Hsslive-Xi-Chem-12. Organic Chemistry Some Basic Principles and Techniques

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UNIT 12
ORGANIC CHEMISTRY: SOME BASIC PRINCIPLES AND TECHNIQUES
 Organic chemistry is defined as the chemistry of carbon compounds.

 Because all organic compounds contain carbon as their essential constituent.
 All carbon compounds are not considered as organic compounds.
 Organic chemistry can be defined as the branch of chemistry that deals with
hydrocarbons and their derivatives.
 Hydrocarbons are organic compounds which contain only carbon and hydrogen
atoms.
 All other organic compounds are formed by replacing one or more hydrogen
atoms of hydrocarbons by other atoms or groups.
 They are called hydrocarbon derivatives.
GENERAL INTRODUCTION
 In 1828, Frederic Wohler synthesized the first organic compound urea from an
inorganic compound, ammonium cyanate.
 Urea is prepared by heating ammonium cyanate (NH 4CNO).
 Later, Kolbe synthesized acetic acid and Berthelot synthesized methane in the
laboratory.
CATENATION
 Carbon can combine with other carbon atoms to form straight chains or
branched chains or rings of different sizes and shapes.
 This self-linking property of carbon atoms through covalent bonds is called
catenation.
QUESTIONS
1. How many  and  bonds are present in each of the following molecules.
a) HC  CCH=CHCH b) CH =C=CHCH
3 2 3
Answer
a) Sigma Bonds: 10 Pi Bonds: 3
b) Sigma Bonds: 9 Pi Bonds: 2
2. What is the type of hybridization of each carbon in the following compounds?
a) CH3Cl (b) (CH3)2CO (c) CH3CN (d) HCONH2 (e) CH3CH=CHCN

Answer
a) SP3 b) SP3, SP2 c) SP3, SP d) SP2 e) SP3, SP2, SP2, SP
Prepared by Haizel G. Roy, H.S.S.T Chemistry, Govt. H.S.S. Kalamassery, Ernakulam. Page | 1
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3. Write the state of hybridization of carbon in the following compounds and

shapes of each of the molecules.
(a) H2C=O (b) CH3F (c) HCN
Answer
(a) SP2 hybridised carbon, trigonal planar
(b) SP3 hybridised carbon, tetrahedral
(c) SP hybridised carbon, linear
STRUCTURAL REPRESENTATIONS OF ORGANIC COMPOUNDS

1. LEWIS STRUCTURE
 The Lewis structure can be simplified by representing the two electron covalent
bond by a dash (—).
 A single dash represents a single bond.
 Double dash represents double bond.
 A triple dash represents a triple bond.
 Such structural representations are called complete structural formula.
2. CONDENSED STRUCTURAL FORMULA

 The structural formula can be abbreviated by omitting some or all the dashes
representing the covalent bonds.
 It is indicated by the number of identical groups attached to an atom by a
subscript.
 The resulting expression of the compound is called a condensed structural
formula.
3. BOND LINE STRUCTURAL FORMULA

 In this representation, carbon and hydrogen atoms are not shown.
 The lines representing carboncarbon bonds are drawn in a zig zag fashion.
 The terminals denote methyl groups.
 The line junctions denote carbon atoms bonded to appropriate number of
hydrogens required to satisfy the valency of the carbon atoms.
a) 3-methyl octane b) 2-bromo butane c) Chlorocyclo hexane
d) Cyclopropane e) Cyclopentane
QUESTIONS
1. Expand each of the following condensed formulas into their complete structural
formulas.
a) CH3CH2COCH2CH3
b) CH3CH=CH(CH2)3CH3
Answer
2. For each of the following compounds, write a condensed formula and also their
bond line formula.
Answer
Bond line formula
3. Expand each of the following bond line formulas to show al lthe atoms
including carbon and hydrogen
Answer
THREE DIMENSIONAL REPRESENTATION OF ORGANIC MOLECULES

 The structure of an organic molecule can be represented by using solid
( ) wedges and dashed ( ) wedges.
 The solid-wedge is used to indicate a bond projecting out of the plane of paper,
towards the observer.
 The dashed-wedge indicates the bond projecting out of the plane of the paper
and away from the observer.
 The broad end of the wedge is always towards the observer.
 The bonds lying in plane of the paper are depicted by using a
normal line (—).
 This is called wedge and dash representation.
 Eg: Methane
CLASSIFICATION OF ORGANIC COMPOUNDS
 Based on their structure, organic compounds are broadly classified into two
types.
 They are i) Acyclic or Open Chain Compounds
 ii) Closed Chain or Cyclic or Ring Compounds.
1. ACYCLIC OR OPEN CHAIN COMPOUNDS OR ALIPHATIC COMPOUNDS
 It consists of straight or branched chain compounds.
 These compounds are also called aliphatic compounds
2. CLOSED CHAIN OR CYCLIC OR RING COMPOUNDS

