ethanoic acid Quick lime Calcium ethanoate
(Calcium acetate)
4. Reaction with caustic alkali: Carboxylic acid reacts with caustic alkali like NaOH or KOH, to
give corresponding salt of carboxylic acid and water.
RCOOH + NaOH RCOONa + H2O
CH3COOH + KOH CH3COOK + H2O

Potassium ethanoate
(Potassium acetate)
Note:
The concentration of ethanoic acid (acetic acid) in vinegar may be determined by titrating the vinegar solution with sodium
hydroxide solution using phenolphthalein indicator.
5. Reaction with metal carbonates and bicarbonates: Test of carboxylic acids: Carboxylic acid
reacts with sodium carbonate and sodium bicarbonate giving brisk effervescence of carbon
dioxide. This reaction serves as the test of the carboxylic acid.
2 RCOOH + Na2CO3 2RCOONa + CO2↑ + H2O
RCOOH + NaHCO3 RCOONa + CO2↑ + H2O

(Sodium bicarbonate)
Example:
CH3COOH + NaHCO3 CH3COONa + CO2↑ + H2O
Note:
The two important classes of organic compound with acidic nature which change blue litmus red are carboxylic acids and
phenols. However, phenols are weak acid and unable to decompose sodium carbonate and bicarbonate. Hence, reaction of
carboxylic acid with sodium carbonate and bicarbonate can be used to dintinguish carboxylic acids from phenols and other
organic acids.
6. Reaction with ammonia: Carboxylic acids react with ammonia to form ammonium salts
(ammonium carboxylate), which upon heating give amides.
RCOOH + NH3 RCOONH4 RCONH2 + H2O
Δ
Self Test
13.8 Write the suitable chemical test to distinguish between the following pairs of compounds:
i. Ethyl alcohol and acetic acid. ii. Acetone and acetic acid.
iii. Phenol and acetic acid. iv. Phenol and benzoic acid
Explanation for acidic nature of carboxylic acid:

In aqueous solution, there exists a measurable equilibrium between acid and H3O+.

Carboxylic acid Carboxylate ion Hydronium ion
O¯ O
O
R—C R—C R—C –
O O
O¯
Resonance hybrid
(III) (IV)
Resonance structure of
carboxylate ion
Since the carboxylate ion (conjugate base of the carboxylic acid) is stabilized by resonance, its
corresponding acid (carboxylic acid) is fairly acidic.
Note:
Conjugate base of the strong acid is relatively stable.
Though carboxylic acid and alcohol both contain –OH group, alcohol is far less acidic than
carboxylic acid due to the absence of resonance in alkoxide ion.
–
R—O—H R — O + H+
Alkoxide ion
Alcohol (highly unstable)
X-ray and electron-diffraction measurements show that the two carbon to oxygen bonds in carboxylate ion are of equal
length. This fact supports that carboxylate ion is a resonance hybrid and each resonating structure has equal contribution.
1.27Å O
1.23Å O
H—C
H—C 1.27Å O
1.36Å OH
Carboxylic acids are stronger acids than phenols. In resonance structures of carboxylate ion
(Structures III and IV), the negative charge is identically distributed over two oxygen atoms
while in resonance structure of phenoxide ion, it is present in oxygen and also in carbon (electro
positive element). Hence carboxylate ion is more stabilized than phenoxide ion. Therefore,
carboxylic acids ionize to the greater extent than phenols and behave as strong acids than
phenols.
δ–
O
O
δ− δ−
R—C
O
δ−
Resonance hybrid
(Phenoxide)
Distinction between alcohols, phenols and carboxylic acids:

Property Alcohols Phenols Carboxylic acids
1. Action of litmus No action Turn blue litmus red Turn blue litmus red
2. Action of NaHCO3 No action No action Effervescence of CO2
3. Action of NaOH No action Form sodium phenoxide Form sodium carboxylate
4. Action of FeCl3 No action Form violet blue, red etc. No action
Effect of Substituent(s) on Acidity of Carboxylic Acids

a. Effect of electron donating substituents
Any factor that destabilises the carboxylate ion decreases the acidity of the acid. The electron-
donating (releasing) substituent donates electron, intensify the negative charge on carboxylate
ion and destabilizes the carboxylate ion and thus decreases the acidic nature of the
corresponding carboxylic acid.
O
G C
O
G= donates electron
destablises the anion by intesifying negative charge
decreases the acidic nature of the acid
Example:
Alkyl groups behave as electron releasing groups. The sequential order of electron donating
effect is: H– < CH3– < CH3CH2– < CH3CH2CH2–.
Hence formic acid is more acidic than acetic acid and acetic acid is more acidic than propionic
acid and so on.
Acidic order: HCOOH > CH3COOH > CH3CH2COOH.

Compound Ka pKa
HCOOH 1.77 ×10-4 3.75
CH3COOH 1.75 ×10-5 4.74
CH3CH2COOH 1.3 ×10-5 4.87
b. Effect of electron withdrawing substituents
Any factor that stabilises the carboxylate ion increases the acidity of the acid. The electron-
withdrawing substituent withdraws electron, disperse the negative charge on carboxylate ion
and stabilizes the carboxylate ion and thus increases the acidic nature of carboxylic acid.
O
G C
O
G = withdraws electron
stablises the anion by dispersing negative charge
h d f h d
The following factors also govern the acidity of carboxylic acids due to the electron-
withdrawing substituents:
Case I: Number of substituents:
Chloride (Cl—) withdraws electron due to -I effect. Greater the number of electron withdrawing
substituents, higher is the acidic nature of acids. Hence chloroacetic acid is more acidic than
acetic acid. Dichloroacetic acid is even more acidic than chloroacetic acid and so on.
H H Cl Cl
H C COOH < Cl C COOH < Cl C COOH < Cl C COOH
H H H Cl
Acetic acid Chloroacetic acid Dichloroacetic acid Trichloroacetic acid
Ka = 1.75 ×10-5 Ka = 136 ×10-5 Ka = 5530 ×10-5 Ka = 23200×10-5
Case II: Nature of substituents:

The electron withdrawing inductive effect (-I effect) of halogen is F > Cl > Br > I. Hence
fluoroacetic acid is more acidic than chloroacetic acid, chloroacetic acid is more acidic than
bromoacetic acid and iodoacetic acid is the least acidic among the four haloacetic acids.
Compound Common name Ka pKa
F CH2COOH Fluoroacetic acid 260 ×10-5 2.59

Cl CH2COOH Chloroacetic acid 136 ×10-5 2.87
Br CH2COOH Bromoacetic acid 125 ×10-5 2.90

I CH2COOH Iodoacetic acid 67×10-5 3.16
Case III: Position or location of substituents:
δ γ β α O
C C C C C
O
Electron withdrawing inductive effect (-I effect) decreases rapidly with distance from the carboxyl
group.
Compound Common name Ka
CH3—CH2—CH2—COOH Butyric acid 1.52 ×10-5
Cl α-Chlorobutyric acid 139 ×10-5

CH3—CH2—CH—COOH
Cl β-Chlorobutyric acid 8.9 ×10-5

CH3—CH—CH2—COOH
Cl γ-Chlorobutyric acid 2.96 ×10-5

CH2—CH2—CH2—COOH
Electron withdrawing inductive effect (-I) effect decreases rapidly with distance or number of carbon
atoms from the carboxyl group and becomes non effective after four atoms. Hence, β-Chlorobutyric
acid is less acidic than α-Chlorobutyric acid, γ-Chlorobutyric acid is less acidic than β-Chlorobutyric
acid and so on.
Self Test
13.9 Why is methanoic acid stronger than ethanoic acid?
13.10 Which one of the following is a stronger acid in each of the following pairs?
i. Propionic acid and acetic acid.
ii. Chloroacetic acid and acetic acid
iii. Chloroacetic acid and dichloroacetic acid.
iv. α-chloropropionic acid and β-chloropropionic acid.
v. Acetic acid and benzoic acid.
B. Reaction due to replacement of —OH part of —COOH group:

A category of reactions given by carboxylic acids where the –OH part of the –COOH group is
replaced by electron rich species like —Cl, —OR', —NH2 and —OCOR' groups to yield acid chloride
(R—COCl), ester (R—COOR'), acid amide (R—CONH2) and acid anhydride (R—COOCOR')
respectively. These compounds are, therefore called functional derivatives of carboxylic acids.
O O G = Cl (acid chloride)
—OH = OR (ester)
R—C R—C = NH2 (acid amide)
+G
OH G = OCOR (acid anhydride)
Acid derivative
1. Formation of acid chlorides:

Carboxylic acids react with phosphorus trichloride (PCl3), phosphorus pentachloride (PCl5) or
thionyl chloride (SOCl2) to give corresponding acid chlorides.
Examples
50°C
3 CH3COOH + PCl3 3 CH3COCl + H3PO3
Acetyl chloride Phosphorous acid
100°C
CH3COOH + PCl5 CH3COCl + POCl3 + HCl
Ethanoyl chloride Phosphorus
(Acetyl chloride) oxychloride
pyridine, reflux
CH3COOH + SOCl2 CH3COCl + SO2 ↑ + HCl ↑
Thionyl chloride is more conveniently used than that of phosphorus chlorides to prepare acid
chloride from carboxylic acid since the products formed besides the acid chloride are gases
(HCl and SO2), which can be easily separated from the acid chlorides. Any excess of thionyl
chloride is easily removed from the reaction by distillation due to its low b.pt. (79°C).
2. Formation of acid anhydrides: Dehydration of carboxylic acid: Monocarboxylic acid except
formic acid on heating with strong dehydrating agent like P2O5 or conc. H2SO4 undergoes
intermolecular dehydration (elimination of water molecule) into acid anhydrides.
O O
R C OH P2O5 R C
O + H2O
R C OH Δ R C
O O
Alkanoic anhydride
Example: (Acid anhydride)
O O
CH3 C OH P2O5 CH3 C
O + H2O
CH3 C OH Δ CH3 C
O O
two molecules of ethanoic acid Ethanoic anhydride
(Acetic anhydride)
Note:
Formic anhydride is unknown because formic acid undergoes dehydration with conc. H2SO4 to give CO and water.
Conc.H2SO4
HCOOH CO + H2O
3. Formation of ester:
The carboxylic acids are converted into esters as follows:
i. Direct method: When a mixture of carboxylic acid and alcohol is heated in the presence of a
little mineral acid like conc. H2SO4 or dry hydrogen chloride, ester is formed. This reaction
is called esterification.
O O
H+
R—C + R'—OH R—C + H2O
OH OR'
ester
Example:
Conc. H2SO4
CH3COOH + HOCH2CH3 CH3COOCH2CH3 + H2O
Ethanol Ethyl ethanoate
(Ethyl acetate)
Note:
i. This reaction can be used to test alcohol or carboxylic acid in laboratory because of distinct fruity smell of ester.
ii. It should be noted that always –OH group from the acid and H-atom from the alcohol are eliminated as water in esterification
reaction.
The reaction is reversible. A reversible reaction is not generally a good choice from
synthetic point of view due to low yield of product. Therefore, the indirect method as
given below is the method of choice for quantitative prepration of ester. However, in the
esterification, the equilibrium can be shifted in the forward direction for quantitative yield
of ester by using one of the reactants in excess and/or removing one of the products as
soon as it is formed. Therefore, in order to shift the reaction in forward direction water is
removed as soon as it is formed.
Reactivity of alcohol: CH3OH > 1° > 2° > 3°
Reactivity of acid: HCOOH>CH3COOH>RCH2COOH>R2CHCOOH> R3CCOOH
ii. Indirect method: Carboxylic acids are frequently converted into their esters via the acid
chlorides since it is irreversible and go to completion.
O O O
SOCl2 R'OH
R—C R—C R—C + HCl
pyridine/reflux
OH Cl OR'
acid chloride ester
iii. Diazomethane method: Carboxylic acids react with diazomethane to produce methyl
esters.
RCOOH + CH2N2 RCOOCH3 + N2
4. Formation of amide: Amides are prepared from carboxylic acids as follows:
i. Direct Method: Carboxylic acid reacts with ammonia to form ammonium carboxylate
(ammonium salt), which upon strong heating loses H2O to give amide.
O O O
Δ
R—C + NH3 R—C R—C + H2O
OH ONH4 NH2
Ammonium carboxylate Acid amide
Example:
CH3COOH + NH3 CH3COONH4 CH3CONH2 + H2O

Δ
Ammonium acetate Ethanamide
(Acetamide)
ii. Indirect Method: Carboxylic acids are converted into amide via the formation of acid
chloride, when acid chloride is treated with ammonia.
O O O
Pyridine NH3
R—C + SOCl2 R—C R—C + HCl
OH Cl NH2
Acid chloride Acid amide
Example:
Pyridine NH3
CH3COOH + SOCl2 CH3COCl CH3CONH2 + HCl
Ethanoyl chloride Ethanamide
(Acetamide)
C. Reaction due to >C= O part of — COOH group:

Partial Reduction: Formation of alcohols: Carboxylic acid can be reduced to the corresponding
primary alcohol with LiAlH4 or with hydrogen in the presence of catalyst like copper chromite
(CuCr2O4)
Example:
LiAlH4
CH3COOH CH3CH2OH + H2O
pressure
Ethanoic acid Ethanol
Note:
Reduction of carboxylic acids into alcohols does not take place with NaBH4.
D. Reaction due to complete—COOH group:

1. Complete reduction: Formation of alkane: On prolonged reduction of carboxylic acids with HI
in red phosphorus at about 200°C in a sealed tube, corresponding alkanes are obtained, where -
COOH group is reduced to -CH3 group.
red P
RCOOH + 6 HI RCH3 + 2 H2O + 3 I2
200°C
alkane
red P
CH3COOH + 6 HI CH3—CH3 + 2 H2O + 3 I2
200°C
Ethane
2. Formation of carbonyl compounds: When vapours of carboxylic acids are passed over heated
alumina or mangenous oxide at 300°C, carbonyl compounds are formed.
a. Formic acid gives formaldehyde.
O O O
MnO, 300°C
H—C—OH + H O—C—H H—C—H + CO2 ↑ + H2O
2 molecules of formic acid Formaldehyde
b. A mixture of formic acid and other carboxylic acid gives aldehyde other than formaldehyde.
O O O
MnO, 300°C
R—C—OH + H O—C—H R—C—H + CO2 ↑ + H2O
Carboxylic acid Formic acid Aldehyde
Example:
O O O
MnO, 300°C
CH3—C—OH + H O—C—H CH3—C—H + CO2 ↑ + H2O
Acetic acid Formic acid Acetaldehyde
c. All carboxylic acids other than formic acids give ketones.
O O O
MnO, 300°C
2 molecules of carboxylic acid Ketone
Example:
O O O
MnO, 300°C
CH3—C—OH + H O—C—CH3 CH3—C—CH3 + CO2 ↑ + H2O
2 molecules of acetic acid Acetone
E. Reaction due to alkyl (R—) group of carboxylic acid:

1. α-Halogenation of aliphatic acids: Hell-Volhard-Zelinsky reaction: Reaction with halogens:
Carboxylic acid having α-hydrogen atom reacts with halogens (Cl2 or Br2) in presence of red
phosphorus as a catalyst to yield α-halo carboxylic acid. This reaction is known as Hell-
Volhard-Zelinsky (HVZ) reaction. For example,
CH3 O CH3 Br O
red P4/Br2
CH3—CH—CH2—C—OH CH3 CH CH C—OH
— — —
–HBr
Isovaleric acid α-Bromo isovaleric acid
Polyhalogenation is possible, if halogen is in excess.For example,

O O O O
red P4/Cl2 red P4/Cl2 red P4/Cl2
CH3 C—OH
— CH2Cl—C—OH CHCl2—C—OH CCl3—C—OH
–HCl –HCl –HCl
Acetic acid Chloroacetic acid Dichloroacetic Trichloroacetic
acid acid
The function of the phosphorus is to convert a little of the acid into acid halide. The acid and acid halide sooner or later
undergo α-halogenation into α-halo acid.
P + X2 PX3
3 R—CH2—COOH + PX3 3 R—CH2—COX + H3PO3

X
R—CH2—COX + X2 R—CH—COX + HX
X X
R—CH—COX + R—CH2—COOH R—CH—COOH + R—CH2—COX
α- halo acid
Formic acid does not undergo Hell-Volhard-Zelinsky reaction (α-halogenation) due to absence of α–hydrogen.
This reaction is not applicable to fluorine and iodine.
2. Oxidation:
a. When carboxylic acid is treated with H2O2 as a mild oxidizing agent, the alkyl group is oxidized
at the β- position to form β- hydroxy carboxylic acid.
OH
H2O2
CH3—CH2—CH2—COOH CH3—CH—CH2—COOH + H2O
[O]
Butyric acid (β-hydroxybutyric acid)
b. Selective oxidation: On the other hand, when carboxylic acid is heated with SeO2 (selenium
dioxide) as a selective oxidizing agent, the alkyl group is oxidized at the α- position to form α-
keto acid.
O
SeO2
CH3—CH2—COOH CH3—C—COOH + H2O
[O]
Propionic acid 2-Ketopropanoic acid
(α-ketopropionic acid)
F. Reactions involving salt of carboxylic acids

1. Reaction involving calcium salt of carboxylic acid: When calcium salt of carboxylic acid is
strongly heated (dry distillation), carbonyl compound is formed.
a. Dry distillation of calcium salt of formic acid gives formaldehyde.
O O O
Δ
(H—C—O)2 Ca + Ca (O—C—H)2 2 H—C—H + 2 CaCO3
2 molecules of calcium formate Formaldehyde
b. Dry distillation of a mixture of calcium salt of formic acid and salts of other acid give
aldehydes other than formaldehyde.
O O O
Δ
(R—C—O)2 Ca + Ca (O—C—H)2 2 R—C—H + 2 CaCO3
Calcium carboxylate Calcium formate Aldehyde
Example:
O O O
Δ
(CH3—C—O)2 Ca + Ca (O—C—H)2 2 CH3—C—H + 2 CaCO3
Calcium acetate Calcium formate Acetaldehyde
c. Dry distillation of calcium salts of carboxylic acids other than formic acid gives simple
ketones.
O O O
Δ
2 molecules of calcium carboxylate Ketone
Example:
O O O
Δ
(CH3—C—O)2 Ca + Ca (O—C—CH3)2 2 CH3—C— CH3 + 2 CaCO3
2 molecules of calcium acetate Acetone
d. Dry distillation of a mixture of different calcium carboxylates gives mixed ketone. But this
method gives a mixture of ketone.
O O O
Δ
(R—C—O)2 Ca + Ca (O—C—R')2 2 R—C—R' + 2 CaCO3
2 molecules of different calcium carboxylate Mixed ketone
Example:
O O O
Δ
(CH3—C—O)2 Ca + Ca (O—C—C2H5)2 2 CH3—C— C2H5 + 2 CaCO3
Calcium acetate Calcium propionate Butanone
2. Reactions involving silver salt of carboxylic acid: Silver salt of carboxylic acid reacts with
chlorine or bromine in carbon tetrachloride as solvent to form corresponding alkyl halide. This
is called Hunsdiecker or Borodine-Hunsdiecker reaction (1935).
RCOOAg+ Cl2 RCl +CO2 + AgCl

RCOOAg+ Br2 RBr +CO2 + AgBr
Note:
Iodine, however, forms ester with silver salt of carboxylic acid. This is called Birnbaum-Simonini reaction(1892).
2 RCOOAg+ I2 RCOOR + CO2 + 2 AgI

ester
3. Sodalime decarboxylation: When sodium or potassium salt of carboxylic acid is heated with
sodalime, alkane havine one carbon less than the acid is formed. The reaction involves removal
of carbon dioxide in presence of sodalime hence called sodalime decarboxylation.
CaO, Δ
R—COONa + NaO H R—H + Na2CO3
Example:
CaO, Δ
CH3—COONa + NaO H CH4 + Na2CO3
This reaction is utilized in decreasing the carbon chain in organic conversion.

4. Kolbe's electrolytic decarboxylation (1849): Electrolysis of a concentrated aqueous solution of
sodium or potassium salt of carboxylic acid gives higher alkane at anode.
-
RCOONa RCOO + Na +
H2O H+ + OH–
At anode, 2 RCOO– R—R + 2CO2 + 2e–

Alkane
At cathode,
H+ + e– H
H+ + H H2
Since discharge potential of H+ is lower than that of Na+, H+ is preferrably discharged.
5. Reactions involving ammonium salt of carboxylic acid:
a. when ammonium salt of carboxylic acid is heated alone, amide is formed.
O O
Δ
R—C—ONH4 R—C—NH2 + H2O
Ammonium carboxylate Amide
b. when ammonium salt of carboxylic acid is heated with P2O5, nitrile is formed.
O
P2O5, Δ
R—C—ONH4 R—C ≡ N + 2H2O
Ammonium carboxylate Nitrile
Formic Acid
Formic acid is the the first member of aliphatic monocarboxylic acid. Its name is derived from Latin
word "Formica" meaning "ant" since it was obtained from distillation of red ants for the first time. It
occurs naturally in insects like bees, ants, wasps, etc. It is colourless liquid with pungent odour with
boiling point 100.5°C. It is soluble in water alcohol, ether, etc.
13.1.6 Laboratory Preparation

Principle
Formic acid is prepared in the laboratory by heating crystalline oxalic acid with anhydrous glycerol
at about 110oC.
COOH
glycerol
.2H2 O HCOOH + CO2 + 2H2O
COO H 110°C

i. Oxalic acid reacts with glycerol to form glycerol-monooxalate.
H O O H O O
H—C—O H + HO—C—C—OH. 2H2O H—C— O—C—C—O—H + 3H2O
H—C—O H 110°C
H—C—O H
H—C—O H H—C—O H
H H
Glycerol
Glycerol-monoxalate (ester)
ii. Glycerol-monooxlate is decomposed at 110°C into glycerol-monoformate.
H O O H O
H—C— O—C—C—O—H
110°C
H—C—O—C—H + CO2
H H
Glycerol-monoxalate (ester) Glycerol-monoformate (ester)
iii. When the effervescence of CO2 ceases completely, further amount of crystalline oxalic acid
[(COOH)2.2H2O] is added when glycerol-monoformate is hydrolyzed with water of
crystallization of crystalline oxalic acid into formic acid.
H O H
H—C—O—C—H + HO—H O H—C—OH
110°C
H—C—O H (From new crop of H—C—OH + H—C—OH
crystalline oxalic acid)
H—C—O H Formic acid H—C—OH
H H
Glycerol-monoformate Glycerol
Thermometer 110º
Water out
Water condenser
Crystalline
oxalic acid +
glycerol
Sand bath
Cold water in
HCOOH (aq.)
Fig. 13.1: Laboratory Preparation of Aqueous Formic Acid
Procedure
In a distillation flask, a mixture of about 40 g crystalline oxalic acid and 50 g of anhydrous glycerol is
taken. The apparatus is fitted as shown in the figure 13.1 and heated to 110°C. As the effervescence of
CO2 ceases, the flask is cooled then fresh batch of oxalic acid crystals (40 g) is again added, and the
flask is heated to about 110°C. Formic acid formed distils off and is collected in the receiver as
aqueous formic acid.
Preparation of anhydrous formic acid from aqueous formic acid
Aqueous formic acid cannot be subjected to fractional distillation to remove water since boiling point
of formic acid (100.5°C) is very closer to that of the boiling point of water (100°C).
The dehydrating agents like anhydrous P2O5, concentrated H2SO4 and solid KOH can not be used for
drying because formic acid itself reacts with them.
Conc. H2SO4
HCOOH CO↑ + H2O
Δ
P2O5
HCOOH CO↑ + H2O
Δ
HCOOH + KOH HCOOK + H2O
Hence, chemical method of seperation is applied. This can be carried out by using water condenser
as a separating device.
In this method, aqueous formic acid is neutralized with lead carbonate (PbCO3) until the completion
of effervescence of CO2 to get aqueous saturated solution of lead formate. The solution is filtered
then subjected to crystallization and recrystallization.
2 HCOOH(aq) + PbCO3(aq) (HCOO)2Pb (aq) + CO2 ↑ + H2O

Formic acid Lead formate
(HCOO)2Pb(aq) (HCOO)2Pb
Crystallization
Lead formate Crystals
The crystals of lead formate are taken in the inner tube of a water condenser and the apparatus is
fitted as in figure 13.2 . Water condenser is heated by means of steam passing through the outer
jacket of the condenser. H2S gas is passed under pressure from upper end. The reaction takes place
forming anhydrous formic acid which is collected in the receiver. The precipitate of PbS does not
enter to the flask due to glass wool plug placed at the lower end of water condenser. The anhydrous
formic acid may contain dissolved H2S which is removed by redistilling anhydrous formic acid with
fresh lead formate crystals. In this way, pure and dry anhydrous formic acid is prepared in the
laboratory.
100°C
(HCOO)2Pb(s) + H2S(g) 2 HCOOH(l) + PbS(s) ↓
Anhydrous Lead sulphide
formic acid (black precipitate)
Steam out Crystalline lead formate

H2S gas in
Condenser
Cotton/Glass wool
Guard tube with

anh. CaCl2
Steam in
Anh. formic
acid
Fig. 13.2: Generation of anhydrous formic acid from lead formate crystals
Formic acid is commercially obtained by heating sodium hydroxide with carbon monoxide at 210°C under the pressure of
6-10 atmosphere followed by acidification.
210°, 6-10 atm
NaOH + CO HCOONa
2 HCOONa + H2SO4 (dil.) 2 HCOOH + Na2SO4
13.1.7 Abnormal Behaviour of Methanoic Acid

(Comparison of Properties of Formic Acid with Acetic Acid)
Formic acid differs from the other monocarboxylic acid. This is because besides the carboxyl group, it
contains -CHO group. So, formic acid behaves both as an acid as well as an aldehyde.
O O
H—C—OH H—C—OH
Aldehyde group
Carboxyl group
oxidizing agent
HCOOH + [O] CO2 + H2O
H COOH CH3COOH
1. Tollens' test: When formic acid is warmed with 1. Tollens' test: It does not give
Tollen's reagent in water bath, it is oxidized to Tollen's test.
CO2 and Tollen’s reagent is reduced to the silver.
Hence silver mirror is deposited on the inner
wall of the test tube. The only carboxylic acid that
gives Tollen's or silver mirror test is formic acid.
HCOOH + 2 [Ag(NH3)2]OH
Methanoic acid Tollen's reagent
Warm
2 Ag ↓ + CO2↑ + 2 H2O + 4 NH3

Silver mirror
2. Fehling's test: When formic acid is warmed with 2. Fehling's test: It does not give
Fehling’s solution in water bath, it is oxidized to Fehling test.
CO2 and Fehling’s solution is reduced to Cu2O,
which gives red precipitate. The only carboxylic
acid that gives Fehling’s solution test is formic
acid.
HCOOH + [2 Cu++ + 4 OH¯]
Methanoic acid Fehling's solution
Tartarate
Warm
Cu2O↓ + CO2↑ + 3 H2O
3. Reaction with acidified KMnO4: When formic 3. Reaction with acidified KMnO4: It
(permanganate test) acid is warmed with does not react.
acidified solution of potassium permanganate,
the pink colour of KMnO4 is discharged.
5 HCOOH + 2 KMnO4 + 3 H2SO4
pink colour
K2SO4 + 2 MnSO4 + 5 CO2 + 8 H2O
4. Reaction with mercuric chloride: When formic 4. Reaction with mercuric chloride: It
acid is treated with mercuric chloride, it gives does not react.
white precipitate of mercurous chloride (Hg2Cl2)
and then finally gives black mercury.
HCOOH + 2 HgCl2 Hg2Cl2↓+CO2+2 HCl
white ppt
HCOOH + 2 Hg2Cl2 CO2+2 HCl +2 Hg
2 HCOOH + HgCl2 2 CO2+4 HCl+2 Hg↓
black
5. Action of conc. H2SO4: Dehydration: Formic 5. Action of conc. H2SO4: No action

acid is dihydrated with conc. H2SO4 into CO and
H2O. This reaction can be utilized for the
laboratory preparation of carbon monoxide.
conc. H2SO4
HCOOH H2O + CO
6. Action of Heat: When formic acid is heated to 6. Action of Heat: No action

about 160°C, it decomposes into hydrogen and
carbon dioxide.
160°C
HCOOH H2 + CO2
pressure
7. Action with P2O5: When formic acid is heated 7. Action with P2O5: It gives
with anhydrous P2O5, it gives CO and H2O. corresponding acid anhydride.
P2O5 O
HCOOH CO + H2O O
Δ
CH3—C—O H
P2O5 Δ CH3 C
O + H2O
CH3—C— OH CH3 C
O O
Ethanoic anhydride
8. Reaction with PCl5: Formic acid reacts with PCl5 8. Reaction with PCl5: Acetic acid
to give methanoyl chloride (formyl chloride), reacts with PCl3, PCl5 or SOCl2 to
which decomposes into carbon monoxide and give acetyl chloride.
HCl. O
O O CH3—C—OH+PCl5
H—C—OH + PCl5 H—C—Cl + POCl3 + HCl O
CH3—C—Cl +POCl3+HCl
HCOCl CO + HCl
HCOOH + PCl5 2HCl + CO + POCl3
9. Sodalime decarboxylation: Gives H2 gas 9. Sodalime decarboxylation: Gives

CaO methane CaO
HCOOH + NaOH H2 + Na2CO3 CH3 COOH + NaOH CH4 + Na2CO3
Δ Δ
In above reaction number 1, 2, 3 and 4, formic acid behaves as a reducting agent and itself is
oxidized to CO2 whereas all other carboxylic acids do not show reducing behaviour.
Note:
Pure acetic acid is called glacial acetic acid since it solidifies forming ice like solid when cooled (melting point 16.6°C)
Self Test
13.11 Suggest a suitable chemical test to distinguish
a. Formic acid and acetic acid b. Formic acid and ethyl alcohol
c. Formic acid and phenol d. Formic acid and formaldehyde
13.12 What happens when methanoic acid is:
a. Warmed with Tollen's reagent b. Warmed with Fehling's solution
c. Added into acidified potassium permanganate solution
13.13 Why does methanoic acid give Tollen's test but ethanoic acid does not?
Note:
Formic acid does not give 2,4–DNP test of aldehydes.
13.1.8 Uses of Carboxylic Acids

1. Use of formic acid
i. It is used in leather tanning.
ii. It is used in textile industry for dyeing process.
iii. It is used in laboratory for preparation of carbon monoxide.
iv. It is used as medicine in the treatment of gout.
2. Use of acetic acid
i. It is used in plastics, rubber industries.
ii. It is used as a coagulant in the manufacture of rubber from latex and caesin from milk.
iii. It is used as vinegar.
iv. It is used as solvent.
13.2 Aromatic Carboxylic Acids
The organic compounds having carboxyl group (—COOH) directly bonded to aromatic ring are
called aromatic carboxylic acids. They are regarded as the carboxyl derivatives of aromatic
hydrocarbons when one or more ring hydrogen atoms have been substituted by carboxyl groups.
The most important members of the aromatic carboxylic acids are benzoic acid and phthalic acid.
COOH COOH COOH COOH
COOH
COOH
Benzoic acid Benzene-1,2-dicarboxylic acid Benzene-1,3-dicarboxylic acid
COOH
(Phthalic acid) (Isophthalic acid)
Benzene-1,4-dicarboxylic acid
(Terephthalic acid)
Preparation of benzoic acid
Benzoic acid is prepared by following methods:
1. By the oxidation of alkyl benzene: Oxidation of alkyl benzene with acidic or alkaline KMnO4,
acidified K2Cr2O7, conc. HNO3 or chromic anhydride gives benzoic acid. Many aromatic acids
are obtained industrially by this method.
CH3 COOH
KMnO4/OH–
+ [O] + H2O
Δ
Toluene Benzoic acid
The alkyl side chain (R—) to the aromatic ring gets oxidized to —COOH groups, which is
irrespective of the size of the side chain.
CH3 COOH
KMnO4 /OH–
+ 3 [O] + H2O
Δ
C2H5 COOH
conc. HNO3
+ 6 [O] + CO2 + 2 H2O
Δ
Ethyl benzene Benzoic acid
2. By the oxidation of toluene: Oxidation of toluene with air in presence of cobalt acetate or
manganese acetate at 170°C, gives benzoic acid. (Commercial method of preparation).
CH3 COOH
Co(CH3COO)2
+ O2 + H2O
170°C
3. By the hydrolysis of benzotrichloride: When benzotrichloride is boiled with Ca(OH)2 (milk of

lime) in presence of Fe, it gives benzoic acid. Benzochloride required for the reaction itself is
prepared by passing chlorine through boiling toluene in presence of light at 110°C (Commercial
method of preparation).
OH
Cl
CH3 Cl—C—Cl HO—C—O H COOH
3 Cl2, 100°C Ca(OH)2, Fe/170°

– 3HCl – 3HCl —H2O
Toluene Benzotrichloride Unstable Benzoic acid
4. By oxidation of benzyl alcohol: Oxidation of benzyl alcohols with acidified KMnO4 or K2Cr2O7
gives benzoic acid
O [O]
K2Cr2O7/H2SO4
CH2OH + [O] C—H COOH
— H2O K2Cr2O7/H2SO4
Benzyl alcohol Benzaldehyde Benzoic acid
5. From benzonitrile: Nitrile synthesis of carboxylic acid: Hydrolysis of benzonitrie with dilute
acid or dilute alkali gives benzoic acid.
CN COOH
H2O/H+
+ 2 H2O + NH4+
Benzonitrile Benzoic acid
The preparation can be performed from the following given compounds
NO2 NH2 N2Cl CN COOH

Conc.HNO3 + NaNO2 + HCl
Conc.H2SO4, 60°C Sn/Conc. HCl Ice cold Cu2(CN)2 H2O/H+
Benzene Nitrobenzene Aniline Benzene diazonium Benzonitrile Benzoic acid

chloride
6. By Grignard synthesis: By the reaction of CO2 with phenyl magnesium bromide (Grignard
reagent):
O O
MgBr + O = C = O C—OMgBr C—OH
inert atm
Benzoic acid
Phenyl magnesium bromide
Self Test
13.14 Convert benzene into benzoic acid and vice versa.
13.15 Which acid is formed when p-bromotoluene is oxidized?
Physical properties
1. Benzoic acid is a white crystalline solid with melting point 121°C.
2. It is slightly soluble in cold water but highly soluble in hot water. It is also soluble in organic
solvents.
3. It is steam volatile.
Chemical properties
Reaction of benzoic acid can be categorized into:
A. Reaction due to benzene ring
B. Reaction due to carboxyl group
A. Reaction due to benzene ring: Electrophilic aromatic substitution reaction.
deactivating group
COOH
Meta director
Like other aromatic compounds, benzoic acid gives electrophilic aromatic substitution reaction.
The carboxyl (–COOH) group is electron-withdrawing group which creates positive charge in
the aromatic ring due to resonance effect. Therefore, —COOH group deactivates the benzene
ring towards electrophilic substitution reacion and hence makes the electrophilic attack
difficult. The carboxyl (–COOH) group is meta- directing that directs the incoming electrophile
towards meta- positions of the benzene ring to the –COOH group, which can be described as
follow:
– –
– δ+ δ–
HO O HO O HO O HO O HO O HO O
C C C C C C

+ + δ+ δ+

+
δ+
I II III IV V
Resonance hybrid
Resonating structures of benzoic acid
In resonance hybrid of benzoic acid, the partial positive charge (δ+) is developed at ortho- and
para- positions. The electron density is low at ortho- and para- positions. So, electrophilic attack
becomes difficult in these positions. Therefore, electrophile preferentially attacks at meta-
positions to the –COOH group to give meta- substituted products.
Hence, –COOH group of benzoic acid is deactivating and meta- directing towards electrophilic
substitution reaction. Deactivation is so strong that the Friedel–Crafts reaction does not take
place.
Benzoic acid undergoes some common electrophilic reactions like nitration, sulphonation and
halogenation vigorous at meta- positions.
COOH
Halogenation
+ HCl
Cl2, FeCl3, Δ
Cl
m–Chlorobenzoic acid
COOH COOH
Sulphonation + H2O
Fuming H2SO4
SO3H
Benzoic acid
m–sulphobenzoic acid
COOH
Nitration + H2O
conc. HNO3 + conc. H2SO4
NO2
m–Nitrobenzoic acid
B. Reaction due to carboxyl group
1. Acid nature: Benzoic acid is acidic nature. The following reaction justify its acidic behaviour
COOH + NaOH COONa + H2O
Sodium benzoate
COOH + NaHCO3 COONa + CO2 + H2O
Sodium benzoate
Benzoic acid is less acidic acid than formic acid but more acidic than acetic acid. This is due to
the fact that phenyl (C6H5-) group of benzoic acid is weaker electron releasing group than that
of the methyl (CH3−) group of acetic acid. The CH3– group of acetate ion enhances the negative
charge of the ion strongly, which makes it less stable then benzoate ion.
O O
CH3 C C
O O
Carboxylate Benzoate ion

i
The order of acidic character is: HCOOH > C6H5COOH > CH3COOH
13.2.1 Effect of substituents on acidity of carboxylic acids

1. Effect of electron donating substituent
Any factor that destabilises the carboxylate ion decreases the acidity of the acid. The electron-
releasing substituent donates electron, intensify the negative charge on carboxylate ion and
destabilizes the carboxylate ion and thus decreases the acidic nature of carboxylic acid.
COO¯
Electron releasing groups

G = —NH2
—OH
G —OCH3
—NHCOCH3
G= donates electron — C6H5
— CH3
destablises the anion by intesifying negative charge
decreases the acidic nature of the acid.
2. Effect of electron withdrawing substituent

Any factor that stabilises the carboxylate ion increases the acidity of the acid. The electron-
withdrawing substituent withdraws electron, disperse the negative charge on carboxylate ion
and stabilizes the carboxylate ion and thus increases the acidic nature of carboxylic acid.
COO¯
Electron withdrawing groups

G = —NO2
G —CN
—SO3H
—COOH
G = withdraws electron — CHO
stablises the anion by dispersing negative charge
— COR
increases the acidic nature of the acid. —X
COOH COOH COOH COOH COOH COOH
> > > > >

NO2 Cl CH3 OCH3 OH
Ka = 30×10–5 Ka = 10.5×10–5 Ka = 6.3×10–5 Ka = 4.2×10–5 Ka = 3.3×10–5 Ka = 2.6×10–5
3. Effect of the position of susbtitutions: The acidity is more pronounced at ortho-position as

compared to that at para- and meta- positions. This is called ortho effect.
COOH COOH COOH COOH

NO2
< < <
NO2
NO2
Self Test
13.16 Which one of the following is a stronger acid in each of the following pairs?
(a) m-hydroxy benzoic acid and p- hydroxy benzoic acid.
(b) Ethanoic acid and benzoic acid.
(c) Methanoic acid and benzoic acid.
4. The other reactions of benzoic acid are summarized as:

O
PCl5 or SOCl2
C—Cl
Benzoyl chloride
O
NH3
C—NH2
Benzamide
O
LiAlH4, ether
C—OH CH2—OH
Benzyl alcohol
Benzoic acid
C2H5OH O
C— OC2H5
Conc. H2SO4, Δ
Ethyl benzoate (ester)
NaOH + CaO
Δ
Benzene
Uses of Benzoic acid
1. Salt of benzoic acid like sodium benzoate is used as food preservatives.
2. Esters of benzoic acid are used in perfumery.
3. It is used to make aniline blue dye.
4. It is used in synthesis of various organic compounds.
13.3 Functional Derivatives of Carboxylic Acids

Functional derivatives of carboxylic acids are closely related to those classes of organic compounds
which can be structurally obtained by the replacement of —OH part of the —COOH group of the
carboxylic acid by electron rich species. The electrons rich species includes —Cl, —OR', —NH2 and
—OCOR' groups which yield acid chloride (R—COCl), ester (R—COOR'), acid amide (R—CONH2)
and acid anhydride (R—COOCOR') respectively. These compounds are, therefore called functional
derivatives of carboxylic acids.
O
– (OH)
R C X
+ (–X) Acid halide
(Acyl halide)
O O
– (OH)
R C O C R
O + (–OCOR) Reactivity decreases
R Acid anhydride
C OH
– (OH)
O
R C OR'
+ (–OR')
Ester
– (OH)
O
R C NH2
+ (–NH2)
Acid amide
Acid derivatives where R and R'

may be aliphatic or aromatic.
Example: PCl5 O
CH3—C—Cl Ethanoyl chloride (Acetyl chloride)
or SOCl2
O O
P2O5
CH3—C—O—C—CH3 Ethanoic anhydride (Acetic anhydride)
O Δ
CH3—C—OH
Ethanoic acid
O
C2H5OH/H+
(Acetic acid) CH3—C—OC2H5 Ethyl ethanoate (Ethyl acetate)
NH3 O
CH3—C—NH2 Ethanamide (Acetamide)
Δ
PCl5 O
C—Cl Benzoyl chloride
or SOCl2
O
C
P2O5
O Benzoic anhydride
O Δ C
C—OH O
Benzoic acid NH3 O
Δ C—NH2 Benzamide
C2H5OH/H+ O
C—OC2H5 Ethyl benzoate
Relative reactivity of acid derivatives

The reactivity of the acid derivatives for nucleophilic substitution reaction in general, follows the
order:
O
R R—C R R
C=O > C=O > C=O > C=O
Cl R—C RO H2N
O
The above order of reactivity can be explained in terms of the: (i) Basicity of leaving group
(ii) resonance effect.
1. Basicity of leaving groups: Weaker the basic character of the leaving group (anion) is, more
will be the ease with which the bond can be raptured and hence more is the reactivity. Among
the given compounds Cl¯ ion is the weakest base and hence chlorides are most reactive. The
correct order of basicity of the leaving group and their tendency to leave is:
Basicity: Decrease :NH2 > :OR > RCOO: > :Cl

Reactivity: Increase :NH2 < :OR < RCOO: < :Cl
2. Resonance effect: In general, all the acid derivatives show resonance as follows:
R R
C=O C—O
L L
L = leaving group: —Cl, —OCOR, —OR, —NH2

In the resonating structures, it is clear that the carbon to leaving group (L) bond acquires a
double bond character due to which stabilization occurs. Now more is the stabilization, leaser is
the reactivity and vice-versa. As the stabilization is the least in the case of acid chloride because
the X-atom exerts a high magnitude of –I electron withdrawing effect as compared to the other
groups, therefore, its reactivity is the most.
13.3.1 Acid Halides (Acyl Halides)

Acid halides are halogen derivatives of carboxylic acid that are obtained by replacing –OH group of
carboxyl group by halogens (—Cl, —Br, —I).
O O
(–) OH
R—C R—C
(+) X
OH X
Acid halide
Nomenclature
The names of acyl chlorides are derived from the common or IUPAC names of the parent acids by
replacing the suffix −ic acid with —yl chloride.
Compounds Common name IUPAC name

O
Acyl halide Alkanoyl halide
R—C—X
O
Acetyl chloride Ethanoyl chloride
CH3—C—Cl
O
Propionyl chloride Propanoyl chloride
CH3—CH2— C—Cl
O
C—Cl
Benzoyl chloride Benzoyl chloride
HCOCl is unstable.
Preparation
1. From carboxylic acid: When carboxylic acid is refluxed with thionyl chloride (SOCl2),
phosphorus trichloride (PCl3) or phosphorus pentachloride (PCl5), corresponding acid chloride
is formed.
O O
pyridine, reflux
CH3—C—OH + SOCl2 CH3—C—Cl + SO2↑ + HCl ↑
Ethanoic acid Ethanoyl chloride
O O
pyridine, reflux
C—OH + SOCl2 C—Cl + SO2↑ + HCl ↑
Benzoic acid Benzoyl chloride
O O
50°C
3 CH3—C—OH + PCl3 3 CH3—C—Cl + H3PO3
O O
100°C
CH3—C—OH + PCl5 CH3—C—Cl + POCl3↑ + HCl ↑
O O
100°C
C—OH + PCl5 C—Cl + POCl3 + HCl ↑
2. Using phosgene: Aromatic acid chloride can be prepared by treating arenes with phosgene.
O O
H + Cl—C—Cl C—Cl + HCl ↑
Physical properties
1. Physical state: Lower members of acid chlorides are colourless liquid having irritating odour
and higher members are colourless solid.
2. Boiling point: The boiling point of acid chloride is less than that of parent acid due to absence
of intermolecular H-bonding.
3. Solubility: Acid chlorides are insoluble in water due to lack of intermolecular H-bonding but
soluble in organic solvents.
Self Test
13.17 Acyl chlorides have lower boiling points than corresponding acids, explain.
Chemical properties
The most common and typical reaction of acid chloride is nucleophilic substitution.
O
–O O
R—C—Cl + Nu R—C—Cl R—C—Nu + Cl¯
Nu Product
Acid chlorides are most reactive of the functional derivative of carboxylic acids. This is due to–I
effect of -Cl and hence a partial positive charge on carbonyl carbon is intensified. Aromatic acid
chlorides (ArCOCl) are considerbly less reactive than the aliphatic acid chlorides (RCOCl).
1. Reaction with water: Hydrolysis: Acid chloride reacts with water, to give parent carboxylic
acid.
O O
H+
R—C + H2O R—C + HCl
Cl OH
Carboxylic acid
Examples: O + O
H
CH3—C—Cl + H—OH CH3—C—OH + HCl (Fast reaction)
O + O
H
C—Cl + H—OH C—OH + HCl (Slow reaction)
Benzoyl chloride Benzoic acid
2. Reaction with ammonia: Ammonolysis: Acid chloride reacts with ammonia, to give amide.
O O
R—C + NH3 R—C + HCl
Cl NH2
Amide
Examples:
O O
CH3—C—Cl + NH3 CH3—C—NH2 + HCl
Ethanoyl chloride Ethanamide
(Acetyl chloride) (Acetamide)
O O
C—Cl + NH3 C—NH2 + HCl
Benzoyl chloride Benzamide
3. Reaction with alcohol: Alcoholysis: Acid chloride reacts rapidly with alcohols to give ester.
O O
pyridine
R—C + R'OH R—C + HCl
Δ
Cl OR'
Ester
Examples: O O
CH3—C—Cl + C2H5OH CH3—C—OC2H5 + HCl
Acetyl chloride Ethyl alcohol Ethyl acetate
4. Schotten–Baumann reaction: Benzoylation: The reaction of aromatic acid chlorides (Benzoyl

chloride) with an alcohol or a phenol in presence of a base, usually aqueous sodium hydroxides
or pyridine to give aromatic esters is called Schotten-Baumann reaction
O O
aq. NaOH
C—Cl + C2H5OH C—OC2H5 + HCl
Benzoyl chloride Ethyl benzoate
Example:
O O
aq. NaOH
+ HO C + HCl
C
Cl O
Benzoyl chloride Phenyl benzoate
In this reaction, acid chloride is added in portions followed by vigorous shaking to a mixture of
alcohol or phenol and a base. Base serves not only to neutralize the HCl that would be liberated,
but also to catalyze the reaction.
5. Reaction with benzene: Friedel-Crafts acylation: When acid chloride is treated with benzene in
presence of lewis acid (anh. AlCl3) as a catalyst, aromatic ketone is formed. This reaction is an
example of Friedel-Crafts acylation.
O O
anh. AlCl3
R—C + ArH R—C + HCl
Cl Ar
Example: Ketone
O O
anh. AlCl3
CH3—C—Cl + H CH3—C + HCl
6. Reduction into aldehyde: Rosenmund reaction: When acid chlorides are heated with H2 in
presence of Pd–BaSO4 partially poisoned by quinoline, aldehydes are obtained. This reaction is
called Rosenmund reaction.
O O
Pd-BaSO4
R—C—Cl + H2 R—C—H + HCl
Acid chloride Quinoline, Δ Aldehyde
Example:
O O
Pd-BaSO4
CH3—C—Cl + H2 CH3 C—H + HCl
—
Ethanoyl chloride Quinoline, Δ Ethanal
(Acetyl chloride)
Note
If LiAlH4 is used as a reducing agent here, aldehydes are further reduced to alcohols.
7. Reduction with dialkyl cadmium: Acid chlorides reacts with dialkyl cadmium to form ketones.
2 RCOCl + R'2Cd 2 RCOR' + CdCl2
Example:
2 CH3COCl + (CH3)2Cd 2 CH3COCH3 + CdCl2
8. Reduction into alcohol: Acid chloride is reduced by LiAlH4 to form primary alcohol.
Example: O
LiAlH4
CH3—C—Cl CH3CH2OH + HCl
ether
Ethanoyl chloride Ethanol
9. Reaction with Grignard reagent: When acid chloride is treated with Grignard reagent (RMgX),
an addition product of adduct, which upon hydrolysis gives tertiary (3°) alcohol .
- + –
O O Mg Br O
Ether
CH3—C—Cl + CH3MgBr CH3—C—Cl CH3—C—CH3
– Mg(Br)Cl
Ethanoyl chloride CH3
CH3MgBr
(second molecule)
OH OMgBr
H+/H2O
Mg(OH)Br + CH3—C—CH3 CH3—C—CH3
CH3 CH3
2-Methylpropan–2–ol
(3° alcohol)
Self Test
13.18 Why does acetyl chloride fume on air?
13.3.2 Acid Anhydrides

Functional group of acid anhydride is –CO–O–CO–. The most important member of acid anhydride
is acetic anhydride. The name is given since it is formed by intermolecular dehydration of the parent
acid.
O O
R C OH P2O5 R C
O + H2O
R C OH Δ R C
O O
Alkanoic anhydride
(Acid anhydride)
O O O
R—C CH3—C C
O O
R—C CH3—C O
O O C
O
Acid anhydride Acetic anhydride
Benzoic anhydride
Nomenclature
Compound Common name IUPAC name
O O
Acid anhydride Alkanoic anhydride
R—C—O—C—R
O O
CH3—C—O—C—CH3 Acetic anhydride Ethanoic anhydride
or
(CH3CO)2O
O O
—C—O—C— Benzoic anhydride Benzoic anhydride
Preparation
1. From ketene: By the reaction of acetic acid with ketene, an acetic anhydride is formed.
Example: O O O
CH2= C = O + CH3—C—OH CH3—C—O—C—CH3
Ketene Acetic acid Acetic anhydride
Ketene is prepared at high temperature dehydration of acetic acid to 700° in presence of aluminum phosphate (AlPO4).
AlPO4
CH3COOH CH2 = C = O + H2O
700°C
Ketene
Ketene is an extremely reactive, it is also prepared in laboratory by pyrolysis of acetone, and ordinarily used as soon as it is
prepared
700-750°C
CH3COCH3 CH2 = C = O + CH4
2. From carboxylic acid: When carboxylic acid is heated with strong dehydrating agent like P2O5,
it gives acid anhydride.
Example: O O O O
P2O5
CH3—C—OH + OH —C—CH3 CH3—C—O—C—CH3 + H2O
Δ
(Acetic anhydride)
Acetic acid
3. From acid chloride: Acid chloride reacts with carboxylic acid to form acid anhydride.
RCOCl + R'COOH RCO—O—COR' + HCl

Example:
CH3COCl + CH3COOH CH3CO—O—COCH3 + HCl
4. By heating dicarboxylic acids: Dehydration of certain dicarboxylic acid yield acid anhydride on
simple heating only, where five- or six- membered ring of anhydride is produced.
O
O
C C
CH2 OH CH2
O + H2O
Δ CH2
CH2 OH
C C
O O
Succinic acid Succinic anhydride
(five membered ring)
Example:
O O
C 200°C C
OH O + H2O
C O H C
O
O
Phthalic acid Phthalic anhydride
(Five membered ring)
Physical properties
1. Physical state: Lower members of acid anhydrides are colourless liquids with sharp pungent
smell and higher members are colourless solid.
2. Solubility: Lower members are soluble in water.
3. Boiling point: They have higher boiling point than their parent acid because of large molecular
size.
Chemical properties
Acid anhydrides give nucleophilic substitution reaction but less reactive than acid chlorides.
Oδ– O δ–
O
O R—C—O—C—R
δ+ δ+
R—C—Cl
Cl shows - I effect Lone pair of electrons
neutralizes partial +ve charge
1. Reaction with water: Hydrolysis: Acid anhydride on hydrolysis yield parent carboxylic acid.
Example:
O O O
Δ
CH3—C—O—C—CH3 + H2O 2 CH3—C—OH
Acetic anhydride Acetic acid
2. Reaction with ammonia: Ammonolysis: Acid anhydride reacts with ammonia to give amide.
Example: O O
O O
CH3—C—O—C—CH3 + 2 NH3 CH3—C—NH2 + CH3—C—ONH4
Acetamide Ammonium acetate
Acetic anhydride
3. Reaction with alcohol: Alcoholysis: Acid anhydride reacts with alcohol to give ester and acid.
Example:
O O O
CH3—C—O—C—CH3 + H O—CH2CH3 CH3—C—O—CH2CH3 + CH3COOH
Acetic anhydride Ethyl acetate
4. Friedel-Crafts acylation: Formation of ketone: Acid anhydride reacts with benzene in presence
of lewis acid like anhydrous AlCl3 as catalyst, aromatic ketone is formed. This reaction is called
Friedel-Crafts acylation.
Example:
O O O
anh. AlCl3 CH3—C + CH3COOH
CH3—C—O—C—CH3 + H Δ
Acetic anhydride Acetophenone
Benzene
5. Reduction into alcohol: Acid anhydride is reduced by LiAlH4 into primary (1°) alcohol.
Example: O O LiAl H4
CH3—C—O—C—CH3 2 CH3CH2OH + H2O
Acetic anhydride
6. Reaction with PCl5: When acid anhydride is treated with PCl5, acid chloride is produced.
Example:
O O O
CH3—C—O—C—CH3 + PCl5 2 CH3—C—Cl + POCl3
Acetic anhydride Acetyl chloride
13.3.3 Esters
Ester is a functional derivative of carboxylic acid, which is obtained by replacing –OH group of
carboxylic acid by -alkoxy (–OR) group.
O O
(–OH)
R—C R—C
(+OR')
OH OR'
Ester
O
CH3 C O CH2
Phenylmethyl ethanoate
(Benzyl acetate)
Flowering jasmine plant

The natural flavours of many fruits and fragrance of flowers are blends of many organic compounds. Many of
them are esters. For example, phenylmethyl ethanoate( an ester) is the major constituent of oil of jasmine It is
naturally obtained from jasmine plant. Now, it is produced by chemical synthesis for perfumes industry.
The flavours and fragrances of many esters are widely used in food flavourings and perfumes.
Ester Flavour
CH3 O
Apple
CH3CH2—CH—C—OC2H5
Ethyl 2-methylbutanoate
O CH3
Banana
CH3—C—O—CH—CH2—CH2—CH3
1-Methyl butylethanoate
O
CH3CH2CH2—C—O—CH2CH2CH2CH3 Pineapple
Butyl butanoate
Fats and oils are also esters of glycerol (trihydric alcohol) with fatty acids.
Esters are used as solvent in chemical industries. For example, ethylethanoate (ethyl acetate) is used
as nail polish remover.
Nomenclature
The ester are named by writing the alkyl or aryl group of —OR part of the molecule before the
names of the parent carboxylic acid and replacing the suffix—ic of the common or IUPAC name of
the acid by —oate.
Compound Common name IUPAC name
O Alkyl carboxylate Alkyl alkanoate

R—C—OR'
O Methyl formate Methyl methanoate
H—C—OCH3
O Methyl acetate Ethyl methanoate
H—C—OC2H5
O Ethyl acetate Ethyl ethanoate

CH3—C—O—C2H5
O Methyl benzoate Methyl benzoate
C—O—CH3
Preparation
1. From carboxylic acids: Esterification: When carboxylic acid is heated with an alcohol in
presence of dehydrating agents like concentrated H2SO4, fruity odour of an ester is obtained.
This reaction is called esterification.
O O
Conc.H2SO4
R —C— OH + H O—R' R—C— OR' + H2O
Δ ester
Ocarboxylic acid alcohol O
Conc.H2SO4
CH3—C—OH + H—OCH2CH3 CH3— C—O—C2H5 + H2O
Δ
Ethanoic acid Ethanol Ethyl ethanoate
O O
conc.H2SO4
CH3—C—OH + H—OCH2 CH3— C—O + H2O
Δ
Ethanoic acid Benzyl alcohol
Phenyl ethanoate
2. Acylation: From acid chlorides or acid anhydrides: When acid chloride or acid anhydride is
heated with alcohol in presence of pyridine or conc. H2SO4, ester is obtained.
O O
NaOH or Pyridine
R —C— Cl + H O—R' R—C— OR' + HCl
Acid chloride alcohol ester
Examples:
O O O
R—C—O—C - R + H O—R' R—C—O—R' + RCOOH
Δ
Acid anhydride Alcohol Ester
O O
Conc.H2SO4
CH3—C—Cl + H O—CH2CH3 CH3—C—O—CH2CH3 + HCl
Δ
Ethanoyl chloride Ethanol Ethyl ethanoate
O O O
CH3—C—O—C - CH3 + H O—CH2CH3 CH3—C—O—CH2CH3 + CH3COOH
Δ
Acetic anhydride Ethanol Ethyl ethanoate
O O
Pyridine, Δ
CH3—C—Cl + H O CH3—C—O + HCl
Ethanoyl chloride Phenyl acetate
Phenol
3. By trans-esterification: When an ester reacts with alcohol in presence of conc. H2SO4, a new
ester is formed. The reaction is called trans-esterification.
O O
Acid or base
R — C — OR' + R''OH R — C — OR'' + R'OH
Ester Ester
(new type)
Examples:
O O
Conc.H2SO4
CH3—C—O—CH3 + H O—C2H5 CH3—C—O—C2H5 + CH3OH
Methyl acetate Ethanol Ethyl acetate Methanol
4. Action of alcoholic silver salt of carboxylic acid: When alkyl halide is refluxed with alcoholic
solution of silver salt of carboxylic acid, ester is formed.
O O
δ+ δ–
—
R X R' C—O¯Ag+(alc.)
+ — R'—C—OR + AgX
Silver carboxylate Alkylalkanoate
(Ester)
Examples:
O O
CH3CH2—Br + CH3—C—OAg(alc.) CH3—C—OCH2CH3 + AgBr
Silver ethanoate Ethylethanoate
(Ethylacetate)
Chemical properties
Esters are less reactive than acid chloride and acid anhydride but more reactive than amide towards
nucleophilic substitution reaction.
δ– –
O O
+
R— C — O R CH3—C O R
δ+
1. Hydrolysis: Ester can be hydrolyzed in acidic as well as in alkaline medium.

O
H+
R—C + R'O¯
(acid)
O OH
R—C + H2O
OR' O
OH¯
R—C + R'OH
(base)
O
a. Conversion into acids: Acidic hydrolysis: Hydrolysis of ester with dilute solution of
mineral acid gives carboxylic acid and alcohol. The reaction is reversible.
O O
R—C—OR' + H2O H+ R—C—OH + R'OH
Ester Carboxylic acid Alcohol
Examples:
O O
H2SO4
CH3—C—OCH2CH3 + H2O CH3—C—OH + C2H5OH
Ethyl acetate Acetic acid Ethanol
b. Alkaline hydrolysis: Hydrolysis of ester with dilute solution of base gives carboxylate salt
and alcohol.
Example: O O
NaOH
CH3—C—OC2H5 + H2O CH3—C—ONa + C2H5OH
Ethyl acetate Sodium acetate Ethyl alcohol
2. Conversion into amide: Reaction with NH3: Ammonolysis: On treatment of an ester with
ammonia in presence of alcohol yields amide.
O O
R—C—OR' + NH3 (alc.) R—C—NH2 + R' OH
Ester Amide Alcohol
Examples:
O O
CH3—C—OC2H5 + NH3 (alc.) CH3—C—NH2 + C2H5OH
Ethyl acetate Acetamide Ethyl alcohol
3. Reaction with Grignard reagent: An ester reacts with Grignard reagent, forms aldehyde or
ketone at first, which further reacts with another molecule of Grignard reagent followed by
hydrolysis, gives corresponding alcohol.
i. Ester of formic acid reacts with Grignard reagent, then aldehyde is formed at first, which
further reacts with another molecule of Grignard reagent followed by hydrolysis and gives
secondary (2°) alcohol.
Example:
O OMgBr O
δ–
H—C—OCH3 + CH3MgBr H—C—OCH3 —Mg(CH3O)Br CH3—C—H
CH3 Acetaldehyde
Methyl formate
CH3MgBr
(second molecule)
OH OMgBr
H2O/ H+
Mg(OH)Br + H—C—CH3 H—C—CH3
CH3 CH3
Propan-2-ol
(2° alcohol)
ii. When an ester of carboxylic acid other than formic acid react with Grignard reagent, then
ketone is formed at first, which further reacts with another molecule of Grignard reagent
followed by hydrolysis and gives tertiary (3°) alcohol.
Example:
O OMgBr O
δ–
CH3—C—OCH3 + CH3MgBr CH3—C—OCH3 —Mg(CH3O)Br CH3—C—CH3
CH3 Acetone
Methyl acetate
CH3MgBr
(second molecule)
OH OMgBr
H2O/ H+
Mg(OH)Br + CH3—C—CH3 CH3—C—CH3
CH3 CH3
2-Methyl-2-propanol
(3° alcohol)
4. Reduction into alcohol: Esters are reduced to primary (1°) alcohol from acid part of the ester.
The reduction can takes place in the following ways:
i. Catalytic hydrogenation: Hydrogenolysis: Catalytic hydrogenation of ester with
molecular hydrogen in presence of Adkin catalyst (CuO.CuCr2O4) gives primary alcohol
from acid part of ester.
O
CuO.CuCr2O4
R—C—OR’ + 2 H2 RCH2OH + R’OH
Δ, high pressure
1° alcohol
Example:
O
CuO.CuCr2O4
CH3—C—OCH3 + 2 H2 CH3CH2OH + CH3OH
150°C, high pressure
Methyl acetate Ethyl alcohol Methyl alcohol
ii. Chemical reduction: When an ester is reduced by reducing agent like Na/C2H5OH or
LiAlH4, primary alcohol is formed from acid part of ester.
O
Na/C2H5OH
R—C—OR’ + 4 [H] RCH2OH + R’OH
1° alcohol
O
Na/C2H5OH
CH3—C—OC2H5 + 4 [H] CH3CH2OH + C2H5OH
Ethyl acetate Ethyl alcohol
5. Conversion into acid chloride: Action of phosphorous chloride on esters.

O O
R—C—OR' + PCl5 R—C—Cl + R'Cl + POCl3
Δ
O O
CH3—C—OC2H5 + PCl5 CH3—C—Cl + C2H5Cl + POCl3
Δ
6. Claisen condensation: When an ester having at least one α–hydrogen atom undergoes self
condensation reaction in presence of strong base like sodium ethoxide (C2H5ONa), ethyl
acetoacetate or acetoacetic ester is formed. Acetoacetic ester is β– ketoester. The reaction is
known as Claisen condensation.
O H O O O
i) C2H5ONa
CH3—C—OC2H5 + CH2—C—OC2H5 CH3—C—CH2—C—OC2H5 + C2H5OH
ii) H+
(Ethyl acetate) Ethyl acetoacetate (EAA) or acetoacetic ester
(β - ketoester)
Self Test
13.19 Why is ethyl acetate more reactive than acetyl chloride?
13.3.4 Acid Amides

Acid amides are functional derivative of carboxylic acids in which –OH group of carboxylic acid is
replaced by –NH2 group. They are often simply called as amides.
O O
(–OH)
R—C R—C
(+NH2)
OH NH2
Amide
The amide is aliphatic if R = alkyl
group and aromatic if R = aryl group.
Nomenclature
Acid amides are named by replacing the suffix −ic acid of common or IUPAC name of the parent
carboxylic acids by −amide.
Compounds Common name IUPAC name
O
R—C—NH2 Acidamide Alkanamide
O
Formamide Methanamide
H—C—NH2
O
Acetamide Ethanamide
CH3—C—NH2
O
C—NH2 Benzamide Benzamide
Preparation
1. Amides are prepared from carboxylic acids by two ways:
i. Using ammonium salt: Carboxylic acid reacts with ammonia to form ammonium
carboxylate (ammonium salt), which upon strong heating loses H2O to give amide.
O O O
Δ
R—C + NH3 R—C R—C + H2O
OH ONH4 NH2
Ammonium carboxylate Acid amide
Examples:
CH3COOH + NH3 CH3COONH4 CH3CONH2 + H2O
Δ
Ammonium acetate Ethanamide
(Acetamide)
ii. By using acid chlorides : Acid chloride reacts with ammonia to give amide.
O O O
Pyridine NH3
R—C + SOCl2 R—C R—C + HCl
OH Cl NH2
Acid chloride Acid amide
Examples:
O O
CH3—C—Cl + 2NH3 CH3—C—NH2 + NH4Cl
Acetamide
Acetyl chloride
2. From alkane nitrile: By partial hydrolysis: Alkane nitrile (R – C ≡ N) is partially hydrolyzed

with concentrated acid into amide.
+ O
H
R—C ≡ N + H2O R—C—NH2
Alkanenitrile Amide
Examples:
+ O
H
CH3—C ≡ N + H2O CH3—C—NH2
Ethanenitrile Ethanamide
(Methyl cyanide) (Acetamide)
3. From esters: Ammonolysis: Action of alcoholic solution of ammonia on ester gives amide.
O
RCOOR' + NH3 (alc.) R—C—NH2 + R'OH
Ester Amide
Examples:
O
CH3COOC2H5 + NH3 (alc.) CH3—C—NH2 + C2H5OH
Ethyl ethanoate Ethanamide
Physical properties
1. Physical state: The first memer, formamide, is liquid. All the other amides are colourless
crystalline solids.
2. Solubility: The amides with carbon number up to six are soluble in water due to the fact that
they can form intermolecular hydrogen bonding with water. Solubility decreases with increase
in size of alkyl group.
δ+
O H
δ+ δ– δ+
R C N H '''''''''''''''''' O—H
δ–
H
δ+
Intermolecular H–bonding
Chemical properties
Amides are the least reactive of functional derivatives of carboxylic acids towards nucleophilic
substitution reaction. This is due to less polarity of C-N bond as compared to C-O bond and due to
resonance.
O O + H
.. H
C N C N
H R H
R
I II
From the given resonating structures, it is clear that amide is amphoteric in nature. The presence of
partial positive charge on nitrogen atom in resonance structure (II) can easily lose proton (H+) to
behave as an acid. On the other hand, presence of lone pair of electrons on nitrogen atom in
resonance structures (I) can denote lone pair of electron to acid as a base. Thus, amides are weak base
than amines.
1. Hydrolysis: Hydrolysis of amide is nucleophilic substitution reaction, in which the —NH2
group of amide is repaced by —OH group.
O
H+
(acid)
R—C + NH4+
O OH
R—C + H2O
NH2 O
OH¯
R—C + NH3
(base)
O
a. Acidic hydrolysis: Hydrolysis of amide in acidic medium gives carboxylic acid, which in
turn reacts with NH3 to give ammonium carboxylate.
O + O O
H NH3
R—C—NH2 + H2O R—C—OH R—C—ONH4
Ammonium carboxylate
Example:
O + O O
H NH3
CH3—C—NH2 + H2O CH3—C—OH CH3—C—ONH4
Ethanamide Ammonium acetate
b. Alkaline hydrolysis: Hydrolysis of amide in basic medium gives carboxylic acid, which in
turn reacts with alkali to give carboxylate salt and ammonia.
O O O
NaOH
R—C—NH2 + H—OH R—C—OH R—C—ONa + H2O
– NH3
Carboxylic acid
Example:
O O O
NaOH
CH3—C—NH2 + H—OH CH3—C—OH CH3—C—ONa + H2O
– NH3
Acetic acid
2. Conversion into imides: An organic compound with both - CONH2 and –COOH groups in its
molecule on simple heating eliminates a molecule of H2O and a cyclic ring compound is
formed, the product thus, obtained is called imide.
O O
C—NH2 C
Δ
NH
–H2O
C—OH C
O O
Phthalamic acid Phthalimide
3. Reduction: Amides are reduced by either LiAlH4/ether or by Na/C2H5OH into corresponding

primary amine.
O
Na/C2H5OH
R—C—NH2 + 4 [H] RCH2NH2 + H2O
or LiAlH4
1° amine
Example:
O
LiAlH4
CH3—C—NH2 CH3CH2NH2 + H2O
Ethanamine
4. Conversion of amides into primary amines: Hofmann bromamide reaction: Hoffman

rearrangement: (See amines unit 15 for details.)
O
Δ
R—C—NH2 + Br2 + 4 NaOH R—NH2 + Na2CO3 + 2 NaBr + 2 H2O
Amide Primary amine
Example:
O
Δ
CH3—C—NH2 + Br2 + 4 NaOH CH3—NH2 + Na2CO3 + 2NaBr + 2H2O
Ethanamide Methanamine
(acetamide)
5. Reaction with P2O5: When amide is heated with anhydrous P2O5, alkane nitrile is formed.
O
P2O5
CH3—C—NH2 CH3—C ≡ N + H2O
Δ
Ethanamide Ethanenitrile
6. Reaction with HNO2: Amide reacts with nitrous acid to give carboxylic acid with the evolution
of nitrogen gas.
Example:
O
NaNO2 + HCl
CH3—C—NH2 + HNO2 CH3—COOH + N2 + H2O
0°C
Ethanamide Ethanoic acid
Solved Questions
1. Why carboxylic acids do not give the characterstics reactions of carbonyl group?
¬ The functional carboxyl group (−COOH) of carboxylic acid is resonance hybrid of the following structures
O O
C R C
R
O—H O—H
+
(I) (II)
Resonance structure of carboxylic acid
In this structures, the carbonyl part (>C=O) of the carboxyl group does not have a double bond
character but has a reduced double bond character. Hence, carboxylic acids do not give the
characteristics reactions of carbonyl group.
Questions
1. Name the type of isomerism that can be shown by an acid with formula C4H8O2.
2. Write the functional isomer of ethnoic acid and give its IUPAC name.
3. You are given two test tubes one containing methanoic acid and another containing ethanoic
acid. Suggest a suitable chemical test to identify them.
4. How would you prepare benzoic acid from (a) Benzene (b) Aniline
5. Why are carboxylic acids stronger acid than phenols and alcohols?
6. How is benzoic acid prepared by the carbonation of Grignard reagent?
7. Why is formic acid not fractioned to get anhydrous formic acid?
8. Why is ethanoic acid halogenated with halogens in red phosphorus but methanoic acid is not
halogenated?
9. Why is amide amphoteric in nature?
10. In the esterification reaction of carboxylic acid with alcohol, the ester so formed is distilled as
fast as it is formed, why?
11. Why is benzamide less easily hydrolyzed than methyl benzoate?
12. Suggest method to prepare benzoic acid from ethanol.
13. How can the presence of carboxylic acid be detected?
1. How can you convert the following organic compounds:
(a) Ethanoyl chloride to (i) methanol (ii) Acetaldehyde
(b) Ethanoic acid to methanoic acid and vice versa.
(c) Ethanoic acid to (i) Ethanoic anhydride (ii) Ethamamide (iii) Methanol (iii) Ethanol (iv)
Methane (v) Methylethanoate (vi) Ethyl ethanoate (vii) Chloroform
(d) Anilline to benzoic acid and vice versa.
(e) Toluene to (i) benzoyl chloride (ii) m-nitrobenzoic acid

(f) Benzyl alcohol to benzoic acid.
(g) Benzene to phenyl acetic acid.
(h) Benzamide to (i) Toluene (ii) Phenyl isocyanide
(i) Benzoic acid to (i) benzophenone (ii) benzene
(j) Benzoyl chloride to benzoic acid
2. What happen when:
(a) Ethanoyl chloride and ammonia is heated with Br2 and aqueous KOH.
(b) Ethanoic acid is allowed to react with (i) NaOH (ii) NaOH/CaO (ii) PCl5 (iii) Heated with
P2O5 (iv) SOCl2 (v) LiAlH4 (vi) HI in presence of red phosphorus (vii) Hot MnO (viii)
Warmed with ethanol in presence of conc. H2SO4. (ix) Ethanol/conc.H2SO4
(c) Methanoic acid act upon: (i) Conc. H2SO4 (ii) methanol / H+ (iii) Fehling's solution (iv)
ammoniacal silver nitrate
(d) Benzoic acid is nitrated
(e) Ethyl acetate is treated with methyl magnesium iodide
(f) Acetyl chloride reacts with phenol in presence of anhydrous AlCl3.
(g) benzamide is heated with bromine and aq. KOH.
3. How would you prepare ethanoic acid from:
(a) Ethane (b) Ethene (c) Ethyne (d) Iodomethane (e) Methanol (f) Methyl magnesium iodide
(g) Tribromoethane (h) Ethanenitrile
4. Explain and give an example of each of: (a) Carboxylation reaction (b) decarbonylation reaction
(c) Perkin condensation (d) Hell-Volhard-Zelinsky reaction (e) Claisen condensation (f) Kolbe's
electrolytic decarboxylation (g) Friedel-Craft acylation
5. How is anhydrous formic acid prepared in the laboratory? Why does formic acid give silver
mirror with tollen's reagent?
6. Why is P2O5 not used for the preparation of anhydrous formic acid? Suggest a suitable method
for the preparation of anhydrous formic acid from impure farmic acid.
7. Identify each lettered in the following reaction sequence.
SOCl2 H2/Pd HCN H2O/H+

CH3 COOH A B C D
Δ
What major product would you obtain when B is treated with alkaline solution of hydrazine
and ethylene glycol?
8. Consider the following reactions:
i. PCl5 Br2/NaOH HNO2

a. A B C D
ii. NH3 Δ Δ
The compound A is a carboxylic acid. Calcium salt of A on heating gives acetone. Identify A, B,
C and D.
NH3 Br2/NaOH NaNO2/HCl
b. A SOCl2 B C D E
Δ Δ
The compound E is a primary alcohol which has positive iodoform test. Identify A, B, C, D and
E.

1. Fatty acids include 6. HCHO and HCOOH can be distinguished by
a. All carboxylic acids a. Tollen’s reagent b. Fehling’s solution
b. Aliphatic carboxylic acids c. Ferric chloride d. Sodium carbonate
c. Aromatic carboxylic acids 7. Which of the following is a food preservative?
d. Open chain monocarboxylic acids a. Sodium acetate b. Sodium propionate
2. Which of the following can directly convert c. Sodium benzoate d. Sodium oxalate
Carboxylic acid into alkane 8. Ethanamide is
a. LIAlH4 b. NaBH4 a. Neutral b. Basic
c. Na in ethanol d. HI and Red P c. Acidic d. Amphoteric
3. Which of the following has lowest boiling point? 9. The acid showing salt like behavior is
a. Propan-1-ol b. 1-Aminopropane a. Acetic acid b. Formic acid
c. Ethanoic acid d. Methoxymethane c. Benzoic acid d. Aminoacetic acid
4. Which of the following order of acidity is correct? 10. Salicylic acid and phenol can be distinguished by
a. HCOOH > CH3COOH > C6H5COOH using.
b. HCOOH >C6H5COOH > CH3COOH a. NaHCO3 b. Neutral FeCl3
c. C2H5COOH > CH3COOH > HCOOH c. 5 % NaOH d. Red litmus
d. C6H5COOH > HCOOH > CH3COOH
5. The reaction of formic acid with conc. H2SO4 gives
a. CO2 b. CO
c. Oxalic acid d. Acetic acid
1 2 3 4 5 6 7 8 9 10
d d d b b d c d d a
Nitro Compounds
2,4,6-Trinitritoluene (TNT)
2,4,6-Trinitrotoluene (TNT) is a nitro compound. It is yellow solid and used as an explosive in quarrying,
controlled demolition of buildings, in military warfare, etc.
14.1 Aliphatic Nitro Compounds (Nitroalkanes)

14.1.1 Introduction
+ O
Organic compounds having nitro group ( N ) as functional group are called nitro compounds.
Examples: O¯
NO2
CH3—NO2 CH3CH2—NO2
Nitromethane Nitroethane Nitrobenzene
When one of the hydrogen atom in alkane is replaced by nitro group (–NO2), the resulting organic
compound is called nitroalkane. Hence, nitroalkanes are nitro derivates of alkanes.
Example:
R—NO2 CH3—NO2 CH3CH2—NO2
R = alkyl group Nitromethane Nitroethane
Nitro group is resonance hybrid of structures I and II or III and IV.
O O O O
+ + O¯ +
R N R N Or R N R N R N
O O¯ O O
O
I II III IV Resonance hybrid
14.1.2 Classification
Depending upon type of carbon to which nitro group is bonded, nitroalkanes are classified into three
different classes; primary, secondary and tertiary nitroalkanes.
1. Primary nitroalkanes: If nitro group is bonded to primary carbon, the nitroalkane is called
primary nitroalkane.
Examples: H
R C NO2 CH3CH2NO2
H Nitroethane
2. Secondary nitroalkanes: If nitro group is bonded to secondary carbon, the nitroalkane is called
secondary nitroalkane.
Examples:
R CH3 CH CH3
R C NO2 NO2
H 2-Nitropropane
Nitro Compounds Unit 14 459
3. Tertiary nitroalkanes: If nitro group is bonded to tertiary carbon, the nitroalkane is called
tertiary nitroalkane.
Example: R CH3
R C NO2 CH3 C NO2
R CH3
2-Methyl-2-nitropropane
14.1.3 Nomenclature
Nitro compounds are named taking Nitro- as prefix.
CH3NO2 Nitromethane
CH3CH2NO2 Nitroethane
CH3CH2CH2NO2 1-Nitropropane
CH3 CH CH3 2-Nitropropane
NO2
CH3CH2CH2CH2NO2 1-Nitrobutane
CH3CH2 CH CH3 2-Nitrobutane
NO2
CH3 CH CH2 NO2 2-Methyl-1-nitropropane

CH3
CH3
CH3 C NO2
CH3
14.1.4 Isomerism
Nitroalkanes can show following types of structural isomerism.
Examples:
CH3CH2CH2CH2NO2 CH3 CH CH2 NO2
CH3
1-Nitrobutane
group or substituent are called positional isomers.
Examples:
CH3CH2CH2NO2 CH3 CH CH3

1-Nitropropane NO2
2-Nitropropane
c. Functional isomerism: Isomers that differ in their functional group are functional isomers.
Nitroalkanes are isomeric with alkyl nitrites.
Example
+ O + O
R N CH3CH2 N CH3CH2 O N O
O R O N O O¯
Alkyl nitrite Nitroethane Ethyl nitrite
Nitroalkane
4. Tautomerism: Primary and secondary nitro compounds having α- hydrogen atoms show
tautomerism, which is called nitro-acinitro tautomerism.
H
+ O + OH
R Cα N R C N
O¯ O¯
H H
Nitro form Aci form (Isonitro form)
(Pseudo acid form) (Nitronic acid)
H O + OH
+ C N
C N
O¯ H O¯
H
Phenyl nitronic acid
Phenyl nitromethane

1. From alkyl halides: When a primary alkyl halide (especially bromides and iodides) is heated
with aqueous ethanolic solution of silver nitrite, nitroalkane is obtained along with little alkyl
nitrite.
Δ + O
CH3CH2Br +AgNO2 CH3CH2 N + AgBr
O¯
Bromoethane Nitroethane
Potassium nitrite instead of silver nitrite gives alkyl nirite.

Δ
CH3CH2Br +KNO2 CH3CH2 O N O + KBr
Ethyl nitrite
Bromoethane
Self Test
14.1 KNO2 is not used instead of AgNO2 to prepare nitroalkanes, give reason.
Hint: See in haloalkanes.
2. From alkanes: When alkane is heated with fuming nitric acid at about 400ºC (vapour phase
nitration), a mixture of all possible nitroalkanes are formed by carbon chain fission reaction of
alkanes.
Examples:
HNO3, 400°C
CH4 CH3NO2
HNO3, 400°C
CH3CH3 CH3CH2NO2 + CH3NO2
HNO3, 400°C
CH3CH2CH3 CH3CH2CH2NO2 + CH3 CH CH3 + CH3CH2NO2 + CH3NO2
NO2
1-Nitropropane 2-Nitropropane Nitroethane Nitromethane
This is an example of substitution reaction where H- atom of alkane is substituted by NO2

group and ease of abstraction of hydrogen atom is in the order 3º>2º>1º.

1. Nitroalkanes are colorless liquids with pleasant odor.
2. They are sparingly soluble in water.

Primary and secondary nitro compounds having α hydrogen atoms are acidic, hence, 1° and 2° nitro compounds react with
aqueous NaOH to form salt.
H O O
+ – + + O¯
H Cα N + OH¯ H2O + H C N H C N
O¯ O¯ O¯
H H H
The acidic nature of α- hydrogen is due to i) -I effect of -NO2 ii) resonance stabilization of anion formed.
1. Reduction
a. Nitroalkane can be reduced in acidic solution using metal and acid usually Sn/HCl, Fe/HCl,
Zn/HCl into primary amine.
Sn/HCl
RNO2 + 6 [H] RNH2 + 2H2O
Fe/HCl
CH3CH2NO2 + 6 [H] CH3CH2NH2 + 2H2O
Nitroethane Ethanamine
Sn/HCl
CH3CH2CH2NO2 + 6 [H] CH3CH2CH2NH2 + 2H2O
1-Nitropropane Propanamine
Reduction of nitro compounds with H2 in presence of Ni or Pt catalyst or by LiAlH4, also give

primary amines.
Ni
CH3CH2NO2 + 3H2 CH3CH2NH2 + 2H2O
LiAlH4
CH3CH2NO2 CH3CH2NH2 + 2H2O
b. Nitroalkanes can be reduced in neutral solution using zinc dust in aqueous ammonium chloride
into N-alkylhydroxylamine.
O Zn/NH4Cl(aq) H
+
R N + 4 [H] R N + H2O
O¯ OH
N - Alkylhydroxylamine
2. Hydrolysis
a. Primary nitroalkanes are hydrolyzed by boiling with aq. HCl or 85% sulphuric acid to
carboxylic acid and hydroxylamine.
HCl
RCH2NO2 + H2O RCOOH + NH2OH
HCl
CH3CH2NO2 + H2O CH3COOH + NH2OH
b. Secondary nitroalkanes are hydrolyzed by boiling with HCl to ketone and nitrous oxide.
H
HCl
2R C NO2 2R C O + N2O + H2O
R R
c. Tertiary nitroalkanes do not undergo hydrolysis.

3. Reaction with nitrous acid
Different classes of nitroalkanes react with nitrous acid to give different products. Hence, this
reaction can be used to distinguish 1°, 2° and 3° nitroalkanes as Hofmann's method.
a. Primary nitroalkanes form crystalline compound of nitrolic acids which is soluble in aqueous
NaOH to give red solution.
H
NaNO2 + HCl R C NO2 + H2O
R Cα NO2 + H O N O
H N OH
Nitrolic acid
b. Secondary nitroalkanes form colorless crystalline compound pseudonitroles which is soluble in

aqueous NaOH to give blue solution.
R R
NaNO2 + HCl
R Cα NO2 + H O N O R C NO2 + H2O
H N=O
Pseudonitrol
c. Tertiary nitralkanes do not react with nitrous acid since they do not have α- hydrogen atom.
R
NaNO2 + HCl
R Cα NO2 + H O N O No reaction
R
4. Halogenation
Primary and secondary nitroalkanes when treated with Cl2 or Br2 in presence of NaOH, undergo α -
halogenation.
H Cl
NaOH
H Cα NO2 + 3Cl2 Cl C NO2 + 3 HCl
H Cl
Trichloronitromethane
Nitromethane
(Chloropicrin)
H H Br
NaOH
CH3 Cα NO2 + Br2 CH3 C NO2 + CH3 C NO2 + HBr
H Br Br
H Br
NaOH
CH3 Cα NO2 + Br2 CH3 C NO2 + HBr
CH3 CH3
14.1.8 Differences between Nitroalkanes and Alkyl Nitrites

Nitroalkanes Alkyl nitrites
1. Boiling point 1. Boiling point
Nitroalkane has higher boiling point than Alkyl nitrite has lower boiling point than that of
that of isomeric alkyl nitrite since the former isomeric nitroalkanes since the former is less polar
is polar compound. compound.
+ O
CH3CH2 O N O
CH3CH2 N
O¯ Ethyl nitrite
Nitroethane
2. Reduction 2. Reduction
Nitroalkane on reduction gives primary Alkyl nitrite on reduction gives alcohol and
amine. ammonia or hydroxylamine.
CH CH NO + 6 [H] Fe/HCl
3 2 2 Fe/HCl CH CH OH + NH + H O
CH3CH2 O N O 3 2 3 2
CH3CH2NH2 +2 H2O
3. Hydrolysis 3. Hydrolysis
Nitroalkane on hydrolysis with acid forms Alkyl nitrite on hydrolysis with acid gives alcohol
carboxylic acid. and nitrous acid. H+
CH3CH2NO2 + H2O H+ CH3CH2—O—N = O + H2O
CH3COOH + NH2OH CH3CH2OH + HNO2
4. Reaction with nitrous acid 4. Reaction with nitrous acid

Nitroalkanes react with nitrous acid to give Alkyl nitrite does not react with nitrous acid.
different products, the nature of products
formed dependent upon the classes of
nitroalkanes (see section 14.1.7)
14.2 Aromatic Nitro Compounds

14.2.1 Introduction and Nomenclature
Nitro derivatives of arenes in which nitro group (-NO2) is directly bonded to aromatic ring are called
aromatic nitrocompounds.
NO2
Nitrobenzene
NO2
NO2 NO2
CH3
CH3 CH3
3-Nitrotoluene 4-Nitrotoluene
2-Nitrotoluene
NO2 NO2 NO2
NO2 NO2 NO2 Cl Br
1.3-Dinitrobenzene 1,3,5-Trinitrobenzene 3-Bromo-5-chloronitrobenzene
CH3 CH3
NO2 NO2 NO2 NO2 NO2
4-Nitrobiphenyl
NO2 2,6-Dinitrotoluene
2,4,6-Trinitoluene
(TNT)
Artificial musks
Polynitro derivatives of benzene having a tertiary butyl group possess musk like odour and hence, is used in perfumery as
artificial musk.
CH3
NO2 NO2
CH3
C CH3
NO2 CH3
'Toluene-musk'
14.2.2 Preparation of Aromatic Nitro Compounds

By nitration of aromatic hydrocarbons (arenes):
Aromatic nitro compounds are prepared by direct nitration of aromatic hydrocarbons. The most
commonly used nitrating reagent is a mixture of concentrated nitric acid and concentrated sulphuric
acid.
NO2
Conc.H2SO4
60°C
NO2
Conc.H2SO4
+ 2HNO3 (conc.) + H2O
90°C
NO2
1.3-Dinitrobenzene
NO2
Conc.H2SO4
+ 3HNO3 (fuming) + H2O
100°C
NO2 NO2
1,3,5-Trinitrobenzene
CH3 CH3
NO2 NO2
Conc.H2SO4
230°C
NO2
2,4,6-Trinitrotoluene (TNT):
Explosive compound
Other reagents used for nitration are (i) concentrated or fuming HNO3 (ii) HNO3 in organic solvents
like acetic acid, nitromethane (iii) nitronium salt in organic solvents (iv) acyl nitrates (v) N2O5 in
CCl4, N2O4.
14.3 Nitrobenzene (Oil of Mirbane)

14.3.1 Laboratory Preparation of Nitrobenzene
Theory: Nitrobenzene is prepared in laboratory by refluxing benzene with a mixture of concentrated
nitric acid and concentrated sulphuric acid to about 40-60°C.
NO2
conc.H2SO4
60°C
Benzene Nitrobenzene
(colourless liquid) (pale yellow oily liquid)
This is an electrophilic aromatic substitution reaction, where the electrohile is nitronium ion (NO2+),
which is generated from a mixture of conc. HNO3 and conc. H2SO4.
Water out
Water condenser
Cold water in
Benzene + HNO3 (conc.) + H2SO4 (conc.)
Water bath
Fig. 14.1: Laboratory preparation of nitrobenzene (reflux)
Procedure
50 ml of benzene is taken in a R.B. flask. A nitrating mixture is prepared by mixing 60 ml of
concentrated HNO3 with 60 ml of concentrated H2SO4 with shaking and cooling. The nitrating
mixture is then added slowly into the R.B. flask a little at a time with shaking and cooling, after each
addition. The temperature of mixture should be maintained below 60ºC. When whole nitrating
mixture is added, the mixture is refluxed on water bath for an hour at about 60°C (at higher
temperature polynitration takes place). Appearance of pale yellow oily layer in the flask indicates the
formation of nitrobenzene. It is allowed to cool and poured it in cold water (for the dilution of
remaining acid). The layer of nitrobenzene is separated using separating funnel.
Purification
i. Nitrobenzene thus obtained is washed with dilute
Na2CO3 to remove acidic impurities.
Aqueous layer
ii. It is then washed with water several times to Nitrobenzene
remove salts.
iii. It is dried with anhydrous CaCl2.
iv. Finally, it is distilled to about 210-215°C using air
condenser to get pure nitrobenzene. Fig. 14.2: Separating funnel, separation
of nitrobenzene from reaction mixture
Thermometer (210°C)
Air condenser
Impure
nitrobenzene Sand bath
Nitrobenzene
Fig. 14.3: Purification of Nitrobenzene by distillation
Mechanism of Nitration
Generation of NO2+ Nitronium ion electrophile is generated from a mixture of conc. HNO3 and conc. H2SO4.
– +
2 H2SO4 + HNO3 H3O+ + 2HSO4 + NO2
Nitronium ion
Step I: NO2 electrophile) is attracted toward π electron cloud of benzene ring to form arenium ion as an intermediate. This
+(
step is slow since aromatic character is destroyed and it determines the rate of reaction (rds).
H NO2 H NO2 H NO2 H NO2

Slow + +
+
+ NO2 (rds) +
+ Resonance hybrid
(Arenium ion)
–
Step II: Abstraction of proton(H+) by HSO4 to give nitrobenzene. This step is fast since aromatic character is restored.
NO2
O2N H
+ Fast
+ HSO4 ¯ + H2SO4

1. Nitrobenzene is pale yellow oily liquid with almond like odour.
2. It is insoluble in water but soluble in organic solvents.
3. All nitro compounds are more dense than water.
4. Its freezing point is 5.7ºC (greenish-yellow crystal) and boiling point is 211ºC.

A. Reaction due to -NO2: Reduction
Nitrobenzene can be reduced to different products depending upon conditions as well as the
nature of reducing agents used in different medium.
1. Reduction in acidic solution: Nitrobenzene can be reduced into aniline in acidic solution using
metal and acid usually Sn/HCl, Fe/HCl, Zn/HCl.
NO2 NH2
Sn/HCl
+ 6 [H] + 2H2O
Aniline
2. Reduction in neutral solution: Nitrobenzene can be reduced into phenylhydroxylamine in

neutral solution using zinc dust in aqueous ammonium chloride .
H N OH
NO2
Zn/NH4Cl(aq.)
+ 4[H] + 2H2O
or Fe/H2O(g)
Phenylhydroxylamine
3. Reduction in alkaline solution: Nitrobenzene can be reduced in different reduced products in

alkaline solution using different reagents.
NO2
Zn/NaOH (aq.) + 4 H2O
2 + 10 [H] N N
H H
Hydrazobenzene
NO2
Zn/NaOH
2 + 8 [H] N N + 4 H2O
or Na2SnOh2/NaOH
( l)
Azobenzene
NO2
Na3AsO3/NaOH + 3 H2O
2 + 6 [H] N N
or Glucose/NaOH
O
Azoxybenzene
4. Catalytic reduction: Nitrobenzene can be reduced catalytically into aniline with H2 in presence
of Ni, Pt or Pd catalyst .
NO2 NH2
Ni
+ 3 H2 + 2H2O
Aniline
5. Reduction with LiAlH4: Nitrobenzene can be reduced into azobenzene with lithium aluminum
hydride .
NO2
LiAlH4 + 2 H2O
2 N N
Azobenzene
6. Electrolytic reduction: Nitrobenzene is reduced into p-Aminophenol by electrolysis in strongly

acidic medium (p-aminophenol is photographic developer).
H OH
NO2 N NH2
conc. H2SO4 Rearrangement
Electricity
H OH
Phenylhydroxyl amine p-Aminophenol
m-Dinitrobenzene can be reduced by sodium sulphide stepwise as;
NO2 NH2 NH2

Na2S or NH4HS Na2S or NH4HS
NO2 NO2 NH2

m-Dinitrobenzene
m-Nitroaniline 1,3-Diaminobenzene
(m-phenylenediamine)
B. Reaction due to benzene ring: Electrophilic aromatic substitution reaction

Nitro group (-NO2) present in benzene governs the reactivity and orientation in electrophilic
aromatic substitution reaction.
Deactivating group
NO2
meta director

Nitrobenzene is less reactive than benzene in electrophilic aromatic substitution reaction:
Nitro group (-NO2) withdraws electrons from benzene ring due to electron withdrawing inductive
effect (- I effect) of – NO2 group since nitrogen is more electronegative than carbon. Similarly - NO2
group also withdraws electron from benzene ring due to resonance effect to give the following
resonance structures.
NO2
–I effect of –NO2 in nitrobenzene

– – – – – – – –
δ– δ–
O + O O + O O + O O O
O +
N
O
N N N
O +
N O +
N
+
+

δ+ δ+

+
δ+
I II III IV V
Resonance hybrid
Resonating structures of nitrobenzene
The electron-withdrawing –NO2 group decreases the electron density in benzene ring of
nitrobenzene as compared to that in benzene. A substituent which makes the benzene ring less
reactive than benzene in electrophilic aromatic substitution is called deactivating group. Hence,
−NO2 is a deactivating group. Therefore, nitrobenzene is less reactive than benzene in electrophilic
aromatic substitution reaction. Nitrobenzene is roughly one million times less reactive than benezne.
Nitrobenzene gives meta substituted products in electrophilic aromatic substitution reaction.
The electron-withdrawing deactivating –NO2 group
decreases the electron density in benzene ring of
nitrobenzene as compared to benzene which makes
each position of nitrobenzene less reactive than δ– δ–
O + O
benzene towards electrophilic aromatic substitution
N
reaction. However, due to resonance, the partial
positive charge (δ+) is developed at ortho- and para- δ+ δ+ +
E (Electrophile)
positions. The electron density is low at ortho- and para-
δ+
positions. So, electrophilic attack becomes difficult in
these positions. Hence, in electrophilic aromatic
substitution reaction, –NO2 electrophile selectively
attacks the meta position to give meta substituted
products.
A substituent which directs the incoming electrophile chiefly at meta position to it in electrophilic
aromatic substitution is called meta director. Hence, -NO2 is meta director.
1. Halogenation
NO2 NO2
FeCl3 + HCl
+ Cl2
Cl
m- Chloronitrobenzene
2. Nitration NO2 NO2

Conc.H2SO4 + H2O
+ HNO3 (conc.)
90°C
NO2
m-Dinitrobenzene
NO2 NO2
Conc.H2SO4
+ 3HNO3 (Fuming) + 3 H2O
100°C
O2N NO2
1,3,5-Trinitrobenzene
3. Sulphonation
NO2 NO2
Δ + H2O
+ H2SO4(Fuming)
SO3H
m-Nitrobenzenesulphonic acid
4. Friedel-Crafts reaction
Nitrobenzene does not give Friedel-Crafts reaction. This is due to strongly deactivating effect of
–NO2.
Nucleophilic substitution: When nitrobenzene is fused with solid KOH, ortho and para nitrophenols are obtained. This
is nucleophilic substitution reaction.
NO2 NO2 NO2
KOH (s), Δ OH +
Nitrobenzene o-Nitrophenol OH
p-Nitrophenol
14.3.4 Uses of Nitrobenzene

i. Nitrobenzene is used to prepare aniline.
ii. It is also used in shoes polishes, paint solvent to mask unpleasant odour.
iii. It is also used used as inexpensive perfume for soaps.
iv. It is also used as solvent.
Solved Questions
1. Convert benzene into azoxybenzene.
¬ NO2
Conc.HNO3 +Conc.H2SO4 Glucose/NaOH

N N
60°C
Benzene Nitrobenzene O
Azoxybenzene
2. How do you get m-Bromoaniline from benzene?

¬
NO2 NH2
NO2
Conc.HNO3 +Conc.H2SO4 Br2, FeBr3 Sn/HCl

60°C
Br Br
Benzene Nitrobenzene m- Bromonitrobenzene m- Bromoaniline
3. Write the functional isomers of molecular formula C2H5NO2 and suggest a suitable
chemical test to distinguish them.
¬
+ O
CH3CH2 N CH3CH2 O N O
O¯ Ethyl nitrite
Nitroethane
Nitroethane gives red solution when treated with nitrous acid followed by dil. NaOH but ethyl nitrite does
not.
H
CH3—C—NO2 + H—O—N = O NaNO2 + HCl CH —C—NO + H O NaOH
3 2 2 red solution
H —
N OH
Nitrolic acid
4. Nitro group (-NO2) is meta director in electrophilic aromatic substitution reaction,

explain.
¬ Nitro group (-NO2) withdraws electrons from benzene ring due to –I effect of –NO2 since nitrogen is more
electronegative than carbon.
NO2
Inductive effect
(–I) in nitrobenzene
Nitro group (-NO2) withdraws electrons from benzene ring due to resonance effect too.
– – – – – – – –
δ– δ–
O + O O + O O + O O + O O + O O + O
N N N N N N
+ + δ+ δ+
+
δ+
I II III IV V
Resonance hybrid
Resonating structures of nitrobenzene
Hence, nitro group decreases the electron density in benzene ring of nitrobenzene as compared to benzene
making each positions of nitrobenzene less reactive than corresponding positions in benzene towards
electrophilic aromatic substitution reaction. However, due to resonance, the partial positive charge (δ+) is
developed at ortho- and para- positions. The electron density is low at ortho- and para- positions. So,
electrophilic attack becomes difficult in these positions. Hence electrophile attacks the meta positions to give
meta substituted products.
δ– δ–
O + O
N
δ+ δ+ +
E (Electrophile)
δ+
A substituent which directs the incoming group chiefly at meta to it in electrophilic aromatic substitution is
called meta director.
Questions
1. Nitroethane boils at higher temperature than ethyl nitrite although both have the same
molecular weight, explain.
2. Suggest a suitable chemical test to distinguish nitroethane from ethyl nitrite.
3. Identify A, B, C, D and E giving complete equations.
Zn/NH4Cl(aq)
a. Nitrobenzene A
Zn/NaOH(aq)
b. Nitrobenzene B
Zn/NaOH(alc)
c. Nitrobenzene Glucose
C
Zn/HCl
d. Nitrobenzene D
Conc. H2SO4
e. Nitrobenzene Electrolysis
E
4. Identify X and Y
Conc. HNO3, Conc.H2SO4 Na2S
X Y
90°C
5. Why is nitrobenzene less reactive than benzene in electrophilic aromatic substitution reaction?
6. How can you distinguish
a. 1°, 2° and 3° nitroalkanes
b. Amines and nitroalkanes
1. Identify A, B, C and D in the given reactions.
(a)
NO2
Sn/HCl NaNO2/HCl H2O/H+ CHCl3/KOH
A B C D
ice cold Δ Δ
(b)
conc.HNO3 Fe/HCl CHCl3,KOH LiAlH4

A B C D
conc.H2SO4
2. a. How is nitribenzene prepared in laboratory in pure and dry state?

b. Identify A and B giving complete reactions.
P4+I2 KNO2(alc) H2O/H+

CH3CH2OH A1 A2 A3 + A4
reflux
SOCl2 AgNO2(alc) H2O/H+

CH3CH2OH B1 B2 B3 + B4
reflux
3. How can you convert nitrobenzene into
a. Phenylhydroxylamine b. Azobenzene
c. Azoxybenzene d. p-Aminophenol
e. m-Nitroaniline f. p-Hydroxyazobenzene
4. Write short notes on:

a. Reduction of nitrobenzene in acidic, neutral, and alkaline medium
b. Laboratory preparation of nitrobenzene
5. How can you convert
a. Ethane into nitroethane
b. Phenol into nitrobenzene
c. Nitroethane into ethene
d. Nitroethane into ethanol
a. 1–Nitropropane is hydrolysed
b. 2–Nitropropane is hydrolysed
c. Nitrobenzene is reduced using Zn +NaOH
d. Iodoethane is treated with alcoholic KNO2
e. Nitroethane is reduced in neutral medium.
Q Multiple Choice Questions

1. Nitro compounds do not exhibit c. Free redical substitution d. Electrophilic addition
a. Functional isomerism b. Tautomerism 9. Which of the followings is the least reactive in
c. Chain isomerism d. Metamerism electrophilic aromatic substitution?
2. Nitroethane and ethyl nitrites are a. Aniline b. Toluene
a. Tautomers b. Metamers c. Chlorobenzene d. Nitrobenzene
c. Functional isomers d. Isomers 10. Reduction of nitrobenzene with zinc and aqueous
3. Reduction of nitroalkane gives NaOH gives
a. Alohol b. Alkane a. Hydroxylamine b. Azobenzene
c. Alkyl amine d. Ammonia c. Hydrazobenzene d. Azoxybenzene
4. Hydrolysis of nitroethane gives 11. Reduction of nitrobenzene with zinc dust and
a. Acetic acid and hydroxyl amine aqueous ammonium chloride gives
b. Alcohol and nitrous acid a. Phenylhydroxylamine b. Azobenzene
c. Alcohol and ammonia c. Hydrazobenzene d. p-Aminophenol
d. Ketone and Nitrous oxide 12. When nitrobenzene is fused with caustic alkali, o‐
5. Hydrolysis of secondary nitroalkane gives and p‐nitrophenol are formed.The reaction is
a. Carboxylic acid b. Alcohol a. Electrophilic substitution
c. Ketone d. Hydroxyl amine b. Nucleophilic substitution
6. When treated with nitrous acid followed by caustic c. Free redical substitution
alkali, secondary nitroalkane gives d. Electrophilic addition
a. Red colour due to nitrolic acid 13. Reduction of nitrobenzene with lithium aluminium
b. Blue colour due to pseudonitrol hydride gives
c. Red colour due to pseudonitrol a. Hydroxylamine b. Azobenzene
d. Blue colour due to salt of nitrolic acid c. Hydrazobenzene d. p-Aminophenol
7. Nitrobenzene is 14. Electrolytic reduction of nitrobenzene in
a. Oil of wintergreen b. Oil of vitriol concentrated sulphuric acid gives
c. Paraffin oil d. Oil of mirbane
a. Hydroxylamine b. Azobenzene
8. Nitration of benzene with concentrated nitric acid in c. Hydrazobenzene d. p-Aminophenol
presence of sulphuric acid is
a. Electrophilic substitution b. Nucleophilic substitution
1 2 3 4 5 6 7 8 9 10 11 12 13 14
d c c a c b d a d c a b b d
Amines
Adrenal glands
Kidneys
OH H
OH H
N
N C H
C CH3 HO CH
HO CH
HO
HO
Noradrenaline
Adrenaline
Adrenaline and noradrenaline are hormones and neurotransmitters produced by adrenal glands.
15.1 Introduction
When one, two or all three hydrogen atoms in ammonia molecule are replaced by alkyl or aryl
groups, the resulting organic compounds are called amines.
Examples:
H N H R N H R N R R N R
H H H R
ammonia where R= alkyl or aryl group

amines
Amines are classified into two broad classes; aliphatic amines and aromatic amines.
If R is alkyl group, the amines are called aliphatic amines.
Examples:
CH3 N H CH3 N CH3 CH3 N CH3 CH3 CH2 N CH3

H H CH3 CH3
If R is aryl group (at least one ), the amines are called aromatic amines.
Examples:
H H H CH3 CH3 CH3

N N N
N N
If aromatic ring is not directly bonded to amino group, e.g. ArCH2NH2, the amines are called aryl
substituted aliphatic amines aryl alkyl amine since they behave very much like aliphatic amines.
Example:
CH2 NH2
Benzyl amine
When all alkyl or aryl groups are same, the amines are called simple amines otherwise called mixed
amines.
Examples:
CH3—N—CH3 CH3—N—CH3 CH3—N—CH2CH3 CH3CH2—N—CH3
H CH3 H CH3
simple amine simple amine mixed amine mixed amine
In nature, amino functional group occurs in wide range of organic compounds like amino acids,
dyes, drugs, vitamins, hormones etc.
Amines Unit 15 477
15.2 Classification
Depending upon number of alkyl or aryl group present on nitrogen atom, amines are classified into
three different classes; primary, secondary and tertiary amines.
1. Primary amines: When only one hydrogen atom of ammonia molecule is replaced by alkyl or
aryl group the amine is called primary or 1° amine. It is represented by RNH2. The functional
group of primary amine is -NH2 (amino group).
Examples:
CH3 H H
H N
CH3—C—CH3 CH3—C—CH2—NH2
CH3CH2NH2
NH2 CH3
2. Secondary amines: When two hydrogen atoms of ammonia molecule are replaced by alkyl or
aryl groups, the amine is called secondary or 2°amine. It is represented by R2NH. The functional
group of secondary amine is -NH- (imino group).
Examples:
H CH3
N
H
CH3—N—CH3 CH3—N—CH2CH3
N
H H
3. Tertiary amines: When all three hydrogen atoms of ammonia molecule are replaced by alkyl or
aryl groups, the amine is called tertiary or 3° amine. It is represented by R3N. The functional
group of tertiary amine is N (tertiary nitrogen atom).
Examples:
CH3 CH3
N
CH3—N—CH3 CH3CH2—N—CH3
N
CH3 CH3
Wurtz (1849) discovered amines by boiling alkyl isocyanates with alkali.