 In these compounds carbon atoms joined in the form of a ring.
 sometimes atoms other than carbon are also present in the ring.
 These rings may be homocyclic or heterocyclic.
 If the ring contains only carbon atoms, it is called homocyclic compound.
 If it contains atoms other than carbon it is called heterocyclic compound.
CLASSIFICATION OF HOMOCYCLIC COMPOUNDS

1. ALICYCLIC COMPOUNDS
 It contains at least one carbo-cyclic ring.
 Alicyclic hydrocarbons are of three types.
 They are cycloalkanes, cycloalkenes and cycloalkynes.
2. AROMATIC COMPOUNDS
 Aromatic hydrocarbons are also known as arenes.
 In Greek, the word ‘aroma’ means pleasant smelling.
 Aromatic compounds are those compounds which have a plesant smell.
BENZENOID AROMATIC COMPOUNDS
 Aromatic compounds containing benzene ring are known as benzenoid
aromatic compounds.
NON BENZENOID AROMATIC COMPOUNDS

 Aromatic compounds that do not contain a benzene ring are
known as non-benzenoid aromatics.
HETEROCYCLIC AROMATIC COMPOUNDS

 An organic compound whose molecules contain one or more rings of atoms, at
least one atom being an element other than carbon, most frequently oxygen,
nitrogen, Sulphur etc are called heterocyclics.
FUNCTIONAL GROUP
 An atom or group of atoms that determines the characteristic properties of an
organic compound is called functional group.
 Compounds having the same functional group have similar properties.
 They constitute one class or family.
 Some important functional groups, their names and name of the compounds
are listed below.
Functional Group Name of the group Name of the compound
-OH Hydroxyl group Alcohol
-NH2 Amino group Amine
-X Halo group Halo compound
-CHO Aldehydic group Aldehyde
-CO- or >CO Carbonyl group Ketone
-COOH Carboxyl group Carboxylic acid
-O- Oxy group Ether
-CN Cyano group Nitrile
-NO2 Nitro group Nitro compound
HOMOLOGOUS SERIES
 A series of similarly constituted compounds in which the members possess the
same functional group and have similar chemical characteristics.
 The members of a homologous series can be represented by a general
molecular formula.
 The successive members differ from each other by a -CH2 unit.
NOMENCLATURE OF ORGANIC COMPOUNDS
 For naming organic compounds, a systematic method of naming has been
developed.
 It is known as the IUPAC system of nomenclature.
IUPAC NOMENCLATURE OF ALKANES
STRAIGHT CHAIN HYDROCARBONS
 The names of these compounds end with the suffix ‘-ane’.
 It carries a prefix indicating the number of carbon atoms present in the chain.
Name Molecular Formula Name Molecular Formula
Methane CH4 Heptane C7H16
Ethane C2H6 Octane C8H18
Propane C3H8 Nonane C9H20
Butane C4H10 Decane C10H22
Pentane C4H12 Icosane C20H42
Hexane C6H14 Triacontane C30H62
BRANCHED CHAIN HYDROCARBONS

 In these compounds, small chains of carbon atoms are attached at one or
more carbon atoms of the parent chain.
 The small carbon chains are called alkyl groups.
 An alkyl group is derived from a saturated hydrocarbon by removing a
hydrogen atom from carbon.
 An alkyl group is named by substituting ‘yl’ for ‘ane’ in the corresponding
alkane.
ALKANE ALKYL GROUP
Molecular Formula Alkane Structural Formula Alkyl
CH4 Methane -CH3 Methyl
C2H6 Ethane CH2  CH3 Ethyl
C3H8 Propane CH2  CH2  CH3 Proplyl
C4H10 Butane CH2  (CH2 )2  CH3 Butyl
C4H12 Pentane CH2  (CH2 )3  CH3 Pentyl
C6H14 Hexane CH2  (CH2 )4  CH3 Hexyl
C7H16 Heptane CH2  (CH2 )5  CH3 Heptyl
C8H18 Octane CH2  (CH2 )6  CH3 Octyl
C9H20 Nonane CH2  (CH2 )7  CH3 Nonyl
C10H22 Decane CH2  (CH2 )8  CH3 Decyl
 Abbreviations are used for some alkyl groups.

 Methyl is abbreviated as Me, Ethyl as Et, Proply as Pr and Butyl as Bu.
BRANCHED ALKYL GROUPS
 Propyl groups can be either be n-Propyl group or Isopropyl group.
 The branched butyl groups are sec-Butyl, Iso-butyl and tert-butyl groups.
 Pentyl groups can be a neopentyl group.
RULES FOR THE NOMENCLATURE OF BRANCHED CHAIN ALKANES