Boil
RNCO + 2 KOH RNH2 + K2CO3
15.3 Structure of Amines

sp3 sp3 sp3
N N N
H H CH3 H CH3
CH3
H H CH3
Ammonia Primary amine Tertiary amine
Like in ammonia molecule, nitrogen atom of an amine molecule is sp3 hybridised to form four sp3
orbitals. One sp3 orbital is fulfilled and does not take part in bonding but remaining three sp3 orbitals
are half filled and participate in bonding.
In primary amine like methyl amine, one half filled sp3 orbital of nitrogen atom overlaps with half
filled sp3 orbital of carbon atom forming N–C sigma bond. The remaining each half filled sp3 orbital
of nitrogen overlaps with half filled 1s orbital of hydrogen forming N–H sigma bonds.
1s
sp3
sp3
sp3 sp3
sp3 N sp3
C
1s 1s
sp3 sp3
1s 1s
Orbital picture of methyl amine
15.4 Nomenclature
In IUPAC system, aliphatic amines are named by taking amino- as prefix to the name of parent
alkane and they are also named by taking the word- amine as suffix to the name of parent alkane. If
alkyl group is present on nitrogen atom as substituent, it is indicated by writing N - before the
substituent. In common system, amines are named by naming alky group followed by the ending -
amine.
Structural formula IUPAC name Common name

CH3NH2 Aminomethane or Methanamine Methyl amine
CH3CH2NH2 Aminoethane or Ethanamine Ethyl amine
CH3 N CH3 N-Methylaminomethane Dimethyl amine
H
CH3CH2CH2NH2 1-Aminopropane n-Propyl amine
CH3 CH CH3 2-Aminopropane Isopropyl amine
NH2
CH3CH2 N CH3 N-Methylaminoethane Ethyl methyl amine
H
CH3 N CH3 N,N-Dimethylaminomethane Trimethyl amine
CH3
If two or more amino groups are present, then their position is indicated.
Example:
H2N—CH2CH2—NH2
Ethane-1,2-diamine
Amines Unit 15 479
Putrescine and cadaverine are amines which are largely responsible for the foul odour of decaying
dead animal body (proteins).
H2N—CH2CH2CH2CH2—NH2 H2N—CH2CH2CH2CH2CH2—NH2
1,4-Diaminobutane 1,5-Diaminopentane
(Putrescine) (Cadaverine)
15.5 Salts of Amines

Like ammonia, all classes of amines are basic in nature hence react with acids to form ammonium
salts. These salts are generally named by replacing -amine by -ammonium or aniline by anilinium and
adding the name of the anion.
NH3 + HCl NH4Cl
or
H +
–
H N H + HCl H N H Cl
H H
Ammonium chloride
Examples:
H +
R N H –
R N H + HX X
H H
1º amine Alkyl ammonium
Ammonium salts
halide
H +
–
R N R + HX R N R X
H H
2º amine
Dialkyl ammonium halide
(Secondary ammonium salt)
H +
–
R N R + HX R N R X
R R
3º amine Trialkyl ammonium
halide
Tertiary amine reacts with alkyl halide to form a salt of type R4N+X- which is called quaternary
ammonium salt. Here, nitrogen atom is quadricovalent unielectrovalent.
Examples:
H +
R N R –
R N R + RX X
R R
Tetraalkyl ammonium halide

CH3 +
CH3 +
–
– CH3CH2 N CH3 Cl
CH3 N CH3 Cl or (CH3)4N+ Cl–
CH3 CH3
Ethyltrimethylammonium chloride
Tetramethylammonium chloride
Quaternary ammonium salts are white crystalline solids and soluble in water.
Quaternary ammonium salts having a long chain alkyl group have detergent properties. They are also known as invert soaps
because their surface activity is due to positive ion ( +

N ). Surface activity of detergents and soaps are due to negative ion
(
– ).
O
15.6 Isomerism
Amines can show following types of structural isomerism.
Examples:
CH3
CH3—CH—CH2—NH2 CH3—C—NH2
CH3CH2CH2CH2NH2 CH3 CH3
1-Aminobutane 2–Methyl-1-aminopropane 2–Methyl-2-aminopropane
1-Butanamine
group or substituents are called positional isomers.
Examples:
CH3
CH3CH2CH2NH2 CH3—C—NH2
H
1–Aminopropane 2–Aminopropane
3. Functional isomerism: Isomers that differ in their functional group are functional isomers. 1°,
2° and 3° amines are functional isomers.
Examples: CH3—N—CH3
CH3CH2NH2
H
Aminoethane N-Methylaminomethane
Functional group= —NH2 Functional group = —NH—
(1° amine) (2° amine)
4. Metamerism: Isomers that differ in alkyl group present on either side of the same functional
group are called metamers. Secondary amines can show this type of isomerism. For example,
C4H11N has following three metamers.
Amines Unit 15 481
Examples:
CH3CH2—N—CH2CH3 CH3CH2CH2—N—CH3 CH3—CH—N—CH3
H H CH3 H
N-Ethylaminoethane N-Methyl-1-aminopropane N-Methyl-2-aminopropane
Self Test
15.1 What are amines? Write structure of amines of molecular formula C3H9N, indicate their
functional group, classify them as primary, secondary and tertiary amines and give their name.
Hint: 4 isomers
15.2 Write structures of amines of molecular formula C4H11N, classify them as primary, secondary
and tertiary amines and give their name. Hint: 8 isomers
15.7 General Methods of Preparation

A. Methods Giving Mixture of Amines
1. From alkyl halides (Hofmann's ammonolysis of alkyl halides): When an alkyl halide is heated
with aqueous or alcoholic solution of ammonia at 100°C in a sealed tube or allowed to stand at
room temperature, amine is formed. By varying the proportions of ammonia and alkyl halide,
particular class of amine can be obtained in large proportion.
a. If ammonia is in excess, primary amine is obtained.
δ δ–
H—N—H + R X R—N—H + HX
H H
Example: 1° amine
H
δ+ δ–
H—N—H + CH3 — C — Br CH3CH2—N—H + HBr
H H H
Ethylamine
b. If alkyl halide is in excess, a mixture of primary, secondary and tertiary amines and quaternary
ammonium salt is obtained.
δ+ δ–
H—N—H + R X R—N—H + HX
H H
1° amine
δ+ δ–
R—N—H + R X R—N—R + HX
H H
1° amine 2° amine
δ+ δ–
R—N—H + R X R—N—R + HX
R R
2° amine 3° amine
Example: when ammonia is heated with excess ethyl bromide,

H
δ+ δ–
H—N—H + CH3 — C — Br CH3CH2—N—H + HBr
H H H
Ethylamine
H
δ+ δ–
CH3CH2—N—H + CH3 — C — Br CH3CH2—N—CH2CH3 + HBr
H H H
Diethylamine
H
δ+ δ–
CH3CH2—N—CH2CH3 + CH3 — C — Br CH3CH2—N—CH2CH3 + HBr
H H CH2CH3
Triethylamine
+
(CH3CH2)3N + CH3CH2Br (CH3CH2 )4N Br–
Tetraethylammonium
bromide
or,
NH3 CH3CH2Br CH3CH2Br
CH3CH2Br CH3CH2NH2 (CH3CH2 )2NH (CH3CH2 )3N
Ethyl bromide Ethyl amine Diethyl amine Triethyl amine
CH3CH2Br
+
(CH3CH2 )4N Br–
Tetraethyl ammonium
bromide
Note:
i. This method has disadvantage of getting mixture of different classes of amines.
ii. The order of reactivity of alkylhalides with amines is RI > RBr > RCl.
iii. This is nucleophilic substitution reaction. Here, ammonia, primary and secondary amine acts as nucleophile. Primary alkyl
halide gives good yield of amine by nucleophilic substitution but tertiary alkyl halide gives alkene by elimination reaction.
CH3 CH3
CH3—C—Br + NH3 CH3—C = CH2 + NH4Br
CH3 2-Methylpropene
3°alkyl halide
iv. This method is not suitable for the preparation of aryl amines since aryl halides are less reactive towards nucleophilic
substitution reaction.
Self Test
15.3 Identify A in the following reaction sequence:
NH3 CH3I CH3I CH3I
CH3I A1 A2 A3 A4
2. From Alcohols: When alcohol is heated with ammonia in presence of catalyst like alumina or
copper chromite, a mixture of primary, secondary and tertiary amines is obtained.
Amines Unit 15 483
Example:
Al2O3, 450°C
CH3 OH + H N H H N CH3 + H2O
H H
Al2O3, 450°C
CH3 OH + H N CH3 H N CH3 + H2O
H CH3
Al2O3, 450°C
CH3 OH + H N CH3 CH3 N CH3 + H2O
CH3 CH3
B. Preparation of Primary Amines

1. From nitro compounds: Catalytic reduction of nitro compounds with H2 in presence of finely
divided Ni or Pt catalyst or chemical reduction with metal and acid usually Sn/HCl, Fe/HCl
give primary amines.
Examples: Sn/HCl
CH3CH2CH2NO2 + 6 [H] CH3CH2CH2NH2 + 2H2O
1-Nitropropane 1-Aminopropane
NO2 NH2
Ni
+ 3 H2 + 2H2O
Nitrobenzene Aniline
NO2 NH2
Sn /HCl
+ 6 [H] + 2H2O
This is the most useful method of preparing aromatic amines. This is because starting material,
aromatic nitro compound, is readily available (by direct nitration of aromatic hydrocarbons)
and the product primary aromatic amine is the most important kind of amine.
2. From nitriles: Reduction of nitriles with H2/Ni, Na/C2H5OH , LiAlH4 give primary amines.
H2/Ni
RCN LiAlH4 R—CH2NH2

Nitrile Na/C2H5OH 1° amine
CH3CH2CN + 4 [H] Na/C2H5OH CH3CH2CH2NH2
Propane nitrile 1-Aminopropane
CN CH2NH2
Ni
+ 2 H2
Benzonitrile Benzylamine
This method is useful for increasing carbon chain length by one carbon atom.
Examples:
PBr3 alc. KCN H2/Ni
CH3CH2OH CH3CH2Br CH3CH2CN CH3CH2CH2NH2
Ethanol Bromoethane Propane nitrile 1-Aminopropane
Reduction of nitrile into primary amine with Na/C2H5OH is called Mendius reaction.
Self Test
15.4 Convert ethyl amine into n-propyl amine.
3. From amides: From amides, amines can be obtained by two different ways:
a. By reduction: Reduction of amide with LiAlH4 or Na/C2H5OH gives primary amine.
O
LiAlH4
R—C—NH2 RCH2NH2 + H2O
b. By Hofmann hypobromite rearrangement/Hofmann degradation (1881): When acid amide is

warmed with bromine (or chlorine) and aqueous or alcoholic caustic alkali, primary amine
having one carbon less than the amide is formed. This reaction is commonly known as
Hofmann degradation.
O
Warm
R—C—NH2 + Br2 + 4 KOH(aq) RNH2 + 2KBr + K2CO3 + 2H2O
Amide Primary amine
Examples:
O
Warm
CH3—C—NH2 + Br2 + 4 KOH(aq) CH3NH2 + 2KBr + K2CO3 + 2H2O
Ethanamide Methyl amine
O
Warm CH3CH2NH2 + 2KBr + K2CO3 + 2H2O
CH3CH2—C—NH2 + Br2 + 4 KOH(aq)
Propanamide Ethyl amine
O
Warm
C—NH2 + Br2 + 4 KOH(aq) NH2 + 2KBr + K2CO3 + 2H2O
Benzamide Aniline
O
The overall result is removal of carbonyl group, C from amide. Hence this reaction is
decabonylation reaction.
This method is utilized in descending the series by one carbon. This can be illustrated by the
conversion of ethyl amine into methyl amine.
Amines Unit 15 485
O O
NaNO2+HCl KMnO4/H+ SOCl2
CH3CH2NH2 CH3CH2OH CH3 C OH CH3 C Cl
reflux Acetyl chloride
Ethyl amine Ethyl alcohol Acetic acid
NH3
Br2,NaOH O
CH3NH2 CH3 C NH2
Methyl amine warm Acetamide
Self Test
15.5 What is Hofmann's degradation reaction? Illustrate its application by the conversion of ethyl
amine into methyl amine.
O
NaOH, Br2, warm
Mechanism R—C—NH2 R—NH2
2 NaOH + Br2 2 NaBr +NaOBr +H2O

+
K
R N H R N + OH¯ R N—Br
C + O—Br C C
H H
O O O
–KBr
N–Bromamide
(I)
R N
H2O Rearrangement C
RNH2+ Na2CO3 R—N = C = O
Isocyanate 1, 2-alkyl shift
(II)
O
N-bromamide (I), its salt and isocyanate (II) have been isolated.
Note:
This reaction is also called Hofmann hypobromite reaction the actual reagent for this reaction is hypobromite ion,O-Br). In
Hofmann bromamide reaction, N-bromamide is formed as intermediate which can be isolated and Hofmann rearrangement
takes place in a stage of this reaction.
4. From alkyl halide (Gabriel phthalimide synthesis, 1887): In this method, phthalimide is
converted into its salt by treating with alcoholic caustic potash. The salt is then treated with
primary alkyl halide to get N-alkylphthalimide, which is hydrolyzed by heating with 20% HCl
or KOH to get primary amine and phthalic acid. If KOH is used potassium salt of phthalic acid
is obtained.
O O O O
C C δ+
δ– C C
— KOH
N— H K OH N– K+ R X N— R RNH2 +
OK
–H2O OK
C C C C
1° amine
O O O O
Phthalimide Potassium phthalimide N–alkyl phthalimide
This method gives pure primary amine and phthalimide is regenerated from phthalic acid.
Aromatic primary amines cannot be prepared by this method because aryl halides do not
undergo nucleophilic substitution easily.
5. From aldehydes and ketones (Reductive ammination): Aldehydes and ketones react with
ammonia in presence of reducing agent like H2/Ni or NaBH3CN (sodium cyanohydridoborane)
to give primary amine. This is called reductive ammination of aldehydes and ketones.
H H H
H H2/Ni
R—C = OH+ N—H R—C = N—H R—C—NH2
H –H2O
H
imine
1° amine
Example:
H H
H2/Ni
CH3—C = O + NH3 CH3—C = N—H CH3CH2NH2
–H2O
Acetaldehyde Aminoethane (1°)
CH3 CH3 CH3

H2/Ni
CH3—C = O + NH3 CH3—C = N—H CH3—C—NH2
–H2O
Acetone H
2-Aminopropane (2°)
H H
H2/Ni
C = O + NH3 C = N—H CH2NH2
–H2O
Benzaldehyde Benzylamine
6. From isocyanides: Alkyl isocyanides are hydrolyzed to an primary amine and formic acid by
dilute acids but not hydrolyzed by alkalis.
RNC + 2 H2O H2O/H+ RNH2 + HCOOH
CH3—N H2O/H+
C + 2 H2O CH3—NH2 + HCOOH
Preparation of primary amines: An overview

alc KCN H2/Ni RCH2CH2NH2
RCH2CN
(amine with one carbon more)

PBr3 )
RCH2Br
reflux
NH3 (excess)
RCH2NH2
RCH2OH (amine with same carbon)
LiAlH4
O O O
KMnO4/H+ SOCl2 NH3 Br2,NaOH
R C OH R C Cl R C NH2 RNH2
reflux warm
(amine with one carbon less)
Amines Unit 15 487
Self Test
15.6 How do you prepare n-propyl amine from i) 1-Nitropropane ii) n-Propyl bromide
iii) n-Propyl alcohol iv) n-Butyl alcohol v) Ethyl alcohol
C. Preparation of Secondary Amines

1. From alkyl halides: When primary amine treated with calculated amount of alkyl halide,
secondary amine is obtained.
δ+ δ–
R—N—H + R—X R—N—R + HX
H H
2° amine
2. From aldehydes and ketones: Aldehydes and ketones react with primary amine in presence of
reducing agent like H2/Ni or NaBH3CN (sodium cyanohydridoborane) to give secondary
amine.
H H H
H2/Ni
CH3—C = O + CH3CH2NH2 CH3—C = N CH2CH3 CH3CH2—N—CH3
N- Methylaminoethane
(2° amine)
3. From N-substituted amides: Reduction of N-substituted amide with LiAlH4 or Na/C2H5OH

gives secondary amine.
O
LiAlH4
CH3—C—N—CH3 CH3CH2—N—CH3 + H2O
H H
N–Methylethanamide N–Methylethanamine
4. From isonitriles: Reduction of isonitrile with H2/Ni, LiAlH4 or Na/C2H5OH gives secondary
amines. H2/Ni or
LiAlH4 or
Na/C2H5OH
RNC R—N—CH3
Isonitrile
Examples: H
2° amine
Na/C2H5OH
CH3CH2NC + 4[H] CH3CH2—N—CH3
Ethyl carbylamine H
(Ethyl isonitrile / Ethyl isocyanide) N–Methylehanamine
N C H—N—CH3
Na/C2H5OH
+ 4[H]
Phenyl carbylamine N–Methylaniline

(Phenyl isocyanide)
D. Preparation of Tertiary Amines

1. From aldehydes and ketones: Aldehydes and ketones react with secondary amine in presence
of reducing agent like H2/Ni or NaBH3CN (sodium cyanohydridoborane) to give tertiary
amine.
H
H2/Ni
CH3—C = O + CH3—N—H CH3CH2—N—CH3 + H2O
CH3 CH3
N,N–Dimethylaminoethane
2. From N,N-disubstituted amides: Reduction of N,N-disubstituted amide with LiAlH4 or

Na/C2H5OH give tertiary amine.
O
LiAlH4
CH3—C—N—CH3 CH3CH2—N—CH3 + H2O
CH3 CH3
N,N–Dimethylethanamide N,N–Dimethylaminoethane
3. From quaternary ammonium salt: Quaternary ammonium salt reacts with moist silver oxide or
methanolic KOH to give quaternary ammonium hydroxide.
+ – + –
R4 N X + AgOH R4 N OH + AgX ↓
When quaternary ammonium hydroxide is heated strongly ( to 125°C or higher), it undergoes

decomposition to give alkenes, tertiary amine and water.
CH3 CH3
+ –
CH3—N—CH2CH2CH3OH CH3—N + CH3CH = CH2 + H2O
Δ
CH3 CH3
Trimethyl-n-propylammonium hydroxide
–
(CH3)4 N+OH (CH3)3N + CH3OH
Δ
Note:
Quaternary ammonium hydroxides are white deliquescent crystalline solids. Their solution is strongly alkaline comparable to
that of NaOH or KOH due to complete dissociation producing OH¯.
15.8 Separation of Amines

1. Fractional distillation: Primary, secondary and tertiary amines can be separated from their
mixture by fractional distillation since they differ in their boiling point. The success of this
method is due to high efficiency of fractionation apparatus.
2. Hofmann method: This method is a convenient method for the separation of different classes of
amines from their mixture. In this method, the mixture of amines is treated with diethyl oxalate.
Different classes of amines react differently.
i. Primary amine reacts with diethyloxalate to form dialkyloxamide which is solid.
δ–
O
O H
R—N—H + δ+ C—OC2H5
C—N—R + 2 C2 H5OH
H
δ+ C—OC2H5 C—N—R
R—N—H
δ– O O H
H
1° amine Diethyloxalate Dialkyloxamide (solid)
Amines Unit 15 489
ii. Secondary amine reacts with diethyloxalate to form dialkyloxamic ester which is generally
liquid.
δ– O
O R
R—N—H + δ+ C—OC2H5
C—N—R + C2 H5OH
R
C—OC2H5 C—OC2H5
2° amine
O O
Diethyloxalate Dialkyloxamic ester (liquid)
Dialkyl oxamic ester does not react further with another molecule of 2º amine due to steric
hinderance.
iii. Tertiary amine does not react with diethyloxalate presumely due to lack of hydrogen with
nitrogen.
The resulting mass (dialkyl oxamide, dialkyloxamic ester, 3º amine and ethyl alcohol) is
subjected to fractional distillation. Here, 3º amine distills first followed by ethyl alcohol.
The remaining mass is filtered. The residue (dialkyloxamide) is treated with caustic alkali
to recover primary amine.
O H
O
C—N—R
C—OK + 2 R—N—H
+ 2 KOH
C—N—R C—OK H
O H O
Potassium oxalate 1° amine
Dialkyloxamide
The filtrate (dialkyloxamic ester) is treated with caustic alkali followed by fractional
distillation to get secondary amine and ethyl alcohol on different fractions.
O R O
C—N—R C—OK
+ 2 KOH + R—N—H + C2H5OH
C—OC2H5 C—OK R
O O
Dialkyloxamic ester Potassium oxalate 2° amine
(liquid)
In this way, different classes of amines are separated.
15.9 Physical Properties

1. State: Lower members of amines are gases and liquids, higher members are solid.
2. Odour: Methyl amines and ethyl amines have ammonical odour and higher alkyl amines have
fishy odour.
3. Solubility: All classes of amines can form intermolecular H-bond with water. Hence, lower
members are soluble in water. The solubility decreases with increase in size of water insoluble
hydrocarbon part. Amines are soluble in organic solvents.
δ– δ+ δ– δ+
R—N—H '''''''''''''''' O—H
δ+
R H
4. Boiling point
i. There exists intermolecular H-bond in primary and secondary amines due to polar nature
of N-H bond. Tertiary amines have no N-H bond and can not form intermolecular H-bond
among their molecules. Hence, amines, except tertiary amines have higher boiling point
than nonpolar compounds of comparable molecular weight. Order of boiling points of
amines is primary> secondary> tertiary
ii. Amines have lower boiling point than alcohols of comparable molecular weight.
This is because intermolecular H-bond in amine is weaker than that in alcohol since N-H
bond is less polar than O-H bond.
R
δ– δ+ δ– δ– δ+ δ– δ+
R—O '''''''''''''''' H—O R—N—H '''''''''''''''' N—H
δ+
H R H δ+ H δ+
Intermolecular H-bonding in alcohol
Intermolecular H-bonding in primary amine
Self Test
15.7 Ethyl amine has lower boiling point than that of ethyl alcohol, explain.
15.8 The boiling point of following isomeric amines is observed in the order: n-Propyl amine(B Pt.
49ºC) > Ethylmethyl amine(B. Pt 36ºC ) > Trimethyl amine (3ºC). How do you account for this
order of their boiling point?
15.10 Chemical Properties

Amines have an unshared pair of electrons in nitrogen atom which governs the chemical behaviour
of amines. Due to unshared pair of electrons, an amine can act as a nucleophile as well as a base. The
number of alkyl or aryl groups bonded to nitrogen atom also decides the pattern of reaction and
reactivity of amines. This is why 1°, 2° and 3° amines differ in many reactions.
1. Reaction with acids: Basic nature: Like ammonia, all classes of aliphatic as well as aromatic
amines are basic. Amines show appreciable basicity enough to turn red litmus into blue. They
react with mineral acids and carboxylic acids to form salt.
Examples:
RNH2 + HX RNH3+X–
Alkylammonium halide
R2NH + HX R2NH2+X–
Dialkylammonium halide
R3N + HX R3NH+X–
Trialkylammonium halide
Amines Unit 15 491
+
δ– δ+ δ– δ+
CH3NH2 + HCl CH3NH2 HCl or [CH3 NH3] Cl¯
Methyl amine Methyl ammonium
hydrochloride chloride
+
(CH3)2NH + HNO3 [(CH3)2NH2] NO3¯
Dimethyl ammonium nitrate
+
N(CH3)2 + CH3COOH N(CH3)2CH3COO¯
H
N,N - Dimethyl aniline N,N - Dimethyl anilinium acetate
Amines are displaced by caustic alkalis form their salts.
+ – – –
RNH3X + OH RNH2 + H2O + X
Comparison of basic strength of amines

A convenient way to compare basic strength of amines is to measure the basicity constant (Kb),
which measures the extent to which the amine accepts the H+.
Each amine has its characteristic Kb. Larger the value of Kb, or smaller the value of pkb the more
basic the base.
Aliphatic amines have Kb of about 10-4 whereas aromatic amines have Kb of 10-10. This indicates
that aliphatic amines are somewhat more basic than ammonia and aromatic amines are
considerably less basic than ammonia.
RHN2 + H2O RNH3+ + OH¯

+
[RNH 3 ] [OH¯]
Kb = Keq [H2O] = [RNH2]
Table 15.1: Basicity constant ( Kb ) of amines ( For ammonia, Kb = 1.8 x 10-5)

-4 -10
Aliphatic amines Kb = (10 ) Aromatic amines Kb= (10 )
-4 -10
Methylamine 4.5 x 10 p-Phenylediamine 140 x 10
-4 -10
Dimethylamine 5.4 x 10 p-Anisidine 20 x 10
-4 -10
Trimethylamine 0.6 x 10 p-Toluidine 12 x 10
-4 -10
Ethylamine 5.1 x 10 Aniline 4.2 x 10
-4 -10
Diethylamine 10 x 10 p-Chloroaniline 1 x 10
-4 -10
Triethylamine 5.6 x 10 p-Nitroaniline 0.001 x 10
a. Aliphatic amines are more basic than ammonia: Ammonia as well as amines are basic
due to presence of a lone pair of electron present on nitrogen atom which is available for
sharing with proton. Alkyl groups are electron releasing groups. Therefore, lone pair of
electron is more available on nitrogen atom of aliphatic amines than that in ammonia.
Hence, aliphatic amines are more basic than ammonia.
R N—H
H—N—H
H
H
'R' releases electrons, makes
unshared pair more available
b. Aryl amines are less basic than ammonia: Lone pair of electron present on nitrogen atom
of aryl amines is involved in resonance with the ring hence less easily available for sharing
with proton than that in ammonia. Hence aryl amines are less basic than ammonia.
H H H + H H + H H + H H H
N N N N N
–
–
–
I II III IV V
Resonating structures of aniline
c. Basic strength of 1°, 2° and 3° amines: In gas phase, basic strength of different classes of
aliphatic amines is found in the order R3N > R2NH > RNH2 (This is found to be true for
R= -CH3, -C2H5, -C3H7 ).This can be explained on the basis of +I effect of alkyl group.
In aqueous solution, however, the basic strength is R2NH > RNH2 > R3N for R=CH3. This
can be explained as follows;
In aqueous solution, effect of water called hydration effect also comes into play in addition
to inductive effect of alkyl group.
i. Hydration effect: In aqueous solution, protonated amines are hydrated and hence
stabilized due of formation of intermolecular hydrogen bond with water as shown.
δ+ δ–
H
H '''''''''''''''''''' O
H
δ+ δ–
H + + H
R N + H R N H '''''''''''''''''''' O
H H
δ+ δ–
H
H '''''''''''''''''''' O
Protonated 1° amine
H
R
δ+ δ–
R + + H
R N + H R N H '''''''''''''''''''' O
H H
δ+ δ–
H
H '''''''''''''''''''' O H
R
δ+ δ–
R + + H
R N + H R N H '''''''''''''''''''' O
H
R R
Protonated primary amine is the most hydrated and most stabilized whereas
protonated tertiary amine is the least hydrated and least stabilized. Hence basic
strength due to hydration effect is 1° > 2° > 3°.
Amines Unit 15 493
ii. Inductive effect: Alkyl group releases electrons towards nitrogen atom due to
inductive effect and neutralizes the positive charge and stabillizes protonated amines.
Protonated tertiary amine is stabilized the most and protonated primary amine is
stabilized the least. Hence due to inductive effect of alkyl group, the basic strength is in
the order 3°> 2°> 1°.
In aqueous solution, both effects come to play which are exactly opposite order. The net
result of both effects is the basic strength of aliphatic amines in aqueous solution in the order
2°> 1°> 3°.
Steric Factor: In 3° amine, N is attached with three bulky alkyl groups around it, which cause
large steric hinderance for attack by an acid. So, 3° amines are less basic than 1° and 2°
amines (due to setric factor, the basic nature of amines is 1°>2°>3°).
d. Effect of substituent(s) on basicity of amines: Electron releasing substituent increases the
basicity of amines since lone pair of electron on nitrogen atom becomes more easily
available. Electron withdrawing substituent decreases the basicity of amines since lone
pair of electron on nitrogen atom becomes less easily available.
NH2
NH2 NH2
G G
G releases electrons, makes
G releases electrons, makes
unshared pair less available
unshared pair more available
NH2 NH2 NH2 NH2 NH2 NH2
NH2 OCH3 CH3 Cl NO2

p–Phenylenediamine p–Anisidine p–Toluidine Aniline p–Nitroaniline
p–Chloroaniline
(Kb = 140 × 10–10) 20 × 10–10 12 × 10–10 4.2 × 10–10 0.001 × 10–10
1 × 10–10
Decreasing order of basic character
e. Ortho effect: Any substituent, whether electron releasing or electron withdrawing, present
on ortho position to amino group decreases the basicity. All the following compounds are
less basic than aniline. (Compare Kb values).
NH2 NH2 NH2 NH2
NH2 OCH3 CH3 NO2
o-Phenylenediamine o -Anisidine o-Toluidine o-Nitroaniline
(Kb= 3 × 10–10) (Kb= 3 × 10–10) (Kb= 2.6 × 10–10) (Kb= 0.00006 × 10–10)
H H CH3 CH3 H CH3 H H

N N N N
N
H
Cyclohexylamine N,N-Dimethylaniline N-Methylaniline Aniline Diphenylamine
Kb = 5 x 10-4 Kb = 11.7 x 10-10 Kb= 7.1 x 10-10 Kb = 4.2 x 10-10 Kb = 0.0006 x 10-10
Self Test
15.9 Explain
i. Ethyl amine is more basic than ammonia ii. Aniline is less basic than ammonia
iii. Aliphatic amine is more basic than aniline
15.10 Arrange aniline, p-nitroaniline and cyclohexyl amine in the decreasing order of their basic
character. Give explanation for your arrangement.
Some multiple choice questions related to basicity of amines
1. In aqueous solution, the basicity of the following compounds is in the order;
a. (CH3)4N+OH- b. CH3CH2NH2
c. NH3 d. C6H5NH2
Answer: a) >b) > c)> d)
(Quaternary ammonium hydroxide> aliphatic amine> ammonia> aromatic amine)
2. Arrange the following compounds in the decreasing order of their basicity;
a. Ammonia b. Methylamine
c. Ethylamine d. Aniline
Answer: c) >b) > a)> d)
3. Arrange the following compounds in the decreasing order of their basicity in aqueous solution;
a. Ammonia b. Methylamine
c. Dimethylamine d. Trimethylamine
Answer: c) >b) > d)>a)
4. Which one is more basic?
a. Aniline or N-Methylaniline b. N-Methylaniline or N,N-Dimethylaniline
c. Aniline or Diphenylamine d. Aniline or Cyclohexylamine
Answer:
a. N-Methylaniline (-CH3 releases electron on nitrogen)
b. N,N-Dimethylaniline (Two-CH3 release more electron)
c. Aniline (Unshared pair of electron one delocalized in two rings)
d. Cyclohexylamine (Aliphatic amine)
5. Arrange the following compounds in the decreasing order of their basicity;
NH2 NH2 NH2 NH2
Cl OCH3 CH3
(a) (b) (c) (d)
Answer: (c) > (d) > (a) > (b)
2. Reaction with alkyl halides: Alkylation: When an amine is treated with an alkyl halide,
hydrogen of N atom are successively replaced by alkyl group to form amines of next higher
class and finally forms quaternary ammonium salt.
δ+ δ–
R N H + R X R N R + HX
H H
2° amine
Amines Unit 15 495
δ
R N R+ R Xδ– R N R + HX
H R
3° amine
R +
δ+ δ– –
R—N—R + R X R—N—R X
R R
Quaternary ammonium salt
32. Reaction with acid chlorides and anhydrides: Acylation

a. Primary amine reacts with acid chloride or acid anhydride to from N-substituted amide.
δ– O
O
Pyridine
R—N—H + R'—C—Cl R'—C —N—R + HCl
δ+
H H
1° amine Acid chloride N–substituted amide
δ–
O O
Pyridine
CH3CH2—N—H + CH3—C—Cl CH3 —C—N—CH2CH3 + HCl
δ+
H H
Aminoethane Acid chloride N–Ethylethanamide
δ–
O O O
Pyridine
CH3CH2—N—H + CH3—C CH3—C—N—CH2CH3 + CH3—C—OH
δ+ O
H CH3—C H
O
Ethanoic anhydride N–Ethylethanamide
(Acetic anhydride)
b. Secondary amine reacts with acid chloride to from N,N-disubstituted amide.

δ–
O O
Pyridine
R—N—H + R'—C—Cl R'—C—N—R + HCl
δ+
R R
2° amine Acid chloride N,N–disubstituted amide
δ–
O O
Pyridine
CH3—N—H + R'—C—Cl CH3—C—N—CH3 + HCl
δ+
R CH3
N-Methylaminomethane Ethanoyl chloride N,N–Dimethylethanamide
c. Tertiary amines do not react since they have no hydrogen atom on nitrogen to stabilize the
product.
4. Reaction with nitrous acid: Different classes of aliphatic and aromatic amines react with
nitrous acid differently. Nitrous acid is unstable hence prepared in situ by mixing sodium nitrite
and mineral acid usually HCl under cold condition.
a. Reactions of primary amines

i. Primary aromatic amine reacts with nitrous acid in ice cold solution to form diazonium
salt. The reaction is called diazotization.

H + –
N H N2 Cl
Ice cold
(0°-10°C)
Note
When the temperature of the reaction exceeds than 5°C, benzene diazonium chloride is hydrolysed into phenol.
Δ
N⊕ ≡ N Cl– + H – OH OH + N2 + HCl
Phenol
The relative stability of aromatic diazonium salt over aliphatic diazonium salt is due to its resonance stabilization.
+ + + – + –
N N N ≡N N N N N
+
So on
Resonating structures of aromatic diazonium ion

+
ii. Primary aliphatic amine reacts with nitrous and in ice-cold solution to give alcohol. N2 (as
bubbles) is evolved quantitatively. Hence this reaction can be used as a test for primary
aliphatic amine since none of other classes of amines evolve N2.
R— N H2 NaNO2 + HCl
+ ROH + N2 + H2O
HO N O
NaNO2 + HCl
CH3CH2NH2 + HNO2 CH3CH2OH + N2 + H2O
In fact, the products are isomeric alcohols, isomeric alkyl halides, alkene and very little
cycloalkanes when structure permits. Hence, reaction of primary aliphatic amines with
nitrous acid is not important from synthetic point of view.
Amines Unit 15 497
Aliphatic diazonium salts are unstable even at low temperature hence decompose forming carbocation which then gives a
mixture of compounds. For example, n-propylamine when treated with nitrous acid; the products are a mixture of propene,
Propan-1-ol, Propan-2-ol, 1-Chloropropane, 2-Chloropropane etc. Very little cyclopropane is also observed.
NaNO2 + HCl + -
CH3CH2CH2NH2 [CH3CH2CH2 – N ≡ NCl ]
CH2
–N2, – Cl -
H2C CH2
Cyclopropane
H H H
H2O
CH3CH2CH2OH H— C—C—C+
– H+ Cl -
( 7%) H H H
1° carbocation CH3CH2CH2Cl
H2O H H H
Cl -
CH3CHCH3 H—C—C—C—H CH3CHCH3
– H+ +
OH H H Cl
( 7%) 2° carbocation
– H+
CH3CH CH2 (32%)
b. Secondary aliphatic as well as aromatic amine reacts with nitrous acid to give N- nitroso amine
which appears as insoluble yellow oily layer.
NaNO2 + HCl N N O + H2O

N H + HO N O
CH3
CH3
N– Methylaniline N– Nitroso-N-methylaniline
(Yellow oily compound)
CH3CH2 N H + HO NaNO2 + HCl

N O CH3CH2 N N O + H2O
CH3 CH3
N– Nitroso-N-methylethanamine
(Yellow oily compound)
c. Reactions of tertiary amines

i. Tertiary aromatic amine reacts with nitrous acid to form p-nitroso compound.
H3C CH3 H3C CH3

N N
NaNO2 + HCl
+ HO — N O + H2O
H N O
p-Nitroso-N,N-dimethylaniline
N,N-Dimethylaniline (Green flakes)
ii. Tertiary aliphatic amine reacts with nitrous acid to form water soluble nitrite salt.
(CH3CH2)3 N + HNO2 NaNO2+ HCl + NO–
(CH3CH2)3 NH 2
Triethylamine Triethylammonium nitrite

Hence, reaction of amines with nitrous acid can be used as a test for distinguishing
primary, secondary and tertiary amines.
5. Reaction with chloroform: Carbylamine reaction: When primary amine, aliphatic as well as
aromatic, is warmed with chloroform and alcoholic caustic alkali, carbylamine (isocyanide) is
formed which gives offensive smell. This reaction is commonly known as carbylamine reaction.
H Cl H warm
+ C + 3KOH (alc) R—N C + 3KCl + 3H2O
R—N
Carbylamine/ isocyanide/ isonitrile
H Cl Cl
(unpleasant ordour)
Primary amine Chloroform
H Cl H
+ C Δ
H Cl H
Δ
H Cl Cl
Phenyl carbylamine
Secondary and tertiary amines do not give this test. Hence this reaction can be used as a test of
primary amines in the name of carbylamine test or isocyanide test.
Self Test
15.11 How do you distinguish primary, secondary and tertiary aliphatic amines using nitrous acid?
15.12 Can you distinguish benzyl amine and aniline using nitrous acid?
15.13 Write isomers of molecular formula C2H7N and suggest three different tests to distinguish
them. Hint: nitrous acid test, carbylamine test, Hinsberg test
6. Reaction with Grignard reagents: Primary and secondary amines have active hydrogen atoms
hence react with Grignard reagent to form alkane. Tertiary amines do not react since they have
no active hydrogen.
Ether
CH3MgI + RNH2 CH4 + MgI (RNH)
Ether
CH3MgI + R2NH CH4 + MgI (R2N)
Primary amines have two active hydrogen atoms. At room temperature, only one hydrogen
atom is removed. Another active hydrogen atom is removed only at high temperature.
CH3 MgI + MgI(RNH) CH4 + (MgI)2RN
Δ
7. Reaction with metal ions: Like ammonia, lower aliphatic amines like CH3NH2, C2H5NH2 etc.
form complex with many transition metal ions. This is due to a lone pair of electron present on
nitrogen atom which is accepted in vacant d-orbital of transition metal ions.
Amines Unit 15 499
Examples:
H H +
Ag –
AgCl + 2NH3 H—N N—H Cl
H H
Diamminesilver(I) chloride
(colourless solution)
H H +
AgCl + 2C2H5NH2 C2H5—N Ag N—C2H5 Cl –
H H
Bis(ethylamine)silver(I) chloride
(colourless )
CuSO4+ 4C2H5NH2 [Cu(C2H5NH2)4] SO4

Tetrakis(ethylamine)copper(II)sulphate
(Deep blue solution)
Here, ammonia and amines are called ligands.
Self Test
15.14 Identify A and B in the following reaction sequence:
AgCN (alc) Na/C2H5OH NaNO2+ HCl
(i) CH3CH2Br A1 A2 A3
NH2
CHCl3, KOH, warm H2/Ni HNO2
(ii) B1 B2 B3
Aniline
15.11 Aromatic Amine (Aniline)

15.11.1 Nomenclature
Aromatic amines are named as derivatives of the simplest aromatic amine, aniline.
H H CH3 CH3
N H N CH3 N
Aniline N–Methylaniline N,N–Dimethylaniline

(Benzenamine)
( 2° aromatic amine) ( 3° aromatic amine)
( 1° aromatic amine)
NH2 NH2 NH2

1 1 1
6 Br 6 6
2 2 2
3 5 3 3
5
4
Br 5
4 4
2– Bromoaniline
Br
3– Bromoaniline 4– Bromoaniline
(o–Bromoaniline) (m–Bromoaniline) (p–Bromoaniline)
NH2
NH2 NH2
CH3
CH3 CH3
2– Aminotoluene 3– Amino toluene 4– Bromoaniline
(o–Toluidine) (m–Toluidine) (p–Bromoaniline)
NH2
NH2
Br Br
OCH3
Br o–Anisidine
2, 4, 6–Tribromoaniline
Self Test
15.15 Write isomeric amines of molecular formula C7H11N having benzene ring, classify them as
primary, secondary and tertiary amines and give their name. Hint: 5 isomers
15.11.2 Preparation of Aniline

1. From nitro compounds: Reduction of nitro compounds with H2 in presence of Ni or Pt catalyst
(catalytic reduction) or with metal and acid usually Sn/HCl, Fe/HCl (chemical reduction) give
primary amines.
NO2 NH2
Sn/HCl
+6[H] + 2 H2O
Nitrobenzene Aniline
This is the most useful method of preparing aromatic amines. This is because starting material
(aromatic nitro compounds) is readily available and the product is the most important kind of
amine, primary aromatic amine.
2. From chlorobenzene
i. When chorobenzene is heated with aqueous ammonia solution under pressure in presence
of cuprous oxide, aniline is formed.
Cl NH2
Cu2O or Cu2Cl2
+ 2 NH3 + NH4Cl
200°C, 60 atm
Aniline
Amines Unit 15 501
ii. When chlorobenzene is treated with NaNH2 or KNH2 in liquid ammonia, aniline is
obtained. The reaction follows elimination-addition mechanism through benzyne
intermediate.
Cl NH2
Liq. NH3
+ KNH2 + KCl
3. From benzamide (Hofmann's degradation reaction): When benzamide is warmed with

bromine (or chlorine) and aqueous or alcoholic caustic alkali, aniline is obtained.
O
warm
C—NH2 + Br2 + 4KOH(aq) NH2 + 2KBr + K2CO3 + 2H2O
Benzamide Aniline
4. From phenol: When phenol is heated with NH3 in presence of dehydrating agent anhydrous
ZnCl2, it gives aniline.
OH NH2
Anhydrous ZnCl2
+ NH3 + H2O
15.11.3 Laboratory Preparation of Aniline

Theory
Aniline is prepared in the laboratory by the reduction of nitrobenzene with granulated tin and
concentrated hydrochloric acid.
Sn + 4 HCl SnCl4 + 4 [H] } ×3

NO2 NH2
+6[H] + 2 H2O } ×2
NO2 NH2
2 + 3 Sn + 12 HCl 2 + 3 SnCl4 + 4 H2O
Aniline produced reacts with hydrochloric acid and stannic chloride to form addition compound.
NH2 NH3Cl
+ HCl
NH3Cl NH3Cl
2 + SnCl4 . SnCl4
2
aniline stannichloride (solid)

Aniline is recovered from addition compound by the action of caustic soda solution followed by
steam distillation.
NH3Cl NH2
. SnCl4 + 8 NaOH 2 + Na2SnO3 + 6 NaCl + 5 H2O

2
Water out
Water condenser
Cold water in
Nitrobenzene + tin + HCl (conc.)
Water bath
Fig. 15.1 Laboratory preparation of aniline (refluxing)
Procedure
About 25 g of nitrobenzene and 50 g of granulated tin are taken in a R B flask and 100 ml of
concentrated HCl is added into the flask, about 20 ml at a time with shaking and cooling in cold
water.
Amines Unit 15 503
Steam
Safety tube
Water out
Steam
generator
Impure aniline
to be distilled
Cold water in
Aniline
Fig. 15.2: Steam distillation of aniline
When whole acid is added, it is refluxed on water bath for an hour until the smell of nitrobenzene
disappears. On cooling, the solid mass appears due to addition compound.
Concentrated NaOH is added to the solid mass to get clear and alkaline solution. Here, the dark
brown layer of aniline separates out. The whole mass is subjected to steam distillation1 and aniline is
obtained as distillate.
Purification
Aniline obtained as distillate contains water. Aniline is slightly soluble in water (solubility is 3.7),
hence, it is difficult to separate using separating funnel directly.
i. Solid sodium chloride is added to aniline till saturation. Sodium chloride is more soluble in
water than aniline hence layer of aniline separates out and separated.
ii. Aniline is then extracted with ether in small lots. Ether is evaporated using hot water.
iii. Aniline is dried over solid NaOH or KOH.
iv. Finally, aniline is redistilled to about 182-190°C to get pure aniline.
Self Test
15.16 What would you do to distinguish aniline from nitrobenzene chemically?
1 Steam distillation (Co-distillation with water): This method is applied for the separation and purification of organic compounds
(solids and liquids) which are insoluble in water, volatile in steam and have high vapour pressure at boiling point of water.
Impurities must be non-volatile. Here, steam lowers the boiling point of organic compound.
A liquid boils when its vapour pressure is equal to the atmospheric pressure. In steam distillation, two immiscible compounds,
water and organic compound, exert their own vapour pressure independently and the mixture boils when sum of vapour pressure
of organic compound (P1) and vapour pressure of water (P2) becomes equal to the atmospheric pressure (P).
P1+ P2 = P or P1= P- P2
This means organic compound ( as well as water) boils below its normal boiling point. For example, aniline (b pt. 184°C) boils at
98.5°C in presence of steam.
15.11.4 Physical Properties of Aniline

i. It is colorless liquid with unpleasant odour and very sensitive to oxidation, so it rapidly
becomes brown when exposed to air.
iii. Its Boiling point is 184°C and solidifies at - 6.2°C.
iv. It is sparingly soluble in water (3.7 g/100ml water) but soluble in organic solvents.
v. It is steam volatile and poisonous.
15.11.5 Chemical Properties of Aniline

Chemical properties of aniline can be divided into two groups;
A. Reaction due to -NH2
B. Reaction due to benzene ring
A. Reaction due to -NH2 group
1. Salt formation: Aniline reacts with mineral acids to form salt.The basic nature of aniline is due
to a lone pair of electron present on nitrogen atom which is available for sharing with a proton.
NH2 NH3Cl
+ HCl
Anilinium chloride
(Aniline hydrochloride)
2. Alkylation: When aniline is treated with alkyl halide, alkylation occurs giving secondary
amine, tertiary amine and finally quaternary ammonium salt.
H H CH3 CH3 CH3

N H N N N(CH3)3 I
CH3 —I CH3 —I CH3 I
—HI —HI
Aniline N–methylaniline N,N–Dimethylaniline Trimethylanilinium iodide
(1° amine) (2° amine) (3° amine) (Quaternary ammonium salt)
3. Acylation: When aniline is treated with acid chloride or anhydride, acylation occurs giving N-
phenylamide called anilide.
H
N H
Oδ– O
Pyridine CH3—C—N + HCl
+ CH3—C—Cl
δ+
H
N– phenylethanamide
(Acetanilide)
Amines Unit 15 505
H H
N
Oδ– O O
CH3COONa
+ CH3—C CH3—C—N + CH3—C—OH
δ+ O
CH3—C H
O
Ethanoic anhydride N– phenylethanamide
(Acetic anhydride) (Acetanilide)
H H
N O
Oδ–
Pyridine
+ C—Cl C N + HCl
δ+ or NaOH
H
Benzoyl chloride N– phenylbenzamide
(Benzanilide)
Reaction of aromatic acid chloride (like benzoyl chloride) with amine or alcohol or phenol in
presence of base like aqueous sodium hydroxide or pyridine is called Schotten-Baumann
reaction.
4. Carbylamine reaction: When aniline is warmed with chloroform and alcoholic caustic alkali,
phenyl carbylamine (phenyl isocyanide) is formed which gives offensive smell (unpleasent
odour).
H Cl H
Δ
H Cl Cl
Phenyl carbylamine
5. Reaction with nitrous acid: Diazotization: Aniline reacts with nitrous acid in ice cold solution
to form diazonium salt. This process is called diazotization. Nitrous acid is prepared in situ
taking sodium nitrite and a mineral acid.
NH2 N2Cl
0–10°C
+ HNO2 + HCl + 2H2O
6. Reaction with Potassium: When aniline is heated with sodium or potassium, hydrogen gas is
evolved. — +
NH2 NH K
+K + H2
7. Reaction with benzaldehyde: Aniline undergoes condensation with aromatic aldehydes to

form anils(Schiff bases).
H H
H
N + O=C N C + H2O
H
Aniline Benzaldehyde Benzylideneaniline
8. Reaction with phenol: When aniline is heated with phenol in presence of zinc chloride,
diphenyl amine is formed.
anhd ZnCl2, 260°C

N H + HO N + H2O
H H
Aniline Phenol Diphenylamine
9. Oxidation: Aniline is easily oxidized by different oxidizing agent into different oxidation
products. NH2
H2CrO4
O O
p-Benzoquinone
NH2 N O
H2SO5
(Caro's acid)
Nitrosobenzene
NH2 NO2
CF3COOOH
(Peroxytrifluoroacetic acid)
With potassium dichromate, a black dye (aniline black) is obtained. With bleaching powder, p-
aminophenol (a purple colour) is obtained.
B. Electrophilic aromatic substitution reaction
Amino group (-NH2) in aniline determines the reactivity and orientation in electrophilic aromatic
substitution reaction. -NH2 is a strongly activating group and ortho para director. Aniline is roughly
one million times as reactive as benzene in electrophilic aromatic substitution reaction.
1. Halogenation: Aniline reacts with aqueous chlorine or bromine immediately to form precipitate
of 2,4,6- Trihaloaniline.
NH2 NH2
Br Br
+ 3 Br2(aq) + 3 HBr
Br
2, 4, 6 – Tribromoaniline
(White ppt)
Amines Unit 15 507
The yield is quantitative, hence, this reaction is used for the estimation of aniline. Due to strong
activating effect of -NH2, reactivity of benzene ring in aniline is very high, so polyhalogenation
occurs even in absence of catalyst.
To get p-bromoaniline, strongly activating effect of -NH2 is lowered by acylation. This is called
protection or masking of -NH2. -NHCOCH3 (acetamido group) is ortho para director
(predominantly p- director) and moderately activating group hence no polyhalogenation
occurs. p-bromoacetanilide is separated then hydrolyzed to get p-bromoaniline. Here, -NH2 is
regenerated. This is called deprotection or demasking of -NH2.
NH2
H N H
Br
p–Bromoaniline
Protection (CH3CO)2O, Acylation
(of –NH2) Deprotection H2O/OH¯
(of – NH2)
O O
H N C CH3 O
H N C CH3
Br2, CH3COOH H N C CH3
+
Br
Br
Acetanilide
p–Bromoacetanilide o–Bromoacetanilide
(80%)
Can be separated by steam distillation
2. Nitration: Aniline is not directly nitrated using nitrating mixture to get p-nitroaniline. The main
problem arises due to very high reactivity of aniline.
In strongly acidic nitrating medium, -NH2 is converted into -NH3+. Substitution is thus
controlled by -NH3+ which is a meta director. (Nitration of aniline yields a mixture of about
66% meta and 33% ortho product).
-NH2 ( amino group) is strongly activating group. It increases the reactivity of benzene ring to a
very large degree. Therefore, polynitration takes place giving a mixture of mono-, di- and tri-
nitro compounds.
Concentrated HNO3 is an excellent oxidizing agent. Therefore, HNO3 not only nitrates but also
oxidizes aniline into oxidation products. The aromatic ring structure gets destroyed.
To get p-nitroaniline, first of all, -NH2 of aniline is protected by acylation. -NHCOCH3
(acetamido group) is ortho para director (predominantly p- director) and only moderately
activating group ( -NH2 is strongly activating group), hence no such problems occur on
nitration. This is called protection or masking of -NH2.
NH2
H H
N
NO2
Aniline p–Nitroaniline
Protection (CH3CO)2O, Acylation

(of –NH2) Deprotection H2O/OH¯
(of – NH2)
O O
O
H N C CH3 H N C CH3
H N C CH3
HNO3, H2SO4, 15°C
NO2
+
Acetanilide NO2
p–Nitroacetanilide o–Nitroacetanilide
(90%) (1-2%)
Can be separated by chromatography
p-nitroacetanilide is separated then hydrolyzed to get p-nitroaniline. Here, -NH2 is regenerated.

This is called deprotection or demasking of -NH2.
3. Sulfonation: Aniline reacts with concentrated sulphuric acid to from anilinium hydrogen
sulfate which on heating at 180 – 200°C produces p–aminobenzenesulphonic acid commonly
called sulfanilic acid as major product which exists as zwitter ion (German, Zwitter =
hermaphrodite).
+ –
NH2 NH3HSO4 NH2 NH 3
+
5hr, 180–200°C
+ H2SO4 ≡ + H2O
'baking'
Aniliniumhydrogen sulfate –
SO3H SO3
Zwitter ion
p–Aminobenzene sulfonic acid
(Sulfanilic acid)
4. Friedel-Crafts reaction: Aniline does not undergo Friedel-Crafts reaction because catalyst used(
Lewis acid) coordinates with basic -NH2 group. Due to this, N atom of aniline acquires positive
charge and hence acts as a strong deactivating group for further reaction.
5. Reaction with diazonium salt: Coupling reaction: Aniline reacts with diazonium salt solution in
slightly acidic medium to form p-aminoazobenzene which appears as orange-yellow
compound. Electrophile of this reaciton is eliazonium ion.
pH = 4-5
N N—Cl + H NH2 N N NH2 + HCl
40°C
Aniline p-Aminoazobenzene
Diazonium salt
(orange-yellow soild)
M Pt = 126°C
Amines Unit 15 509
Self Test
15.17 What happens when
i. Aniline is warmed with chloroform in presence of alcoholic caustic alkali ?
ii. Aniline is added to diazotized solution of aniline?
iii. Aniline is treated with bromine water?
15.18 Write the reaction involved when aniline is treated with excess methyl iodide.
15.19 Convert aniline into
i. N-Methylaniline ii. N-Phenylethanamide iii. Diphenyl amine
i. o-Nitroaniline ii. m-Nitroaniline iii. p-Nitroaniline
i. o-Bromoaniline ii. m-Bromoaniline iii. p-Bromoaniline
15.11.6 Uses of Aniline

i. For the preparation of dyes, drugs
ii. For the preparation of antioxidants in rubber industry
15.12Test for Amines

1. Hinsberg test: Primary, secondary and tertiary amines can be distinguished best by Hinsberg
test. In this method, amine is shaken with benzenesulfonyl chloride and aqueous caustic alkali.
Different classes of amines react differently.
i. Primary amine gives a clear solution which forms insoluble compound on acidification.
O O O
KOH –
S—Cl + H—N—R S—N—R S—N—R
–HCl –H2O +
O H O H O K
1° amine N–Alkyl benzene sulfonamide (Soluble)
(insoluble) HCl
(Acidification)
O
S—N—R + KCl
O H
N–Alkyl benzene sulfonamide
(insoluble)
ii. Secondary amine gives insoluble compound which is unaffected on acidification.
O O
KOH
S—Cl + H—N—R S—N—R No reaction
–HCl –H2O
O R O R
2° amine N,N–Dialkyl benzene sulfonamide
(insoluble)
iii. Tertiary amine is unaffected and remains as insoluble compound.

Note
Now, p-toluenesulphonyl chloride (tosyl chloride) is used instead benzenesulphonyl chloride.
2. Nitrous acid test (discussed earlier)

3. Carbylamine test (discussed earlier)
15.13Diazonium Salts and their Reactions

Primary aromatic amine reacts with nitrous acid in ice cold solution to form diazonium salt. This
process is called diazotization. Nitrous acid is unstable hence prepared in situ taking sodium nitrite
and a mineral acid. This reaction was discovered by Griess in 1858.
NH2 N+2Cl–
NaNO2, HCl + 2H2O

+ HNO2 + HCl
ice cold
+ –
NH2 N2HSO4
NaNO2, H2SO4
+ HNO2 + H2SO4 + 2H2O
Benzene diazonium hydrogen sulfate
+ –
NH2 N2BF4
NaNO2, HBF4
+ HNO2 + HBF4 + 2H2O
Benzene diazonium fluorobonte
In the preparation of diazonium salt, usually, primary amine is dissolved or suspended in excess dilute mineral
acid, cooled in ice bath and a cooled aqueous solution of sodium nitrite is added slowly with stirring.
Aniline + dil. HCl
NaNO2 (aq)
Ice bath
Fig. 15.3: Preparation of diazonium salt
Diazonium salts are colorless solids, highly soluble in water, explode especially nitrates in solids and
decompose slowly even at ice bath. Hence they are used immediately after preparation.
Reactions of Diazonium Salts
Diazonium salts are very important synthetic reagents for the preparation of wide range of valuable
aromatic compounds. A large number reactions of diazonium salt may be divided into two groups;
1. Coupling reactions
2. Replacement reactions
Amines Unit 15 511
1. Coupling reactions: In this type of reaction, diazo-group is retained in the product. Diazonium
salt reacts with aromatic compounds having strongly activating group (-NH2,-NHR,-NR2, -OH)
to form azo compounds (Ar-N=N-Ar). The reaction is called coupling reaction. Azo compounds
are colored hence they are of great importance to dye industry.
Examples:
pH = 4-5
N=N—Cl + H NH2 N=N NH2 + HCl
Aniline p–Aminoazobenzene
Orangr-yellow dye
pH = 9-10
N=N—Cl + H OH N=N OH + HCl
Phenol p–Hydroxyaobenzene
orange dye
2. Substitution reactions: In this type of reactions, diazo-group is replaced by some other atom or
group. Many atoms or groups can be attached to the aromatic ring by replacing diazo group.
i. Replacement by -F, -Cl, -Br, and -I: Discussed in Haloarenes
ii. Replacement by –OH: When diazonium salt solution is boiled, steam distilled or added to
boiling dilute sulphuric acid, diazo group is replaced by -OH to form phenol.
+
N2Cl – OH
boil
+ H2O + N2 + HCl
Phenol
iii. Replacement by –H: When diazonium salt solution is mixed with hypophosphorous acid
(H3PO2), diazo group is replaced by -H.
+
N2Cl – H
+ H3PO2 + H2O + H3PO3 + N2 + HCl

Phosphorous acid
Hypophosphorous acid
iv. Replacement by –CN: When cyanide salt solution is mixed with cuprous cyanide
dissolved in aqueous potassium(a special case of Sandmeyer reaction) or aqueous KCN
and copper powder (a special case of Gattermann reaction), diazo group is replaced by -
CN.
+ –
N2Cl CN
KCN
+ CuCN + N2 + CuCl
Benzonilide
+ –
N2HSO4 CN
Cu
+ KCN + N2 + KHSO4
Reactions of diazonium salt: A summary
F
i. HBF4
ii. heat
Fluorobenzene
Cl
CuCl/ HCl
Chlorobenzene
Br
CuBr/HBr
Bromobenzene
I
KI, warm
Iodobenzene
+
NH2 N2Cl – OH
NaNO2 + HCl H2O, warm O
Dil. HCl
0-10 ºC C—OH
Complete hydrolysis
Aniline Diazonium salt Phenol
Benzoic acid
CN
O
CuCN, warm Conc. HCl
C—NH2
Partial hydrolysis
Benzonitrile Benzamide
H2/Ni or LiAlH4
H or C2H5OH/Na
CH2NH2
H3PO2 (aq), warm Reduction
Benzyl amine
Benzene
H NH2
N=N NH2
pH = 4-5
p–Aminoazobenzene
(Yellow dye)
H OH
N=N OH
pH = 9-10
p–Hydroxyaobenzene
(orange dye)
Amines Unit 15 513
Self Test
15.22 Starting from benzene outline the synthesis of following organic compounds;
i. Sulfanilic acid ii. Carbolic acid iii. Picric acid
iv. Salicylic acid v. Benzoic acid vi. Benzamide
vii. Benzyl amine viii. p-Hydroxyazobenzene
ix. p-Aminoazobenzene
15.23 Convert nitrobenzene into
i. Chlorobenzene ii. Iodobenzene iii. Benzene
iv. Phenol v. 1,3,5-Tribromobenzene
Synthesis using Benzene Diazonium Chloride

Diazonium salts also offers a means of preparing substituted aromatic compounds in which
substituents are in positions which are not possible by direct substitution. For example,
1. Synthesis of m-Bromophenol
OH
Br
m-Bromophenol
Here, the problem is two ortho para directing groups( -OH and -Br) are situated meta to each
other. To solve the problem, bromination of nitrobenzene is carried out to get
m-Bromonitrobenzene then -NO2 is converted into -OH through the formation of diazonium
salt.
NO2 NO2 NH2

+ –
conc. HNO3,conc.H2SO4 Sn/HCl N2Cl
Br2, FeBr3 NaNO2 + HCl
60°C 0-10 ºC
Br Br
Benzene Br
Nitrobenzene m-Bromonitrobenzene m-Bromoanilile m-Bromobenzenediazonium
bromide
H2O/H+
2. Synthesis of m-Dibromobenzene OH
Br
Br
Br m-Bromophenol
m-Dibromobenzene
(target molecule)
Here, the problem is same i.e. two ortho para directing groups( -Br) are situated meta to each
other. To solve the problem the same technique is applied; bromination of nitrobenzene is
carried out to get m-Bromonitrobenzene then -NO2 is converted into -Br through the formation
of diazonium salt.
+ –
NO2 NO2 NH2 N2Cl
conc.
HNO3,conc.H2SO4 Br2, FeBr3 Sn/HCl NaNO2 + HCl
60°C 0-10 ºC
Br Br Br
Benzene
Nitrobenzene m-Bromonitrobenzene m-Bromoanilile m-Bromobenzenediazonium
bromide
Cu2Br2/HBr
Br
Br
m-Dibromobenzene
3. Synthesis of 1,3,5-Tribromobenzene: Bromination of aniline gives its tribromoderivatie. -NH2

is then converted to -H through the formation of diazonium salt.
NO2 NH2 NH2
Br Br
conc. HNO3,conc.H2SO4 Sn/HCl Br2 (aq)
60°C
Benzene Nitrobenzene Br
Aniline
0-10 ºC NaNO2 + HCl
+ –
N2Cl
Br Br H3PO2(aq) Br Br
Br Br
1,3,5- Tribromobenzene 2, 4, 6 – Tribromobenzenediazonium
chloride
Self Test
15.24 Convert benzene into (i) m-Dichlorobenzene (ii) m-Chloroiodobenzene
Solved Questions
1. Write the isomeric amines of molecular formulaC3H9N and give their IUPAC names.
¬
i. CH3CH2CH2NH2 ii. CH3CH2NHCH3
Propanamine N-methylethanamine
iii. CH3N(CH3)2 iv. (CH3)2CHNH2

N, N-dimethylmethanamine 1-Methylethanamine
Amines Unit 15 515
2. What are amines? How do different classes of amines react with diethyloxalate?
¬ When one, two or all three hydrogen atoms in ammonia molecule are replaced by alkyl or aryl groups, the
resulting organic compounds are called amines.
:
H—N—H R—N—H R—N—R R—N—R
H H H R
Ammonia 1° amine 2° amine 3° amine
Different classes of amines react with diethyloxalate differently.
i. Primary amine reacts with diethyloxalate to form dialkyloxamide which is solid.
δ–
O O H
R—N—H + δ+ C—OC2H5 C—N—R
H + 2 C2 H5OH
δ+ C—OC2H5 C—N—R
R—N—H
δ– O O H
H
1° amine Diethyloxalate Dialkyloxamide (solid)
ii. Secondary amine reacts with diethyloxalate to form dialkyloxamic ester which is generally liquid.
δ– O O R
R—N—H + δ+ C—OC2H5 C—N—R
+ C2 H5OH
R
C—OC2H5 C—OC2H5
2° amine
O O
Diethyloxalate Dialkyloxamic ester (liquid)
Dialkyl oxamic ester does not react further with another molecule of 2º amine due to steric
hinderance.
iii. Tertiary amine does not react with diethyloxalate presumely due to lack of hydrogen with nitrogen.
3. Convert ethylamine into methylamine.
¬ O O
NaNO2+HCl KMnO4/H+ SOCl2
CH3CH2NH2 CH3CH2OH CH3 C OH CH3 C Cl
reflux Acetyl chloride
Ethyl amine Ethyl alcohol Acetic acid
NH3
Br2,NaOH
O
CH3NH2 CH3 C NH2
Methyl amine warm Acetamide
4. Convert ethylamine into n-propyl amine.

¬ NaNO2+HCl PBr3 alc. KCN H2/Ni
CH3CH2NH2 CH3CH2OH CH3CH2Br CH3CH2CN CH3CH2CH2NH2
Ethanol Bromoethane Propane nitrile 1-Aminopropane
5. How do primary aliphatic and aromatic amine react with nitrous acid?
¬ Reactions of primary amines
i. Primary aromatic amine reacts with nitrous acid in ice cold solution to form diazonium salt. The reaction is
called diazotization.

H H + –
N2 Cl
N
Ice cold
(0°-10°C)
ii. Primary aliphatic amine reacts with nitrous to give alcohol. N2 (as bubbles) is evolved quantitatively.
Hence this reaction can be used as a test for primary aliphatic amine since none of other classes of amines
evolve N2.
R— N H2 NaNO + HCl
+ 2 ROH + N2 + H2O
HO N O
NaNO2 + HCl
CH3CH2NH2 + HNO2 CH3CH2OH + N2 + H2O
6. Identify A and in the following reaction sequence.

¬ CH3CH2Br A1 A2 A3

CH3CH2Br CH3CH2NC CH3CH2 N H CH3CH2 N O
CH3 CH3
Ethyl isocyanide, A1 N-methylethanamine, A2 N– Nitroso-N-methylethanamine
(Yellow oily compound), A3
7. Identify B and in the following reaction sequence

¬ NH2
CHCl3, KOH, warm H2/Ni HNO2
B1 B2 B3
Aniline O
NH2 NC H N CH3 N CH3
N
CHCl3, KOH, warm H2/Ni NaNO2 + HCl
Phenyl isocyanide, B1 N-Methylaniline, B2 N-Nitroso-N-Methylaniline

Aniline (Yellow oily compound), B3
8. What happens when

a. Aniline is warmed with chloroform and alcoholic caustic alkali?
b. Aniline is shaken with aqueous bromine?
Amines Unit 15 517
¬ a. Offensive odor is obtained due to formation of phenyl isocyanide.
H Cl H
Δ
H Cl Cl
Phenyl carbyamine
b. White precipitate is obtained due to formation of 2,4,6-Tribromoaniline.
NH2 NH2
Br Br
+ 3 Br2(aq) + 3HBr
Br
(White ppt)
9. How do you get p-Aminoazobenzene from benzene?

¬ NH2
+ –
NO2 NH2 N2Cl
conc. HNO3,
conc.H2SO4 Sn/HCl NaNO2 + HCl
N=N NH2
60°C 0-10 ºC pH = 4-5
Benzene p–Aminoazobenzene
Nitrobenzene Benzenediazonium chloride
Aniline
Questions
1. How can you distinguish primary and secondary amines?
2. What happes when primary amines are treated with diethyl oxalate?
3. What happes when secondary amines are treated with diethyl oxalate?
4. What do you mean by diazotization process?
5. How can you distinguish aniline and ethyl amine?
6. What happens when primary and secondary amines are separately treated with Hinsberg
reagent + aq. KOH?
7. Why is –NH2 group of aniline protected before nitration?
8. How are suphanilic acid and acetanilide prepared from aniline?
9. Write isomers of C3H9N with their IUPAC and common names.
a. Aniline is shaken with aq. Br2?
b. Aniline is coupled with benzene diazonium chloride?
c. Aniline is heated with methyl iodide?
d. Benzamide is allowed to react with bromine in KOH solution?
e. Aniline is warmed with chloroform and alcoholic KOH?
11. Why is aniline less reactive than ethanamine?
1. What are amines? How are they classified? Indicate the functional groups of different classes of
amines. How do different classes of amines react with diethyl oxalate?
2. Briefly discuss the Hofmann's method for the separation of primary, secondary and tertiary
amines from their mixture.
3. How is aniline prepared in laboratory in pure and dry state? Convert aniline into benzamide
and vice versa.
4. How would you convert:
a. methanamine into ethanamine and vice-versa?
b. ethanamine into propanamine?
c. aniline into (i) azodye (ii) N-methyl aniline (iii) o-nitroaniline (iv) picric acid (v) phenol
(vi) phenyl isocyanide (vii) sulphanilic acid (viii) p- benzoquinone (ix) benzenediazonium
chloride
5. Explain with an example of each of the following:
a. Diazotization reaction
b. Diazo coupling reaction
c. Acylation of aniline
d. Carbylamine test
e. Holfmann bromamide reaction
6. How can you distinguish:
a. Ethnamine and aniline
b. Ethanamine and N-methylethanamine
c. Nitrobenzene and aniline
d. N-methylethanamine and N, N–dimethylethanamine.

1. Hofmann's ammonolysis of alkyl halides gives 6. Primary aliphatic amine and primary aromatic amine
a. Primary amine b. Secondary amines can be distinguished by
c. Tertiary amines d. Mixture of amines a. Carbylamine test b. Nitrous acid test
2. In Hofmann's ammonolysis of alkyl halides, the good c. Victor Mayer test d. Lucas test
yield id is obtained in 7. Which of the following exists as zwitter ion?
a. Primary alkyl halide b. Secondary alkyl halide a. Suifanilic acid b. Salicyalic acid
c. Tertiary alkyl halide d. Haloarene c. Succinic acid d. Urea
3 Which of the followings is not involved in 8. Which of the followings does not give CH4 when
degradation of carbon chain? treated with CH3MgI?
a. Hofmann degradation a. Trimethyl amine b. Ethyl amine
b. Hofmann elimination c. Dimethyl amine d. Ammonia
c. Hofmann bromamide reaction 9. Primary and secondary amines can not be
d. Hofmann rearrangement
distinguished by
4. Gabriel Phthalimide synthesis gives a. Nitrous acid test b. Hinsberg test
a. Primary amine b. Secondary amines c. Isocyanide test d. DNP test
c. Tertiary amines d. Mixture of amines
10. n‐Propyl amine and Ethylmethyl amine are
5. Boiling point is highest a. Chain isomers b. Functional isomers
a. Ethyl amine b. Ethyl alcohol c . Positional isomers d. Metamers
c. Formic acid d. Trimethyl amine
1 2 3 4 5 6 7 8 9 10
d a b a c b a a d b
Molecules of Life
The complex lifeless molecules which built up body of organisms and essential for growth, development, regulation
and maintenance of life are called biomolecules or molecules of life. In general, biomolecules are larger and more
complicated than other organic molecules. The principal classes of biomolecules are carbohydrates, proteins, nucleic
acids and lipids which are briefly discussed here.
16.1 Carbohydrates
Rice (starch) Sugarcane(sucrose) Cotton (cellulose)
16.1.1 Introduction
Carbohydrates are naturally occurring organic compounds which provide us the necessities of life:
food, shelter, and clothing. For example, glucose, sucrose, starch, cellulose etc. Glucose is the key
source of energy in human body which is obtained by enzymatic hydrolysis of starch mainly from
rice, potatoes etc. Sucrose is obtained mainly from sugarcane. Similarly, cotton is cellulose and wood
is chiefly cellulose which provides us clothing and shelter.
Chemically, carbohydrates are organic compounds which are composed of C, H and O. The name
carbohydrate was given originally to signify ‘hydrates of carbon’ since carbohydrates satisfy formula
Cx(H2O)y. For example, glucose (C6H12O6 or C6(H2O)6, sucrose (C12H22O11 or C12(H2O)11 etc. However,
this concept is not correct in all the cases. There are some compounds which satisfy the given
formula but they are not carbohydrates e.g. acetic acid (CH3COOH or C2(H2O)2) , formaldehyde
(HCHO ) etc., while there are some compounds which do not satisfy the given formula but they are
carbohydrates e.g. deoxyribose (C5H10O4), rhamnose (C6H12O5). Modern theories show, structurally
carbohydrates are not hydrates of carbon.
Carbohydrates are polyhydroxyaldehydes or polyhydroxyketones or any organic compounds that
produce these compounds on hydrolysis. Carbohydrates are optically active compounds.
16.1.2 Classification of Carbohydrates

Carbohydrates can be classified by different ways;
A. Based on hydrolysis
B. Based on solubility and taste
C. Based on reducing behavior
Molecules of Life Unit 16 521
A. Based on hydrolysis
Based on hydrolysis, carbohydrates are classified into three classes:
1. Monosaccharide: Carbohydrates which can not be hydrolyzed into simpler compounds are
called monosaccharides. They are the simplest carbohydrates. For example, glucose, fructose,
galactose etc.
Monosaccharides are further classified as follows;
i. On the basis of functional group in the molecule: On the basis of functional group
present in the molecule, monosaccharides are classified as aldoses and ketoses. A
monosaccharide having aldehyde (-CHO) group is called an aldose and a monosaccharide
having a keto group (>C=O) is called a ketose.
Examples:
O H O H
1C CHO 1CH2OH 1C
H C OH C O H C OH
2 H OH 2 2
HO 3C H HO 3C H HO 3C H
HO H
H OH or H 4C OH HO 4C H
4C H OH
H OH H 5C
OH H 5C OH
5C H OH
6 CH2OH 6 CH2OH 6 CH2OH
D-(+)- Glucose CH2OH D-(–)- Fructose D-(+)- Galactose
ii. On the basis of total number of carbons in the molecule: On the basis of total number of
carbons present in a molecule, monosaccharides are further classified as triose, tetrose,
pentose, hexose and heptose for the carbohydrates containing three, four, five, six and
seven carbon atoms respectively. Pentoses and hexoses are most common naturally
occurring monosaccharides.
CHO CH2OH CHO CH2OH
C O CHOH C O
CHOH
CH2OH CH2OH CHOH CHOH
Ketotriose CH2OH CH2OH

Aldotriose
(Dihydroxyacetone) Aldotetrose Ketotetrose
(Glyceraldehyde)
CHO CH2OH
CHO CHOH C O
CHOH CHOH CHOH
CHOH CHOH CHOH
CHOH CHOH CHOH
CH2OH CH2OH CH2OH
Aldopentose Aldohexose Ketohexose
2. Oligosaccharide: Carbohydrate which on hydrolysis gives two to ten monosaccharides is called

oligosaccharide (Greek; oligos = few, sacchar = sugar). Carbohydrate which produces two
monosaccharides on hydrolysis is called disaccharide and so on.
Examples: Sucrose, maltose, lactose etc are naturally occuring dissaccharides.
H+ or invertase
C12H22O11 +H2O C6H12O6 + C6H12O6
Sucrose glucose fructose
(cane or beet sugar)
H+ or maltase
C12H22O11 +H2O C6H12O6 + C6H12O6
Maltose glucose glucose
(malt sugar)
H+ or lactase
C12H22O11 +H2O C6H12O6 + C6H12O6
Lactose galactose glucose
(milk sugar)
Raffinose is a trisaccharide, which is mostly found in beet molasses and on hydrolysis gives
fructose, glucose and galactose.
C18H32O16 +H2O C6H12O6 + C6H12O6 + C6H12O6
Raffinose fructose glucose galactose
3. Polysaccharide: Carbohydrate which on hydrolysis gives more than ten monosaccharides is
called polysaccharide. Polysaccharides are represented by general formula (C6H10O5)n where
n=100 to 4000. For example, cellulose, starch etc. They are natural polymers of
monosaccharides. Cellulose and starch are polymers of D-(+)-glucose.
B. Based on solubility and taste
Based on solubility and taste, carbohydrates are classified as sugars and non sugars.
1. Sugars: Carbohydrates which are soluble in water and sweet in taste are called sugars. They are
crystalline. All monosaccharides and oligosaccharides are sugars. Fructose is the sweetest of all
carbohydrates.
Sweetening power of common sugars: fructose > invert sugar > sucrose > glucose > galactose >
maltose > lactose
2. Non sugars: Carbohydrates which are insoluble in water and not sweet in taste are called non
sugars. They are amorphous. All polysaccharides are non-sugars. For example, cellulose, starch
etc.
O Saccharin is not a carbohydrate. It is about 550 times sweeter than sugar. It is almost
C insoluble in water and hence commercially available in its sodium salt. It is used
NH instead of sugar mainly for diabetics and obese persons.
SO2
o-Sulphobenzoic imide (Saccharin)
C. Based on reducing behavior

Carbohydrates which reduce Fehling’s solution, Benedict’s solution or Tollen’s reagent are called
reducing sugars. All monosaccharides and most disaccharides are reducing sugars. Exceptionally,
sucrose, a disaccharide, is a non-reducing sugar. Polysaccharides are non-reducing sugars.
Test Reducing sugar Non reducing sugar

Tollen's test positive negative
Fehling test positive negative
Benedict test positive negative
Mutarotation Yes No
Self Test
16.1 What are biomolecules? Give examples.
16.2 What are carbohydrates? Give the examples of monosaccharides, oligosaccharides and
polysaccharides.
16.3 How does a sugar differ from a non-sugar? Justify with example.
16.4 Differentiate a reducing sugar from a non-reducing sugar.
16.5 What are disaccharides? Write the open chain structure of monosaccharides produced on
hydrolysis of table sugar.
16.6 Draw the structure of (i) aldotriose, (ii) ketohexose, (iii) aldopentose, (iv) ketotetrose.
16.1.3 Meaning of (+) and (-): Optically Active Compounds

A compound which rotates plane of polarized light is called optically active compound and the
phenomenon is called optical activity. Optical activity is detected and measured by an instrument
called polarimeter.
An optically active compound rotates plane of polarized light either in clockwise direction or in
anticlockwise direction. If it rotates the plane of polarized light in clockwise direction, the compound
is called dextrorotatory (Latin: dexter,= right) and represented by d- or (+). Similarly, if it rotates
plane of polarized light in anticlockwise direction, the compound is called laevorotatory (Latin:
laevo,= left) and represented by l- or (-). Mostly, naturally occurring substances are dextrorotatory.
For example, naturally occurring glucose rotates pane of polarized light in clockwise direction.
Hence it is called (+)-glucose or d-glucose. Lactic acid obtained from muscle is (+)-Lactic acid.
COOH COOH 1CHO

1CHO
H C OH HO C H H C OH HO 2
C H
2
CH3 CH3 HO 3C H H 3C OH
HO 4C H
(–)-Lactic acid (+)-Lactic acid H 4C OH
(Object) (Mirror image) HO 5C H
H 5C OH
6 CH2OH
6 CH2OH
Enatiomers (+) - Glucose (–) - Glucose
16.1.4 D and L Designations: Relative Configuration

All monosaccharides are divided into two families; D-family and L-family, by taking the
configuration of glyceraldehyde, the simplest carbohydrate, as standard. Configuration I was
arbitrarily assigned D-glycealdehyde and II was assigned L-glyceraldehyde (proposed by American
chemist Rosanoff in 1906 then universally accepted). The carbohydrates having the same
configuration to that of D-glyceraldehyde at the chiral carbon1 farthest away from the carbonyl
1 Carbon which is bonded to four different atoms or group of atoms are called chiral carbon or asymmetric carbon. An aldohexose has
four chiral carbons hence 16 configurations are possible. One of them is D-(+)-Glucose. (Total optical isomers = 2n, n is number of
chiral carbon if two ends of compounds are not same.) Chiral carbon is indicated by asterisk(*) in glyceraldehyde.
group (-OH on right hand side) are assigned D and those having configuration opposite to D (-OH
on left hand side) are assigned L. It should be noted that D- and L- designations do not indicate the
sign of rotation (d- and l-) of the plane polarized light.
CHO CHO
H C* OH HO C* H
CH2OH CH2OH
I II
D-Glyceraldehyde L-Glyceraldehyde
CHO 1
CHO
1
CHO H C OH HO C H
2 2
CHO H C OH HO C H H C H
3 3
H OH H H C OH HO C H
C C OH 4 4
H C OH H C OH H C OH HO C H
5 5
CH2OH CH2OH 6 CH2OH 6 CH2OH
D-Erythrose D-Ribose D-Glucose L- Glucose
Self Test
16.7 Indicate chiral carbon and predict the number of optical isomers in aldotriose, aldotetrose and
aldopentose. Hint: 2, 4, 9 optical isomers respectively.
16.1.5 (+)-Glucose (Dextrose, Grape Sugar, Blood Sugar)
D(+)— Glucose solution is given orally as well as intravenously to the weak patients
D-(+)-Glucose (grape sugar) is the most common monosaccharide. It occurs in honey and most sweet
fruits especially in ripen grapes (20 – 30% in free state). It is also an essential constituent of human
blood hence it is known as blood sugar. Naturally occurring glucose is dextrorotary hence it is also
called dextrose. Commercially, it is obtained by hydrolysis of starch at high temperature and
pressure.
(C6H10O)n + n H2O n C6H12O6
Starch glucose
In glucose, chiral carbons are C2, C3, C4 and C5.

Open chain structure of glucose is

O H
1C
H 2
C OH
HO 3C H
H 4C OH
H 5C OH
6 CH2OH
D– (+) - Glucose
Open chain structure can not explain some of the properties of glucose.
i. D-(+) Glucose does not give some typical reactions of aldehydes. It gives positive Tollen's test,
Fehling test but does not form bisulphite addition product.
ii. D-(+)- Glucose exists in two crystalline forms; one with melting point 146ºC (α- form which is
obtained by crystallization in aqueous solution at 30ºC) and another with melting point 150°C (
β- form which is obtained by crystallization in acetic acid above 98ºC).
To account these facts, cyclic structure2 was proposed. The cycle structure of glucose is represented
crudely by Fischer formula (Ia and IIa) and Haworth3 pyranose ring structure (Ib and IIb) and more
accurately by structures Ic and IIc.
H
6 CH2OH 6
CH2OH
H OH O 4 H
1C 5 O
H H H 5
H 2C
OH 4 1
HO
O OH H
HO 3C H HO H OH HO
2
3 2 H 1
H 4C OH 3 OH
H OH
H C OH
5 H
6 CH2OH
Ia Ib Ic
α - D-(+)-Glucose (m.pt 146°C)
2 In 1883 Tollens proposed the cyclic structure of glucose. However, he suggested five membered ring
structure for it instead of six membered.
3 In 1926, Haworth established the six membered ring of glucose (aldohexose) and introduced hexagonal
ring structure resembling pyran. α- and β- forms of D-(+)- glucose are represented by Haworth formula
as Ib (α-D-Glucopyranose) and IIb (β -D-Glucopyranose) respectively. Their name is also given in term
of pyran to indicate their ring size.
O Pyran (a six membered of heterocyclic compound)

H
6 CH2OH 6
O CH2OH
5 4
OH H O
HO 1C H H H 5
4 1 HO
H C OH OH OH
2
O HO H H 2
HO 3C H 3 2 HO
3 H 1
H C OH H OH OH
4
H C H H
5
6 CH2OH
IIb IIc
IIa
β - D-(+)-Glucose (m.pt 150°C)
The two forms of glucose (α- and β-) differ in the orientation of –OH group at C1. Hence they are
anomers. These two forms exist in different crystalline forms with different melting point and
specific rotation. O H
C
1 6 CH2OH
6 CH2OH
O
O H C OH 5
OH
5 2 H H
H H H
HO C H 4 1
4 1 3 OH
HO H H
HO OH H OH H C OH 3 2
3 2 4
H C OH H OH
H OH 5
β - D-(+)-Glucose
α - D-(+)-Glucose 6 CH2OH
m.pt 150°C
m.pt 146°C Specific rotation = +19°
D– (+) - Glucose
Specific rotation = +112° 64%
0.01%
36%
When any of these forms is dissolved in

+112° α - D-(+)-Glucose (m.pt 150°C)
water, an equilibrium mixture is obtained
having about 36% of α- form, about 64% of
β- form and very low percentage (0.01%) of
open chain form. This low concentration of
Specific Rotation →
open chain form (aldehyde) is sufficient to

give positive Tollen's and Fehling test but
not sufficient to give the bisulphite +52.7°
addition product which is reversible.
When any of these forms is dissolved in +19°
water, the specific rotation gradually β - D-(+)-Glucose (m.pt 150°C)
changes to +52.7o. The change in specific
rotation to the equilibrium value is called time →
mutarotation.
Fig. 16.1: Mutarotation of D - (+) - glucose
16.1.6 (-)-Fructose (Laevulose, Fruit Sugar)
D-(-)-Fructose is the most common ketohexose. It occurs in honey and most sweet fruits. Naturally
occurring fructose is levorotatory hence it is also called laevulose. Commercially, it is obtained by
hydrolysis of inulin.
H2SO4, Δ
(C6H10O5)n + n H2O n C6H12O6
Inulin Fructose
1CH2OH
6
CH2OH O 1 CH OH 2
C O 6
2
CH2OH O OH
5 2 HO 3C H
H O 5 2
H 4 3 OH H 4C
OH H
H O CH2OH
4 3
1
OH H H 5C OH
OH H
α - D-(–)-Fructose or
6 CH2OH β - D-(–)-Fructose or
α-D(–)-Fructofuranose
Specific rotation = –21° D-(–)- Fructose β-D(–)-Fructofuranose
Structure of fructose Specific rotation = –133°
The name fructofuranose is given to fructose to indicate its ring size like furan (five membered
heterocyclic compound).
O
Furan
16.1.7 Sucrose (Common Table Sugar)

Sucrose is common table sugar and obtained from sugarcane and sugar beets. It is a disaccharide. On
hydrolysis with dilute acid or by enzyme invertase, it gives equal amounts of D-(+)-glucose (dextrose)
and D-(-) fructose (levulose).
H+ or invertase
C12H22O11 +H2O C6H12O6 + C6H12O6
Sucrose D-(+)-glucose D-(-)fructose
(Cane or beet sugar) (dextrose) (levolose)
Specific rotation = + 66.5°
Invert sugar
Specific rotation = –19.9°
Sucrose is dextrorotatory with specific rotation +66.5º. On hydrolysis, the specific rotation changes to
-19.9º. This change in sign of rotation from (+) to (-) is called inversion and hydrolyzed mixture is
called invert sugar.
Note:
D-(+)-glucose has specific rotation +52.7º. D-(-)-fructose has specific rotation – 92.4º. The net specific rotation of an equimolar
+52.7° – 92.4°
mixture of D-(+)-glucose and D-(-)-fructose is 2 = -19.9º
Sucrose has no free carbonyl group, so it does not reduce Tollen's reagent, Fehling solution,
Benedict's solution. Hence, it is called non reducing sugar.
6 CH2OH
5 O
H H 6 CH2OH
H
4 1 5 O
HO OH H H H H
3 2 4 1
α, β-Glycoside bond OH H
H OH HO OH
3 2
H OH
Sugarcane O H+ or invertase
α - D-(+)-Glucose
+
6
CH2OH O 6
5 CH2OH O OH
H OH
H 4 3 CH2OH 5
1 H OH
H 4 3 CH2OH
OH H 1
OH H
Beet sugar Sucrose
β-D-(–)-Fructose
Self Test
16.8 Aqueous solution of sucrose is called invert sugar, give reasons.
Starch
It is a polysaccharide and forms reserve food of plants. It contains 20% of water soluble fraction
called amylose and 80% of water insoluble fraction called amylopection. On complete hydrolysis, it
gives D-(+)- glucose.
16.1.8 Functions of Carbohydrates

Carbohydrates provide us the necessities of life: food, shelter and clothing. The roles of
carbohydrates categorized as;
1. Energy source (bio-fuels): Carbohydrates (all except cellulose) are the ultimate source of most
of our food. Starch is the reserve food in plants and glycogen in animals.
C6H12O6 +6O2 6CO2 + 6H2O +2832KJ
2. Structural role: Cellulose is the chief structural component in plant cells. Cellulose in the form
of wood is used for houses and furniture, cellulose in the form of cotton, linen, rayon is used
for clothing and cellulose in the form of paper is used for books, newspapers, money, bags,
boxes, sheets and rolls etc. Chitin forms exoskeleton of arthropods and crustaceans. Cellulose
can be used to prepare explosive like gun cotton.
3. Carbohydrates are also the constituent of DNA and RNA (deoxyribose sugar in DNA and
ribose sugar in RNA).
16.1.9 Test for Carbohydrates: Molicsh's Test

Carbohydrates produce deep purple solution with Molisch's reagent (10% α-Napthol in alcohol) in
presence of concentrated H2SO4.
16.2 Proteins
16.2.1 Introduction
Proteins are complex nitrogenous organic compounds of high molecular mass. They make up a large
part of animal body and essential for growth, development and maintenance of life. They are found
in all living cells. The name protein is given to signify their prime importance to life (Greek; proteios =
first). Chemically, proteins are high molecular mass polymers of α-amino acids.
Cereals, milk, fishes, meat, eggs are some major sources of proteins.
Source Protein Source Protein

Soya bean 42% Cashuenut 21%
Pea 28% Almonds 21%
Milk powder (whole) 25% Mutton 18%
Fish 22%
16.2.2 Amino Acids

In chemistry, amino acids are organic compounds having amino group(-NH2) and carboxyl group
(-COOH) in the same molecule. The position of amino group varies. For example,
H
γ β α
CH3CH2—C—COOH CH3CHCH2COOH CH2CH2CH2COOH
NH2 NH2 NH2
α-Aminocarboxylic acid β-Aminocarboxylic acid γ-Aminocarboxylic acid
Amino acids found in proteins are only α-aminocarboxylic acid. The general formula is
H
α
H2N—C—COOH
R
General formula of α-amino acid
Examples:
H H H H
α α α α
H2N—C—COOH H2N—C—COOH H2N—C—COOH H2N—C—COOH
H CH3 CH2SH CH2Ph
Glycine Alanine Cysteine Phenylalanine
Gly Ala Cys Phe
There are altogether 26 α- amino acids known, out of them only 23 amino acids are found in the
proteins ( used by cells in the protein biosynthesis), remaining are found in the special tissues.
List of natural amino acids
Name Abbreviation Structure

(+)-Alanine Ala or A H
α
H2N—C—COOH
CH3
(+)-Argenine
e
Arg or R H
α
H2N—C—COOH
CH2CH2CH2 NH—C—NH2
NH
(-)-Asparagine Asn or N H
H2N—C—COOH
CH2CONH2
(+)-Aspartic acid Asp or D H

H2N—C—COOH
CH2COOH
(-)-Cysteine Cys or C H
α
H2N—C—COOH
CH2SH
(-)-Cystine Cys-Cys H
H2N—C—COOH
CH2S—SCH2—CHCOOH
NH2
(+)-Glutamic acid Glu or E H
α
H2N—C—COOH
CH2CH2COOH
(+)-Glutamine Gln or Q H
H2N—C—COOH
CH2CH2CONH2
Glycine Gly or G H
H2N—C—COOH
H
e
(-)-Histidine His or H H
α
H2N—C—COOH
CH2
N
N
(-)-Hydroxylysine Hyl H
H2N—C—COOH
CH2CH2CHCH2NH2
OH
(-)-Hydroxyproline Hyp HO
COOH
N
H
e
(+)-Isoleusine Ile or I H
H2N—C—COOH
CHCH2CH3
CH3
(-)-Leucine
e
Leu or L H
H2N—C—COOH
CH2
H3C—C—CH3
H
e
(+)-Lysine Lys or K H
H2N—C—COOH
CH2CH2CH2CH2NH2
e
(-)-Methionine Met or M H
H2N—C—COOH
CH2CH2—S—CH3
e
(-)-Phenylalanine Phe or F H
α
H2N—C—COOH
CH2
(-)-Proline Pro or P
COOH
N
H
(-)-Serine Ser or S H
H2N—C—COOH
CH2OH
e
(-)-Threonine Thr or T H
H2N—C—COOH
CH—CH3
OH
e
(-)-Tryptophane Trp or W H
H2N—C—COOH
CH2
(-)-Tyrosine Tyr or Y H
H2N—C—COOH
CH2 OH
e
(+)-Valine Val or V H
H2N—C—COOH
CH3—CH—CH3
e = essential amino acid
Out of 23 α- amino acids found in proteins, 10 α- amino acids cannot be synthesized by animals in
their body; therefore they must be ingested in the form of food for the proper growth. These α-
amino acids are called essential or indispensable amino acids. The remaining α- amino acids are
synthesized in the body and are called non essential or dispensable amino acids.
All amino acids found in proteins are optically active compounds except glycine. Glycine is optically
inactive since it has no chiral carbon.
Some amino acids contain second acidic group (carboxyl group) which are called acidic amino acids.
For example, Aspartic acid, Glutamic acid. Some amino acids contain another basic group which are
called basic amino acids. For example, Arginine, Histidine,Lysine.
Amino acids are insoluble in non-polar solvents like petroleum ether, ether, benzene but soluble in
water. They are crystalline solids with high melting point. Various experiments show that amino
acids exist as zwitter ions.
H H
α + α
H2N—C—COOH H3N—C—COO¯
R R
Zwitter ion
In an amino acid, since acidic group (-COOH) and basic group (-NH2) are in the same molecule, -
COOH loses a proton and -NH2 accepts a proton forming dipolar ion or zwitter ion.(Greek: Zwitter=
hermaphrodite).
Self Test
16.9 What are proteins? Name major proteins found in milk and egg.
16.10 What are amino acids? How do essential amino acids differ from non-essential amino acids?
Give any two examples of each.
16.11 Give the name of
(i) All essential amino acids (ii) Acidic amino acid (any two)
(iii) Basic amino acid( any two) (iv) Amino acid having sulphur
(v) Amino acid having aromatic ring
16.2.3 Isoelectric Point of Amino Acids

H H H
α H+ + α H+ + α
H2N—C—COO¯ H3N—C—COO¯ H3N—C—COOH
R OH– R OH– R
anion Zwitter ion cation
(II) (I) (III)
Migrates towards anode Migrates towards cathode
Amino acid exists as dipolar ion (zwitter ion). In alkaline medium, amino acids exist mostly in the
anion (II) form, which migrates towards anode in the electric field. While in acidic medium, cation
(III) exists in excess and migrates towards cathode. At certain pH, concentration of anion (II) becomes
equal to that of cation (III), in which, there is no net migration of amino acid towards any electrode in
the electric field. Such pH at which amino acid does not migrate is called isoelectric point. It is
characteristics of all amino acids and each amino acid has its own characteristics isoelectric point.
Example: Isoelectric point of glycine, phenylalanine and glutamic acid are 6.1, 5.5 and 3.2
respectively.
An amino acid shows minimum solubility at its isoelectric point due to highest concentration of its
zwitter ion.
H
H H H + α
+ α + α + α H3N—C—COO¯
H3N—C—COO¯ H3N—C—COO¯ H3N—C—COO¯
CH2CH2COOH
H CH3 CH2OH
Serine Glutamic acid
Glycine Alanine
Ser Glu
Gly Ala
Self Test
16.12 What is a zwitter ion? Illustrate with an example of α amino acid.
16.13 What is isoelectric point of an amino acid?
16.2.4 Peptides and Peptide Bond

Acidic carboxyl group (-COOH) of an amino acid reacts with the basic amino group (-NH2) of other
amino acid to give–NHCO- group, which is called peptide bond or peptide linkage. The compound
formed by the condensation reaction between to aminoacids is called dipeptide.
H O H O H O H O
H N C C OH + H N C C OH H N C C N C C OH + H2O
H R H R' H R H R'
Amino acid Amino acid Peptide bond

A dipeptide
(R & R' may be same or different)
Depending upon number of amino acid residue per molecule, the molecules are called dipeptide,
tripeptide and so on, and finally polypeptide.
Examples:
H O H O H O H O
H N C C OH + H N C C OH H N C C N C C OH + H2O
H H H H H H H H
Glycine Glycine Glycylglycine
Gly Gly (Gly-Gly)
A dipeptide
H O H O H O H O H O H O
H N C C OH + H N C C OH + H N C C OH H N C C N C C N C C OH
– 2H2O
H H H CH3 H CH(CH3)2 H H H CH 3 H CH(CH3)2
Glycine Alanine Valine
Gly Ala Peptide bonds
Val
Glycylalanylvaline
(Gly-Ala-Val)
A tripeptide
According to convention, the N- terminal amino acid residue is written at the left end and the C-
terminal amino acid residue at the right end in polypeptides.
Oxytocin is nonapeptide (a polypeptide having nine amino acid residues) is a pituitary hormone
concerned with contraction of uterus.
Insulin is a polypeptide. It consists of two polypeptide chains; chain A and chain B which are hold
together by disulphide bond. Chain A consists of 21 amino acids and chain B consists of 30 amino
acids. Insulin is a hormone produced by β-cells of pancreas and has a key role in the metabolism of
carbohydrates, proteins and fats. Deficiency of insulin causes the disease called diabetes mellitus.
Gly
Chain A
|
Ile
|
Val S S
|
Glu
Glu—Cys—Cys—Ala—Ser—Val—Cys—Ser—Leu—Tyr—Gln—Leu—Glu—Asn—Tyr—Cys—Asn
S S
S S
His— Leu— Cys — Gly — Ser —His — Leu —Val—Glu—Ala — Leu—Tyr— Leu—Val—Cys
| |
Glu Gly
| |
Asn Chain B Glu
| |
Val Arg
| |
Phe Ala— Lys — Pro — Thr — Tyr — Phe — Phe —Gly
Insulin
Human insulin is the synthetic insulin

which is laboratory grown to mimic the
insulin in humans and approved for
pharmaceutical use in 1982.
By convention, proteins are polypeptides of high molecular masses above 10,000 are called proteins
and hence they are macromolecules.
Some proteins molecular mass
Insulin 12,000
Egg albumin 45,000
Haemoglobin 70,000
Casein 1,80,000
Hydrolysis of proteins
Proteins are hydrolyzed by dilute mineral acids, alkalis and by enzymes. The final products of
hydrolysis are α-amino acids. For example,
H O H O H O H O
H N C C N C C OH + H2O H N C C OH + H N C C OH
H R H R' H R H R'
A dipeptide Amino acid Amino acid
Self Test
16.14 What is a peptide bond? Give an example of a dipeptide.
16.15 Give a chemical reaction for hydrolysis of dipeptide.
16.16 What happens when a protein is completely hydrolyzed?
16.2.5 Classification of Proteins

1. On the basis of molecular structure, proteins are broadly classified into two classes;
i. Fibrous proteins
ii. Globular proteins
i. Fibrous proteins: Molecules of fibrous proteins are long threadlike and tend to lie side by side
to form fibers. They are insoluble in water. Fibrous proteins serve as the chief structural materials
of animal tissues, a function to which their insolubility and fiber forming tendency suit them.
For example, keratin in skin, hair, nails, wool, horn, and feathers; myosin in muscle, fibroin in
silk etc.
ii. Globular proteins: Molecules of globular proteins are folded into compact units of spheroidal
shapes. Globular proteins are soluble in water and aqueous solutions of acids, bases and salts.
Globular proteins serve a variety of functions related to the maintenance and regulation of the
life processes, functions that require mobility and solubility. For example, all enzymes, many
hormones, albumin, hemoglobin etc.
2. On the basis of constituents in the molecule, proteins are classified into two classes;
i. Simple proteins: Protein which gives only α-amino acids on hydrolysis are called simple
proteins. For example, albumin, globulin, histone etc.
ii. Conjugated proteins: Protein which gives non protein part in addition to α-amino acids are
called conjugated proteins. For example, glycoprotein, lipoprotein nucleoprotein, hemoglobin
etc.
Self Test
16.17 How do fibrous proteins differ from globular proteins?
16.2.6 Structure of Proteins

Proteins are the high molecular mass polymers of α- amino acids. The structure is complex and can
be divided into following levels of organization.
1. Primary structure: It is the sequence of amino acids in the protein. A protein molecule has its
own sequence of amino acids. Just as the letters of the alphabet combined in a different ways to
form an almost endless variety of words, amino acids linked together on varying sequence form
a huge variety of proteins.
2. Secondary structure: It tells us about the spatial arrangement of polypeptide in a protein. The
arrangement may provide twisting of polypeptide chain which is mainly maintained by H-
bond of β-flat structure.
O H R H
C N C
H N C C
δ+ N
C N Intermolecular H-bond
H R H O H
δ– O
δ+ Hδ
+ δ+
C C O R H H O
δ– O C Oδ–
N– C C N C
δ
O N C C
Hδ Hδ
+ +
H O R H
N– N–
δ C δ β-flat sheet structure
O
α-helix structure of polypeptide
3. Tertiary structure: It is three dimensional arrangement of protein structure in native

environment. It is compact structure with H-bond, S-S-bond, ionic interaction, and hydrophobic
interaction to produce a specific shape which is most stable called native state.
16.2.7 Denaturation of Proteins

Denaturation is the disorganization of native protein
structure. During denaturation, tertiary and secondary
structures of protein are destroyed whereas primary structure
remains the same. During denaturation, the biological
activities of protein are lost and its physical properties are
changed, but chemical properties remain same. In Fig. 16.2 Denaturation of Protein of Egg
denaturation, soluble globular protein gets converted into

insoluble fibrous protein. Proteins can be denatured by
various agents such as;
i. physical agents like heat
ii. radiations
iii. chemicals agents like strong solutions of acids, bases or salts
Examples:
1. Coagulation of egg- white (albumin) on heating: Soluble globular albumin changes into
insoluble fibrous albumin.
2. Conversion of milk (casein) into cheese: Soluble globular casein changes into insoluble fibrous
casein.
Self Test
16.18 What is denaturation of protein? What physical, chemical and biological changes take place
during denaturation?
16.2.8 Enzymes
Enzymes are a group of globular proteins that catalyze the biochemical reactions in cells. Hence they
are also called biological catalysts.
Each cell produces particular enzymes to speed up the reactions. Even a primitive cell of bacteria
contains about 3000 different enzymes. Without enzymes, food materials like carbohydrates, proteins
cannot be digested.
Characteristics of enzymes
1. Enzymes catalyze the reactions up to ten millions times faster than unanalyzed reactions.
2. Enzymes are highly specific in their actions.
3. Enzymes are highly efficient i.e. small amount of enzyme can bring a large extent of reactions.
4. Enzymes function at moderate temperature and pH range in living cells. If conditions are
changed catalytic activities are decreased or lost.
5. Catalytic activities of enzymes are enhanced by some non-proteins which are called cofactors. It
may be some metal cations like K+, Na+, Cu+, Mg++, Zn++, Ca++, Ni++, Fe++, CO++ or other smaller
organic compounds.
If the cofactors are organic compounds, they are called coenzymes. The peptide portion of enzyme
without coenzyme is called apoenzyme and the enzyme with its cofactor is called holoenzyme.
Self Test
16.19 What are enzymes? Give any two characteristics of them.
16.2.9 Functions of Proteins

1. Enzymes: All enzymes are proteins.
2. Structural: Proteins are the major structural materials of animal tissues. E.g. keratin
3. Transport proteins: Globin in hemoglobin of blood transport oxygen
4. Storage proteins: Some proteins are food storage. E.g. albumin of egg, casein of milk
5. Hormones: Many hormones are proteins e.g. Insulin which regulates blood sugar.
16.2.10 Some Visual Tests of Proteins

1. Ninhydrin test: This test is given by amino acid as well as proteins.
2. Biuret test
3. Xantho-proteic test
4. Millon's test
5. Hopkins-Cole test
16.3 Nucleic Acids (DNA and RNA)
Cell
Base pair
DNA
Nucleus
Chromosome
Histone protein
Fig 16.3: DNA: Important unit of heridity carrier
16.3.1 Introduction
Nucleic acids are non-protein, nitrogenous substances which are polymers of nucleotides hence they
are also called polynucleotides. Nucleic acids are genetic materials of the cells which are responsible
for transmission of heredity character and also carry out biosynthesis of proteins.
There are two different types of nucleic acids found in living organizations.
1. RNA (Ribonucleic acid)
2. DNA (Deoxyribonucleic acid)
16.3.2 Components of Nucleic Acids

Nucleic acids are made up of three components;
1. Pentose sugar 2. Nitrogenous bases 3. Phosphate group
1. Pentose sugar: There are two types of pentose sugars (Carbohydrate having five carbon atoms)
in nucleic acids; deoxyribose sugar in DNA and ribose sugar in RNA.
5
HOH2C OH 5
O HOH2C
4 1 O OH
H H
4 1
H H
H 3 2H
H 3 2H
OH OH
OH H
β-D(–) Ribose
(found in RNA) β-D(–) -2-Deoxyribose
( found in DNA)
2. Nitrogenous bases: These are heterocyclic organic compounds having nitrogen atoms. There
are two types of nitrogenous bases in nucleic acid; purine bases and pyrimidine bases.
i. Purine bases: It includes adenine and guanine.
NH2 O
N H N N
N
N H2N N N
N
H H
Adenine (A) Guanine (G)
ii. Pyrimidine bases: It includes uracil, thymine and cytosine.

O O NH2
H N CH3 N
H N
O N O N O N
H H H
Uracil (U) Thymine (T) Cytosine (C)
Nucleic acid Purine bases Pyrimidine bases

DNA Adenine, Guanine Cytosine, Thymine
Uracil is absent
RNA Adenine, Guanine Cytosine,Uracil
Thymine is absent
N N N
N N N
H Pyrimidine
Purine
3. Phosphoric acid unit

O
HO P OH
OH
Phosphoric acid
Nucleotide: Pentose sugar combines with nitrogenous base at its C1 and with phosphoric acid
at C5 to give phosphate-sugar-base unit which is called nucleotide.
Phosphate
Nitrogenous Base
Pentose (A,T,C or G)
Sugar
Example: A Nucleotide NH2

NH2
N N
N N
Adenine N
N
N N
H O Adenine
O + 5
5 HO P OH2C O
HO P OH + HOH2C O OH
4 1
4 1 OH H H
OH H H H H
H H Phosphate 3 2
Phosphoric acid 3 2
OH H
OH H
β-D(–) -2-Deoxy Ribose
β-D(–) -2-Deoxy Ribose
A nucleotide
Polynucleotide: Phosphoric acid unit of one nucleotide combines with sugar unit of other nucleotide
at C3 of sugar (ester linkage) to give finally polynucleotide which is nucleic acid.
16.3.3 Double Helix Structure of DNA

In 1953, James Watson and Francis Crick reported the double helix structure of DNA and received
the Nobel Prize in 1962 for this work. According to this model, DNA is made up of two
polynucleotide chains wound as right handed helix round a common axis forming a double helix but
heading in opposite direction so that the sequence is C-3, C-5 in one chain and C-5, C-3 in the other
chain.
The two polynucleotide chains are held
together at intervals by hydrogen bonds
between purine and pyrimidine base pairs.
Thymine is always bonded to adenine by
two H-bonds and cytosine is always boned to
guanine by three H- bonds. Hence two
chains are not identical but complementary.
A double helix is 20Å(2nm) in diameter and
each complete turns is 34Å(3.4nm) along the
axis and has ten nucleotide units.
Sugar – Base pair Sugar –

Phosphate Phosphate
Backbone Backbone
↑
H-bond
↓
34 Å
3' 20 Å 5'
Fig. 16.4: Structure of DNA (A portion)
16.3.4 Differences between RNA and DNA

Some of the important difference between DNA and RNA are listed in the table:
DNA RNA
1. It is double stranded and helical. (except in 1. It is single stranded and non-helical.
paraovins)
2. The pentose sugar is deoxyribose . 2. The pentose sugar is ribose.
3. Purine nitrogenous bases found in DNA 3. Purine nitrogenous bases found in RNA
are Adenine (A) and Guanine (G). are Adenine (A), Guanine (G).
Pyrimidine nitrogenous bases found are Pyrimidine nitrogenous bases found are
Thymine (T) and Cytosine (C). Uracil (U) is Uracil (U) and Cytosine (C). Thymine (T) is
absent. absent.
4. DNA can undergo replication. 4. It does not replicate.
5. It transmits heredity characters. 5. It plays main role in protein synthesis.
16.3.5 Biological Functions of Nucleic Acids

1. The nucleic acid DNA carry genetic information from parent to offspring.
2. DNA synthesizes RNA by the process of transcription.
3. DNA controls all biological activities of cell.
4. The nucleic acid RNA plays major role on protein biosynthesis.
5. In some of the virus like HIV and TMV viruses, RNA acts as genetic material.
Self Test
16.20 What are the nucleic acids? Point out their constituents.
16.21 Name purine and pyrimidine bases of DNA and RNA.
16.22 Write the differences of DNA and RNA.
16.4 Lipids
16.4.1 Introduction
The term lipid is derived from the Greek word Lipos; meaning fat. Water insoluble compounds like
fats and oils and their derivatives occurring in the living organisms are called lipids. Lipids are a
group of bio-molecules which are greasy, insoluble in water (hydrophobic) and soluble in organic
solvents like ether, chloroform etc. Lipids are the constituents of all cell membranes.
Lipids are classified as;
1. Simple lipids (fats and oils)
2. Phospholipids
3. Waxes
16.4.2 Simple Lipids (Fats and Oils)

Fats are the major constituents of fat cells in animals and plants, and are the important food reserves
of organisms. They are found mainly under skin, around intestine in animals and in seeds and fruits
in plants.
H O
H—C—O—C
O
H—C—O—C
O
H—C—O—C
H
Olive (Olea europaea) branch with fruits Olive oil Triglyceride (Oil molecule)
Chemically, a fat or an oil molecule is an ester of glycerol ( a trihydric alcohol) with fatty acids (long
chain mono carboxylic acids) ie. Triacylglycerol or triglyceride.
H O HO
H—C—O H HO—C—R' H—C—O—C—R'
+ O O
H—C—O H HO—C—R'' H—C—O—C—R" + 3H2O
O O
H—C—O H HO—C—R'" H—C—O—C—R'"
H H
Fatty acids A triacylglycerol
Glycerol
(Triglyceride)
Fat or oil
If R' = R'' = R''', the triglyceride is called simple triglyceride otherwise called mixed triglyceride. All
natural fats and oils are a mixture of mixed triglycerides.
Fatty acids
Fatty acids are open chain monocarboxylic acids having carbon number 3 to 18. Except for C3 and C5
acids, only acids with even number of carbons are present in substantial amount. Fatty acids are
saturated as well as unsaturated.
Some saturated fatty acids
H H H H H H H H H H H H H H H H O
C 17 C 15 C 13 C 11 C 9 C 7 C 5 C 3 C1
C 18 C C C C C C C C OH
H
H H H H H H H H H H H H H H H H H H
O
Or, 17 15 13 11 9 7 5 3 1
18 16 14 12 8 6 4 2
OH
10
Octadecanoic acid (Stearic acid), melting point 70°C
O
15 13 11 9 7 5 3 1
OH
16 14 12 10 8 6 4 2
Hexadecanic acid (Palmitic acid), melting point 63°C
O
13 11 9 7 5 3 1
OH
12 10 8 6 4 2
Tetradecanic acid ( Myristic acid), melting point 55°C

Saturated fatty acids are linear and fit well together hence have high melting point.
Some unsaturated fatty acids
O O
9 7 5 3
10
8 6 4 2
1 OH
12 11
14 13 Trans -9-Octadecenoic acid
16 15
cis-9-Octadecenoic acid
18 17
(cis-Oleic acid)
Melting point 16°C
O O
OH OH
CH3
CH3
cis,cis,cis-9,12,15- Octadecatrienoic acid

cis,cis-9,12- Octadecadienoic acid
( Linolenic acid), melting point -11°C
( Linoleic acid), melting point -5°C
cis-unsaturated fatty acid has a bent at the double bond i.e. the molecule is nonlinear and fits poorly
hence has a low melting point.
Self Test
16.23 How do you account for the fact that octadecanoic acid is solid but cis-9-octadecanoic acid is
liquid at room temperature though both have nearly equal molecular weight?
Hint: Compare surface area and molecular geometry
Table 16.1: Fatty acid composition of some fats and oils

fats and oils saturated fatty acids unsaturated fatty acids
Butter -gf}gL £o"_ Myristic acid (8-13%) Oleic acid (22-29%)
Palmitic acid (25-32%) Linoleic acid (3%)
Stearic acid (8-13%) Linolenic acid (2-10%)
Lard (pig fat) Myristic acid (1%) Oleic acid (41-51%)
Palmitic acid (25-30%) Linoleic acid (3-8%)
Stearic acid(12-16%)
Soybean oil Palmitic acid (7-11%) Oleic acid (22-34%)
Stearic acid (2-5%) Linoleic acid (50-60%)
Linolenic acid (2-10%)
Olive oil -h}t'gsf] t]n_ Palmitic acid (7-20%) Oleic acid (53-86%)
Stearic acid (1-3%) Linoleic acid (4-22%)
16.4.3 Differences between Fats and Oils

Fats Oils
Natural triglycerides that are solid at room Natural triglycerides that are liquid at room
temperature are called fats. temperature are called oils.
Fat contains a large proportion of saturated fatty acid Oils contain large proportions of cis-
residues like palmitic acid (mpt.63°C), stearic acid unsaturated fatty acid residues like oleic acid
(mpt.70°C). The molecules of fats fit well together (mpt.16°C), linoleic acid (mpt.–5°C), linolenic
since the acid residues are saturated and hence linear acid(mpt.-11°C),. The molecules do not fit each
due to which intermolecular force of attraction is other well since the acid residues are
stronger thus has high melting point. unsaturated and hence nonlinear due to which
intermolecular force of attraction is weak thus
H has low melting point.
O
H—C—O—C H
O O
H—C—O—C H—C—O—C
O O
H—C—O—C
H—C—O—C
O
H H—C—O—C
H
Saturated triglyceride
Fat molecule
Unsaturated triglyceride
Oil molecule
16.4.4 Hydrogenation of Oil

For hydrogenation, oil is heated to 150-200°C and hydrogen is passed in under pressure in presence
of finely divided nickel catalyst.
Ni, Δ
Oil + H2 Semisolid
(Vanaspati ghee)
Hydrogenation of oil changes its physical as well as chemical properties. It hardens the oil and
lowers rancidity.
1. Hardening of oils: Oils contain large proportions of cis-unsaturated fatty acid residues. The
molecules do not fit each other well since the acid residues are cis-unsaturated and hence
nonlinear. This makes intermolecular force of attraction weak thus low melting point i.e. liquid
at room temperature. On hydrogenation, the molecules become saturated and hence linear due
to which intermolecular force of attraction increases i.e. melting point increases. Hence oils are
converted into solid form. The process is also called hardening of oil. Only partial
hydrogenation is carried out otherwise a fat as hard as tallow is formed.
2. Rancidity of fats and oils: when fats and oils are exposed to moist air for a long time, bad smell
and sour taste are developed and fats and oils are said to be rancid. Rancidity is due to presence
of volatile, bad smelling acids and aldehydes which result at least from attack of oxygen at
double bond positions (allylic positions). Hydrogenation slows down the rancidity by
decreasing the number of double bonds.
Drying oils: Oils with high degree of unsaturation like linseed oil (oil obtained from the ripe seeds of the flax plant Linum
usitatissimum), tung oil (oil obtained from the seeds of the tung tree, Aleurites fordii.) polymerize in presence of air to
form a thin tough waterproof film which protect the surface and gives good finish. Such oils are called drying oils. Drying
means not the evaporation of solvent . Drying oils are used as vehicles in paints, varnishes, and printing inks.
16.4.5 Hydrolysis of Fats

Fat (ester) can be hydrolyzed in acidic as well as in alkaline medium. Hydrolysis of fat with mineral
acid gives glycerol and a mixture of carboxylic acids. They can be separated by fractional distillation
of over 90% purity. Fats are thus the source of monocarboxylic acids of even carbon number ranging
from six to eighteen carbons.
HO H O
H—C—O—C—R' H—C—OH HO—C—R'
O H+ O
H—C—O—C—R" + 3H2O H—C—OH + HO—C—R''
O O
H—C—O—C—R'" H—C—OH HO—C—R'"
H H
A triacylglycerol Glycerol Fatty acids
(Fat)
Alkaline hydrolysis of fat gives a mixture salt of fatty acids which is called soap and the process is
called saponification.
H O H
H—C—O—C—R' H—C—OH +
R' COO Na
O
H—C—O—C—R" H—C—OH +
+ 3NaOH (aq) + R'' COO Na
O
H—C—O—C—R'" H—C—OH +
R'" COO Na
H H
A triacylglycerol Mixture of sodium salt of
Glycerol
(Triglyceride) fatty acids (Soap)
Fat
A soap molecule is amphipathic ie. has a polar end (hydrophilic) and nonpolar hydrocarbon end
(lipophilic). In water, nonpolar ends huddle together in the center projecting polar ends outwards in
the solvent forming a spherical cluster called micelle.
Polar head Non-polar hydrocarbon end
(Hydrophilic) (Lipophilic)
A soap molecule
Water
A soap micelle
Water
Fig 16.5: Soap micelles dispersed in water

16.4.6 Phospholipids
Phospholipids are triglycerides in which two hydroxyl groups of glycerol are esterified with fatty
acids and the third hydroxyl group is esterified with derivatives of phosphoric acid having nitrogen.
H O Polar head (Hydrophilic)

H—C—O—C—R'
O
Non-polar hydrocarbon end
H—C—O—C—R" Phospholipid
O
(Lipophilic)N
molecule
H—C—O—P—O—
+
H O—CH2CH2NH3
Non-polar hydrocarbon end

(Lipophilic)
Polar head
(Hydrophilic)
Phospholipid bilayer in cell membrane
16.4.7 Waxes
Waxes are esters of higher fatty acids with long chain monohydric alcohols. For example,
beeswax is largely myricyl palmitate.
O
C15H31 —C—OC30H61
Triacontanyl palmitate (myricyl palmitate)
16.4.8 Functions of Lipids

1. Lipids are goods source of energy. They provide energy on oxidation.
2. Body stores food as reserve food in the forms of lipid because they are insoluble in water
3. They are structural components of cell membrane.
4. They act as carrier of fat soluble vitamins A, D and E.
5. They surround vital organs and protect from mechanical shock and injury.
6. Fats are present below skin acts as insulator which reduces heat loss.
7. Drying oils are used as vehicles in paints, varnishes, and printing inks.
Self Test
16.24 What are lipids? Mention their role in a human body.
16.25 What are fats and oils chemically?
16.26 What are physical and chemical difference of fat and oil?
16.27 What is saponification?
Solved Questions
1. What are carbohydrates chemically?
¬ Carbohydrates are polyhydroxyaldehydes or polyhydroxyketones or any organic compounds that produce
these compounds on hydrolysis.For example,
O H
1C
H C
2
OH
HO 3C H
H 4C OH
H 5C OH
6 CH2OH
Glucose
2. What are fibrous and globular proteins?

¬ On the basis of molecular structure, proteins are broadly classified into two classes;
a. Fibrous proteins
b. Globular proteins
a. Fibrous proteins: Molecules of fibrous proteins are long thread like and tend to lie side by side to form
fibers. They are insoluble in water. Fibrous proteins serve as the chief structural materials of animal
tissues, a function to which their insolubility and fiber forming tendency suit them. For example, keratin
in skin, hair, nails, wool, horn and feathers; myosin in muscle, fibroin in silk, etc.
b. Globular proteins: Molecules of globular proteins are folded into compact units of spheroidal shapes.
Globular proteins are soluble in water and aqueous solutions of acids, bases and salts. Globular proteins
serve a variety of functions related to the maintenance and regulation of the life processes, functions that
require mobility and solubility. For example, All enzymes, many hormones, albumin, hemoglobin etc.
3. What is denaturation of protein?
¬ Denaturation is the disorganization of native protein structure. During denaturation, tertiary and secondary
structures of protein are destroyed whereas primary structure remains same. During denaturation, the
biological activities of protein are lost and its physical properties are changed, but chemical properties
remain same. In denaturation, soluble globular protein gets converted into insoluble fibrous protein. Proteins
can be denatured by various agents such as;
i. physical agents like heat,
ii. radiations,
iii. chemicals agents like strong solutions of acids, bases or salts
For example, coagulation of egg- white (albumin) on heating: Soluble globular albumin changes into
insoluble fibrous albumin.
4. What are fats and oils chemically? Why do they exist in different physical states?
¬ Chemically, a fat or an oil molecule is an ester of glycerol (a trihydric alcohol) with fatty acids (long chain
mono carboxylic acids) i.e. Triacylglycerol or triglyceride.
H O H O
H—C—O H HO—C—R' H—C—O—C—R'
+ O O
H—C—O H HO—C—R'' H—C—O—C—R" + 3H2O
O O
H—C—O H HO—C—R'" H—C—O—C—R'"
H H
Fatty acids A triacylglycerol
Glycerol
(Triglyceride)
Fat or oil
Natural triglycerides that are solid at room temperature are called fats otherwise oils. The difference in their
physical states is due to differences in their molecular geometry.
Fat contains a large proportion of saturated fatty acid residues like palmitic acid (mpt. 63°C), stearic acid
(m.pt.70°C). The molecules of fats fit well together since the acid residues are saturated and hence linear due
to which intermolecular force of attraction is stronger thus has high melting point.
Oils contain large proportions of cis-unsaturated fatty acid residues like oleic acid (mpt.16°C), linoleic acid
(m.pt.-5°C), linolenic acid (m.pt.-11°C). The molecules do not fit each other well since the acid residues are
unsaturated and hence nonlinear due to which intermolecular force of attraction is weak thus has low
melting point.
5. What happens when oil is hydrogenated?
¬ For hydrogenation, oil is heated to 150-200°C and hydrogen is passed in under pressure in presence of finely
divided nickel catalyst.
Ni, Δ
Oil + H2 Semisolid
(Vanaspati ghee)
Hydrogenation of oil changes its physical as well as chemical properties. It hardens the oil and lowers
rancidity.
i. Hardening of oils: Oils contain large proportions of cis-unsaturated fatty acid residues. The molecules
do not fit each other well since the acid residues are cis-unsaturated and hence nonlinear. This makes
intermolecular force of attraction is weak thus low melting point i.e. liquid at room temperature. On
hydrogenation, the molecules become saturated and hence linear due to which intermolecular force of
attraction increases i.e. melting point increases. Hence oils are converted into solid form. The process is
also called hardening of oil. Only partial hydrogenation is carried out otherwise a fat as hard as tallow is
formed.
ii. Rancidity of fats and oils: when fats and oils are exposed to moist air for a long time, bad smell and sour
taste are developed and fats and oils are said to be rancid. Rancidity is due to presence of volatile, bad
smelling acids and aldehydes which result at least from attack of oxygen at double bond positions (allylic
positions). Hydrogenation slows down the rancidity by decreasing the number of double bonds.
Questions
1. Write an example of each of the following
i. reducing sugar ii. simple lipid
iii. non-sugar iv. disaccharide
2. What is meant by peptide bond? Write an example of dipeptide.
3. Write molecular formula of each of the following:
i. Simple lipid
ii. Dipeptide
4. What are disaccharides? What happens when they get hydrolysed?
5. Distinguish between sugars and non-sugars.
6. What is denaturation of protein? Give an example:
7. What are lipids? Give one example of it.
8. What happens when;
i. fats get hydrolysed
ii. Protein is heated
9. How would you obtain glucose from cane sugar?
10. What are the constituent of nucleic acid?
11. What is different between essential and non-essential amino acids?
12. Name the pyrimidine bases found in RNA.
13. Point out any two differences between RNA and DNA molecules.
14. Distinguish both chemically and physically between a fat and a vegetable oil.
15. Write the open chain structure of glucose and fructose.
16. What happens when fats are hydrolysed using aq. NaOH?
17. Write important functions of lipids.
18. Writet the structures of the compounds obtained by the hydrolysis of sucrose.
19. How can the presence of sugar be tested in urine?
20. Write any two important functions of carbohydrates.
21. Write any two examples each for sugars and non-sugars.

1. Which of the followings is a carbohydrate? 14. Charring of sugar is
a. Glyceraldehyde b. Casein a. Oxidation b. Dehydration
c. Insulin d. Saccharin c. Reduction d. Reduction and dehydration
2. Which of the followings is a disaccharide? 15. In our body glucose is stored as
a. Galactose b. Lactose a. Protein b. Fat
c. Deoxyribose d. Ribose c. Glycogen d. Lipid
3. Which of the followings is a disaccharide? 16. The carbohydrate present plant cell wall is
a. Cellulose b. Starch a. Cellulose b. Maltose
c. Cellobiose d. Glycogen c. Sucrose d. Starch
4. Water soluble component of starch is 17. Amino acids found in proteins are
a. Amylose b. Amylopectin a. α- amino acids b. β- amino acids
c. Sucrose d. Inulin c. γ- amino acids d. Mixture of all
5. Glucose is 18. An example of Zwitter ion is
a. A hexose b. A non sugar a. Alanine b. Glycine hydrochloride
c. Non reducing sugar d. invert sugar c. Urea d. Ammonium acetate
6. Milk sugar is 19. Which of the followings is an essential amino acid?
a. Lactose b. Maltose a. Serine b. Glycine
c. Glucose d. Casein c. Alanine d. Histidine
7. Which of the followings is non sugar? 20. Albumin is
a. Glucose b. Cellulose a. Simple protein b. Conjugated protein
c. Sucrose d. Galactose c. Derived protein d. Lipoprotein
8. Which of the followings is non reducing sugar? 21. Protein responsible for regulation of body function is
a. Maltose b. Sucrose a. Denatured protein b. Fibrous protein
c. Fructose d. Lactose c. Globular protein d. Derived protein
9. Invert sugar is 22. Which of the following test is given by proteins?
a.
Sucrose a. Tollen's test b. Molisch's test
b.
Equimolar mixture of D (+)-Glucose and D (-)-Fructose c. Ninhydrin test d. Benedict's test
c.
Equimolar mixture of D (+)-Glucose and D (+)-Fructose
23. Primary structure of protein refers to
d.
Equimolar mixture of D (-)-Glucose and D (+)-Fructose
a. Amino acid sequence
10. α‐D (+)‐Glucose and β‐D (+)‐Glucose differ in b. Arrangement of polypeptides
a. Configuration at C-1 c. Orientation of polypeptides
b. Configuration at C-2 d. α-helix form
c. Configuration at C-5
24. Denaturation of protein destroys its
d. Configuration at C-1 and C-2
a. Primary structure b. Chemical properties
11. α‐D (+)‐Glucose and β‐D (+)‐Glucose are c. Secondary structure d. Amino acid sequence
a. Enantiomers
25. An enzyme is
b. Epimers
c. Mirror image of each other a. Carbohydrate b. Fibrous protein
d. Anomers c. Globular protein d. Metal ion
12. Cotton is 26. Protein part of enzyme after removal of prosthetic
a. Protein b. Starch group is called
c. Polysaccharide d. Cellulose a. Apoenzyme b. Coenzyme
13. Carbohydrates are tested by c. Holoenzyme d. Cofactor
a. Ninhydrin test b. Molisch's test
c. Millon's test d. Biuret test
27. DNA is
37. Which of the followings base is not present in RNA?
a. Simple protein b. Nucleoprotein a. Adenine b. Thymine
c. Nonprotein d. Lipid c. Uracil d. Cytosine

28. Nucleic acid is polymer of 38. Which of the following base pair is not present in
a. Nucleoside DNA?
b. not a polymer a. A-T b. G-C
c. Base, sugar and phosphate c. T-A d. U-C
d. Nucleotide
39. Which of the followings is hydrocarbon?
29. DNA is polymer of
a. Animal fat b. Vegetable oil
a. Nucleotide b. Ribonucleotide c. Beewax d. Paraffin oil
c. Deoxyribonucleotide d. Nucleoside
40. Chemically, fats and oils are
30. In nucleic acid, sugar‐phosphate unit forms the
a. Esters of glycerol with fatty acids
backbone. Here, sugar is bonded to phosphate unit b. Esters of monohydric alcohols with fatty acids

by c. Esters of glycols with fatty acids
a. H- bond b. Ether bond d. Esters of glycols with stearic acids
c. Ester bond d. Glycoside bond 41. Oil contains a large proportions of

31. In DNA, two strands of polydeoxyrionucleotides are a. Saturated fatty acid residues

held by b. Cis unsaturated fatty acid residues
c. Trans unsaturated fatty acid residues
a. Peptide bond b. Covalent bond
d. Unsaturated fatty acid residue
c. Ester bond d. H-bond

32. The sugar present in DNA is 42. Drying oils must have
a. Carboxyl group b. High saturation
a. Hexose sugar b. Pentose sugar
c. D- Ribose d. Deoxyribose c. High unsaturation d. High m.pt.
43. Biuret test is done for
33. Which of the followings base is not present in DNA?
a. Oils b. Sugars
a. Adenine b. Thymine
c. Uracil d. Cyosine c. Fats d. Proteins
34. Which of the followings base is a purine base ? 44. The calorific values is in the order

a. Adenine b. Thymine
a. Fats > carbohydrates > proteins
c. Uracil d. Cyosine b. Fats> proteins > carbohydrates
c. Proteins > carbohydrates > fats
35. In DNA, cytosine pairs with
d. Carbohydrates > fats > proteins
a. Adenine b. Thymine 45. Soap molecule is
c. Uracil d. Gunine
a. Hydrophilic b. Hydrophobic

36. The number of hydrogen bond between adenine and c. Amphipathic d. Lipophilic
thymine is

a. 1 b. 2
c. 3 d. 4
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
a b ca a a a b b b a d d b b c
16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
a a a d a c c a c c a c d c c
31 32 33 34 35 36 37 38 39 40 41 42 43 44 45
d d c a d b b d d a b c d b c
Chemistry in the
Service of Mankind
Chemistry has been in the service of mankind since the first birth. Food, clothing, shelter, diseases and employment
are the major challenges of our society. Chemistry not only tells all about natural substances but also enables us to
design and make new products. Chemistry has helped in getting more food by providing chemical fertilizers,
pesticides for agriculture. Polymers like nylon, orlon, dacron, rayon etc. which are synthesized in laboratories are
major fabrics of clothing. Chemistry has helped in the construction of houses by providing cement, steel, plastics etc.
Synthetic dyes make them colourful. Modern synthetic drugs have played wonderful role to cure and eradicate many
deadly diseases. Many industries are based on principles of chemistry which provide employments for people. Some
important classes of organic compounds in service to mankind are polymers, dyes, drugs, chemical fertilizers,
pesticides which are briefly discussed here.
17.1 Polymers
17.1.1 Monomer, Polymer and Polymerization
A polymer (Greek: poly = many, meros = parts) is a giant molecule (macromolecule) with high
molecular mass which is made up of a number of smaller repeating units. The repeating units are
usually obtained from low molecular mass simple molecules which are called monomers. The process
of forming a polymer from monomers under the suitable conditions of temperature, pressure and or
catalyst is called polymerization.
Example:
Temperature, pressure and or catalyst

nA -A- n
monomer polymer
H H H H
250°C, 1500 atm
n C=C C—C
Traces of O2
H H H H n
Ethene Polyethene
(Monomer) (Polymer)
A polymer may be linear, branched or cross linked.
Monomer Linear polymer Branched polymer Cross linked polymer
17.1.2 Classification of Polymers

Polymers can be classified by different ways;
17.1.3 Addition and Condensation Polymers

Based on mode of synthesis, polymers can be classified into addition polymers and condensation
polymers.
A. Condensation polymers or step growth polymers: A polymer formed by addition of
monomers with elimination of smaller molecules (condensation reaction) is called condensation
polymer and the process is called condensation polymerization. Monomers in this type of
polymerization have at least two functional groups. Polyamides and polyesters are two
important types of condensation polymers.
Some examples,
1. Nylon-6,6: It is the polymer having many amide linkage hence belongs to polyamide. It is
formed by condensation of two types of monomers: adipic acid (dicarboxylic acid) and
hexamethylenediamine (diamine). The name nylon-6,6 is given since each type of
monomer has six carbon atoms.
Chemistry in the Service of Mankind Unit 17 555
O O
HO—C—(CH2)4—C—OH + H—N—(CH2)6—N—H
H H
Hexanedioic acid Hexane-1,6 diamine
(Adipic acid) 200°C (Hexamethylene diamine)
Monomer Monomer
–H2O
O O
HO—C—(CH2)4—C—N—(CH2)6—N—H
H H
Dimer
O O
—C—(CH2)4—C—N—(CH2)6—N—
H H
n
Nylon-6,6
Polyamide
Polymer
Fig 17.1 Nylon rope has high tensile strength hence used in rock climbing, mountain climbing and parachute
2. Terylene or dacron is the polymer having many ester linkage hence belongs to polyester. It
is formed by condensation of two types of monomers; terephthaleic acid (dicarboxylic
acid) and ethylene glycol (dihydric alcohol).
O O
HO—C C—OH + HO—CH2CH2—OH
Benzene-1,4- dicarboxylic acid Ethane-1,2-diol
(Terephthalic acid) 300°C (Ethylene glycol)
Monomer –H2O Monomer
O O
HO—C C—O—CH2CH2—OH
Dimer
O O
—C C—O—CH2CH2—O—
n
Terylene or Dacron
Polyester
Polymer
Condensation polymers are also called step growth polymers since the polymers are formed in
stepwise manner. i.e.
Monomer + Monomer = Dimer
dimer + monomer = trimer and or
dimer + dimer = tetramer and finally polymer.
B. Addition polymers or chain polymers: A polymer formed by addition of monomers
without elimination of any molecule is called addition polymer and the process is called
addition polymerization. Monomers in this type of polymerization are unsaturated. High
molecular mass polymer is formed at once but not step by step.
Examples:
1. Polyethene: Commercially, it is prepared from ethene in presence of Ziegler-Natta
catalyst; Al(C2H5)3 + TiCl4.
H H H H
50-75°C, 5-7 atm
n C=C C—C
Al(C2H5)3+TiCl4
H H H H n
Ethene Polyethene
(Monomer) (Polymer)
Ziegler and Natta were awarded Nobel Prize in 1963 for this work. It is resistant to the
action of water, acids, alkalis, salts, can be molded, folded. It is used to prepare house
wares like baukets, dustbins, carpet backing, packaging materials, cable insulation, etc.
2. Polyvinyl chloride (PVC): It is obtained by polymerization of vinyl chloride. It is used for
pipes and fittings, imitation lather, floor covering, containers, window and door frames,
gramophone recorders, blood bags etc.
H H H H
n C=C C—C
H Cl H Cl n
Vinyl chloride Polyvinyl chloride
(Monomer) (Polymer)
(a) (b) (c)

Fig 17.2 PVC in different purposes (a) pipes (b) cosmetic bottles (c) blood bag and saline bottle and pipes
3. Polytetrafluroethene (Teflon or PTFE): It is obtained by polymerization of

tetrafluoroethylene. It is inert to chemical reagents, even to boiling aqua regia, resistant to
heat and electricity and used as nonstick coating especially for cooking utensils,
waterproof clothing, for insulation of electrical items, for the manufacture of gaskets,
valves etc.
F F F F
n C=C C—C
F F F F n
Tetrafluroethene Polytetraflueroethene
(Monomer) (Polymer)
(a) (b)
Fig 17.3 Polytetrafluoroethene in (a) nonstick coating on frying pan and waterproof jacket (b) gaskets and valves
4. Polyvinylcyanide (Orlon): It is obtained by polymerization of vinyl cyanide(acrylonitrile).

It is used as synthetic textiles fiber and in clothing and carpeting.
H H H H
n C=C C—C
H CN H CN n
Vinyl cyanide Polyvinyl cyanide
(Monomer) (Polymer)
5. Polypropylene: It is obtained by polymerization of propylene. It is used in the

manufacture of house wares, toys, medical equipments, laboratory equipments etc.
H H H H
n C=C C—C
H CH3 H CH3 n
Propylene Polypropylene
(Monomer) (Polymer)
Fig 17.4: Different uses of polypropylene
6. Polystyrene: It is obtained by polymerization of styrene. It is used for the manufacture of

safety cabinets for electrical and electronic items, food containers etc.
H H H H
n C=C C—C
H H n
Styrene Polystyrene
(Monomer) (Polymer)
Fig 17.5: Different uses of polystyrene: foams, safety box for electronic items, food containers (from left to right)
7. Styrene butadiene rubber (SBR): It is obtained by polymerization of styrene and

butadiene in presence of sodium metal. Hence the name is given Buna S. It is rubber and
used in the manufacture of tubes and tyres.
H H H H H H H H H H H H
Na C—C—C—C = C—C
n C=C + n C = C—C = C
H H H H H H
n
Styrene Buta-1,3-diene
Styrene butadiene rubber
(Buna S)
8. Neoprene: It is obtained by polymerization of chloroprene.
H Cl H H H Cl H H
n C= C C =C C C C C
H H H H
Chloroprene n
Neoprene
(rubber)
Fig 17.6 Different uses of rubber
17.1.4 Homopolymers and copolymers

Based on the types of monomers, polymers can be classified as homopolymer and copolymers.
1. Homopolymers: A polymer formed by only one type of monomers is called homopolymer.
Polyvinyl chloride (PVC) is made up of only one type of monomer, vinyl chloride. Hence it is
an example of homopolymer. Some examples are; polyethene, teflon, orlon etc.
2. Copolymers: A polymer formed by more than one type of monomers is called copolymer.
Nylon-6,6 is made up of two types of monomers; adipic acid (dicarboxylic acid) and
hexamethylenediamine (diamine). Hence it is an example of copolymer. Other examples are;
nylon, dacron, SBR etc.
17.1.5 Natural and Synthetic Polymers

On the basis of source or origin, polymers can be classified as natural and synthetic polymers.
1. Natural polymers: The polymers formed in the body of plants and animals are natural
polymers. They are
i. Polysaccharides: Starch and cellulose are common polysaccharides. They are polymers of
glucose (monomer). Starch is the chief food reserve in plants and cellulose is chief
structural material of plants.
ii. Proteins: They are the polymers of α-amino acids. Protein is chief material of animal body.
Wool, natural silk, leather, etc. are proteins.
iii. Nucleic acids: They are the polymers of nucleotides. Nucleic acids include DNA and
RNA.DNA is the polymer of deoxyribonucleotide and RNA is the polymer of
ribonucleotide.
iv. Natural rubbers: They are the polymers of isoprene (2-Methyl-1,3-butadine). It is obtained
from rubber tree.
H CH3 H H H CH3 H H
n C=C C=C C C C C
H H H H
Isoprene n
Polyisoprene
(Natural rubber)
Raw rubber is weak (tensile strength is 200 Kg/cm2), non resistant to vegetable and mineral oils, and other organic
solvents, soft at high temperature and brittle at low temperature so can be used in the range of only 10-60°C, has high
water absorption capacity. To improve the quality of rubber, raw rubber is heated with sulphur. The process is called
vulcanization of rubber.
Fig.17.7: Rubber being collected from rubber tree ig. 17.8: Cotton (cellulose) is obtained from cotton plant
17.1.6 Fibers, Elastomers, Thermoplastics and Thermosetting Polymers

The utilities of polymers depend upon their mechanical properties like tensile strength, elasticity,
toughness etc which is governed by intermolecular force of attraction. According to intermolecular
force of attraction, polymers can be divided as;
1. Fibers 2. Elastomers
3. Thermoplastics 4. Thermosetting polymers
1. Fibers
Fibers are long thread like material with high tensile (pulling) strength. The molecules of fiber are
long, thin and linear with polar groups which permits side by side alignment and strong
intermolecular force to maintain this alignment and prevent slipping of molecules. Hence fibers
have high tensile strength. Fibers are twisted into threads which can be woven into cloth or
embedded in plastics material to impart strength. For example, nylon-6,6,
H O H
N C N
C N C
O H O
H O H
N C N
C N C
O H O
Intermolecular hydrogen bonding in nylon -6,6
2. Elastomers
An elastomer has a high degree of elasticity i.e. can be deformed (for example: can be stretched up to
eight times) but retains its original shape. Molecules of elastomer are long but remain in random
nonlinear forms due to unsaturation and have no polar groups. Hence fibers lack of strong
intermolecular force to hold them linear except occasional cross links and can be stretched upto
certain limit.
3. Thermoplastics
Polymers which becomes soft on heating and hard on cooling reversibly are called thermoplastics.
Molecules in thermoplastics are long and linear which are held together by weak Van der Waal force
of attraction. There are no covalent cross links among molecules. Hence intermolecular force of
attraction can be overcome by heating easily. Therefore, thermoplastics can be moulded, remoulded
and reused. Example: polyethene, PVC, polystyrene, etc.
4. Thermosetting polymers
Polymers which once hardened on heating can not be soften are called thermosetting polymers.
Molecules in thermoplastics are cross linked by covalent bonds forming three dimensional network.
Hence intermolecular force of attraction can not be overcome by heating. Therefore, thermosetting
polymers can not be remoulded and reused. Example: bakelite. (See phenols for details.)
Differences between thermoplastics and thermosetting polymers

Thermoplastics Thermosetting polymers
1. They becomes soft on heating and hard on 1. Once hardened, they can not be soften on
cooling reversibly. Hence they can be heating. Hence they can not be reshaped,
reshaped, reused and reclaimed from wastes. reused and reclaimed from wastes.
2. They consists of long, linear molecules held 2. Their molecules are cross linked by covalent
together by weak Van der Waal force of bonds forming three dimensional networks.
attraction. 3. They are formed by condensation
3. They are formed by addition polymerization. polymerization.
4. They are generally hard, infusible, strong and
4. They are generally soft, fusible, weak and less brittle.
brittle.
Some polymers in biomedical uses
Polymers Applications
Polyurethane Artificial heart, heart valves etc
Polydimethyl siloxane(silicone rubber) Heart valves
Polypropylene Heart valves, disposable syringes
Polymethyl methacrylate Contact lenses
Polyethene, PVC disposable syringes
Self Test
17.1 Define the following terms with suitable examples.
a. Monomer b. polymer c. polymerization
17.2 How do condensation polymers differ from addition polymers?
17.3 What is copolymerization? Give an example.
17.4 Write main differences between thermoplastics and thermosetting polymers.
17.5 Write the structure of monomer and polymer of
a. polystyrene b. teflon c. polypropylene
d. bakellite e. nylon 66 d. dacron
17.6 How do fibres differ from elastomers?
17.2 Dyes
Fig. 17.8: Dyes
17.2.1 Introduction
Dyes are chemical substances, generally organic compounds, used in imparting color to textiles,
leather, wool, plastics, foodstuffs etc.
All coloured substances are not necessarily dyes. For a substance to act as a dye, certain conditions
must be fulfilled;
i. It must have a suitable color,
ii. It must be able to fix itself or be capable of being fixed to the fabric,
iii. The fixed dye must not have fastness to light, water, dilute acids , dilute alkalis, various organic
solvents used in dry cleaning etc.
17.2.2 Structural features

A dye possesses two main constituents;
1. Chromophores: These are certain unsaturated groups responsible for the colour of dye (Greek:
Chroma =colour, phoros=bearer). For example, (>C=C<)n, > C=O ( carbonyl group), –N=N- (azo
group), –NO2 (nitro group) , p-quinoid group etc.
2. Auxochromes: These are some functional groups which do not produce colour themselves but
when present along with chromophore increase the intensity of colour of dye. (Greek: auxo =
increase, chroma=colour).e.g. –OH, –SO3H, –COOH, –NH2, –NHR, –NR2 etc. Polar auxochromes
make the dye water soluble and bind the dye to the fabric.
Example:
Chromophore
N=N OH
p–Hydroxyazobenzene Auxochrome
(orange dye)
17.2.3 Classification of Dyes

Dyes can be classified by different ways. Some of them are as follows;
1. Classification based on the source
2. Classification based on the chemical constitution
3. Classification based on the mode of application
17.2.4 Classification Based on the Source

On the basis of source, dyes can be classified into natural dyes and synthetic dyes.
1. Natural dyes: Dyes obtained from plants and animals are called natural dyes. In ancient times,
people used various plant and animal extracts for coloring household materials, clothes etc. For
example, indigo (indigotin) is obtained from plants of the indigofera group. It is a dark blue
solid with coppered lustre. It is the oldest known dye. Mummy clothes of 5000 years old have
been found dyed with indigo. The name of the dye is from Greek word indikon, meaning
substance from India. Evidences show that, indigo was used in India since ancient times. Even
today, people in different regions use plant extracts to get colour. Today, however, all dyes are
obtained by synthesis .
2. Synthetic dyes: Dyes prepared in laboratories are called synthetic dyes.
17.2.5 Classification Based on the Chemical Constitution

On the basis of chemical constitution, dyes are classified into different classes;
Azo dyes: Dyes having azo group (-N=N-) joined to aromatic system as chromophore are called
azo dyes.
Example:
Chromophore
Chromophore
N=N NH2
N=N OH
p–Aminoazobenzene Auxochrome
p–Hydroxyazobenzene Auxochrome (orange red dye)
(orange yellow dye)
Azo dyes are the largest class of synthetic dyes. They are prepared by coupling of diazonium
salt with phenols or aromatic amines. Some other types are tabulated as follows;
Types of Dye Structural unit Examples Uses
O O
C C
O O
C C Indicator in acid
1. Phthalein dyes O and base
titration
OH OH
Phenolphthalein
OH OH
NO2 NO2 NO2
N dye used in
2. Nitro dye
wool
NO2 NO2
Martius yellow Picric acid
O H
O
C N
C
C= C=C for making
3. Indigo dye
N C printing inks
N
H H O
Indigo
O O
OH
C C OH
4. Anthroaquinone used for dying
dye C C cotton
O O
Alizarin
5. Triaryl methane +
C N CH3 Cl
dye C
CH3
Malachite green
17.2.5 Classification Based on the Mode of Application

A dye molecule may be bounded to the fabric by covalent bond, hydrogen bond, ionic bond as well
as Van der Waal force. The mode of application of a dye depends upon the nature of the dye as well
as the nature of the fiber. On the basis of mode of application, dyes are classified into different
classes;
1. Vat dyes: These dyes are insoluble in water. It is reduced into colourless soluble form ( leuco
form) when agitated with alkaline reagents like sodiumhyposulphite then applied to the fabric
and oxidized in air. When exposed in air, insoluble dye is regenerated in the fabric. For
example, Indigo. Such dying was done in wooden vats hence the name vat dyes.
2. Direct dyes: These dyes are directly applied to the fabric in hot aqueous solution. The acidic or
basic auxochrome of the dye combine directly with the fibre. These dyes are suited to the fabric
which can form hydrogen bonds and used for silk, nylon, rayon etc. For example, Martius
yellow.
H H
Fibre - NH2 + HO - dye Fibre - N-H ..... O - dye
wool or silk
Hydrogen bonding
3. Mordant dyes: These dyes do not dye the fabric directly and fixed to the fabric with the help of
basic salts of metals like Al, Cr, Fe, Ba etc which are called mordants. The mordant forms an
insoluble coordination complex between the fabric and the dye. If the dye is basic, acidic
mordant like tannic acid is used and vice versa. Mordant dyes are used for dying wool. The
same dye may give different colour depending upon the mordant used. For example, Alizarin
gives red with aluminum, violet black with iron, brown violet with chromium, blue with
barium.
Fiber
O
OH
C O O
OH
+ Al+++ + Fiber Al
C
O O
O
C OH
Alizarin
C
O
4. Disperse dyes: Disperse dyes are insoluble in water and dispersed in water in a colloidal form.
When fabric is immersed in the colloidal form of dye, fine particles are absorbed in the crystal
structure of the fabrics. These dyes are used for dying synthetic fibres like nylons, polysters and
hence these dyes are also called synthetic fiber dyes.
5. Azoic dyes: (ingrain dyes): These are water insoluble azo-dyes which are formed on the fibre.
The fabric is immersed in the solution of the coupling reagents like phenol, aniline, napthol, etc.
and then immersed in appropriate diazonium salts.
Dyes in medical field
Dyes have values in medical field too. Gram staining method (developed by Hans Christian Gram) uses the dye, crystal
violet, to classify pathogenic bacteria into Gram positive and Gram negative. Bacteria which turn purple on staining with
the dye are called Gram positive and bacteria which turn pink on staining with the dye are called Gram negative bacteria.
CH3 CH3
H3C—N C N— CH3
H3C—N—CH3
Cl
Crystal Violet
Certain dyes stain and paralyse micro organisms hence can be used as chemotherapeutic agent. For example, Prontosil is
antibacterial. Crystal violet has antibacterial, antifungal, and anthelmintic properties.
Self Test
17.7 What are dyes? Give examples indicating chromophore and auxochrome.
17.8 Define the followings with suitable example.
a. Azo dyes b. Vat dyes c Mordant dyes d. Synthetic fibre dyes
17.3 Drugs
Fig. 17.9: Drugs
17.3.1 Introduction
The word 'drug' is derived from the French word 'drogue' which means a dry herb. In ancient times,
people used many herbs for the treatment of different diseases. In Nepal, a collection of many
medicinal plants along with their diagram and medicinal value can be found in a book called
'Chandra Nigantu'.
Drug is a substance used in prevention, diagnosis and treatment of diseases in human beings.
According to World Health Organization (WHO), 'a drug is defined as any product (substance) that
is used to modify or explore physiological systems or pathological states for the benefit of recipient’.
The process of treating diseases by using chemicals (drugs) is called chemotherapy. Paul Ehrlich, in
1904, indicated that chemical can interfere with the proliferation of invading microorganisms at a
concentration that is tolerated by the host. This is the principle of chemotherapy. Hence Paul Ehrlich
is called as Father of Chemotherapy.
Characteristics of Drug
An ideal drug must fulfill the following characteristics.
1. The action of drug should be localized at the site where it is desired to act.
2. It should be efficient.
3. It should have minimum side effects.
4. It should not injure host tissues.
5. It should not make the host cell resistant to the drug after its use for a long time.
17.3.2 Classification of Drugs

On the basis of the therapeutic action, drugs are classified as chemotherapeutic agents and
pharmacodynamic agents.
Chemotherapeutic agents
These drugs are used to treat infectious diseases. These are made in such a way that they kill the
invading organism selectively without any harmful effects on host tissues. For example,
antibacterial, antiviral, antifungal, antiprotozoal, antimalarial etc.
1. Antiseptics: These are drugs used to inhibit the growth of microorganism either by inhibiting
their reproduction or causing their death and safe to host tissues.
Examples:
(i) 1% KMnO4,
CH3
(ii) Phenolic compounds
OH CH3 OH
OH CH O2N
Cl NO2
H3C CH3
Thymol H3C OH
NO2
Phenol Chloro-m-xylenol Picric acid
(iii) Benzoic acid derivatives

OH
O
C O
Phenyl salicylate
(salol)
(iv) Iodine and its compounds:

Tincture of iodine (I2+KI dissolved in ethanol),
Iodoform (CHI3)
Iodol etc.
I I
C C
C C
I I
N
H
Tetraiodopyrrole
(Iodol)
Alcoholic solution of chloro-m-xylenol and terpene is commercially available as dettol.

Disinfectants are similar to antiseptics but harmful to host cells. So, they are applied only on
inanimate objects such as floor, instruments, swimming pool etc. For example, chlorine used for
the sterilization of water, sulphurdioxide used in bakery.
2. Antibiotics: Antibiotics are substances originally produced by various species of

microorganisms ( and later synthesized in laboratory) which inhibit the growth of other
microorganisms and ultimately destroy them even given in small concentrations. For example,
penicillin, streptomycin, chloramphenicol, tetracyclines, erythromycin etc. Penicillin is the first
antibiotic which was discovered by Alexander Fleming in 1928.
H
R N H H
S
C C C CH3
O C
C N CH3
O C
H C OH
O
Penicillin
Antibiotics can be classified into two classes.
i. Broad spectrum antibiotics: Antibiotics which are effective against a wide range of
microorganisms are called broad spectrum antibiotics. For example, chloramphenicol,
tetracycline etc.
OH
It is originally obtained from
O2N CH CH CH2OH
bacterium streptomyces venezuelae.
HN C CHCl2 It was introduced into clinical
O practice in 1949 under the trade
name chloromycetin.
Chloramphenicol
ii. Narrow spectrum antibiotics: Antibiotics which are effective against a few
microorganisms are called narrow spectrum antibiotics. For example, Bacitravin, Penicillin,
Streptomycin, etc.
3. Sulpha drugs: They are first chemotherapeutic agents which are derivatives of sulphanilamide.
They are used against bacteria.
Examples:
NH
H2N C NHO2S NH2 H2N SO2NH2
Sulphaguanidine Sulphanilamide
Pharmacodynamic agents
Many disease conditions in human beings appear due to functional disorder or degradation of body
but not due to invading microorganisms. For example, anemia, cardiovascular disorders, cancer,
depressions, diabetes, erectile dysfunction etc. The chemicals used to reduce such disease conditions
are called pharmacodynamic agents.
1. Antipyretics: The drugs which are used to lower body temperature to normal in high fever are
called as antipyretics.
Examples:
O O
H N C CH3 NHCOCH3 NHCOCH3 C CH
C6H5 – N C
CH3
OH OCH3 OC2H5 N
Methacetin Phenacetin CH3

p-Acetamidophenol
(Paracetamol) Antipyrene
2. Analgesics: The drugs which are used to relieve pain without loss of consciousness are called
analgesics. They are commonly called as pain killers.
Examples:
O CH3 O H
N N
C C CH2 SO3Na C C CH2 SO3Na
C6H5— N C C6H5— N C
CH3 CH3
N N
CH3 CH3
Novalgin Melubrin
Analgesics may be further classified as

i. narcotic which are habit forming. For example, morphine, herion etc
ii. non narcotic which are not habit forming. For example, aspirin, novalgin etc.
3. Analgesics and antipyretics: The drugs which are used to lower body temperature as well as
relief pain are called analgesics and antipyretics.
Examples:
COOH NHCOCH3
OCOCH3
Acetylsalicylic acid OCH2CH3

(Aspirin) Phenacetin
4. Psychotropic drugs: The chemical substance which are used for the treatment of mental
disorder like psychosis, neurosis, schizophrenia are called psychotropic drugs. These act on the
central nervous system to reduce anxiety. People used opium, alcohol to be relief from mental
anxiety in ancient times. They are of different types;
i. Sedatives: Sedatives are central nervous system depressants that reduce nervous tension
and promote relaxation without inducing sleep. For example, dizepam, equinil etc.
CH3 O
O CH3 O
N N
CH2 H2N—C—O—CH2—C—CH2—O—C—NH2
Cl C N CH3
C6H5 Equanil
Dizepam
ii. Hypnotics: Hypnotics are central nervous system depressants that induce sleep. For
example, Barbituric acid. O
C
N—H
C C
O N O
H
Barbituric acid
iii. Antidepressants: These drugs provive a feeling of well being in depressed mood. for
example, cocaine.
5. Anaesthatics: The drugs which bring about the loss sensition for certain period of time are
called anaesthetics. Use of anaesthic has made surgery a more comfortable experience for
patients, and allowed surgeons to take more time in which they can work carefully and more
effectively. Hence use of anesthetic has opened a new advances in surgical technology and
medical history.
Generally, there are following types of anaesthetics.
i. General or central anaesthatics: They cause unconsciousness all over the body. For example,
Diethyl ether, Ethylene, cyclopropane, Methyl n-propyl ether, Nitrous oxide (N2O),
chloroform, etc.
ii. Local anaesthetics: The anaesthetic which cause unconsciousness to a limited region is
called local anaesthetics. Examples: benzocaine, procaine, ethyl chloride, etc.
6. Antacid: The chemical substances which neutralize excess acid in
gastric juice are called antacids. For example, NaHCO3, Al (OH)3,
Mg(OH)2, etc. A commercial antacid called 'eno' contains a
mixture of sodium bicarbonate, citric acid and anhydrous sodium
carbonate.
7. Anti diabetic drugs: Diabetes is a disease caused by defects in the metabolism of carbohydrates,
proteins and fats. The disease brings many complications like degeneration of blood cells,
blindness, renal and neurological disorders etc.
The cause of diabetes is not microorganisms but deficiency of insulin due to disorder in body
function. β-cells of pancreas produce a hormone called insulin which has a key role in the
metabolism of carbohydrates, proteins and fats. In some cases, insulin is not produced at all
and causes type I diabetes commonly in juveniles. In other cases, insulin is secreted
insufficiently and cause type II diabetes in adults.
Administration of insulin is only the therapy for type I diabetes. For type II diabetes, many
drugs have been developed to lower the sugar level. For example, pheformin, metformin,
carbutamide etc.
CH3 O O
H2N C N C N CH3 S N C N (CH2)3 CH3
O H H
NH2 NH H2N
Carbutamide
Metformin
8. Drugs for cardiovascular diseases: Disease of heart and blood vessels are called cardiovascular
diseases. Hypertension, high blood pressure caused by narrowing down of blood vessels etc.
For example, Amylnitrite, glyceroltrinitrate, etc.
CH3 CH2 CH2 CH2 CH2 O N O
Amyl nitrite
9. Antihistamines: Histamine is compound which is formed in the body due to biodegradation of
amino acid, histidine. It is responsible for causing many physiological conditions like itching,
hyper secretion of stomach acids etc. and allergy. Drugs used against histamine are called
antihistamine. For example, avil, allegra etc.
17.3.3 Drugs Addiction

Drug addiction is a compulsive desire and dependence on an illegal drug or a medication despite the
negative consequences. Once addiction develops, gene expression alters, alters the way the brain
looks and functions which in turn affect human behavior. It includes wild mood swings, depression,
anxiety, paranoia, violence, decrease in pleasure in everyday life, complication of mental illness,
hallucinations, confusion, desire to engage in risky behavior, etc. These brain changes interfere with
an individual’s ability to make voluntary decisions, leading to compulsive drug craving, seeking and
use. It creates many physical, physiological and psychological effects leading to serious problems in
individual's life, in family and society. Many narcotic drugs like morphine, cocaine, heroin, etc which
were once used as analgesics are responsible for drug addiction.
Drugs addiction can be treated
i. By applying withdrawal of drug under proper medical supervision with the help of counselor
in rehabilitation centre.
ii. By substituting the other less effective type of drug instead of using drug, like methadone
instead of heroin
HO
O
HO
CH3 CH3 – C – O
H CH3
N H CH3
N H
N
O
O
O
HO O
CH3 – O
Morphine CH3 – C – O
Codeine
Heroin
Fig. 17.10: Opium poppy (Papaver somniferum)
Morphine is the most abundantly found in opium, the dried latex from unripe seedpods of Papaver
somniferum (the opium poppy). It is frequently processed chemically to produce heroin which is its
diacetate derivative. The latex also includes the alkaloid codeine which is its methyl derivative.
Morphine and its derivatives, such as heroin and codeine, remain important pain relievers.
Besides their analgesic properties, morphine and other potential analgesic alter mood and produce
sensation of euphoria that can cause then to be habituating. Prolonged use of opium alkaloids leads
to physiological and psychological need for the drug that result addiction.
Self Test
17.9 What are chemotherapeutic drugs ? How do they differ from pharmacodynamic drugs?
17.10 How do antiseptics differ from disinfectants?
17.11 Define with two examples of each:
a. antiseptics b. analgesics c. disinfectants
d. antipyretics e. antibiotics
17.4 Chemical Fertilizers
Fig. 17.11: Chemical Fertilizers
17.4.1 Introduction
To fulfill the needs of society in terms of productivity form the land, people have been using
fertilizers since long. Materials added to soil to provide necessary nutrients for better growth of
plants or for increasing productivity are called fertilizers.
Plants require the following elements for the soil for their proper growth and better productivity.
1. Primary nutrients: Nitrogen, phosphorus and potash are primary nutrient.
Nitrogen: Plants require nitrogen for growth, protein formation and preparation of colouring
materials.
Phosphorus: Plants require phosphorus for the stimulation of root growth, lipid formation and
maturity of crops.
Potash: They require potash for healthy root system, ripening a fruits, formation of chlorophyll
and to fight against the diseases.
2. Secondary nutrients: The elements like Mg and Ca are also required to the plants for
metabolism.
3. Micro nutrients: Elements like Zn, Cu, Mo, Fe, Co, Cl, etc. are required in a very small quantity.
Criteria for an ideal fertilizer: Though pertectly ideal fertilizer is impossible the basic criteria
for an ideal fertilizer are:
i. It should not undergo chemical change with time.
ii. It should be cheap.
iii. It must be easily absorbable in soil or most be soluble in water.
iv. It should not injure the host cells of the plant.
17.4.2 Classification of Fertilizers

Fertilizers are mainly classified in two categories based upon the source.
1. Natural/ organic fertilizers: The fertilizers which are directly obtained by decayed material of
plants and animals are called natural/organic fertilizers. Examples: Cow dung, animal bone
powders, etc.
2. Artificial/ chemical fertilizers: Chemical substances obtained directly for the earth or prepared
artificially are chemical fertilizers. e.g. NPK fertileness, mixed fertilizers.
17.4.3 Nitrogen Fertilizers

The fertilizer value of nitrogen fertilizer is indirectly measured by "aviable nitrogen" in the fertilizers.
Examples:
1. Basic calcium nitrate or Norwegian saltpeture, Ca(NO3)2 or Ca(NO3)2.CaO
2. Ammonium sulphate, (NH4)2 SO4. Excessive use of this fertilizer makes the soil acidic.
3. Calcium ammonium nitrate, Ca(NO3)2. NH4NO3
4. Urea or carbamide, H2NCONH2. Has high % nitrogen and leaves only CO2 in soil. So, it is
considered to be a good nitrogen fertilizer.
5. Calcium cyanamide, CaCN2: It is second (to urea) preferred fertilizer. [Note: nitrolim =
CaCN2+C]
6. Sodium nitrate or chile saltpeter, NaNO3.
17.4.4 Phosphorus Fertilizers

The fertilizer value here is measured by aviable P2O5.
Examples:
1. Super phosphate of lime or calcium super-phosphate,
2. Ca(H2PO4)2 + 2 (CaSO4. 2 H2O). It has 16–20% P2O5.
3. Triple super-phosphate, Ca(H2PO4)2. It has 42–46% P2O5. It is called triple super-phosphate as %
P2O5 in this fertilizer is three times that in calcium super-phosphate.
4. Phosphoric slag or Thomas slag, Ca3(PO4)2. It contains production of more hay.
17.4.5 Potash Fertilizers

Potash fertilizers are important for tobacco, cotton, madow grass, coffee, corn, etc.
The fertilizers value here is measured as available K2O.
Examples:
1. Inuriate of potash or syluine, KCl
2. Potassium nitrate or nitre or saltpeter, KNO3.
3. It contains 50% K2O.
4. Potassium sulphate, K2SO4.
5. Potassium carbonate, K2CO3.
17.4.6. Mixed (NPK) Fertilizers

They are compound or complex fertilizers or the mixture of nitrogen, phosphorus and potash
fertilizers. Their compositions are variable.
17.4.7 Fertilizers as Pollutants

Today, fertilizer has become essential to modern agriculture to feed the growing population.
However, it has created concern in health and environment. The biggest issue facing the use of
chemical fertilizers is water pollution.
Fertilizers especially nitrates and phosphates are soluble in water hence washed and leached from
soil into water bodies like lakes, rivers and oceans making them too rich in nutrients. As a result,
aquatic plants like algae population grow rapidly covering the surface of water. This is called algal
bloom. Visually, water becomes cloudy, typically green, yellow, brown or red. Algal bloom limits
the sunlight available to aquatic plants. This restricts photosynthesis and causes reduction of
dissolved oxygen level in water. As algae die, they are decomposed by bacteria. This process uses
oxygen hence dissolved oxygen level is further decreased. When dissolved oxygen level decline,
aquatic flora and fauna especially bottom dwellers die. Nitrogen groundwater contamination also
responsible to marine "dead zones" which are hypoxic(low oxygen)areas in large lakes and the
oceans due to overabundance of nutrients that deplete the oxygen required to sustain the marine life
in the bottom and near bottom water. This response of ecosystem to overabundance of nutrients
level is called eutrophication. Eutrophication also reduces the value of rivers and lakes for aesthetic
enjoyment.
Nitrates are difficult to remove from drinking water supplies since they can not be precipitated.
High nitrate levels above 100 ppm in water may cause 'blue baby syndrome' in which oxygen
carrying capacity of haemoglobin is decreased in babies leading to death. WHO has recommended
maximum concentration of NO3- in water is 10 ppm.
Fig. 17.12: A river suffering from eutrophication

Self Test
17.12 What are fertilizers? Give characteristics of fertilizers.
17.13 Give examples of nitrogenous, phosphate and potash fertilizers.
17.14 What is effect of fertilizer in environment?
17.5 Pesticides
Fig. 17.13: Pesticides
17.5.1 Introduction
A pest is any organism, either a plant or animal, harmful to human beings or human concerns
especially in agriculture or livestock production. Any substance or mixture of substances used for
the purpose of controlling pests is called pesticide.
The most common use of pesticides is in agriculture to protect crop plants and plant products from
damaging influences of weeds, plant diseases, insects etc. Hence they are also called crop protection
products. Pesticides are also used for non-agricultural purposes such as to control insects which
damage structures, cause nuisance, or spread deadly diseases, in houses and recreational areas
(lawns, gardens, public parks, playing fields, lakes and ponds for public enjoyment). It is also used to
control vegetation that clogs waterways or obstruct highways. Pesticides have become major
weapons for combating pests since as early as 1950.
The use of chemical pesticides began largely after the discovery of DDT for the control of agricultural
pests and vector born diseases. History of chemical pesticide use in Nepal is not old. In 1950, DDT
and pyrethrum was introduced for the first time. In 1955, Paris green /copper(II) acetate triarsenite,
gammexane and nicotine sulfate were imported. All these pesticides were provided by USAID
through grant for malaria control. Chronologically, the use of pesticides in Nepal is organochlorines-
1950s, organophosphates-1960s, carbamates- 1970s and synthetic pyrethrenoids- 1980s.
17.5.2 Classification of Pesticides

Pesticides are often referred and classified to according to the type of pest (target organism) they
control. There are various types of pesticides.
A. Insecticides
The chemical substance or mixture of substances that are used to kill and control insects are called
insecticides. Many insects such as grasshoppers destroy cultivated plants. Many insects like bedbugs
destroy fruits and food grains during processing and storage. Many insects such as termites can
damage wood structures. Many insects cause nuisance in houses and recreational areas and spread
simple to deadly diseases such as mosquitoes are disease vector for malaria, filaria etc. Insecticides
increase agricultural productivity by preventing crop losses to insects. Simple to deadly diseases
caused by insect vectors are under control or at the stage of eradication due to use of insecticides.
Some of commonly used insecticides are;
1. Organochlorine insecticides
i. DDT: DDT is a contact poison against several arthropods. DDT is commercially prepared
by heating chlorobenzene with chloral in presence of dehydrating agent. It is a colorless,
tasteless crystalline compound.
Cl
Cl
Cl
Cl O conc H2SO4,
H Cl + H2O
Cl C C C H
C H +
H
Cl
Cl
Trichloroethanal
(Chloral) Cl
Cl
Chlorobenzene 1,1,1-Trichloro-2,2- bis (4-chlorophenyl)ethane
(DDT)
(Dichlorodiphenyltrichloroethane)
In the second half of World War II, it was used with great success to control malaria and
typhus among civilians and troops. After the war, DDT was made available for use as an
agricultural insecticide and extensively used in agriculture. DDT is toxic to a wide range of
living organisms including human beings. Because of its hazards in health and
environment, the use of DDT as agricultural insecticide was outlawed in 2004 under
Stockholm Convention and restricted to disease vector control.
ii. BHC: Many stereoisomers are possible for the formula C6H6Cl6. out of which γ– isomer is
most effective insecticide therefore BHC is also known as gammexane. Since it contents six
carbon, six hydrogen and six chlorine atoms, it is known as "666". Commercially it is also
called "lindane". It was first prepared by Michael Faraday in 1825 but its pesticidal action
was discovered only in 1942. It has been used to treat food crops and to forestry products
and to treat livestock and pets. It has also been used as pharmaceutical treatment for lice
and scabies. It is very stable and acts more quickly than DDT. It is a persistent organic
pollutant and has health hazards. Now, its use in agriculture has been banned
internationally (the Stockholm Convention on Persistent Organic Pollutants, 2009) except
in second-line treatments for the head lice and scabies; meaning they can only be
prescribed when other "first-line" treatments have failed or cannot be used. It is prepared
as
Cl
Sunlight Cl Cl
+ 3Cl2
(bright)
Cl Cl
Benzene Cl
Benzenehexachloride (BHC)
H Cl
H H
Cl H
Cl 6
4 Cl
5 Cl
H Cl Cl
H
2
Cl H H
3 H 1
H
H Cl Cl Cl
Cl H
γ–isomer (aaaeee)
1,2,3,4,5,6-Hexachlorocyclohexane Gammaxane
(BHC)
2. Organophosphate insecticides: Parathion and malathion are organic phosphate insecticides.
(CH3O)2 P—S—CH—CH2—COOC2H5 OC2H5

S COOC2H5 O2N O—P S
Malathion OC2H5
Parathion
Organochlorine insecticides are persistent organic compounds. However, organophosphates

usually are not persistent in the environment. Use of organochlorine insecticides in agriculture
has been restricted except in second line vector control.
Pyrethroids now constitute the majority of commercial household insecticides against flies,
mosquitoes and cockroaches. Prallethrin, Cyfluthrin, Transfluthrin which are active ingredients of
Baygon.
Nicotine, pyrethrum and neem extracts are used as natural insecticides. Elemental sulfur
powder is used as an insecticide against ticks and mites.
Pheromones are hormones secreted by certain female insects to attract their males. They are sex
attractants. They are specific to attract their males. Pheromones can be used to attract male
insects (which comprises the major insect population)which are then trapped.
B. Weedicides or herbicides
Weeds are undesired plant species grown in an area(plant pests). The chemicals which are used to
kill and control weeds are called weedicides or herbicides. Herbicides are widely used in agriculture
to control plant pests.
Example:
O—CH2COOH O—CH2COOH
Cl Cl
Cl
Cl Cl
2, 4, - Dichloropheoxyacetic acid 2, 4, 5- Trichloropheoxyacetic acid
(2,4-D) (2,4,5-T)
One of the most commonly used herbicides in the world is 2,4-D. It is a selective herbicide and used
to control weed in wheat, maize , rice, and similar cereal grass crops, because it kills dicots (broadleaf
plants), but not most monocots (grasses). Herbicides are also used to control vegetation in highways
and railways, in landscape turf management, clear waste ground, industrial sites, etc.
C. Fungicides
The chemicals used to kill and control fungi are called fungicides. Fungi can cause serious damage
in agriculture, resulting in critical losses of yield as well as quality. Many fungi can damage
structures such as furniture, houses. Fungicides are used both in agriculture and to fight fungal
infections in animals. Some examples are
1. Copper sulphate solution (CuSO4)
2. Aluminum phosphide (AlP)
3. Bordeux mixture (mixture of CuSO4 and lime)
NO2 OH
• Cl Cl
Cl Cl Cl
•
Cl C NO2 Cl
• Cl Cl Cl
Cl Cl Cl
•
Trichloronitromethane Pentachloronitrobenzene Pentachlorophenol
•
Elemental sulfur is one of the oldest fungicides. "Dusting sulfur," elemental sulfur in powdered form,
is a common fungicide for grapes, strawberry, many vegetables and several other crops. In organic
production, sulfur is the most important fungicide. Dusting sulfur is applied to crops with a sulfur
duster or from a dusting plane.
D. Rodenticides
The chemicals which kill and control rodents are called as rodenticides. Some example of
rodenticides are;
1. ClCH2COONa (Sodium monochloroacetate)
2. Zn3P2 (Zinc phosphide)
3. Alphanapthylthiourea (ANTU)
O
HN—S—NH2
ANTU
17.5.3 Pesticides, Environmental Pollution and Human Health

Many pesticides are toxic to living organisms. Sprayed pesticides reach to non-target species, air,
water and soil. Hence, pesticide use reduces biodiversity, contributes to pollinator decline, destroys
habitat and threatens endangered species. Pesticides are one of the causes of water pollution, and
some pesticides are persistent organic pollutants and contribute to soil contamination. Since
chlorinated hydrocarbon pesticides dissolve in fats and are not excreted, organisms tend to retain
them almost indefinitely.
Problems related to the use of synthetic pesticides also arises due to misuse of pesticides which
includes use of pesticides even when it is not necessary, improper selection of pesticides, use of
highly toxic and broad spectrum pesticides, not following pre harvest waiting period, dipping
vegetables in pesticides, use of pesticides in fishing and low public awareness about pesticides and
their safety concern.
Environmental and human health problems related to the use of synthetic pesticides have created an
increasing pressure against their use. Hence, safer and more specific pesticides are to be developed
and technical developments of the application equipment have also improved to enable their proper
application. The non-chemical alternatives are also in use which include methods of cultivation
like polyculture (growing multiple types of plants), crop rotation, (planting crops in areas where the
pests that damage them do not live, timing planting according to when pests will be least
problematic), and use of trap crops that attract pests away from the real crop, choice of resistant
varieties, creation of an environment favorable for natural enemies of pests, and use of biological
products and agents, including beneficial insects.
Self Test
17.15 What are pesticides? Indicate their role in agriculture.
17.16 Define insecticide. Give the structure and IUPAC name of DDT and BHC.
17.17 Give two examples along with their structure.
a. fungicide b. herbicide c. rodenticide
Solved Questions
1. Define polymer and polymerisation.
¬ A polymer (Greek: poly = many, meros = parts) is a giant molecule (macromolecule) with high molecular
mass which is made up of a number of smaller repeating units. The repeating units are usually obtained
from low molecular mass simple molecules which are called monomers. The process of forming a polymer
from monomers under the suitable conditions of temperature pressure and or catalyst is called
polymerization.
For example,
H H H H
250°C, 1500 atm
n C=C C—C
Traces of O2
H H H H n
Ethene Polyethene
(Monomer) (Polymer)
2. What are dyes?

¬ Dyes are chemical substances, generally organic compounds, used in imparting color to textiles, leather,
wool, plastics, foodstuffs etc. A dye must following characteristics;
i. It must have a suitable color,
ii. It must be able to fix itself or be capable of being fixed to the fabric,
iii. The fixed dye must have fastness to light, water, dilute acids, dilute alkalis, various organic solvents used
in dry cleaning etc.
For example, Chromophore
N=N OH
p–Hydroxyazobenzene Auxochrome
(orange dye)
3. What are antibiotics? Give example of broad spectrum and narrow spectrum
antibiotics.
¬ Antibiotics are substances originally produced by various species of microorganisms ( and later
synthesized in laboratory) which inhibit the growth of other microorganisms and ultimately destroy them
even given in small concentrations (dose).For example, penicillin, streptomycin, chloramphenicol,
tetracyclines, erythromycin etc
Antibiotics can be classified into two classes.
i. Broad spectrum antibiotics: Antibiotics which are effective against a wide range of microorganisms are
called broad spectrum antibiotics. For example, chloramphenicol, tetracycline etc.
ii. Narrow spectrum antibiotics: Antibiotics which are effective against a few microorganisms are called
narrow spectrum antibiotics. For example, Penicillin, Streptomycin, etc.
4. What are insecticides? Indicate their importance. Give any two example.
¬ The chemical substance or mixture of substances that are used to kill and control insects are called
insecticides. Many insects such as grasshoppers destroy cultivated plants. Many insects like bedbugs
destroy fruits and food grains during processing and storage. Many insects such as termites can damage
wood structures. Many insects cause nuisance in houses and recreational areas and spread simple to
deadly diseases such as mosquitoes are disease vector for malaria, filaria etc. Insecticides increase
agricultural productivity by preventing crop losses to insects. Simple to deadly diseases caused by insect
vectors are under control or at the stage of eradication due to use of insecticides.
H Cl
Cl H C H
C C
Cl Cl
Cl H C C H
Cl Cl
Cl C C H C
H Cl
Cl
1,2,3,4,5,6- Hexachlorocyclohexane
(BHC)
Cl
1,1,1-Trichloro-2,2- bis (4-chlorophenyl)ethane
(DDT)
Questions
1. What is the difference between an antiseptic and an antipyretic drug?
2. Write an example of each of the following with their formula.
(i) A synthetic fertilizer (ii) An insecticide
3. What are natural and synthetic dyes? Give one example of each.
4. Write any two examples of azo-dyes with their formulae.
5. Classify polymers on the basis of monomer unit.

6. What are the starting materials for preparing the followings:
(i) Polyvinyl chloride (ii) Bakelite
7. Name the monomers of (i) bakelite (ii) Nylon-6,6
8. Name any one condensation polymer and addition polymer. What are their monomers?
9. What are chemical fertilizers? Give two examples.
10 Write a method of preparation of each of the following polymers:
a. Bakelite b. PVC
11. What are insecticides? Give an example.
12. What is meant by copolymer? Give an example.
13. Distinguish between:
a. Addition polymers and condensation polymer
b. Thermaplastics and thermosetting plastics.
c. Natural and synthethic polymere
14. What do you mean by fungicides. Write an example.
15. Define the following terms writing one example each of:
a. Herbicides b. Insecticides
c. Analgesic drug d. Phosphatic fertilizers
e. Germicides f. Phthalein dye
g. Antacids h. Antibiotic drugs
i. Elastomers j. Thermoplastics
k. Potash fertilizers

1. Which of the followings is a natural polymer? 9. The synthetic polymer which resembles the natural
a. Polystyrene b. Nylon-66 rubber is
c. Neoprene d. Protein a. Neoprene b. Chloroprene
2. Polymers have c. Galyptal d. Isoprene
a. Absolute melting point 10. Nonstick coating of cooking utensils is
b. Average molecular weight a. Polypropylene b. PTFE
c. Low molecular weight c. Bakelite d. Polystyrene
d. Absolute molecular weight
11. Terylene is the condensation polymer of ethylene
3. F2C=CF2 is monomer of
glycol and
a. Buna-S b. Orlon
c. Nylon-66 d. Teflon a. Benzoic acid b. Phthalic acid
c. Terephthalic acid d. Salicylic acid
4. Which of the following is an addition polymer?
12. The hexamethylene diamine and adipic acid are the
a. Polyoropylene b. Nylon-66
c. Terylene d. Polyamide monomer of
5. Polymer formed by the addition of two or more a. Dacron b. Nylon-66
c. Rayon d. Teflon
different monomers is
13. Cellulose is the polymer of
a. Addition polymer b. Copolymer
c. Homo polymer d. Chain polymer a. Maltose b. α-glucose
c. Fructose d. β-glucose
6. Polymer used in making heart valve is
14. Bakelite is the polymer of
a. Silicone b. PVC
c. Teflon d. Polystyrene a. Methanal and alcohol b. Aniline and urea
c. Phenol and methanal d. Phenol and chloroform
7. Polymer used in making tyres of fighter aircrafts is
15. Which of the following is thermosetting polymer?
a. Silicone b. Natural rubber
c. Isoprene d. Polystyrene a. Polyethene b. Neoprene
c. PVC d. Bakelite
8. The natural rubber is the polymer of
16. The strongest intermolecular forces are present in
a. Cis-isoprene b. Trans -isoprene
c. Chloroprene d. Styrene a. Elastomers b. Fibers
c. Thermoplastics d. Natural rubber
17. Of the following which one is the step growth a. –C=C- b. –NO2

polymer c. Methyl isocyanide d. N2
a. Bakelite b. Polyethylene 21. Bismarck is an example of
c. Teflon d. PVC a. Phthalein dye b. Azo dye
18. Which of the following is used in contact lense? c. Anthraquinone dye d. Nitro dye
a. Polypropylene b. Polymethylmathacrylate 22. Moth balls are
c. PVC d. Chloroprene a. Napthalene b. Anthracene
19. Which is the correct statement about dye? c. Benzoic acid d. Benzophenone
a. Every colored substance can act as dye 23. Bordeaux mixture contains
b. Presence of chromophore is necessary a. Copper sulphate b. Zinc sulphate
c. Presence of chromophore and auxochrome are necessary c. Zinc phosphide d. DDT
d. Presence of auxochromophore is necessary 24. Oil of wintergreen is
20. Which of the following is an example of a. Methylacetate b. Methyl salicyalate
chromophore? c. Ethyl benzoate d. Sodium salicyalate
1 2 3 4 5 6 7 8 9 10 11 12
d b d a b a a a a b c
13 14 15 16 17 18 19 20 21 22 23 24
b c d b a b c b c a a b
Heavy Metals
The photo is of suspension bridge -emf]n'Ë] k'n_ which connects Kushma to Gyandi, i.e. two cliffs separated by Modi
river situated in Parbat, Nepal. It is at the hiehgt of 135 meters from the base and is considered as suspension bridge
highest height. It is one of the longest bridges with length of 344 meters. It reduces a tough 1 hour walk to about 5
minutes. The bridge has just been completed and in use now. Many people cling to the safety wall of bridge due to the
height and length in fear.
18.1 Introduction to Transition Metals

Elements of group 3 to 12 (IIB, IIIB, IVB, VB, VIB, VIIB, VIII, IB, and IIB) of periodic table are called
d-block elements as the differentiating electron enters into d orbitals in their electronic
configurations. Here, d-orbitals are incompletely filled. These elements are also called transition
elements. On simply saying, transition elements are called so, because their properties lie in between
s-block and p-block elements. In other words, while moving from IIA to IIIA group in the long form
of periodic table, we have to transit through these elements. For example, atomic number of calcium
is 20. Its electronic configuration is [Ar]4s2. Therefore, it is a s-block element. Scandium (Z = 21), has
an electronic configuration of [Ar]4s23d1. Now this is the first member of 3d series in period 4. It
should be placed in group 3 (IIIB). The ten d-block elements of 3d series are scandium ([Ar] 4s23d1) to
zinc ([Ar] 4s23d10). Similar pattern is found in 4d, and 5d elements also.
General Characteristics of Transition Metals (d-block Elements)

1. In transition metals, differentiating electron enters in d orbital. Therefore, their general outer
electronic configuration is ns0–2 (n – 1) d1–10, where n is the principal quantum number of the
valance shell.
2. Their two outermost shells are incompletly filled with electron. They show variable valency as
electrons of both valence shell and penultimate shell take part in bonding
Example: Electronic configurations of
Sc ⇒ [Ar] 4s2 3d1
Sc2+ ⇒ [Ar] 4s0 3d1
Sc3+ ⇒ [Ar] 4s0 3d0
Heavy Metals Unit 18 585
3. Their d-orbitals are incompletely filled with electron. Therefore, they allow d-d electronic
transitions. Hence, most of their compounds are coloured.
When a transition ion is isolated, (n–1) d orbitals are degenerate. But when the ion is surrounded
by anions or ligands, this degeneracy is lost and d-orbitals split-up into eg and t2g sets. Jumping
of electrons in between these sets of d-orbital is associated with absorption and emission of
energy of definite wave length, which corresponds to a particular colour in visible range. So, the
compound of transition metals are coloured.
4. The ionization potential and electronegativity values of d-block elements lie between that of
s-block and p-block elements.
5. Presence of unpaired d-electrons make them hard.
6. These metals or their compounds can act as catalyst in various processes. In some cases, the
metals provide the surface for all reaction (eg Ni in hydrogenation) and in some cases they can
provide alternate path owing to their variable valency (eg TiCl4 in Ziegler-Natta catalysis)
7. Since they have unpaired electrons in d-orbitals, they exhibit paramagnetic property.
8. Their atoms are small sized. Therefore, they can form alloys. eg. Brass (Zn + Cu), Zinc-amalgam
(Zn-Hg), etc.
18.2 Copper
18.2.1 Introduction
Symbol Cu Atomic number 29
Atomic mass 63.57 (amu) Electronic configuration [Ar] 4s1 3d10
Melting point 1083°C Specific gravity 8.85
Boiling point 2350°C
Copper has been known since long time. Romans and Greeks extracted this metal from island of
cuprus, where it was named "Cuprom". The Nepali name of copper is Tama -tfdf_. Copper, silver
and gold are commonly known as coinage metals. This is because, they had been used in past of
making coins for currency.
Fig. 18.1: Copper wire

18.2.2 Position of Copper in Periodic Table

Copper lies in group 11 (IB) of the periodic table. The group members are 29Cu, 47Ag and 79Au. Their
general electronic configuration is ns1 (n–1)d10. They all are hard, malleable and ductile metals. In
combined state, common state of Cu is Cu22+ and Cu2+, Ag is Ag+ and Au is Au3+. Ag2+ and Au+ are
not common, as Au+ is unstable form and Ag2+ is rare. They all lie below hydrogen is electrochemical
serie. Therefore, they don't liberate H2 from dilute acids. Their reactivity order as reducing agents is,
Cu> Ag>Au.
18.2.3 Occurrence
Copper exists in nature in native as well as combined state. Copper has been found in native form
near superior lake of USA and in Sweden. Copper exists in combined form as its sulphides, oxides
and carbonates. Some major ores of copper are given below:
1. Copper pyrites or chalcopyrites Cu2S.Fe2S3 or CuFeS2 2. Malachite CuCO3⋅Cu(OH)2
3. Copper glance or chalcosite Cu2S 4. Cuprite Cu2O
5. Azurite 2CuCO3.Cu(OH)2 6. Bornite Cu3FeS3
18.2.4 Extraction of Copper from Copper Pyrites

Main ore of copper is copper pyrites. Mostly, copper is extracted from copper pyrite using dry
process (pyrometallurgy).
Theory
Copper pyrite is the main ore of copper. Cuprous and ferrous sulphides are obtained after roasting
of copper pyrites. FeS thus obtained is oxidized to FeO and then removed as slag by the action of
flux.
Roasting
2 CuFeS2 + O2 Cu2S + 2 FeS + SO2
Δ
2 FeS + 3 O2 2 FeO + 2 SO2

Δ
FeO + SiO2 FeSiO3

Flux Δ Slag
Cu2S is oxidized partially to Cu2O which undergoes reaction by unreacted Cu2S to give metallic
copper.
Cu2S + 2 Cu2O 6 Cu + SO2
Δ
Steps involved in the metallurgy

1. Crushing and pulverization: Big lumps of ore are crushed using jaw crushers to get crushed
ore which are pulverized (powdered) using pulverisers or ball mills to get powdered ore.
2. Concentration of ore by froth-floatation process: Powdered ore is taken into a tank containing
water and small quantity of pine oil or eucalyptus oil. The mixture is agitated by using blast of
air. Gangue particles are wetted by water and get collected at the bottom of the tank. The ore
particles being wetted by oil come on the surface in froth. The froth is skimmed off to collect the
concentrated ore.
Blast of air
Froth containing
sulphide ore
Water + Pine oil or

eucalyptus oil + ore
Gangue
Fig. 18.2: Concentration of ore by froth-floatation process
3. Roasting: The concentrated ore is heated in a reverberatory furnace in presence of air, at a

temperature insufficient to melt the ore.
Charging hole Flue gases

Furnace
Concentrated ore
Fig 18.3: Reverberatory furnance
Following change occurs during roasting process.

i. Volatile impurities and moistures are removed.
ii. Impurities like P4, As, S, etc., are oxidized.
P4 + 5 O2 2P2O5
Δ
4 As + 5 O2 2As2O5
Δ
S + O2 SO2
Δ
4 Sb + 3 O2 2 Sb2O3
Δ
iii. Iron pyrite is decomposed into cuprous sulphide and ferrous sulphide.
2 CuFeS2 + O2 Cu2S + 2 FeS + SO2 … (i)

Δ
iv. There is conversion of FeS into FeO and partial oxidation of Cu2S into Cu2O.
2 FeS + 3 O2 2 FeO + 2 SO2 … (ii)

Δ
2 Cu2S + 3 O2 2Cu2O + 2 SO2 (Partial oxidation) … (iii)

Δ
4. Smelting: Roasted ore is mixed with sand and coke followed by feeding into a blast furnace.
The modern blast furnace is made of steel lined inside with refractory bricks. The furnace is of
about 15 to 20 feet in height and about 6 feet in diameter. Hot air of about 800°C temperature is
introduced through tuyeres. Coke burns with hot air and temperature inside the furnace
reaches to about 1000°C. The following changes take place here.
Solid charge
(sand + coke + ore)
Waste gases
Steel plate
Tuyeres for passing blast

of hot air into furnace
Slag
Copper matte
Fig 18.4: Blast furnace for smelting of copper ore

i. Most of unreacted FeS gets oxidized to FeO.
2 FeS + 3 O2 2 FeO + 2 SO2

Δ
ii. Cu2O formed by the oxidation Cu2S reacts with unreacted FeS to get Cu2S again. Hence
complete removal of FeS is most important step in the extraction of copper.
2 Cu2S + 3 O2 2 Cu2O + 2 SO2
Δ
Cu2S + FeO … (iv)
2 Cu2O + FeS
Δ
iii. FeO is converted into slag by the action of sand (silica is used as flux).
FeO + SiO2 FeSiO3 (Slag) … (v)
Δ
Slag being light and molten which can be removed from the upper layer.
At the hearth of furnace, molten mass is obtained which is known as "Matte". This mass mainly
contains cuprous sulphide and little ferrous sulphide.
Self Test
18.1 Cu2O is not formed till FeS is present in blast furnance. Given reason.
5. Bessemerisation: Metallic copper is recovered from copper matte by bessemerisation process
which is carried out in a vessel called Bessemer converter.
Blue flame of burning CO
Acidic or basic lining
Refractory brick lining

Pear shaped Bessemer
Slag converter
Trunnion Air
Molten copper matte
Tuyeres
Fig 18.5: Bessemer converter

Bessemer converter is a pear-shaped steel vessel lined with magnetite and quartz. This is special
Bessemer converter where tuyeres are present in the sides mounted in such away that the
converter can be tilted in the desired direction. Copper matte thus obtained after smelting is
transferred to Bessemer converter. Small amount of sand is also added.
Blast of hot air is passed thought tuyeres. Air is blown through the molten matte.
The following changes take place here.
a. Ferrous sulphide left behind in the above mentioned steps is oxidized to ferrous oxide,
which reacts with silica to give light fusible mass, called slag.
2 FeS + 3 O2 2 FeO + 2 SO2
FeO + SiO2 FeSiO3 (Slag)
Slag being light is drained out from the top of molten mass at regular intervals by tilting
the vessel. SO2 escapes out from the converter as waste gas.
b. After entire iron is removed as slag, cuprous sulphide gets partially oxidized to cuprous
oxide. The Cu2O thus formed reacts with remaining Cu2S to give free copper metal.
2 Cu2S + 3 O2 2 Cu2O + 2 SO2 (partial oxidation)
Δ
Cu2S + 2 Cu2O 6 Cu + SO2 ↑ … (vi)

Δ
The reactions from conversion of copper pyrite into cuprous sulphide and ferrous sulphide and
self reduction to copper complete in the Bessemer converter (reaction (i) to (vi)).
The metallic copper is collected from the base of Bessemer converter by tiliting it.
The metal thus obtained is allowed to cool, dissolved SO2 escapes out forming large blisters on
the surface of metal. Therefore, this metal thus formed is called blister copper. Blister copper
contains 98% pure copper.
Self Test
18.1 What is blister copper?
6. Purification or Refining: Blister copper is purified mainly by two method.
a. Poling: Blister copper is heated in a reverberatory furnace lined with silica. Through which
molten mass is obtained. This molten mass is stirred with green wood poles. The
hydrocarbons present in green wood poles reduce the cuprous oxide (as impurity) into
metallic copper. This poling reduces Cu2O into metallic copper.
Cu2O + C 2 Cu + CO ↑
Δ
(from hydrocarbon)
Copper thus obtained after poling is about 99.5% pure. This copper is tough pitch copper.
b. Electro-refining: The copper thus obtained may still contains impurities like Ag, Au, Ni,
Zn, etc. which can be purified further by electrolytic refining. The impure copper (to be
purified) is suspended as anode and thin sheet of pure copper as suspended as cathode in
a large tank. Copper sulphate solution (15%) acidified with sulphuric acid (5%) is taken as
electrolyte. When D.C. is supplied, copper is dissolved from anode and is deposited as
pure copper at cathode. The impurities are left behind near anode as anode mud or anode
slime.
Ammeter
DC source –
+
Pure copper (Cathode)

Impure copper (Anode)
CuSO4 solution
Fig. 18.6: Electrolytic cell for the purification of copper
Following reactions take place during the process.
CuSO4 (aq.) Cu2+ + SO42–
At anode Cu(s) Cu2+(aq.) + 2 e–

Impure
At cathode Cu2+(aq.) + 2 e– Cu (s)

Pure
Copper thus obtained is about 99.95% pure.

1. Copper is reddish brown coloured solid.
2. It is good conductor of heat and electricity.
3. It is highly malleable and ductile.
4. Its melting point is 1083°C, boiling point is 2350°C and specific gravity is 8.85.

1. Action with air: Dry air has no effect on copper. However, if copper is exposed to moist air, it
forms thin green film of basic copper coarbonate, CuCO3.Cu(OH)2.
O2 [H2O] CO2 Cu(OH)2
Cu CuO Cu(OH)2 CuCO3 CuCO3⋅Cu(OH)2
[H2O] –H2O
green
OR
slow
2 Cu + H2O + O2 + CO2 CuCO3.Cu(OH)2
On heating copper with air (O2), it forms cupric oxide (black oxide) which changes to cuprous
oxide (red oxide) if temperature exceeds 1100°C.
< 1100°C
2 Cu + O2 2 CuO
Black oxide
> 1100°C
4 Cu + O2 2 Cu2O
Δ
Red oxide
2. Action with acids: Copper lies below hydrogen in electrochemical series and cannot displace
hydrogen gas from dilute mineral and non-oxidising acids.
a. Non oxidizing warm and dilute acids (dil. HCl, dil. H2SO4) dissolve copper only in
presence of air.
2 Cu + O2 + 2 H2SO4 2 CuSO4 (aq.) + 2 H2O
2 Cu + O2 + 4 HCl 2 CuCl2 + 2 H2O
In absence of air, these acids do not react with copper.

b. With conc. H2SO4, it gives CuSO4 and SO2.
Cu + 2 H2SO4 CuSO4 + 2 H2O + SO2
conc.
c. With nitric acid copper is oxidized to Cu(NO3)2. However, the nature of nitrogen oxide
depends upon the strength of HNO3. Copper reacts with concentrated nitric acid to yield
nitrogen peroxide as one of the products.
Cu + 4 HNO3 Cu(NO3)2 + 2 NO2 + 2 H2O
conc.
when copper reacts with dilute nitric acid, nitric oxide is produced.
3 Cu + 8 HNO3 3 Cu(NO3)2 + 2NO + 4H2O
dil.
Copper reacts with hydrobromic acid and hydro-iodic acid to form complexes.
2Cu + 2 HBr 2 CuBr + H2
2 CuBr + 2 HBr H2[Cu2Br4]
3. Action with non-metals: Copper reacts with non metal.

Cu + Cl2 CuCl2
Δ
Cu + S CuS
Δ
2Cu + O2 2 CuO
Δ
and
2 Cu2O + O2 4 CuO
Δ
4. Action with Ammonia: Copper is dissolved in aqueous ammonia in presence of air, giving a
complex compound.
2 Cu + 8 NH3 + 2 H2O + O2 2 [Cu(NH3)4] (OH)2
5. Displacement reaction: Copper can displace the metals below it in electrochemical series.
Cu + 2 AgNO3 Cu(NO3)2 + 2 Ag
6. Reducing property of copper. Copper acts as reducing agent. In the above reaction mentioned,
copper is oxidized and behaves as reducing agent. It also reduces Ferric salt to ferrous salt.
Cu + Fe2(SO4)3 2 FeSO4 + CuSO4
Cu + 2 FeCl3 CuCl2 + 2 FeCl2
The itching of copper plates using ferric chloride solution is based on this principle.
18.2.7 Uses of Copper

1. Copper is used in manufacture of electrical wires, cables, etc. owing to its good conducting
power.
2. It is used to prepare household utensils, calorimeters, etc.
3. Copper is used in electroplating and electrotyping.
4. It can be used to prepare coins, ornaments and jewellery.
5. It is used to prepare various types of alloys.
Some of the important alloys have been listed below:
Alloy Composition Used in
Brass Cu(70%) + Zn (≈ 30%) Domestic utensils
Bronze Cu(≈80%) + Tin (≈ 20%) Coins, utensils, statues, bells, etc.
Gun metal Cu(87%) + Sn (≈10%) + Zn(≈ 3%) Machine parts, guns
Rolled gold Cu(95%) + zinc (20%) + Nickel (20%) Utensils, ornaments, resistance coils.
German silver Cu (50%) + Zn(30%) + Ni(20%) Utensils, plates, ornaments.
or Nickel silver
Different types of statues are being made since ancient period. Most of them are alloys of copper.
Fig. 18.7: Statues made of copper alloys
18.2.8 Compounds of Copper

A. Cupric Oxide or Black Oxide of Copper, (CuO)
Cupric oxide is black oxide of copper which is insoluble in water.
Preparation
1. From malachite: Cupric oxide can be prepared in commercial scale, by heating malachite.
Malachite is a naturally occurring compound of copper.
CuCO3 . Cu(OH)2 2CuO + H2O + CO2
Δ
Malachite
2. From copper wire: Cupric oxide can be obtained by burning copper with air.
less than 1100°C
2 Cu + O2 2CuO
Δ
3. From water soluble copper salt: Curpic oxide can be obtained by the precipitation reaction of
water soluble of copper salts .
CuSO4 + 2 NaOH Cu(OH)2↓ + Na2SO4
Bluish white ppt
Cu(OH)2 CuO (s) + H2O

Δ
4. From copper hydroxide, copper nitrate or copper carbonate: Cupric oxide can be obtained by
heating copper hydroxide, copper nitrate or copper carbonate.
Cu(OH)2 CuO + H2O
Δ
Cu(NO3)2 2 CuO + 4 NO2 + O2
Δ
CuCO3 CuO + CO2

Δ
Physical properties
Cupric oxide is black, amorphous powder, which is insoluble in water but soluble in mineral acids.
Chemical properties
1. Action of heat: Cupric oxide is not easily decomposed under ordinary conditions, however, it is
decomposed at 1100° – 1200°C to give Cu2O
1100°C – 1200°C
4CuO 2Cu2O + O2
Δ
2. Action of acids: Cupric oxide reacts with mineral acids giving cupric salts.
CuO + H2SO4 CuSO4 + H2O
CuO + 2HCl CuCl2 + H2O
3. Reduction: Cupric oxide can be reduced by H2, C, CO into copper.

CuO + C Cu + CO
Δ
CuO + H2 Cu + H2O
Δ
CuO + CO Cu + CO2
Δ
Uses of Cupric Oxide

1. Cupric oxide is used for coloring glass in blue or black colour.
2. It is used for the estimation of C and H percentage in organic compounds. (Quantitative
analysis of organic compounds).
B. Cuprous Oxide or Red Oxide of Copper (Cu2O)

Cuprous oxide is red oxide of copper which is insoluble in water.
Preparation
1. Cupric oxide can be prepared by the reduction of Fehling's solution with the help of glucose or
an aldehyde.
Fehling's solution A contains aqueous CuSO4 solution acidified with dil. H2SO4 and Fehling's
solution B contains sodium potassium tartarate (Rochelle salt) made alkaline with NaOH.
On mixing Fehling solution A and Fehling solution B, blue coloured solution of Cu(OH)2 or
CuO is obtained.
HCHO + 2 Cu(OH)2 Cu2O ↓ + HCOOH + H2O
i. Δ
Formaldehyde (From Fehling's Red ppt
solution)
or,
HCHO + 2 CuO(aq.) Cu2O ↓ + HCOOH
Δ
Red ppt
ii. C6H12O6 + 2 CuO C6H12O7 + Cu2O ↓

Δ
Glucose Gluconic acid
2. Cuprous oxide can be obtained by heating CuO with Cu

CuO + Cu Cu2O
Δ
3. When copper is heated at about 1100°C then red oxide of copper is obtained
Above 1100°C Cu2O
4 Cu + O2
Physical properties
1. Cuprous oxide is a red coloured powder.
2. Cuprous oxide is insoluble in water.
Chemical properties
1. Action of Acids: Cuprous oxide reacts with dil. HCl to give cuprous chloride which futher
reacts with HCl to give a complex hydro-cupro-chloric acid. Usually lower and less stable
oxidation states of metal are stabilized by complex formation.
Cu2O + 2 HCl Cu2Cl2 + H2O
Cu2Cl2 + 2 HCl 2 H[CuCl2]
Cu2O + 4 HCl 2 H[CuCl2] + H2O
2. Action of NH3: Cuprous oxide reacts with ammonia solution to form amine complex.
Cu2O + 4 NH4OH 2 [Cu(NH3)2]OH
3. Action of Alkali cyanide: Cuprous oxide forms a colourless complex with alkalicyanide.
Cu2O + 6 KCN + H2O 2K2[Cu(CN)3] + 2 KOH

Uses of Cuprous Oxide

1. Cuprous oxide is used for the preparation of ruby red glass.
2. It is used as enamel and pigment.
3. It is used for the preparation of antirust paint.
4. It is used as pesticide.
C. Copper Sulphate or Blue Vitriol (CuSO4. 5H2O)
Cupper sulphate pentahydrate is also called blue vitriol. In Nepali it is called Nilo Tootho. Blue vitriol
is triclinic crystal (a ≠ b ≠ c and α ≠ β ≠ γ ≠ 90°). It is soluble in water.
Preparation
1. From Cu or CuO or CuCO3 or Cu(OH)2 etc.: When CuO or Cu(OH)2 or CuCO3 is treated with
dil. H2SO4 and the resulting solution is crystallized, blue vitriol is obtained.
2 Cu + H2SO4 + O2 2 CuSO4 + 2 H2O
Or
CuO + H2SO4 2 CuSO4 + H2O
CuCO3 + dil. H2SO4 CuSO4 + H2O + CO2
Cu(OH)2 + dil. H2SO4 CuSO4 + 2 H2O

Thus obtained copper sulphate solution is heated upto crystallization point where by triclinic
crystals of blue vitriols are obtained. During the preparation of blue vitriol by this method, it is
to be noted that sulphuric acid should not be excess which otherwise makes blue vitriol crystals
dehydrated.
crystallization
CuSO4 (aq.) CuSO4 . 5 H2O
2. From scrap copper: When scrap copper is treated with dil. H2SO4 in presence of air, CuSO4 is
obtained which on crystallization gives blue vitriol.
Cu + H2SO4 + O2 2 CuSO4 + 2 H2O
Δ
Crystallization
CuSO4 + 5 H2O CuSO4.5 H2O
On larger scale copper sulphate is manufactured by this method.

3. From copper pyrites: Copper pyrite is roasted whereby copper sulphide and iron sulphides are
formed. If temperature is carefully regulated, copper sulphide is converted into copper
sulphate.
4 CuFeS2 + 15 O2 4 CuSO4 + 2 Fe2O3 + 4 SO2

Δ
CuSO4 thus obtained is extracted with water and crystallized to get blue vitriol.
Physical properties
1. CuSO4.5H2O is blue in colour.
2. Anhydrous CuSO4 is white.
Chemical properties
1. Action of heat:
Exposure 100°C 230°C
CuSO4.5 H2O CuSO4.3H2O CuSO4.H2O 750°C
CuSO4 CuO + SO2 + O2
in air
(Bluish white) (White)
1100°C
Cu2O + O2
Red oxide
H H
H O O H H O O
Cu O S
H O H H O O
O
H H
Fig. 18.8: Structure of copper sulphate pentahydrate
2. Formation of double salts: Copper sulphate forms double salts like K2SO4.CuSO4.6H2O;
(NH4)2SO4 .CuSO4.6H2O.
Crystallization
K2SO4 + CuSO4 + 6 H2O K2SO4.CuSO4. 6 H2O
3. Acidic nature: Aqueous copper sulphate solution is acidic due to cationic hydrolysis.
CuSO4 + 2 H2O Cu(OH)2 + H2SO4
OR
Cu++ + 2 H2O Cu(OH)2 + 2H+
4. Complex Formation
CuSO4 + 4NH4OH [Cu (NH3)4] SO4 . 4H2O
(Excess) Tetraamminecopper(II) sulphate
- deep blue colour
- Schweitzer's reagent
When ammonium hydroxide is added dropwise into copper sulphate solution, initially a bluish
white precipitate of copper hydroxide is formed which dissolves to give deep blue solution on
adding excess of ammonia solution. The deep blue colour is due to the formation of tetra-amine
copper (II) sulphate.
NH3 + H2O NH4OH
CuSO4 + 2 NH4OH Cu(OH)2 ↓ + (NH4)2SO4

Bluish white ppt.
CuSO4 + 4 NH3 [Cu(NH3)4] SO4

Excess Tetraammire copper (II) sulphate
The deep blue solution of tetraamine copper(II) sulphate is also known as Schweitzer's reagent.
It has capacity to dissolve cellulose.
5. Oxidising nature: Copper sulphate oxidizes KI solution into iodine and itself get reduced to
cuprous iodide.
CuSO4 + 2KI CuI2 + K2SO4] × 2
2 CuI2 Cu2I2 + I2
2 CuSO4 + 4 KI 2 K2SO4 + Cu2I2 ↓ + I2

(White) (Violet)
The amount of I2 liberated is proportional to the amount of copper in copper sulphate. Hence,
this is the basis to estimate copper by iodometric titration using starch as indicator.
Uses of Copper Sulphate
1. Blue vitriol is used in electroplating and electrotyping
2. It is used as mordant during dying.
3. It is used as fungicide and germicide.
4. It is used as the preservative of wood, gum etc.
5. Anhydrous CuSO4 is used to detect presence of H2O.
Solved Questions
1. What is copper matte?
¬ The copper sulphide (Cu2S) containing little amount of ferrous sulphide (FeS) which is formed in blast
furnace and is collected at shallow hearth is called copper matte.
2. What is blister copper?
¬ When molten copper enriched with sulphur dioxide is solidified, blisters on the copper metal surface are
formed due to escaping of SO2 from the molten mass. This mass of copper is called blister copper.
Blister copper is about 98 - 99% pure.
3. Write the action of heat on blue vitriol.
¬
Exposure 100°C 230°C
CuSO4.5 H2O CuSO4.3H2O CuSO4.H2O 750°C
CuSO4 CuO + SO2 + O2
in air
(Bluish white) (White)
4. What is Schweitzer reagent? Write its one application.

¬ Tetra-amminecopper(II) sulphate i.e. [Cu(NH3)4] SO4.4H2O is called Schweitzer reagent. It is used to
dissolve cellulose.
Questions
1. How is copper matte formed?
2. Write an important use of (a) red oxide (b) black oxide (c) blue vitriol
3. Write a reaction for the preparation of each of the following:
(a) CuO (b) Cu2O (c) CuSO4
4. A light blue colored precipitate 'A' obtained by the addition of caustic soda in the solution of
cupric sulphate is converted to a black precipitate 'B' on heating. What are 'A' and 'B'?
5. Write a compound of Cu (II) which is insoluble in water but soluble in dilute acid without
effervescence.
6. What happens when NH3 is passed over red-hot CuO?
7. Name two important ores of copper with formulae.

8. Give any one method of conversion of cupric sulphate into cuprous oxide with chemical
equations.
9. When copper wire is put into a solution of silver nitrate beautiful crystals are deposited on the
surface of the copper. What are these crystals chemically? Write the reaction involved.
10. What is the effect of heat on copper sulphate penta-hydrate?
11. Mention the important uses of the copper metal.
Short/Long Answer Questions:
1. Write the preparations, properties and uses of Blue vitriol.
2. How is blister copper obtained from copper pyrites?
3. How would you convert copper to blue vitriol? Name any one alloy of each of:
(a) Copper and Zinc.
(b) Copper and tin.
4. How is metal copper extracted from its pyrite ore? How is it refined? Write the action of it
upon: (a) moist air and (b) Conc. H2SO4
Ans: (a) 2Cu + H2O + CO2 + O2 → CuCO3 . Cu(OH)2 (green basic carbonate) (b) Cu + H2SO4 → CuSO4 + 2H2O + SO2
5. Starting from copper pyrite, how would you obtain pure copper? Explain the steps involved in
the process with necessary diagram for it. Give the chemical reaction for the followings:
(a) Copper is exposed to moist air.
(b) Conversion of copper into blue vitriol.
6. How does copper metal react with:
(a) moist air (b) conc. H2SO4 (c) conc. HNO3
7. Write the pertinent reaction
(a) Copper sulphate crystal turns white powder on heating.
(b) A brown gas is obtained when copper is treated with conc. nitric acid.
(c) Copper becomes green when exposed to air for long time.
8. Describe the action of blue vitriol with
(a) ammonia solution till excess
(b) aqueous potassium iodide
9. What happens when?
(a) Ammonium hydroxide is added to a solution of copper sulphate.
(b) A copper coin is dropped into concentrated nitric acid in a test tube.
(c) Copper turning is treated with conc. HNO3.
10. Write short notes on (a) Chemistry of black oxide of copper (b) Chemistry of blue vitriol

1. Ruby copper is 4. Bordeaux mixture is . . .
a. Cu2S b. Cu2O a. insecticide b. fungicide
c. Cu(OH)2 d. Cu(OH)2CuCO3 c. CuSO4 solution d. lime in aqueous CuSO4
2. Blister copper consists . . . percent copper. 5. Malachite is . . .
a. 90 b. 95 a. Cu2S b. CuCO3.Cu(OH)2
c. 98 d. 99.5 c. Cu2O d. CuCO3
3. Solution of Schweitzer's reagent gives the positive 6. Copper matter is a
test of a. CuS containing little amount of FeS.
a. Cu++ b. SO4¯ ¯ b. CuS containing little amount of FeO
b. NH3 d. Cu++, SO4¯ ¯ and NH3 c. FeS containing little amount of CuS
d. Nearly equal amount of CuS and FeS
1 2 3 4 5 6
a c b d b a
18.3 Zinc
18.3.1 Introduction
Symbol: Zn Melting point: 429.4°C
Atomic number: 30 Boiling point: 907°C
Atomic mass: 65.37 (amu) Electronic configuration: [Ar] 3d10 4s2
Density: 7.14 g/cm3
Zinc has been known since long. Its Nepali name is 'Jasta'. It has been used for a long time in the
manufacture of brass (an alloy of copper and zinc).
Fig. 18.9: Zinc Sheet -h:tf kftf_ for roofing house
18.3.2 Position of Zinc in Periodic Table

Zinc lies in group 12 (group IIB) of the periodic table. The members of this group are Zinc (30Zn),
Cadmium (48Cd) and Mercury (80Hg).
1. These elements are known as non-typical transition metals. The reason is that they do not show
typical properties of the transition metals like variable oxidation state, formation of coloured
compounds, etc. They have completely filled d-orbitals. Therefore, they cannot give coloured
compounds. Their d-electrons cannot participate in bond formation. Hence, they do not exhibit
variable oxidation state in general.
2. Their common oxidation state in combined state is +2.
3. All of these elements are metals. Zinc and cadmium are solid and mercury is liquid at room
temperature.
18.3.3 Occurrence of Zinc

Zinc does not occur in free state. In combined form, it exists as sulphides, oxides, carbonates, etc.
Some ores of zinc are:
1. Zinc blende (ZnS) 2. Calamine (ZnCO3)
3. Zincite or red zinc oxide (ZnO) 4. Franklinite (ZnO. Fe2O3)
5. Willemite (Zn2SiO4)
Zinc blende is the major ore of zinc. In Nepal, zinc is found in the form of its ores in Ganesh Himal,
Phulchowki, etc. Zinc is found in the form of organometallic compounds in snake poison also.
18.3.4 Extraction of Zinc

Theory
Zinc blende (ZnS) is the main ore of zinc. Zinc blende after concentration and roasting gives zinc
oxide in dry form. This oxide form of ore when heated strongly with powdered coke at about 1500°C
gives zinc vapors which on condensation gives molten zinc (97.8% pure). This liquid form is called
zinc spelter. Spelter on purification by fractional distillation followed by electrolytic refining gives
pure zinc.
Reactions:
Roasting
ZnS + O2 ZnO + SO2↑
Δ
Smelting
ZnO + C Zn + CO ↑
Steps involved in this metallurgy

2. Concentration of ore by froth-floatation process: Powdered ore is dipped into a tank
containing water and small quantity of pine oil. The mixture is agitated by using blast of air.
Gangue particles are wetted by water and get collected at the bottom of the tank. The sulphide
particles being preferentially wetted by oil come on the surface in the form of froth. The froth is
skimmed off to collect the concentrated ore (figure 18.10).
Blast of air
Froth containing
sulphide ore
Water + Pine oil or

Gangue
Fig 18.10: Concentration of ore by froth-floatation process
3. Roasting: The concentrated ore is heated in a reverberatory furnace in presence of air at a high
temperature of about 900°C (to decompose ZnSO4, if formed) (figure 10.11). On doing so
following changes take place.
i. Zinc sulphide present in the ore is oxidized to its oxide
2 ZnS + 3 O2 2 ZnO + 2 SO2

Δ
ii. If zinc sulphate is formed, it gets decomposed to give zinc oxide.

ZnS + 2O2 ZnSO4
Δ
2 ZnSO4 2 ZnO + 2 SO2 + O2

Δ
iii. If ore contains calamine, it is decomposed to zinc oxide.
ZnCO3 ZnO + CO2

Δ
iv. Volatile impurities are removed.

v. Impurities like sulphur, phosphorus, antimony, arsenic etc. are removed as their oxide.
S + O2 SO2 ↑
Δ
P4 + 5 O2 2 P2O5
Δ
C + O2 CO2 ↑
Δ
Charging hole Flue gases

Furnace
Concentrated ore
Fig.18.11: Reverberatory furnace
4. Reduction. Zinc oxide formed after roasting can be subjected to reduction by any of the
following methods.
a. Continuous vertical retort process.
b. Belgian method (uses circular or elliptical retorts)
c. Silesian process (reverberatory furnace is used)
Vertical retort process is modern and highly economical process (figure 18.12). This process will
be discussed here.
The powdered oxide form of the ore (ZnO) obtained from roasting process is mixed with coke
(C) in a ratio of 2:1 to make small briquets. The briquets are fed into the retort furnace through
charging door. This feeding is a continuous process. The retort is heated externally by burning
the producer gas (CO + N2) at around 1400–1500°C. On doing so, zinc oxide gets reduced by
coke (C) to the zinc as:
ZnO + C Zn + CO ↑
Δ
Charging door
Silicon carbide bricks
Condenser
Waste gases
Spelter trapping hole

Producer gas + air
Spelter
Heating jacket
Roasted ore and coke
Burnt gases
Producer gas
Residue (ash)
Fig. 18.12 : Vertical retort process for the extraction of zinc.
The zinc vapours and carbon-monoxide gas thus obtained are expelled out by the mild current
of producer gas. The mixture of gases pass through a condenser where carbon-monoxide gas is
expelled out as waste gases. Zinc vapours get condensed into a condenser or receiver and
collected in condenser as molten zinc which is called spelter zinc. The spelter zinc is tapped out
from the condenser from time to time. The purity of zinc obtained here is 97.8%.
Different forms of zinc
Molten zinc
Cooling, distillation Atomizing with Poured into

and electrolysis blast of hot air cold water
Pure zinc Zinc dust Granulated zinc
5. Purification or Refining of Zinc: Possible impurities of zinc in zinc spelter are iron, lead,
cadmium, arsenic etc. The methods of purification of the zinc thus obtained are discussed
below:
a. Distillation: The zinc spelter is subjected to distillation at about 1000°C. Where impurities
like iron (B.pt. = 3000°C) and lead (B.pt. = 1620°C) are left behind. Zinc (B.pt. = 907°C) and
cadmium (B.pt. = 767°C) are collected as distillate. The distillate is distilled again at a
temperature of 800°C, where cadmium is distilled off and zinc is left behind. Thus
obtained zinc is about 99% pure.
b. Electrolysis: Thin sheet of pure zinc is made cathode and the zinc to be purified is made
anode. Both electrodes are dipped in a solution containing ZnSO4 solution containing dil.
H2SO4 (as electrolyte). When D.C. is supplied, zinc is dissolved from anode and gets
collected at cathode leaving the impurities at anode. Thus pure zinc is collected at cathode.
At anode Zn (s) Zn2+ (aq.) + 2e–

Impure
At cathode Zn2+(aq.) + 2 e– Zn
Pure
Zinc thus obtained is 99.5% pure.
DC source Ammeter
+ –
Pure zinc (Cathode)

Impure zinc (Anode)
ZnSO4 solution
Fig.18.13: Electrolytic cell for the purification of zinc
18.3.5 Properties of Zinc

Physical properties
1. Zinc is bluish white solid. It is tarnished to grey colour when exposed on moist air.
2. Zinc is a good conductor of heat and electricity.
3. Zinc is malleable and ductile at about 100-150°C, where as it is brittle at about 200°C.
4. Melting point of zinc is 429.4°C and boiling point is 907°C.
5. Zinc forms homogeneous mixture with metal to form alloys.
Zn + Cu Brass
Zn + Hg Zinc amalgam
Chemical Properties of Zinc
Note:
E°Zn2+/Zn = –0.76 V E°Hg+/Hg = + 0.79V E°Hg2+/Hg = + 0.85 V
The above data show that general reactivity of Zn >>> Hg. (as reducing agent)
1. Action of air: Zinc is not affected by dry air, however it gets tarnished when exposed to moist
air giving basic zinc carbonate.
O2 H2O CO2 Zn(OH)2
Zn ZnO Zn(OH)2 ZnCO3 ZnCO3.Zn(OH)2
[H2O] –H2O
Basic zinc carbonate
Overall reaction:
Slow
2 Zn + H2O + O2 + CO2 ZnCO3.Zn(OH)2
When zinc is heated with air at 500°C, it burns with bluish white flame giving white woolly
flocks of ZnO (dense white smoke of zinc oxide) called philosophers' wool or pompholyx.
500°C
2 Zn + O2 2 ZnO
2. Action of water: Pure zinc does not react with water. Impure zinc (commercial or granulated)
decomposes steam to produce H2. Zinc in presence of Cu forms a Zn–Cu couple, which acts as
electrochemical couple. So presence of Cu increases electron donating character of zinc.
500°C
Zn + H2O (steam) ZnO + H2 ↑
3. Action of acids: Zinc lies above hydrogen in electrochemical series. Therefore, it produces H2
gas from dilute, mineral and non-oxidizing acid. Zinc shows amphoteric nature. Hence, it reacts
with acids as well as bases to give salts.
a. Action of sulphuric acid: Zinc is oxidized by hot conc. H2SO4 as
Zn + 2 H2SO4 ZnSO4 + 2 H2O + SO2
conc.
Zinc is oxidized by dil. H2SO4 to give ZnSO4. Zn displaces H2 from dil. H2SO4 as:
Zn + H2SO4 ZnSO4 + H2 ↑
dil.
b. Action of nitric acid (HNO3): Zn is oxidized by nitric acid to Zn(NO3)2. HNO3 gets
reduced to various products like NO2 or NO or N2O or NH4NO3 depending upon the
concentration of nitric acid:
i. With conc. HNO3
Zn + 4 HNO3 Zn(NO3)2 + 2 H2O + 2 NO2
conc.
ii. With moderately concentrated (1:1) HNO3
3 Zn + 8 HNO3 3 Zn(NO3)2 + 2 NO + 4 H2O
iii. With dilute HNO3

4 Zn + 10 HNO3 4 Zn(NO3)2 + 2 N2O ↑ + 4 H2O
dil.
iv. With very dilute HNO3

4 Zn + 10 HNO3 4 Zn(NO3)2 + 3 H2O + NH4NO3
very dil.
c. Action of HCl: With dilute HCl, Zn displaces H2 gas.

Zn + 2 HCl ZnCl2 + H2 ↑
4. Action of alkali: Zinc reacts with alkali (eg. NaOH) to give sodium zincate.
Zn + 2 NaOH Na2ZnO2 + H2
Sodium zincate
5. Action of non-metals. Zn reacts with non-metals such as S, Cl2, etc. to give corresponding salts.
Zn + S ZnS
Δ
White
Zn + Cl2 ZnCl2
Δ
6. Displacement reaction: Zinc can displace less reactive metals (metals below Zn in
electrochemical series) from their salts.
Zn + CuSO4 ZnSO4 + Cu
Zn + 2 AgNO3 Zn(NO3)2 + 2 Ag
18.3.6 Uses of Zinc

1. Zinc is used in making alloys (Examples: Brass (Cu + Zn), German silver (Cu + Zn + Ni).
2. Zinc is used as a reducing agent (disilverization) during the extraction of Ag and Au.
3. It is used as a lab reagent. Examples: Zinc dust in reduction of phenol, Granulated zinc in the
preparation of H2, etc.
4. It is used as anode in dry cells.
5. It is used in galvanization of iron.
18.3.7 Zinc White or Zinc Oxide (ZnO)

Zinc oxide is known as philosopher wool or zinc white or Chinese white. When zinc is heated with
air at 500°C, it burns with bluish white flame giving white woolly flocks of zinc oxide which is called
Philosopher's wool or pompholyx.
Preparation:
Zinc oxide can be prepared by the following method:
1. When zinc carbonate or zinc nitrate or zinc hydroxide is heated, ZnO is obtained
ZnCO3 ZnO + CO2↑

Δ
2 Zn(NO3)2 2 ZnO + 4 NO2 ↑ + O2↑

Δ
Zn(OH)2 ZnO + H2O

Δ
2. It can be obtained by heating zinc with air.
500°C
2 Zn + O2 2 ZnO
Δ
3. It can be obtained by heating zinc sulphide with air.

2 ZnS + 3 O2 2 ZnO + 2 SO2↑
Δ
Physical properties
1. It is a white amorphous powder insoluble in water.
2. It becomes yellow on heating and white on cooling. On heating O2– ions leave the crystal lattice
as O and electrons are trapped by holes or crystal lattice giving yellow colour. On cooling the
reverse process takes place.
3. It sublimes at 400°C.
4. It melting point is high (1975°C).
Chemical properties
1. Amphoteric nature: Zinc oxide reacts with acid as well as base giving salt i.e. it shows
amphoteric nature.
ZnO + 2 dil. HCl ZnCl2 + H2O
Δ
ZnO + 2 NaOH Na2ZnO2 + H2O

Δ
(Sodium zincate)
2. Oxidizing nature: Zinc oxide is reduced by C or H2 into metallic zinc.
Above 450°C
ZnO + C Zn + CO ↑
Δ
Above 450°C
ZnO + H2 Zn + H2O ↑
Δ
3. Action of cobalt nitrate: When zinc oxide is heated with cobalt nitrate, a green coloured mass
of cobalt zincate is obtained (Rinman's green). In laboratory this reaction is utilized for the
identification of Zn2+ in the salt solution, which is known as "Filter Ash Test".
2Co(NO3)2 2 CoO + 4 NO2 + O2 ↑

Δ
ZnO + CoO CoZnO2 or CoO.ZnO

Cobalt zincate
(Rinman's green)
Uses
1. Zinc oxide is used as white pigment in paint under the name zinc white or Chinese white. It is
preferred over the pigment of lead as it does not get blackened by atmospheric gases like H2S.
2. It is used in preparing green pigment called Rinmann's green.
3. It is used as glaze in ceramics.
4. It is used as filler of soft rubber.
5. It is used in cosmetic powders or creams.
18.3.8 White Vitriol, ZnSO4.7H2O

Heptahydrated zinc sulphate is called white vitriol. In nature, it exits as zincosite. It is soluble in
water.
Preparation
1. When zinc or ZnO or ZnCO3 is treated with dil. H2SO4, aqueous solution of ZnSO4 is obtained.
This solution on crystallization gives white vitriol.
Zn + dil. H2SO4 ZnSO4 + H2 ↑
ZnO + dil. H2SO4 ZnSO4 + H2O
ZnCO3 + dil. H2SO4 ZnSO4 + CO2↑ + H2O
and
Crystallization
ZnSO4 (aq.) ZnSO4 . 7 H2O
White vitriol
2. It can be prepared by the controlled oxidation between zinc blende (ZnS) and oxygen
(Roasting), followed by crystallization.
< 800°
ZnS + 2O2 ZnSO4
Crystallization
ZnSO4 (aq.) ZnSO4 . 7 H2O
White vitriol
Physical properties
1. It is crystalline white solid.
2. It is efflorescent solid (loses water of crystallization when exposed to atmosphere).
3. It is highly soluble in water.
Chemical properties
1. Action of heat: When white vitriol is heated to about 70°C, it loses one water molecule to give
hexahydrated zinc sulphate. When temperature reaches to 100°C, it loses 5 more water
molecules giving monohydrated ZnSO4. On heating the monohydrated ZnSO4 at 300°C gives
anhydrous ZnSO4. Anhydrous ZnSO4 gets decomposed at 800°C to give zinc oxide.
40–70°C 100°C 300°C
ZnSO4. 7 H2O ZnSO4. 6 H2O ZnSO4. H2O ZnSO4
–H2O –5 H2O –H2O
800°C
ZnO + SO2 + O2
2. Action of sodium hydroxide: It reacts with NaOH to give white precipitate of Zn(OH)2, which
dissolves in excess NaOH to give sodium zincate.
ZnSO4 + 2 NaOH Zn(OH)2 + Na2SO4
White ppt
Zn(OH)2 + 2 NaOH Na2ZnO2 + 2 H2O
3. Reaction with barium sulphide: When zinc sulphate is treated with barium sulphide, double
salt, lithopone is obtained, which is used as white pigment.
ZnSO4 + BaS ZnS. BaSO4
Lithopone
4. Formation of double salts: White vitriol solution on crystallization with alkali metal sulphates
gives double salts.
Crystallization process
K2SO4 (aq.) + ZnSO4 (aq.) + 6 H2O K2SO4.ZnSO4. 6 H2O
Potassium zinc sulphate
(double salt)
5. Action of potassium ferrocyanide: Zn2+ reacts with potassium ferrocyanide giving white
precipitate of zinc ferrocyanide.
Zn2+ + K4[Fe(CN)6] Zn2[Fe(CN)6] ↓ + K2SO4

White ppt
Uses
1. It is used as electrolyte during electro-galvanization.
2. Its solution is used as eye lotion. (0.1 – 0.2% solution).
3. It is used as mordant for dyeing.
4. It is used for the preparation of lithopone, which is a white pigment.
18.3.9 Galvanization
Introduction
A large amount of iron used as a structural material is being destroyed due to rusting. To protect
iron from rusting, it is coated with a layer of zinc. The process of coating a layer of zinc over the
surface of iron is called galvanisation.
The Galvanisation process
Galvanization of iron is carried out in the following steps:
Step 1: Cleaning: The article to be galvanized is first cleaned by sand blasting.
Step 2: Pickling: After cleaning the article (to be galvanized) using sand blast, it is dipped into dil.
HCl (or HNO3) solution so as to remove the oxide films formed on the iron surface. This process is
called pickling process.
Step 3: Galvanising the article: Coating of Zn on the surface of iron can be achieved by the following
methods.
a. Hot dip Galvanising: In this method, cleaned article is kept in molten zinc, such that thin layer
of Zn is coated. Then a gentle press is given to make the surface smooth and homogeneous.
b. Sherardising: In this method, cleaned article is heated in rotating drum with zinc dust at 800°C
for several hours (At this temperature alloy is not formed). Uniform layer of zinc is coated. But
the process is costly (is being used for galvanizing nuts, bolts, etc.).
c. Metallizing: In this method, molten zinc is sprayed over the article. 'This method is suitable for
galvanization of iron in bridges, ships, etc.
d. Electroplating: In this method, iron is made cathode zinc is made anode. Acidified zinc
sulphate is used as electrolyte. When D.C. is supplied, Zn gets dissolved from anode and is
deposited at cathode.
Step 4: Rolling: Galvanized iron is pressed through rollers to make the surface smooth.
Mode of protection
1. Barrier protection: Zinc acts as barrier between corroding atmosphere and iron. In this way
galvanization process protects from rusting.
2. Cathodic protection (sacrificial protection): Even if small amount of iron is exposed, iron acts
as cathode and zinc acts as anode. Thus oxidation takes place at zinc. Here zinc is sacrificed for
protecting iron.
Solved Questions
1. What is galvanization?
¬ The process of coating a thin layer of zinc on the surface of iron so as to protect it from rusting is called
galvanization.
2. What is sacrificial protection?
¬ If iron surface is exposed to atmosphere from galvanized iron, zinc acts as anode and iron acts as cathode.
A galvanic cell like arrangement is set up, where Zn dissolved form anode end and gets deposited at
cathode end. The iron does not rust so long as all the zinc has not disappeared. Here cathode is protected
by sacrifice of anode. This process is called sacrificial protection or cathodic protection.
3. What is granulated zinc? Why is it more reactive than pure zinc?

¬ When molten zinc spelter is dropped in cold water irregular shape of solid zinc is obtained. This impure
form of zinc is called granulated zinc. It may consist of copper as impurity and forms Zn-Cu couple. These
form a galvanic cell where zinc acts as anode and copper acts as cathode. Zinc loses electron and copper
gains electron. Presence of copper increases the electron donating character of zinc. That is why granulated
zinc is more reactive than pure zinc.
Questions
1. Give a correct balanced chemical reaction for the preparation of
a. White vitriol
b. Philosopher's wool
2. How is Rinman's green prepared? Give its one important use.
3. Write action of heat on white vitriol.
4. What happens when zinc white is heated?
5. Write the molecular formulae of:
i. Philosopher's wool ii. Rimman's green
iii. Calamine iv. Zinc white
6. How would you obtain white vitriol from zinc?
7. What is the action of heat on white vitriol?
8. Why does zinc become dull in contract of moist air?
9. Write the name of two ores of zinc with their molecular formulae.
10. What action takes place when aqueous sodium hydroxide is added to zinc sulphate solution
drop by drop till excess?
11. Why does zinc displace copper from copper sulphate solution?
12. Why is zinc not considered as a transition element?
13. How will you obtain crystals of white vitriol? Give a chemical reaction.
1. Give the chemistry of zinc white.
2. Write the chemistry of blue vitriol.
3. Starting from zinc blende, how would you obtain pure zinc? What is galvanization?
4. Explain the principle and process sketching a well-labelled diagram for the extraction of zinc
from its ore. What happens when zinc is exposed to moist air?
5. Write two chemical reactions for the preparation of Zinc white, and justify its amphoteric
nature by giving suitable chemical reactions. Write its one important use.
6. What happens when zinc white is:
a. Heated with cobalt nitrate
b. Dissolved with caustic alkali
c. Zinc white is heated with cobalt nitrate
d. Metallic zinc is dissolved in hot conc. NaOH
e. Zinc carbonate is heated

1. Rinman's green is 4. Galvanisation is carried out to protect
a. Mixture of ZnO and CO a. Zinc b. Magnesium
b. Mixture of ZnO and COO c. Iron d. Barium
c. Double salt of ZnO and CoO 5. . . . is used as flux in soldering
d. Green pigment a. dil. solution of ZnCl2
2. Phiosopher's wool is . . . b. conc. solution of ZnCl2
a. Zincite b. Red zinc oxide c. Mixture of ZnCl2 an dZnSO4
c. Precipitate of zinc oxide d. Light mass of ZnO d. Mixture of ZnCl2 and PbCl2
3. Lithopone can be used as
a. eye lotion b. antiseptic
c. paint d. Rinmann's green
1 2 3 4 5
c d c c b
18.4 Mercury
18.4.1 Introduction
Symbol Hg Density 13.6 g/cm3
Atomic number 80 Boiling point 357°C
Atomic mass 200 (amu) Melting point – 38.85°C
Electronic configuration [Xe] 5d10 6s2
Mercury has been known since long time. The symbol Hg is taken from Latin name hydrargyrum
[Greek: Hydro = water, Argyros = Silver]. In Nepali it is called paro -kf/f]_. Mercury preparation finds
their applications in "Aayurveda". Aristotle named it as quick silver or liquid silver. It is only the
metal which is found in liquid state at room temperature.
18.4.2 Occurrence of Mercury

Very small amount of mercury is found in free state. In combined form, it exists as its halides,
amalgams, sulphides, etc. Main ore of mercury is cinnabar (HgS).
18.4.3 Extraction of Mercury from Cinnabar

Theory
Cinnabar after concentration by froth-floatation process is subjected to roasting followed by
distillation. Mercury vapour is condensed to get liquid mercury, which on purification by filtration,
treatment with 5% HNO3 and vacuum distillation gives pure mercury.
Main reactions are:
2 HgS + 3 O2 2 HgO + 2 SO2
Δ
2 HgO 2 Hg + O2
Δ

2. Concentration of ore by froth-floatation process: Powdered ore is taken into a tank containing
water and small quantity of pine oil or eucalyptus oil. The mixture is agitated by using blast of
air. Gangue particles are wetted by water and get collected at the bottom of the tank. The ore
particles being wetted by oil come on the surface in froth. The froth is skimmed off to collect the
concentrated ore.
Blast of air
Froth containing
sulphide ore
Water + Pine oil or

Gangue
Fig. 18.14: Concentration of ore by froth-floatation process
3. Roasting and distillation in shaft furnace: Shaft furnace is long cylindrical body having cup
and cone arrangement as feed-end. This cup and cone arrangement allows the charge (ore +
coke + lime) to enter through the furnace but prevents mercury vapours from escaping. The
shaft-furnace contains a Y-shaped side tubes which are passed through cooler.
The concentrated ore, coke (2% only as a fuel) and lime are mixed together and fed through
cup and cone arrangement to the shaft furnace. The furnace is heated by burning fuel (air is
passed along with the flames). The furnace is heated upto red hot. On doing so, mercuric
sulphide gets oxidized to mercuric oxide which subsequently decomposes in to mercury
vapours.
Roasting
2 HgS + 3 O2 2 HgO + 2 SO2
Δ
2 HgO 2 Hg (vapour) + O2
Δ
Mercury vapour thus obtained, is passed through the water-cooled Y-shaped iron pipes. These
vapour gets condensed to give liquid mercury. The spent ore is taken out from the bottom of the
furnace. The waste gases escape through the outlet of the receiver or condenser.
Ore++Charcoal
Ore Charcoal
Mercury
Mercury vapours
vapours
Blast of air
Cooling
Cooling jacket
Jacket
Water
Mercury
Mercury
Fig. 18.15: Shaft furnace for the extraction of mercury

5. Purification of mercury: Main impurities present in the liquid mercury thus obtained are
copper, zinc, bismuth, lead and suspended impurities of metal oxide. The following steps are
employed to obtain pure mercury.
i. Filtration: Mercury thus obtained is filtered (actually squeezed) through chamois leather
or thick canvas. On doing so, suspended oxide impurities are removed.
ii. Treatment with 5% nitric acid solution: Mercury obtained after filtration is passed
through a long tube containing 5% HNO3 solution. Base metals remain in aqueous
solution.
3 Cu + 8 HNO3 3 Cu(NO3)2 + 2 NO + H2O
3 Zn + 8 HNO3 3 Zn(NO3)2 + 2 NO + H2O
Small amount of Hg2(NO3)2 which is formed by the reaction of Hg with HNO3, react with
other more electropositive metals to displace Hg.
6 Hg + 8 HNO3 3 Hg2(NO3)2 + 2 NO + 4 H2O
Zn + Hg2(NO3)2 Zn(NO3)2 + 2 Hg
Pb + Hg2(NO3)2 Pb(NO3)2 + 2 Hg
Impure mercury
5% HNO3
Pure mercury
Fig. 18.16: Purification of mercury
iii. Vacuum distillation: Mercury obtained from the above process still contains some
impurities like Au, Ag, etc. So mercury thus obtained is subjected to distillation under
reduced pressure (vacuum distillation), where mercury gets distilled off leaving behind
the impurities.
18.4.4 Physical Properties of Mercury

1. Mercury is a liquid metal at room temperature.
2. It is silvery-white in colour.
3. It solidifies at –38.85°C and boils at 357°C.
4. Mercury vapours are deadly poisonous.
5. It is a poor conductor of heat and good conductor of electricity.
18.4.5 Chemical Properties of Mercury

1. Action of air:
i. Under ordinary conditions mercury does not react with air.
ii. When it is heated with air at about 350°C, it gives mercuric oxide. It forms red scum of
HgO on the surface of liquid mercury.
350°C
2 Hg + O2 2 HgO
But if temperature exceeds 350°C, the oxide is decomposed into metallic mercury.
Above 350°C
2 HgO 2 Hg + O2
2. Action of water and alkali: It does not react with water and alkali (Difference with zinc)
3. Action of non-metals: Mercury reacts with non metals like sulphur and halogens to give their
salts.
Hg + Cl2 HgCl2
Δ
Rubbed
Hg + S HgS
Δ
4. Action of acids: Mercury does not displace H2 from dilute acids because it lies below hydrogen
in electrochemical series.
i. With hot conc. H2SO4, mercury is oxidized to HgSO4.
Hg + 2 H2SO4 HgSO4 + SO2 + 2 H2O
ii. With dilute HNO3, mercury is oxidized to mercurous nitrate.
6 Hg + 8 HNO3 3 Hg2(NO3)2 + 2 NO + 4 H2O
iii. With conc. HNO3, mercury is oxidized to mercuric nitrate.

3 Hg + 4 HNO3 Hg(NO3)2 + 2 NO2 + 2 H2O
iv. With aqua-regia, mercury gives mercuric chloride.

HNO3 + 3 HCl NOCl + 2 H2O + 2 [Cl]
(aqua-regia)
Hg + 2 [Cl] HgCl2
5. Action of O3: When mercury comes in contact with O3, mercurous oxide is formed. So, the
meniscus of mercury gets depressed (lowered) and it leaves a tail when allowed to run through
an inclined surface. This is called tailing of mercury.
O3 O2 + O
2 Hg + [O] Hg2O
6. Formation of amalgams: Mercury can form amalgams with almost all metals. In fact these
metals dissolve in mercury. Iron does not form amalgam directly with mercury. Therefore,
mercury is transported in iron vessels.
Cu + Hg Cu. Hg
Copper amalgam
Na + Hg Na.Hg
Sodium amalgam
18.4.6 Uses of Mercury

1. Mercury is used as thermometric and barometric liquid.
2. It is used in the manufacture of caustic soda (eg, Castner-Kellner process).
3. It is used in the metallurgy of silver and gold (amalgamations process)
4. It is used in the mercury vapour lamps. The lamps impart bluish light rich in UV rays.
5. It is used in the preparation of various amalgams.
6. It is used in making dental plastic.
7. Mercury fulminate is used as detonator.
18.4.7 Mercury Poisoning: Health Hazards and Environmental Pollution

Mercury and many of its compounds are poisonous substances. They cause instant as well as long-
term effects.
1. If mercury vapors are inhaled, it causes brain and lungs damage.
2. Organometallic compounds have been used as fungicides in agricultural fields or in paper
industries. But exposure of these compounds may cause the possibility of its penetration in
brain via gastrointestinal path. This causes brain damage, loss of vision or even death. A person
may suffer from psychotic behaviour or even death.
3. Hundreds of Japanese in Mina Mata where killed due to the consumption of fishes which
suffered from mercury poisoning. Severe health problems where observed in newly born
babies. This disease was later on natured as "Minamata disease".
4. Mercurous pesticides have been mostly banned these days.
5. Penetration of mercury can take place through skin also.
18.4.8 Calomel (Mercurous chloride or Mercury(I) chloride), Hg2Cl2

Calomel is a non-poisonous mercurous compound. It contains Hg in dimer form as [Hg+–Hg+] ion.
There is a covalent bond between two atoms of Hg. So, its molecular formula is Hg2Cl2 rather than
HgCl.
Preparation
1. From mercurous nitrate
Mercurous chloride is prepared by treating mercurous nitrate with water soluble chloride such
as hydrochloric acid. This is the laboratory method of preparation of calomel.
Hg2(NO3)2 + 2 HCl Hg2Cl2 + 2 HNO3

White ppt
2. From mercuric chloride:

a. It can be prepared by heating mercuric chloride with mercury. This method has been used to
prepare calomel for medical purpose.
HgCl2 + Hg Hg2Cl2↓
Δ
b. When mercuric chloride is reduced with SnCl2 or SO2, calomel is obtained.

2HgCl2 + SnCl2 Hg2Cl2 ↓ + SnCl4
2HgCl2 + 2 H2O + SO2 Hg2Cl2 ↓ + H2SO4 + 2 HCl
3. From mercuric sulphate

It can be prepared by grinding a mixture of mercuric sulphate, sodium chloride and mercury.
HgSO4 + 2 NaCl + Hg Hg2Cl2 ↓ + Na2SO4
Physical properties
1. Calomel is a white powder insoluble in water.
2. It sublimes at a temperature more than 350°C.
3. It is non-poisonous in nature.
Chemical properties
1. Action of ammonia: Calomel reacts with ammonia, to form grey black product due to the
formation of mixture of finely divided Hg (black) and amido-mercuric chloride (white).
Hg2Cl2 + 2 NH3 Hg + Hg(NH2)Cl + NH4Cl
Grey-black colour
2. Action of heat: When strongly heated, calomel is decomposed to mercuric chloride.
Hg2Cl2 HgCl2 + Hg
Δ
3. Oxidation: Calomel is oxidized by the oxidizing agents like Cl2, KClO3, HNO3, etc. to give
mercuric chloride.
3 Hg2Cl2 + conc. 8 HNO3 3 HgCl2 + 3 Hg(NO3)2 + 4 H2O + 2 NO
4. Reduction: Calomel is reduced to metallic mercury using reducing agent like stannous chloride.
Hg2Cl2 + SnCl2 2 Hg + SnCl4
Finely divided
mercury (black)
5. Action of sodium hydroxide: Calomel reacts with aqueous sodium hydroxide solution to give
grey black precipitate of mercurous oxide which gets decomposed to mercuric oxide and
mercury in presence of sunlight.
Hg2Cl2 + 2 NaOH Hg2O + 2 NaCl + H2O

light
Hg2O HgO + Hg
black
Uses of Calomel
1. Calomel is used as purgative drug.
2. It is used as an antiseptic drug also.
3. It is used as a bed pill along with Na2CO3.
4. It is used to make calomel electrode which is a secondary reference electrode.
18.4.9 Corrosive Sublimate (Mercuric Chloride or Mercury (II) Chloride), HgCl2

Mercuric chloride is called corrosive sublimate. Corrosive sublimate is poisonous compound of
mercury (II) state. It can easily sublime which is highly corrosive in nature. Therefore, it is called
corrosive sublimate.
Preparation
1. From mercuric sulphate: When mercuric sulphate is heated with common salt (NaCl) in
presence of manganese dioxide (MnO2), corrosive sublimate is obtained.
MnO2
HgSO4 + 2 NaCl HgCl2 + Na2SO4
Δ
Here, MnO2 prevents the formation of Hg2Cl2. Thus obtained HgCl2 sublimes and is collected at
the cooler parts of the apparatus. This is commercial method of its preparation.
2. From mercuric chloride:
a. When mercury or Hg2Cl2 is treated with aqua-regia, corrosive sublimate is obtained.
HNO3 + 3 HCl NOCl + 2 H2O + 2 [Cl]

aqua-regia
Hg + 2 [Cl] HgCl2
Hg2Cl2 + 2 [Cl] 2 HgCl2
b. When mercury is heated with excess chlorine, corrosive sublimate is obtained.
Hg + Cl2 HgCl2
Δ
3. From mercuric oxide:

Corrosive sublimate can be obtained by dissolving mercuric oxide with dil. HCl. Mercuric oxide
is obtained by the reaction of Hg2+ compound with NaOH.
HgO + 2 HCl HgCl2 + H2O
Physical properties
1. Corrosive sublimate is white crystalline solid and sparingly soluble in cold water.
2. It is soluble in hot water.
3. It is extremely poisonous. Its antidote is "white of egg" (white of egg is coagulated by HgCl2 and
is eliminated with HgCl2 on it).
Chemical properties
1. Reduction: Corrosive sublimate is reduced by excess SnCl2 to calomel and then to Hg.
2 HgCl2 + SnCl2 SnCl4 + Hg2Cl2

and
Hg2Cl2 + SnCl2 SnCl4 + 2 Hg
Excess
Mercuric chloride can also be reduced by SO2
2. Action of alkali: When HgCl2 is treated with sodium hydroxide, mercuric oxide is formed.
HgCl2 + 2 NaOH Hg(OH) + 2 NaCl
2 HgOH Hg2O + H2O

Unstable
3. Action of potassium iodide (KI): When corrosive sublimate is treated with potassium iodide,
scarlet precipitate of mercuric iodide (HgI2) is obtained which dissolves in excess KI to give
colourless water soluble complex of potassium mercuric iodide.
HgCl2 + 2 KI HgI2 + 2 KCl
Scarlet ppt
HgI2 + 2 KI K2[HgI4]
Potassium tetra iodo mercurate(II)
(Potassium mercuric iodide)
Alkaline solution of K2[HgI4] is called Nessler's reagent. This reagent is used to detect NH+4 or
NH3 in a solution.
2 K2[HgI4] + 3 KOH + NH3 HgI.HgO.NH2 + 7 KI + 2 H2O

Iodide of Millon's base
(brown ppt)
4. Action of ammonia: When corrosive sublimate is treated with ammonia, white precipitate of
mercuric amino chloride is obtained.
HgCl2 + 2 NH3 Hg(NH2)Cl↓ + NH4Cl
White ppt
5. Action of heat: On strong heating mercuric chloride gets decomposed into free mercury and
chlorine.
HgCl2 Hg + Cl2 ↑
Δ
Uses of Corrosive Sublimate

1. Corrosive sublimate is used as fungicide in agricultural fields.
2. It is used as preservative of timber and leather.
3. It is used for the preparation of Nessler's reagent and calomel.
4. Its very dilute solution is used to sterilize the surgical instruments.
5. It is used in the preparation of dry cells.
Questions
1. Write an important use of corrosive sublimate
2. Write an important use of calomel
3. Given a balanced chemical equation for the preparation of corrosive sublimate. What is its
action with KI solution?
4. What is Nessler's reagent? How is it prepared?
5. How is corrosive sublimate converted into calomel and vice-versa?
6. How is Nessler's reagent prepared? Give its one use.
7. What is meant by mercury poisoning?
8. Give the molecular formula and one use of the following compounds:
(a) Nessler's reagent (b) Calomel (c) Corrosive sublimate
9. Write the action of (i) Mercury with aqua regia (ii) tin with caustic soda
10. What happens when HgCl2 is allowed to react with SnCl2?
11. What happens when mercuric chloride reacts with excess of KI solution?
1. How is mercury extracted from Cinnabar?
2. Write one method for the preparation of HgCl2 and Hg2Cl2 each. What happens when an
aqueous solution of HgCl2 is treated with:
i. an aqueous solution of KI
ii. an aqueous solution of SnCl2
3. Write short notes on chemistry of calomel
4. Write two methods for the preparation of corrosive sublimate. Give its action upon.
(a) excess of KI (b) NH3.
5. How is calomel prepared? Give its important properties & uses.
6. Write Short Notes on
a. Extraction of mercury.
b. Chemistry of Calomel.
c. Purification of mercury.

1. Mercury can be stored in 4. The sublimation product of mercuric sulphate,
a. Iron b. Copper sodium chloride and mercury is . . .
c. Zinc d. Tin a. Mercurous sulphate b. Mercurous chloride
c. Mercuric chloride d. Mecurous chloride and
2. Mercury tree consists . . .
sodium sulphate
a. Hg b. HgO
5. Antidote of . . . is white of egg
c. Ag–Hg d. AgNO3
3. Nessler's reagent is a. Hg2Cl2 b. HgCl2
a. K2[HgI4] b. acidic K2[HgI4] c. Hg d. Hg and HgCl2
c. Alkaline K2[HgI4] d. Neutral K2[HgI4]
1 2 3 4 5
a c c b b
18.5 Iron
18.5.1 Introduction
Iron has been known since long time. The word iron is derived from scandinavian word. The symbol
Fe is derived from the latin word ferrum. In Nepali iron is called Falam -kmnfd_. The use of iron and
steel by human being is from immemorial time.
Symbol Fe 26Fe 27Co 28Ni
Atomic number 26
44Ru 45Rh 46Pd
Atomic weight 55.85 amu
76Os 77Ir 78Pt
Position in the periodic table,

Period : 4
Group : 8 or VIII
Black : d-block (3d series)
Electronic configuration: 1s2 2s22p6 3s23p6 4s23d6 or [Ar] 4s2 3d6
18.5.2 Occurrence
Iron is widely distributed in the earth's crust. It is easily attacked by moisture and air which makes it
difficult to find in native state. It is mostly found in the combined states, such as oxides, sulphides
and carbonates.
Oxide ore (i) Haematite Fe2O3
(ii) Limonite (Brown haematite) 2 Fe2O3.3H2O
(iii) Magnetite Fe3O4
Sulphide ore (iv) Iron pyrite FeS2
(v) Copper pyrite CuFeS2
Carbonate ore (vi) Siderite (sapathic ore) FeCO3
Iron forms essential constituent in the haemoglobin of blood.
18.5.3 Extraction of Iron

Haematite is the main ore of iron. The following steps are employed to extract iron from its main ore,
haematite.
Theory
Ferric oxide present in the concentrated and calcined ore is reduced with the help of coke (C) to get
iron in molten state.
2C + O2 2CO + 58 kcal
Δ
Fe2 O3 + 3 CO 2 Fe + 3 CO2
Δ
The molten iron thus obtained is cooled to get pig iron. The pig iron is remelted and poured into
moulds to obtain iron in desired shapes. Such iron is called cast iron.

Extraction of iron from its ore such as oxides or carbonates is carried out in the following steps.
1. Crushing and pulverisation: The big lumps of iron ore are broken down into small pieces by
using jaw crusher or hammer. Then, the pieces are further converted into fine powder with the
help of ball mill or stamp mill.
2. Dressing and concentration: The pulverised ore is washed with water and concentrated by
gravity separation method.
This process is based on the difference in the density of the ores and its impurities. The
pulverised ore is washed with running stream of water where by heavy particles settle down
washing the lighter impurities. If iron is to be extracted from its haematite ore, gravity separation
process applied for concentration (fig. 18.17).
Powder ore
Gangue
Water Concentrated ore

Fig. 18.17: Gravity Separation
Oxide ores which contain little impurities can be used directly without concentration.
3. Calcinations: The concentrated ore is heated with some amount of coal till redness in a shallow
kiln. Excess of air is admitted to oxidise volatile impurities. During this process, following
changes take place.
• Moisture and water of crystalization are removed
2 FeO3. 3 H2O 2 Fe2O3 + 3 H2O
Δ
• Volatile impurities such as P, As, S etc are oxidised to their corresponding oxides and these are
expelled.
P4 + 5 O2 2 P2O5
Δ
4 As + 5 O2 2 As2O5
Δ
S + O2 SO2
Δ
• If iron carbonate is present, it decomposes to form ferrous oxide. The ferrous oxide may be
converted into ferric oxide.
FeCO3 FeO + CO2
Δ
4FeO + O2 2 Fe2O3
Δ
Here, it is to be noted that there is probability of combination of ferrous oxide with silica to form
a slag of ferrous silicate and loss of iron takes place.
FeO + SiO2 FeSiO3
Slag
(Iron silicate)
Fortunately conversion of ferrous oxide into ferric oxide prevents the formation of ferrous silicate
(slag) and thus preventing loss of iron.
During calcination, water vapour and carbon dioxide make the whole mass porous which
accelerate, the reduction of iron in successive step.
4. Extraction of crude iron: The calcined or roasted ore is reduced to iron in a blast furnace by
smelting or carbon reduction process.
The blast furnace is cylindrical tower with 30 - 40 meter in height (fig. 18.18). The broadest part of
the furnace is called bosh and upper part is called body. It is about 6 meter wide. The blast
furnace is externally lined with fire-bricks. Hot blast of air is admitted under pressure into the
furnace through water cooled narrow tubes called tuyeres. These tuyeres are fitted above 2 - 3
meter from the base. Since, blast of air is passed into the furnace, it is called blast furnace. The
waste gas can be recirculated for heating purpose.
The lime-stone, desulphurised coke and calcined or roasted ore is mixed in 1:4:8 ratio. The
mixture, also called charge, is fed from the top of furnace through the cup-cone arrangement.
Here, coke acts as reducing agent and CaCO3 acts as flux.
Different zones of the blast furnace possess different temperature and different chemical reactions
take place accordingly. On the basis of range of temperature and nature of chemical reactions, the
region of the blast furnace can be classified into the following zones.
a. Zone of combustion (1300 – 1500 °C)
This region lies near the hearth of furnace. Combustion of carbon takes place in this zone and
being exothermic, large amount of heat is produced.
2 C + O2 2 CO + 58 kcal
C + O2 CO2 + 97 kcal
Temperature reaches upto 1500°C in this zone. This is the hottest region of blast furnace because
heat energy is produced due to the exothermic reaction.
b. Zone of fusion (1200 – 1300 °C)
This region lies above the zone of combustion. Carbondioxide gas produced in the zone of
combustion rises up and meets with hot coke and carbondioxide is reduced to carbon monoxide
as
CO2 + C 2 CO – 58 kcal
Since the reaction is endothermic, the temperature of this zone falls within the range of 1200°C to
1300°C. The spongy (porous) iron sliding from the top of the blast furnace is fused in this region.
Therefore, this region is called zone of fusion. The molten iron may absorb carbon, phosphorus,
silicon, sulphur at the region. Iron combines with carbon to form cementite.
3 Fe + C + Heat Fe3C
If ferric oxide (Fe2O3) is present, it is reduced in this zone to give iron.
Fe2O3 + 3 C 2 Fe + 3 CO
Solid charge
(Fe2O3 + Coke + CaCO3)
Double cup and cone arrangement
Waste gas (N2, CO, CO2, H2 etc)
Zone of reduction
(400 – 700° C)
Steel plate
Zone of slag formation

(700 – 1000° C) Lining of hard fire bricks
Zone of fusion
(1200 – 1300° C)
Zone of combustion
Tuyere for passing blast of
(1300 – 1500° C)
hot air
Tuyere
Fusible slag
Molten iron Slag out from slag hole
Molten iron out from tapping hole

Fig.18.18: Reduction of iron oxide into iron in blast furnace
c. Zone of slag formation (700 – 1000°C)

This region lies almost in the middle part of furnace. Limestone present here is decomposed
according to following reaction.
CaCO3 CaO + CO2

Δ
The temperature of this zone is about 700°C to 1000°C. The lime produced by the decomposition
of CaCO3 combines with silica (which acts as impurities in the ore) to form slag.
CaO + SiO2 CaSiO3
Δ
Impurity Slag
d. Zone of reduction (400 – 700°C)

This region lies near about the top of the furnace. As the charge slides down, the temperature
rises. The temperature of this zone is about 400°C to 700°C. Carbon monoxide coming from the
bottom of the furnace reduces ferric oxide into iron. Thus obtained iron is spongy iron because
the available temperature of this zone is insufficient to melt the iron. Here, it is to be noted that
carbon monoxide is effective reducing agent rather than carbon under the condition. The
reduction of ferric oxide takes place as follows:
3 Fe2O3 + CO 2 Fe3O4 + CO2
Fe3O4 + CO 3 FeO + CO2 ] × 2
FeO + CO Fe + CO2 ] × 6
3 Fe2O3 + 9 CO 6 Fe + 9 CO2
or Fe2O3 + 3 CO 2 Fe + 3 CO2
In this reaction, decomposition of carbon monoxide may be carried out by spongy iron to some
extent.
2 Fe + 3 CO Fe2O3 + 3 C
Besides this, decomposition of CO takes place at bright red heat.

2 CO CO2 + C
Therefore, there exist equilibrium between carbon and its oxide.

Due to high temperature, calcination of ore may take place whereby moisture and water of
crystallization are removed from the top of the furnace.
In this way, spongy iron is obtained from the zone of reduction and at the zone of fusion. It may
contain carbon, phosphorus, silica as impurities.
The fused iron and molten slag fall into the lower part of the furnace or hearth whereby these
form separate layers. Molten iron being heavier, forms lower layer and slag floats over the molten
iron. These two liquids are collected separately. The molten iron is allowed to solidify in a big
lump which is called pig iron.
The pig iron is remelted and poured into mould to obtain in desired shape which is called cast
iron. Cast iron is not pure form of iron. It may consist 2.5 to 4.5 % carbon along with little
quantity of Si, P, S, Mn etc. as impurities.
18.5.4 Different forms of Iron

On the basis of carbon content as the major impurity, iron is classified into following types.
i. Cast iron ii. Steel iii. Wrought iron
Out of these varieties of iron, wrought iron is purest commercial form. It consists up to 0.25% of
carbon while cast iron consists 2 to 4.5% carbon. Steel is an intermediate variety between cast iron
and wrought iron. The comparison of these three forms of iron is given below:
Property Cast Iron Steel Wrought Iron

1. Carbon content 2 – 4.5 % 0.2 – 2 % up to 0.25%
2. Melting point 1200°C 1300 – 1400°C 1500°C
3. Malleability Brittle Malleable and brittle Malleable
4. Magnetization Can't be magnetised Can be magnetised Can be magnetised
permanently permanently temporarily
5. Rusting Does not rust easily Depend upon the Rusts easily
quality of steel
6. Welding Cannot be welded easily Can be welded Can be welded
7. Hardness Hard Depends upon carbon Soft
content
8. Tempering Can't be tempered Can be tempered Can't be tempered
9. Uses Casting metal objects like To prepare knives, To prepare chains
pipes, heavier parts of swords, spring etc and core of magnet
machinery
In cast iron, carbon is present in the form of graphite or in the form of cementite (Fe3C). The cast iron
may be white or grey in colour.
If molten iron is suddenly cooled most of the carbon will be present in cementite form. This variety
of iron is very hard and brittle which is known as white cast iron. On the other hand, if the molten
iron is cooled slowly, most of the carbon will be present in the form of graphite. This variety of iron
is relatively soft and is known as grey cast iron. Cast iron is most fusible form of iron having melting
point around 1200°C. The molten cast iron solidifies with slight expansion and it is used for casting
metal objects.
18.5.5 Properties of Iron

Physical properties
1. Pure form of iron is soft and white solid. Presence of carbon makes iron hard. Ordinary iron is
grey and crystalline. This is due to presence of carbon.
2. Specific gravity of iron is 7.86.
3. Its melting point is 1530°C and boiling point is 2750°C.
4. Iron is magnetic substance and it losses this property if heated at about 760°C.
5. Iron is good conductor of heat and electricity.
6. It is malleable and ductile. It has high tensile strength.
Chemical properties
1. Action of air:
Pure iron is not affected by dry air. When impure iron is exposed to moist air, iron is oxidised to
its hydrated oxide or hydroxide or both. It forms a brown layer on the surface of iron which is
called rust.
4Fe + 3O2 +xH2O 2Fe2O3.xH2O
Finely divided iron when heated with oxygen yields, ferrosoferric oxide.
Δ Fe3O4
3Fe + 2O2
2. Action of water:
Iron is not affected by cold water. Red hot iron decomposes steam to give hydrogen gas.
3Fe + 4H2O Fe3O4 + 4H2

(Red hot) (Steam)
3. Action of acid:
Iron lies above hydrogen in electrochemical series. It liberates hydrogen gas from dilute, mineral
and non-oxidising acid.
(i) Action with HCl
Iron reacts with hydrochloric acid to liberate hydrogen gas
Fe + 2HCl FeCl2 + H2 ↑
(ii) Action with H2SO4

Iron reacts with dilute sulphuric acid to liberate hydrogen gas
Fe + dil. H2SO4 FeSO4 + H2 ↑
But iron reacts with conc sulphuric acid to liberate sulphurdioxide gas
Fe + 2H2SO4 (conc) FeSO4 + SO2 ↑ + 2H2O
(iii)Action with HNO3

Iron reacts with dilute nitric acid to produce ammonium nitrate as one of the products.
4Fe + 10 HNO3(dil.) 4Fe(NO3)2 + NH4NO3 + 3H2O
Iron reacts with moderately conc. nitric acid to produce nitrogen dioxide gas as one of the
products
Fe + 4HNO3(mod. conc.) Fe(NO3)2 + 2NO2 + 2H2O
Hot and conc nitric acid makes iron passive. When Fe reacts with cold and conc. HNO3 an
extremely thin (almost invisible) film of ferroso-ferric oxide (Fe3O4) is formed on the surface of
iron and iron becomes passive (exhibit internees). This phenomenon is called as passivity of iron.
The inertness exhibited by a metal under the condition of expected chemical activity is called
passivity. Besides conc nitric acid, oxidising agents such as KMnO4, K2Cr2O7 also make iron
passive.
2 HNO3 (cold conc.) H2O + 2 NO2 +[O]] × 4
3 Fe + 4 [O] Fe3O4
3 Fe + 8 HNO3 (cold and con.) Fe3O4 + 8 NO2 + 4 H2O
(iv)Reaction with alkali

Iron does not react with alkali
(v) Displacement reaction

Iron can displace the metal lying below it in electrochemical series from their salts.
Fe + CuSO4 FeSO4 + Cu
Fe + 2AgNO3 Fe(NO3)2 + 2Ag
(vi) Reaction with carbon monoxide

When finely divided iron is heated with carbon monoxide at about 120°C, iron pentacarbonyl is
formed.
120°C
Fe + 5CO Fe(CO)5
Iron pentacarbonyl
18.5.6 Some Compounds of Iron

A. Ferrous Sulphate or Green Vitriol (FeSO4. 7 H2O)
It is one of the most important compounds of iron. Ferrous sulphate heptahydrate is also called
green vitriol. The compound is also called copperas or melanterite, which is obtained as oxidation
product of pyrites in presence of air and water.
Methods of Preparation
1. From Iron: When iron is treated with dilute sulphuric acid, ferrous sulphate solution is obtained
which when heated up to crystallization point (C.P.) yields crystals of green vitriol.
Fe + dil. H2SO4 FeSO4 + H2 ↑
C.P.Δ
FeSO4 + 7H2O FeSO4. 7 H2O
Monoclinic crystal
2. From ferrous oxide or iron carbonate or iron (II) sulphides: When iron oxide or iron carbonate
or iron sulphides are treated with dilute sulphuric acid, iron(II) sulphate solution is formed
which when heated up to crystallization point yields crystals of green vitriol.
FeO + dil. H2SO4 FeSO4 + H2O
FeS + dil. H2SO4 FeSO4 + H2S ↑

C.P.Δ
3. From the waste of Kipps apparatus: The waste solution obtained from the Kipps apparatus
during the preparation of H2S gas is taken, filtered and evaporated to crystallization which
produces monoclinic crystals of green vitriol.
FeS + dil. H2SO4 FeSO4 + H2S ↑
C.P.Δ
4. From iron pyrites: Green vitriol is manufactured from iron pyrite (FeS2). The iron pyrite is
exposed to moist air and it is allowed to undergo slow oxidation. Ferrous sulphate is formed
along with free sulphuric acid.
2 FeS2 + 2 H2O + 7 O2 2 FeSO4 + 2 H2SO4
The free acid is neutralized by adding some amount of scrap iron.

H2SO4 + Fe FeSO4 + H2
The ferrous sulphate solution is heated up to crystallization point to obtain monoclinic crystals of
green vitriol.
C.P.Δ
Properties of Green Vitriol

A. Physical Properties
1. It is pale green crystal isomorphous with MSO4. 7 H2O where M = Co, Ni, Cr, Mn, Mg, Zn etc.
2. It effloresces on exposure to air.
3. It has monoclinic crystal structure i.e. a ≠ b ≠ c, α = γ = 90° and β ≠ 90°
B. Chemical properties
1. When green vitriol is exposed to air, the light green colour changes to brownish due to its
oxidation.
4 FeSO4.7 H2O + O2 4 Fe(OH)SO4 + 26 H2O
2. Green vitriol crystals are soluble in water and its aqueous solution is acidic in nature due to
cationic hydrolysis.
4 FeSO4 + 2 H2O Fe(OH)2 + H2SO4
Fe++ + SO4¯ ¯ + 2 H2O Fe(OH)2 + 2 H+ + SO4¯ ¯
Fe++ + 2 H2O Fe(OH)2 + 2 H+

Cationic hydrolysis (Acidic solution)
3. Action of heat: When green vitriol is heated below 300°C, six molecules of water are lost at 300°C
to give anhydrous FeSO4, which is white in colour.
Below 300°C At 300°C
FeSO4. 7 H2O FeSO4.H2O FeSO4
– H2O – H2O
At red hot in vacuum at 140°C, ferrous sulphate decomposes to ferric oxide.

2 FeSO4 Fe2O3 + SO2 + SO3
Fe2O3 thus formed is used as a pigment under the name of Rouge or Venetian Red.
4. Action with NO: FeSO4 solution absorbs NO to give brown colour compound.
2 FeSO4 + NO FeSO4. NO
Nitrosyl ferrous sulphate
5. Reducing behaviour: Ferrous sulphate is good reducing agent. In acidic medium, it reduces
silver ion, acidified KMnO4 solution and acidified K2Cr2O7 solution.
i. Fe++ + Ag+ Fe+++ + Ag
ii. 2 KMnO4 + 3 H2SO4 K2SO4 + 2 MnSO4 + 3 H2O + 5 [O]

2 FeSO4 + [O] + H2SO4 Fe2(SO4)3 + H2O ] × 5
2 KMnO4 + 10 FeSO4 + 8H2SO4 K2SO4 + 2 MnSO4 + 5 Fe2(SO4)3 + 8 H2O
(Pink) (Colourless)
iii. K2Cr2O7 + H2SO4 K2SO4 + Cr2(SO4)3 + 4 H2O + 3 [O]

2 Fe SO4 + [O] + H2SO4 Fe2(SO4)3 + H2O ] × 3
K2Cr2O7 + 2 FeSO4+ 7 H2SO4 K2SO4 + Cr2(SO4)3 + 3 Fe2(SO4)3 +7 H2O
(Orange colour) (Light green)
6. Action of KCN: (KCN is deadly poisonous!) When excess of KCN is added to ferrous sulphate
solution, potassium ferrocyanide is obtained.
Δ K4 [Fe(CN)6] + K2SO4
FeSO4 + 6 KCN
Uses of Green Vitriol

1. It is used in dyeing industry as mordant.
2. It is used in the preparation of writing ink (Mohr's salt).
3. It is used in tanning industries.
4. It is used as weedicide in agriculture.
5. It is used as reducing agent.
B. Ferric Chloride (FeCl3)
Ferric chloride is one of the most important compounds of iron. Its chemical name is Iron (III)
chloride. In vapour sate, it exists as dimer Fe2Cl6. Ferric chloride exits in anhydrous as well as
hydrated form.
Preparation of anhydrous ferric chloride:

When dry chlorine gas is passed into heated iron in a hard glass tube, anhydrous ferric chloride is
sublimed off at 315°C and is collected inside the bottle.
2 Fe + 3 Cl2 2 FeCl3
Preparation of hydrated ferric chloride

a. From iron: When iron is dissolved in aqua - regia then ferric chloride is formed
[HNO3 + 3 HCl NOCl + 2 H2O + 2 [Cl]] × 3
Fe + 3 [Cl] FeCl3] × 2
Fe + 3 (HNO3 + 3 HCl) 3 NOCl + 2 FeCl3 + 6 H2O

(Aqua regia)
b. From ferric oxide or ferric hydroxide: When ferric oxide or ferric hydroxide is reacted with dilute
hydrochloric acid, ferric chloride is obtained
Fe2O3 + 6 HCl 2 FeCl3 + 3 H2O
Fe(OH)3 + 3 HCl FeCl3 + 3 H2 O
2 FeCl2 + Cl2 2 FeCl3
When ferric chloride solution is heated upto crystallization point then yellow crystals of ferric
chloride are formed.
C.P. Δ
FeCl3 + 6H2O FeCl3 .6H2 O
Properties of Ferric Chloride

A. Physical properties
1. Anhydrous ferric chloride is black while hydrated ferric chloride is yellow in colour.
2. Ferric chloride is deliquescent crystalline solid.
3. At lower temperature ferric chloride exists as Fe2Cl6 while at 700°C the dimer dissociates to
monomer.
Cl Cl Cl
Fe Fe
Cl Cl Cl
4. Ferric chloride is highly soluble in water. Its aqueous solution is acidic in nature due to cationic
hydrolysis
2 FeCl3 + 3 H2O 2 Fe(OH)3 + 6 HCl
2 Fe+++ + 6 Cl¯ + 3 H2O 2 Fe(OH)3 + 6 H+ + 6 Cl¯

(Feebly ionized)
Omitting the common ion from both sides
2 Fe+++ + 3 H2O 2 Fe(OH)3 + 6 H+

Cationic hydrolysis (Acidic solution)
Ferric chloride is also soluble in alcohol and ether because it is not ionic compound (it is
covalent compound).
Chemical Properties
1. Action of heat:
283°C 750°C >750°C
Anhydrous FeCl3 Fe2Cl6 2 FeCl3 2 FeCl2 + Cl2
Sublimes
At high temperature Fe2Cl6 decomposed into FeCl3. Above 750°C ferric chloride decomposes to
FeCl2 and Cl2.
On heating FeCl3.6 H2O it is changed into Fe2O3, H2O and HCl.
Δ
2 [FeCl3. 6 H2O] Fe2O3 + 9 H2O + 6 HCl
This reaction clearly shows anhydrous FeCl3 cannot be prepared by simply heating hydrated
ferric chloride (FeCl3. 6 H2O).
2. Oxidising property: Ferric chloride is reduced by Zn + Hcl to ferrous chloride.
Zn + HCl
FeCl3 + [H] FeCl2 + HCl
3. Action with H2S: If hydrogen sulphide gas is passed into ferric chloride solution, ferric chloride
is reduced into ferrous chloride and yellow colloidal sulphur is formed.
2 FeCl3 + H2S 2 FeCl2 + 2 HCl + S
4. Action with phenol: When neutral solution of ferric chloride is added into phenol, violet colour
of iron hexa-phenoxide is formed.
FeCl3 + 6 C6H5 OH [Fe(C6H5O)6]¯ ¯ ¯+ 3H+ + 3HCl
Iron hexaphenoxide
(Violet colour)
This is the test reaction of phenol.
5. Oxidising nature: FeCl3 oxidises KI into I2.
2 FeCl3 + 2 KI 2KCl + I2 + 2 FeCl2
Uses of Ferric Chloride

1. Ferric chloride is used as mordant in dyeing.
2. It is used as disinfectant.
3. Concentrated solution of ferric chloride is used for etching copper to prepare circuit board.
2 Fe+++ (aq) + Cu (S) 2 Fe++ (aq) + Cu++ (aq)
4. FeCl3 solution coagulates blood and hence used as styptic (stops bleeding) reagent.
5. It is used as laboratory reagent.
C. Ferrous ammonium sulphate [FeSO4.(NH4)2SO4. 6 H2O]
Ferrous ammonium sulphate hexahydrate is called Mohr's salt. It is a double salt and is named after
the name of scientist Mohr.
Chemical name of Mohr's salt is ferrous ammonium sulphate hexahydrate.
Preparation
When solution containing equimolar proportion of ferrous sulphate (with little dilute sulphuric acid)
and ammonium sulphate is heated upto crystallization point (at about 210°C), monoclinic crystals of
Mohr's salt are obtained.
Crystallization
FeSO4 (aq.) + (NH4)2SO4 (aq.) FeSO4(NH4)2SO4.6 H2O
Process
Saturated solution Mohr's salt
Uses of Mohr's Salt

1. It is used to prepare standard solution of ferrous ion in volumetric analysis instead of FeSO4
because Mohr's salt is readily soluble in water and does not effloresce. It is less readily oxidised
by atmospheric air than does ferrous sulphate. Therefore, Mohr's salt is used as primary standard
substance but ferrous sulphate is not.
2. It is used to standardise KMnO4 solution.
18.5.7 Rusting of Iron

Metals are extracted form their ores at the expense of energy and pure metals can be regarded in
higher energy state in comparison to their corresponding ores. When metals are used in various
forms, they are likely to be attacked under certain atmospheric condition and tend to revert back into
combined state. This forms the basis of corrosion.
The phenomenon of deterioration and consequent loss of solid metallic substance through unwanted
chemical reaction or electrochemical attack under the set of environmental condition is called
corrosion. If corrosion takes place in iron, it is specially called rusting.
When iron is exposed to moist air for a sufficient period, the surface of iron gets converted into a
mixture of hydrated ferric oxides and ferric hydroxide which is called rusting and the amorphous
brown scale obtained is called rust.
4 Fe + x H2O + 3O2 2 Fe2O3 . xH2O
Rust
Factors affecting the rusting
Some of the factors which affect rusting are as follows.
a. Presence of impurities of other metals
b. Moisture and air
c. Electrolytes
d. Presence of certain gases such as O2, CO2, SO2, H2S, Cl2 etc .
e. Strain in metal
f. Small layer of rust (A small layer of rust further promotes rusting by auto catalysis)
Theories of Rusting
There are different theories about rusting. Out of these theories, two important theories are
explained below.
1. Electrochemical theory: This is modern theory. Commercial forms of iron are not in pure form.
These have non-uniform surfaces with strains or impurities. Due to this, some portion of iron
surface is at lower reduction potential and acts as anode while another portion of iron surface at
higher reduction potential acts as cathode. In this way a kind of tiny voltaic cell is set up. Gases
such as carbon dioxide, sulphur dioxide, hydrogen sulphides etc. dissolved in water and the
solution is believed to act as electrolytic solution. Following electrode reactions take place on iron
and produce rust.
Reaction at anodic area:
Oxidation of iron takes places at anodic area
Fe Fe++ + 2 e– … (i)
Reaction at cathodic area: The electrons liberated at anodic area travells towards the cathodic
area through conducting medium. These electrons are consumed at cathode either by the
evolution of hydrogen or by the absorption of oxygen depending upon the pH of environment in
acidic medium,
2H + + 2e– H2 ↑ … (ii)
The hydrogen necessary for the reaction is obtained by the ionization of water or carbonic acid.
H2O H+ + OH¯
CO2+H2O H2CO3 H+ + HCO–3 …. (iii)
In neutral medium, reduction of oxygen takes place.

1
H2O + 2 O2 + 2 e– 2 OH¯ … (iv)
The Fe++ obtained from anode and OH¯ obtained at cathode combine to form ferrous hydroxide.
++
Fe + 2 OH¯ Fe(OH)2 …(v)
In excess of oxygen and water the ferrous hydroxide is oxidized to ferric hydroxide.
1
2Fe(OH)2 + 2 O2 + H2O 2Fe(OH)3
Being less stable, the ferric hydroxide undergoes decomposition to give hydrated ferric oxides,
called rust.
2 Fe(OH)3 Fe2O3 . 3 H2O
Rust
However, in the limited presence of oxygen the corrosion product may be anhydrous black
powder of composition of ferrosoferric oxide (Fe3O4).
Summary of Rusting
Rust
Fe2O3.3H2O
decomposition
Fe (OH)3
1
H2O + 2 O2
Fe (OH)2
Fe → Fe++ + 2e– 1
H2 + 2 O2 + 2e– → 2 [OH–]
Lower Reduction Potential Higher Reduction Potential

Anodic area Cathodic Area
Oxidation of Fe Reduction of O2
Evidence in the favour of the theory

Presence of Fe++ ions at anode and presence of OH¯ ions at cathode have been detected by
chemical tests.
2. Chemical theory of rusting: This theory was given by Calvert and Crum Brown in 1888.
According to this theory, rusting of iron takes place in presence of water and carbon-dioxide on
the surface of iron. The rusting of iron is considered to take place in the following steps.
i. Formation of carbonic acid
H2O + CO2 H2CO3
The atmospheric carbon-dioxide combines with moisture to form carbonic acid.
ii. Formation of ferrous bicarbonate

The carbonic acid attacks on the iron surface to form ferrous bicarbonate.
Fe + 2H2CO3 Fe(HCO3)2 + H2 ↑
Ferrous bicarbonate
iii. Oxidation of ferrous bicarbonate to ferric hydroxides.

The ferrous bicarbonate gives precipitate in the form of ferric hydroxide in presence of water and
oxygen.
4 Fe(HCO3)2 + 2H2O + O2 4 Fe(OH)3 ↓ + CO2
iv. Decomposition of ferric hydroxide into hydrated ferric oxide.
2 Fe(OH)3 Fe2O3.3H2O
(Rust)
Evidence in the favour of this theory
Alkali prevents the rusting of iron. Alkali combines with carbon-dioxide and prevents the formation
of bicarbonate and hence rusting does not take place.
2 NaOH + CO2 Na2CO3 + H2O
However, this theory fails to explain the rusting of iron in the absence of CO2.
Prevention of Rusting
Iron forms the major constituent of building and industrial constitutent material. Rusting of iron is a
rampant problem in household as well as industrial material. Loss of iron due to rusting or corrosion
can't be measured only in terms of cost of metal, it should be evaluated in terms of cost of
maintenance and time factor too. To avoid the rusting any of the following processes may be
adopted.
a. Cathodic protection or sacrificial protection: It is the best method for the prevention of rusting.
In this method, the iron is kept in contact with more electropositive metal such as Zn, Al, Mg etc.
If iron is likely to be rusted, there should be the formation of electrochemical cell in which the
more electropositive metal forms anode and corrodes while less electropositive iron does not
corrode or rust. Here, the anode sacrifices itself and prevents cathode from being rusted.
Therefore, the process is called sacrificial protection or cathodic protection.
A better way of sacrificial protection of iron is carried out by galvanization process in which iron
surface is coated with thin layer of zinc. The galvanization process protects from rusting by
following two ways.
Zn Zn++ + 2e¯ (takes place)
Fe Fe++ + 2e¯ (does not take place)
i. Zinc layer forms a barrier between iron surface and atmosphere.
ii. If the rusting environment is set up, it is not the iron but zinc which undergoes corrosion. This
is due to lower reduction potential of zinc.
b. By the formation of protective barrier: Moisture and air are inevitable factors for rusting. If a
coating is made on the surface of iron then it prevents the contact of iron and moist air. Hence, it
prevents iron from being rusted. The following methods can be applied to develop protective
barrier.
i. Coating of oil and grease may be used on tools and machinery parts to prevent from rusting.
ii. Thin coating of paint, enamel, lacquer, varnishes may be used to prevent from rusting. (Barrier
protection)
iii. By passing steam on the red hot iron (Barf's protection).

c. By the formation of alloys: If iron forms an alloys with nickel and chromium, the alloy becomes
resistant to corrosion. Chromium is the best suitable alloying metal for iron because its film is self
healing. The alloy has homogenous surface.
d. Environmental medication: The rusting environment can be reduced by:
i. removing harmful constituents e.g. dehumidification
ii. adding specific substance which neutralize the effect of corrosive constituents of environment e.g.
addition of alkaline substance to remove acidic character of corrosive environment.
e. Uses of corrosion inhibitors: The chemical substance which when added to aqueous corrosive
environment decrease the corrosion of metal by altering the surface reaction is called corrosion
inhibitor. Chromates (e.g. K2CrO4), phosphates, tungsten, amine, heavy metal, soap etc are used
as inhibitors.
Self Test
18.1 Do you agree with the statement that rusting is reverse process of extraction of metal?
18.2 Loses occurring due to corrosion can't be measured only in terms of cost of metal. Comment
the statement.
18.5.8 Steel
Introduction
Fig. 18.19: Uses of steel for construction
Steel is an alloy of iron containing 0.2 to 2% carbon as one of the constituents and traces of sulphur,
phosphorous along with some metals. Plain-carbon steel has limited use. Hence, certain special steel
alloys can be prepared by adding metals such as V, Cr, Mn, Co, Ni etc. The reasons for alloying steel
are given below.
i. To improve tensile strength, ductility, toughness, elasticity, heat and corrosion resistance.
This is usually obtained by adding calculated quantity of nickel.
ii. To improve hardness
• Chromium improves hardness and toughness both.
• Addition of 1.0 to 1.5% manganese (Mn) increases strength, toughness and brittleness.
iii. To improve resistance to abrasion, acid and chemical resisting property
• Molybdenum increase corrosion resistance, abrasion resistance.
iv. To improve shock-resistance.
• Tungsten increase toughness, abrasion resistance and shock-resistance.
Some of the applications of special steels are given below:
i. Steel containing 3.5% Mo is used as heat resisting steels.
ii. Chromium is a universal constituent of all heat resisting steel because it increases corrosion
resistance at high temperature. Heat resisting steel contains more than 12% chromium.
The amount of carbon in steel is intermediate to cast iron and wrought iron. Therefore, steel can be
manufactured either by decreasing the carbon content of cast iron or by increasing the carbon
content of wrought iron.
Manufacture of Steel
Steel can be manufactured by any of the following methods.
a. Bessemer process. (From cast iron)
b. Open hearth process (form cast and wrought iron)
c. Cementation process (from wrought iron)
d. Crucible process (form wrought iron)
e. Electrical process (From pure ore and carbon)
Here, we discuss only Bessemer process and open hearth process:
a. Bessemer process
This process was developed by Henry Bessemer in 1856. The cast iron is taken in a pear shaped
vessel called Bessemer converter. A number of holes are provided at the bottom of the converter to
pass the blast of pre-heated air. Depending upon the nature of impurities the internal lining of
Bessemer converter is made of acidic material such as silica (SiO2) or basic materials such as
dolomite. Accordingly, Bessemer process is two types.
Blue flame of burning CO
Acidic or basic lining
Refractory brick lining

Pear shaped Bessemer converter
Slag
Trunnions Air
Molten iron
Tuyeres
Fig.18.20: Schematic diagram of Bessemer converter used for the manufacture of steel from cast iron.
i. Acidic Bessemer Process

If cast iron used for the manufacture of steel consists basic impurities such as Mn and Si or the
phosphorous content is low, acidic Bessemer process is adopted. In this process internal lining of
converter is carried out by an acidic material such as SiO2. Cast iron obtained from the blast
furnace is put into the converter and blast of pre-heated air is admitted through tuyeres at the
bottom. The impurities of cast iron are oxidised and combine with SiO2 to give slag.
2 Mn + O2 2 MnO
MnO + SiO2 MnSiO3

(Slag)
2 C + O2 2 CO
The last to be oxidized is carbon which is oxidized to carbon monoxide with the production of
blue flame at the mouth of the converter. When the flame dies out, it indicates the completion of
oxidation of impurities. When the blue flame dies, calculated quantity of spiegeleisen1 (Mn + Fe
+ C) is added and blast of air is continued so as to mix it thoroughly. Little aluminium or
ferrosilicon is used to remove entrapped O2, NO2, CO2 etc. Steel is poured out by tilting the
converter.
ii. Basic Bessemer process
If cast iron used for the manufacture of steel consists acidic impurities or phosphorus content is
high, basic Bessemer process is adopted. In this process, internal lining of Bessemer converter is
made by basic material such as dolomite (CaCO3 . MgCO3). Cast iron obtained from the blast
furnace is put into Bessemer converter and blast of pre-heated air is admitted through tuyeres at
the bottom. The phosphorus is oxidised to P2O5 which combines with basic lining to form slag.
P4 + 5 O2 2 P2O5
Δ
MgCO3 MgO + CO2
Δ
3 MgO + P2O5 Mg3(PO4)2
Δ
Slag (Gilchrist slag)
CaCO3 CaO + CO2

Δ
CaO + P2O5 Ca3(PO4)2
Δ
Thomas slag
2 C + O2 2 CO
Δ
The Gilchrist slag and Thomas slag can be used as phosphate fertilizer. If Si and Mn are present
these are also oxidized. Carbon is last to be oxidized. When the impurities are completely
combusted, calculated quantity of spiegeleisen (Mn + Fe + C) is added and a blast of air is
passed for some time to ensure thorough mixing. Then steel is poured out by tilting the
converter.
1 Mn and C act as reducing agent and reduce FeO if present. Besides this, carbon is the essential part of steel while Mn increases
hardness and tensile strength of steel.
Advantage of Bessemer process

i. The process is quick to run and it completes within 15 to 20 minute.
ii. It is relatively inexpensive.
Disadvantage of Bessemer process
i. Quality of steel obtained by this process varies from batch to batch.
ii. It can't remove the impurities completely. Thus produced steel rusts easily.
iii. The process is too rapid to carry out analytical test of the product from time to time.
b. Open Hearth Process
This process was developed by Siemen and Martin. This is the modern process for the
manufacture of steel. For the manufacture of steel, 70 - 80% cast iron, 20 - 30% scrap iron and
little haematite is used. The charge is heated by passing producer gas (CO + N2 in 1 : 2) and it
works on the regenerative system of heat economy. In this process, oxidation of impurities is
carried out by using haematite. Depending upon the nature of impurities, the open hearth
process may be acidic process or basic process.
Air
Slag
Molten pig iron + Basic or acidic

low grade wrought lining
iron + scrap iron +
haematite
Hot producer gas Hot gases

Fig 18.21: An open-hearth furnace used for the manufacture of steel.
Acidic Process
If impurities present in the iron are basic in nature such as Mn, Si etc or the phosphorus content is
low, acid process is applied. In acid process, the hearth of the furnace is lined with acidic material
such as SiO2. The impurities are oxidised by haematite ore.
3 Mn + Fe2O3 3 MnO + 2Fe
Δ
3 Si + 2 Fe2O3 3 SiO2 + 4 Fe
Δ
MnO + SiO2 MnSiO3
Δ
Slag
3 C + Fe2O3 2 Fe + 3 CO
Δ
After the impurities are removed, calculated quantity of spiegeleisen (Mn + Fe + C) is added to
obtain desire quality of steel.
Basic Process
If impurities present in cast iron are acidic in nature and consist more quantity of phosphorus
then basic process is adopted. In this process, the hearth of the furnace is lined with basic
materials such as dolomite (CaCO3.MgCO3). The impurities are oxidised by haematite ores.
6 P + 5 Fe2O3 10 Fe + 3 P2O5
3 P4 + 10 Fe2O3 20 Fe + 6 P2O5
CaCO3 CaO + CO2

Δ
3 CaO + P2O5 Ca3(PO4)2

Slag
3 S + 2 Fe2O3 4 Fe + 3 SO2
3 C + Fe2O3 2 Fe + 3 CO
The samples are drawn from time to time and chemical test is carried out. When the test shows
completion of process, the calculated quantity of spiegeleisen (Mn + Fe + C) is added and stirred
thoroughly. The molten steel is taken out and poured into mould to prepare steel of desired
shapes.
The open-hearth process has following advantages over Bessemer process:
1. It is modern process.
2. Loss of iron as slag is very little. (Loss of iron as slag in open hearth process is about 4% while
that in Bessemer process is about 15%)
3. Temperature can be easily controlled because heat is supplied from external sources.
4. The overall process is carried out smoothly within about 8 to 10 hours. Therefore, the product
obtained is remarkably uniform.
5. Scrap iron or steel can be used for the preparation of steel. Open hearth furnace works on the
regenerative principle of heat economy so the overall process is economical.
Self Test
18.3 What are the basic differences between Bessemer process and open heart process?
18.4 What are the points of similarities between Bessemer process and open hearth process?
Iron
Impurities
Basic Process Acid Process
Acidic impurities Basic impurities

• High Content of Phosphorus • Mn, Si
• low content of P
Basic lining of furnace by dolomite Basic lining of furnace by SiO2
• Complete combustion of impurities

• Addition of spiegeleisen
Steel
Heat Treatment of Steel

Properties of steel are mostly determined by carbon content, presence of other metals and heat
treatment. Here heat treatment of steel is described in brief.
The properties of steel are largely determined by degree of heating or cooling and mode of casting.
The phenomenon of heating and cooling solid form of steel under controlled conditions so as to
modify certain physical properties without changing chemical composition is called heat treatment
of steel. Particularly, heat treatment of steel develops following changes in the steel.
1. Refinement of grain structure
2. Removal of imprisoned gases
3. Change in internal stresses.
Some heat treatment processes are given below:
a. Hardening (Quenching): The process of heating steel beyond critical temperature and cooling it
suddenly (quickly) either plunging in oil or in water is called hardening or quenching. The steel
thus obtained is called hardened or quenched steel.
• Faster the rate of cooling, harder will be the steel produced.
• Low carbon steel2 cannot be hardened but medium and high carbon steel can be hardened.
2 Steel can be classified as carbon steel and alloy steel. However alloy steel also cosists carbon. On the basis of carbon content, carbon steel
is further classified in to low carbon -steel, medium carbon - steel and high carbon - steel.
Type of steel Carbon content Nature Used in
A. Carbon Steel
a. Low carbon-steel Less than 0.2% Malleable and ductile Nail and Chain
b. Medium carbon-steel 0.2 – 0.6 % Harder Rail, steel beam
c. High carbon-steel 0.6 – 1.5 % Hard and tough Spring, tools and cutlery
B. Alloy steel Alloy steel is that kind of steel which consists at least one other element besides carbon to give
special properties. Some examples of alloy steels are stainless steel, invar, nickel steel, stainless
steel, chrome steel etc.
Hardening increases the resistance to wear, ability to cut other metals and brittlenes of steel. Such
types of steels are used for cutting tools.
b. Annealing (softening): The process of heating steel to bright redness (200 – 350°C) followed by
slow cooling is called annealing. The steel thus obtained is soft, weak and ductile. It removes
strain in the steel. At high temperature iron forms cementite (Fe3C) with carbon
3 Fe + C Fe3C – Heat
On cooling slowly, Fe3C is partly decomposed and carbon is spreaded uniformly in steel.
Therefore, steel becomes soft and ductile.
c. Tempering of steel: If hardened or quenched steel is heated to a temperature much below
redness and then cooled slowly, it neither becomes too hard nor too brittle. The process is called
tempering of steel and steel thus obtained is called tempered steel. Tempering is quenching
followed by annealing of steel.
In the process of tempering, a thin film of oxide is formed on the surface of hardened steel. The
colour of oxide film depends on temperature at which the hardened steel is heated.
Temperature range (°C) 200-230 225-270 300
Colour of oxide film yellow brown blue
d. Case-hardening of steel: When mild steel (steel containing low % of carbon) is heated with
charcoal and then plunged into oil, a thin coating of hardened or quenched steel is produced on
the surface of the steel, it is called case hardening and steel obtained is called case-hardened
steel. It is resistant to tear and wear and is largely used in the manufacture of armour plates,
locomotive axles etc.
e. Nitriding of steel: When steel is heated in the atmosphere of NH3 in sealed boxes for about 3-4
days, hard coating of iron nitride is produced on the surface of the steel. The process is called
nitriding of steel.
Stainless Steel
It is a special type of alloy steel. It contains (12-14%) Cr and (1-2%) Ni. It resists corrosion, heat and
action of organic acids.
Uses of stainless steel
1. It is used to make cutting tools (cutlery) knives, forks etc.
2. It is used to make cycle and automobile parts.
3. It is used to make food processing machinery.
4. It is used to make surgical instruments, ball bearings etc.
Questions
1. Why cannot anhydrous ferric chloride be prepared by heating hydrated ferric chloride?
2. What are corrosion and rusting?
3. What is the composition of spiegeleisen? Write its one use.
4. What is meant by quenching of steel?
5. What is the composition of stainless steel? Write its one use.
6. Differentiate between cast iron and wrought iron.
7. Why is open-hearth process more advantageous than Bessemer process for the manufacture of
steel?
8. Write the molecular formula of:

(i) Mohr's salt (ii) Green vitriol
9. Write chemical reaction occurring in zone of reduction in the extraction of iron.
10. How is red oxide of copper converted into black oxide and vice versa.
11. What is meant by tempering of steel? Mention one important use of tempered steel.
12. What reaction occurs in the combustion zone in the blast furnace during extraction of iron?
13. What is meant by plumbosolvency?
14. Mention the function of Spiegeleisen in the manufacture of Steel.
15. Name two important ore of iron.
16. What happens when: Few drops of potassium ferrocyanide are added to aqueous solution of
FeCl3.
17. What is meant by galvanization?
18. Write an important use of wrought iron.
19. Write two methods by which rusting of iron can be prevented.
20. What is tempering of steel? What is its use?
21. What is stainless steel?
22. What is the function of limestone in the smelting of during the extraction of iron?
23. What is a transition element? Mention two of its important characteristics?
24. Write the principle involved in manufacture of steel by open hearth process.
1. How is cast iron extracted from Iron pyrites?
2. Write short notes on manufacture of steel by open hearth process.
3. Draw a neat labelled sketch of blast furnace for the extraction of pig iron and write down the
chemical reactions involved in different zones.
4. What is rusting? Describe electrochemical theory for the rusting of iron. List any two methods
of prevention of rusting.
5. How is steel manufactured by open hearth process? Mention its advantage over Bessemer
process.
6. Explain any four methods for preventing rusting of iron.
7. Write short notes on:
a. Theory of corrosion.
b. Rusting of iron and its prevention.
c. General properties of Transition elements.

1. Which of the following consists maximum content a. Annealing b. Tempering
of iron? c. Quenching d. Nitriding
a. Cast iron b. pig iron 4. Iron can be protected by keeping it in . . . with
c. wrought iron d. steel minimum loss.
2. During the extraction of iron spongy iron is formed a. conc. HNO3 b. dil. HNO3
c. dil. HCl d. dil. H2SO4
in
a. Zone of combustion b. Zone of fusion 5. Don't trough the Kipp's waste because you can get
c. Zone of slag formation d. Zone of reduction . . . from it.
3. Alloy of iron with carbon is heated below its melting a. Green vitriol b. Blue vitriol
c. While vitriol d. Oil of vitriol
point and left it for cooling slowly. The process is
1 2 3 4 5
c d a a a
18.6 Silver
The Latin name of silver is Argentum which means white. Silver is very important metal having
ornamental value.
Fig. 18.22: Different uses of silver
Symbol Ag Atomic number 47

Atomic mass 107.9 (amu) Electronic configuration [Kr] 4d10 5s1
18.6.1 Occurrence
Silver is found in native state as well as in combined state. In native state, it is found in USA, Mexico,
Canada, etc. It is found in combined state as sulphide and chloride.
Ores of Silver
1. Argentite or silver glance (Ag2S) 2. Horn silver (AgCl)
3. Silver copper glance (CuAg)2S2 4. Argentiferous galena (PbS. Ag2S)
5. Pyrargyrite or ruby silver 3Ag2S Sb2S3
18.6.2 Extraction of Silver from Argentite ore Using Cyanide Process

This method is also called Mac-Arthur-Forrest process.
Theory
Ag2S present in the argentite ore is converted into solution of sodium argentocyanide (Sodium
dicyanoargentate(I)) by treating ore with dilute NaCN solution
Ag2S + 4 NaCN 2 Na[Ag(CN)2] (aq) + Na2S

Sodium dicyanoargentate(I)
Sodium argentocyanide solution thus obtained on the treatment with zinc gives metallic silver as
precipitate.
2 Na[Ag (CN)2]+ Zn Na2[Zn(CN)4] + Ag ↓
Sodium tetracyanozincate(II)

2. Concentration of ore by froth-floatation process: Powdered ore is dipped into a tank

containing water and small quantity of pine oil. The mixture is agitated by using blast of air.
Gangue particles are wetted by water and get collected at the bottom of the tank. The ore
particles being preferentially wetted by oil come on the surface in the form of froth. The froth is
skimmed out to collect the concentrated ore.
Blast of air
Froth containing
sulphide ore
Water + Pine oil or

Gangue
Fig.18.23: Concentration of ore by froth-floatation process
3. Formation of complex cyanide: Concentrated ore is agitated with dilute sodium cyanide
solution (0.5%) using a current of air. Then solution of sodium argentocyanide is obtained.
Ag2S + 4NaCN 2Na[Ag(CN)2] + Na2S
Sodium argentocyanide
Due to the case that reaction is reversible, air is blown, which removes Na2S from equilibrium
mixture as Na2SO4. So reaction proceeds in forward direction.
2Na2S + H2O + 2O2 Na2S2O3 + 2 NaOH
Na2S2O3 + 2 NaOH + 2 O2 2 Na2SO4 + H2O
2 Na2S + 4 O2 2 Na2SO4
or, Na2S + 2 O2 Na2SO4
Even if ore is horn silver, same process can be carried out.

AgCl + 2 NaCN Na[Ag(CN)2] + NaCl
4. Reduction by precipitation method: The solution obtained from the above method is filtered
off and treated with finely divided Zn where Ag will be precipitated in the form of dark
amorphous powder.
2 Na[Ag(CN)2] + Zn 2 Ag↓ + Na2[Zn(CN)4]
This precipitate of silver is removed by filtration process and the precipitate is dried out.
5. Purification of silver
Steps:
a. Dried silver is heated with KNO3 solid in crucible to get a compact mass.
The impurities are oxidised on the surface. Liquid silver forms compact mass on cooling.
b. Then impure silver (containing Cu, Al, etc.) is purified by electrolysis.
Impure silver is made anode and pure silver is made cathode. 6% AgNO3 solution acidified
with 1% HNO3 is used as electrolyte.
On passing D.C. silver dissolves from anode and gets collected at cathode.
The reactions take place as follows:
At anode: As Ag+ + e–
An cathode: Ag+ (aq.) + e– Ag (s)
Cupellation may also be used if Pb is suspected. In this process, Pb is blown away by air in the
form of PbO
Properties of Silver
Physical properties
1. Silver metal is white in colour. Alchemist used the term luna for silver which means moon.
2. Silver is good conductor of heat and electricity. Due to its good conductance, it is used to
prepare elctrode.
3. Silver is malleable and ductile.
4. The density of silver is 10.52 gram per cc.
5. Melting point of silver is 956ºC and boling point os 1955ºC.
Chemical Properties
1. Action with air: Silver is not chemically active metal. Therefore, under ordinary condition, it
does not react with air. However, it is tarnished by air containing even traces quantity of
hydrogen sulphide.
2Ag + H2S Ag2S ↓ + H2
Black ppt
Due to hydrogen sulphide pollution, silver monuments are being tarnished. This demands
regular cleaning of silver wares.
2. Action with acids: Silver lies below hydrogen in electrochemical series. So it cannot displace
hydrogen gas from dilute, mineral and non-oxidizing acids such as HCl, H2SO4. However,
silver reacts with concentrated nitric acid and concentrated sulphuric acid as follows:
2Ag + 2H2SO4 Ag2SO4 ↓ + SO2 ↑ + H2O
3Ag + 4HNO3 (conc.) 3AgNO3 + 2H2O + NO
Ag + 2HNO3 (dilute) AgNO3 + H2O + NO2
3. Action with non-metals: Some non-metals such as sulphur, chlorine, etc. react with silver on
heating to form corresponding compounds.
Δ
2Ag + S Ag2S
Δ
2Ag + Cl2 2AgCl
Uses of silver
1. In the early days silver were used to prepare coins. An alloy of silver and copper is used to
prepare coins. Hence, it is regarded as coinage metal.
2. It is used to prepare electrodes.
3. It is used in photography.
4. It is used for electrical purposes.
5. It is used to prepare jewellery.
6. It is used to prepare alloy.
18.6.3 Silver Nitrate AgNO3

Chemical formula: AgNO3 Melting point: 209.7ºC
Name: Silver (I) nitrate Boiling point: 440ºC
Molecular mass: 169.87 Solubility : 256 gram per 100mL at 25ºC
Colour: White Hazards: Corrosive, explosively reacts
with ethanol
Silver nitrate is an inorganic salt with chemical formula AgNO3. It is also called lunar caustic because
(luna means moon, caustic = corrosive) it can be cast into sticks and it exhibits strong caustic action.
Preparation
Silver nitrate can be prepared by the action of nitric acid on silver.
3Ag + 4HNO3 (cold and dilute) → 3AgNO3 + 2H2O + NO
Ag + 2HNO3 (hot and conc.) → AgNO3 + H2O + NO2
These reactions should be carried out in fume cupboard or fumehood to expell the toxic nitrogen
oxide gases.
Physical properties
1. Silver nitrate forms colourless, transparent rhombic crystal (a ≠ b ≠ c and α = β = γ = 90º).
2. Its density is 4.35 and melting point is 209.7ºC
3. The fused state of silver nitrate can be casted into sticks due to its profound caustic action. That
is why silver nitrate is called lunar caustic.
4. Silver nitrate is highly soluble in water. Silver nitrate solution darkens slowly in presence of
light. That is why both silver nitrate crystals and silver nitrate solutions are stored in dark
bottles.
5. Silver nitrate is also soluble in alcohol, pyridine, acetone, etc.
6. Decomposition by heat: On heating, silver nitrate above its melting point, it gets decomposed
to silver nitrite and oxygen.
heating above 209ºC

2AgNO3 2AgNO2 + O2
If silver nitrate is heated upto red, it decomposes to metallic silver.

heating upto red
2AgNO3 2Ag +2NO2 + O2
Silver nitrate decomposes completely at about 440ºC. In fact, most of the metal nitrates
decompose to corresponding metal oxides and so does the silver nitrate. Silver oxides
decompose at even lower temperature than does the silver nitrate. Hence, decomposition of
silver nitrate produces metallic silver.
7. Decomposition by organic matter: Some organic compounds such as skin, paper, cloth, etc.
decomposes silvernitrate into finely divided metallic silver (black) in presence of light.
light
2AgNO3 2Ag +2NO2 + O2
organic matter
(e.g. nail or skin)
This property of silver nitrate is used to prepare indelible ink which is used to mark.
This indelible ink is used in nail and skin after casting vote (fig. 18.24).
Fig. 18.24: Uses of silver nitrate in election
Chemical Properties
1. Action with NaOH: Silver nitrate reacts with sodium hydroxide to give brown precipitate of
silver oxide with the production of sodium nitrate and water.
2AgNO3 + 2NaOH → Ag2O ↓ + 2NaNO3 + H2O
2. Action with NH4OH: When ammonimum hyroxide is added into silver nitrate solution, a
brown precipitate of silver oxide is formed which gets dissolved to form a complex in excess of
ammonium hydroxide.
AgNO3 + NH4OH AgOH + NH4NO3] ×2
2AgOH Ag2O + H2O
2AgNO3 + 2NH4OH Ag2O↓ + 2NH4NO3 + H2O
(Brown ppt)
With excess of NH4OH
Ag2O + 2NH4OH + 2NH4NO3 2[Ag(HN3)2 NO3] + 3H2O
Diamminesilver (I) nitrate
3. Displacement reaction: Silver lies below metals such as Na, Mg, Al, Zn, Sn, Pb, Cu, Hg, etc. and
above Pt, Au in electrochemical series. Hence, metals lying above it in electro-chemical series
can displace it from its salt.
Cu + 2AgNO3 Cu(NO3)2 + 2Ag

4. Action with KCN: Silver nitrate gives white precipitate with potassium cyanide.
AgNO3 + KCN AgCN↓ + KNO3
5. Action with halide, sulphate, thiosulphate, thiocyanate, phosphate, sulphide, chromate:
Aqueous solution of halide, phosphate, sulphide, sulphate, thiosulphate, form precipitate of
corresponding silver salts with silver nitrate solution.
i. AgNO3 + Cl¯ AgCl↓ + NO3¯
white ppt
ii. 2AgNO3 + SO4¯ ¯ Ag2SO4↓ + 2NO3¯
White ppt
iii. 2AgNO3 + S2O3¯ ¯ Ag2S2O3 + 2NO3¯
White ppt
iv. AgNO3 + CNS ¯ AgCNS ↓ NO3¯
White ppt
v. 3AgNO3 + PO4¯ ¯¯ Ag3PO4 ↓ + 3Ag
Yellow ppt
vi. 2AgNO3 + S¯ ¯ Ag2S ↓ + 2NO3¯
Black ppt
vii. 2AgNO3 + CrO4¯ ¯ Ag2CrO4 + 2NO3¯
Brick red ppt
viii. AgNO3 + Br ¯ AgBr ↓ + NO3¯
Pale yellow ppt
ix. AgNO3 + I ¯ AgI ↓ + NO3¯
Yellow ppt
Self Test
18.5 A little quantity of water was observed in a sea cargo. Some argued that the water appeared
from condensation of humid air while some other argued it is from sea water leaking from
pores. What test would you prefer to identify it?
Uses
1. It is used as laboratory reagent. For example, it is used for halide test (Cl¯, Br¯, I¯)
conc. HNO3
Cl¯ + AgNO3 AgCl↓ + NO3¯
2. It is used in silvering of mirror.

3. It is used to prepare indelible ink.
4. It is used to prepare some silver based explosives such as silver acetylide, silver fulminate,
silver azide, etc.
5. It is used in the preparation of photographic film where silver nitrate is reacted with sodium or
patassium salts.
6. It is used to prepare Tollen's reagent.
Questions
1. Why does Silver nitrate solution produce black-stain on the skin in presence of sun light?
2. What is the action of heat on silver nitrate?
3. What do you mean by noble metals? Give any two examples.
4. What happens when AgNO3 is heated at 450°C.
5. Give two uses of silver nitrate.
6. How is presence of halide ions are tested with silver nitrate solution?
7. Why silver ores are leached with metal cyanides for the extraction of silver?
8. What do you mean by noble metals? Name at least three noble metals you know.
1. Give the various steps involved in the extraction of silver from silver glance.

1. Mac‐Arthur‐Forrest process is concerned with 4. In the extraction of silver, sodium cyanide is reacted
extraction of with silver sulphide to yield sodium argentocyanide
a. Cu b. Ag and sodium sulphide. Air oxidation of sodium
c. Au d. Pt sulphide is carried out to make sodium sulphate
2. Lunar caustic is because . . .
a. AgNO3 b. AgCl a. Sodium sulphate is less harmful waste product.
c. Ag2C d. AgNO3 + KOH b. Sodium sulphate can be used as useful reagent.
3. Ruby silver is c. Air should be passed during the reaction.
d. The transformation drives the reaction to forward
a. Ag2S b. Sb2S3
direction.
c. AgCl d. Ag2SbS3
5. Black stain is production when . . . comes into
contact of skin in presence of light.
a. AgNO3 b. NaNO3
c. AgCl d. AgBr
1 2 3 4 5
b a d d a

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MODERN APPROACH TO

Edition: First 2015

Distributors: Kasthamandap Pustak Pasal

Price: Rs. 795.00

General & Physical Chemistry (Section A)

Unit 1: Chemical Bonding and Shape of Molecules - 3 teaching hours

Unit 2: Volumetric Analysis - 8 teaching hours

Unit 3: Ionic Equilibrium - 12 teaching hours

Unit 4: Electrochemistry - 10 teaching hours

Unit 5: Energetics of Chemical Reactions - 8 teaching hours

Unit 7: Chemical Kinetics - 10 Teaching hours

Organic Chemistry (Section B)

Unit 8: Aromatic Hydrocarbon - 3 teaching hours

Unit 9: Haloalkanes and Haloarenes - 8 teaching hours

Unit 10: Alcohols and Phenols - 10 teaching hours

Unit 12: Aldehydes and Ketones - 11 teaching hours

Unit 13: Carboxylic Acids - 10 teaching hours

Unit 14: Nitrocompounds: - 4 teaching hours

Unit 15: Amino Compounds (Amines and Aniline) - 7 teaching hours

Unit 17: Chemistry in Service to Mankind - 10 teaching hours

Inorganic Chemistry Section C

Unit 18: Heavy Metals -18 teaching hours

5. Energetics of Chemical Reaction

9. Haloalkanes and Haloarenes

10. Alcohols and Phenols

12. Aldehydes and Ketones

14. Nitro Compounds

16. Molecules of Life

17. Chemistry in the Service of Mankind

Ball and stick models showing geometries of different molecules.

1.2 Valence Shell Electron Pair Repulsion (VSEPR) Theory

1.2.2 Postulates of VSEPR Theory

lp-bp lp-bp repulsion

Electronegativity of oxygen is greater than that of sulphur.

1.2.3 Some More Examples

NH4+ > NH3 > NH2¯.

Table 1.4: Shapes of molecules having four electron pairs.

Table 1.5: Shapes of molecules having five electron pairs.

Table 1.6: Shapes of molecules having six electron pairs.

1.3 Valence Bond Theory

Formation of Hydrogen Molecule

them and form a stable H2 molecule. This –104 kcal

inter-nuclear distance when the energy of

the system is minimum is called bond B

1.3.2 Types of Overlapping: Types of Covalent Bonds

s-orbital s-orbital σ- bond σ- molecular orbital

ii. s-p overlapping

iii. p-p overlapping

px-orbital px-orbital σ- bond σ- molecular orbital

where, x is taken as inter-nuclear axis.

p-orbital p-orbital π-bond

Differences between σ-bond and π bond

2px 2py 2pz

1s 2pz Orbital overlap

2px 2py 2pz

p-p head on overlapping

2pz 2pz Orbital overlap

2px 2py 2pz 2py 2py

2px 2py 2pz

(here, z is taken as internuclear axis) Orbital picture of O2

Multiple Choice Questions