 The longest carbon chain in the molecule is identified.
 The carbon atoms of the parent chain are numbered.
 The numbering is done in such a way that the branched carbon atoms get the
lowest possible numbers.
 The names of the alkyl groups attached as branch are then prefixed to the
name of the parent alkane.
 The position of the substituents is indicated by the appropriate numbers.
 If different alkyl groups are present, they are listed in alphabetical order.
 If two or more identical substituent groups are present then the numbers are
separated by commas and prefixes such as di, tri, tetra etc are used.
 If two substituents are present in equivalent positions, the lower number is
given to the one coming first in the alphabetical listing.
QUESTIONS
1. Write the structures of the following organic compounds
a) 2,4-Dimethyl pentane b) 2,2,4-Trimethyl pentane
c) 3-Ethyl-4,4-Dimethyl heptane d) 3-Ethyl-6-methyl octane
e) 5-sec-Butyl-4-isopropyldecane f) 1-Methyl-3-propylcyclohexane
g) 5-(2,2-Dimethylpropyl)nonane h) 3-Ethyl-1,1-dimethylcyclohexane
i) 5-(-2Ethyl butyl)-3,3-dimethyldecane
2. Write the IUPAC names of the following organic compounds.
2,5,6-Trimethyl octane
3-Ethyl-5-methyl heptane
NOMENCLATURE OF ORGANIC COMPOUNDS HAVING FUNCTIONAL GROUPS
 The longest carbon chain containing the functional group is numbered.
 It is done in such a way that the functional group is attached at the carbon
atom possessing lowest possible number in the chain.
 In the case of poly functional compounds, one of the functional groups is
chosen as the principal functional group.
 The remaining functional groups are named as substituents using the
appropriate prefixes.
 The choice of principal functional group is made on the basis of the order of
preference.
 The order of decreasing priority of some functional groups is
 COOH, SO3H, COOR, COCl, CONH2, CN, CHO, =C=O, OH,
NH2, =C=C=, CC
EXAMPLES
1. Write the IUPAC names of the following compounds.
6-Methyloctan-3-ol
Hexane-2,4-dione 5-oxohexanoic acid
Hexa-1,3-dien-5-yne
2. Derive the structure of the following compounds

i) 2-Chlorohexane ii) Pent-4-en-2-ol iii) Pent-4-en-2-ol
iv) Cyclohex-2-en-1-ol v) 6-Hydroxyheptanal
Answer
i) ii)
iii) iv) v)
NOMENCLATURE OF SUBSTITUTED BENZENE COMPOUNDS

 For IUPAC nomenclature of substituted benzene compounds, the substituent is
placed as prefix to the word benzene.
 If the benzene ring is di-substituted, the position of the substituents is defined

by numbering the carbon atoms of the ring such that the substituents are
located at the lowest numbers possible.
 For tri or higher substituted benzene derivatives, the compounds are named by
identifying substituent positions in the ring by following the lowest locant rule.
LOWEST LOCANT RULE
 The substituent of the base compound is assigned number 1.
 Then the direction of numbering is chosen such that the next substituent gets
the lowest number.
QUESTION
1. Write the structural formula of the following compounds.
a) o-Ethylanisole b) p-Nitroaniline
c) 2,3 - Dibromo -1 – phenylpentane d) 4-Ethyl-1-fluoro-2-nitrobenzene.
ISOMERISM
 Compounds having the same molecular formula but differ from each other in
physical and chemical properties are known as Isomers.
 The phenomenon is known as Isomerism.
 Isomerism can be classified into two types.

1. STRUCTURAL ISOMERISM
 Compounds having the same molecular formula but different structures are
called structural isomers.
 The phenomenon is called Structural Isomerism.
A. CHAIN ISOMERISM
 When two or more compounds have similar molecular formula but different
carbon skeletons, these are referred to as chain isomers.
 The phenomenon is termed as chain isomerism.
B. POSITION ISOMERISM
 When the isomers differ in the position of the functional group or substituent, it
is called position isomerism.
C. FUNCTIONAL GROUP ISOMERISM

 Two or more compounds having the same molecular formula but different
functional groups are called functional isomers.
 The phenomenon is termed as functional group isomerism.
D. METAMERISM
 It arises due to different alkyl chains on either side of the functional group in
the molecule.
CH3  CH2  O  CH2  CH3 CH3  O  CH2  CH2  CH3
Ethoxy Ethane Methoxy Propane
2. STEREOISOMERISM
 It arises due to the difference in relative positions of their atoms or groups in
space.
 Compounds having same molecular formula but different spatial arrangement
of atoms are called stereoisomers.
 The phenomenon is called stereoisomerism.

 There are two types of stereo isomerism.
 They are Geometrical Isomerism and Optical Isomerism.
ORGANIC REACTION MECHANISM

 In an organic reaction, the organic molecule reacts with an appropriate
attacking reagent.
 It leads to the formation of one or more intermediates and finally products.
REACTION MECHANISM
A reaction mechanism is sequential account of each step
 describing the details of electron movement
 energetics during bond cleavage and bond formation
 the rates of transformation of reactants into products.
FISSION OF A COVALENT BOND
 A covalent bond can be cleaved either by hemolytic cleavage or by heterolytic
cleavage.
1. HOMOLYTIC CLEAVAGE
 In homolytic cleavage, one of the electrons of the shared pair in a covalent
bond goes with each of the bonded atoms.
 The single electron movement is shown by ‘half headed’ (fish hook ) curved
arrow.
 Each fragment formed as a result of homolysis carries one unpaired electron

and is called a free radical.
 Free radicals are also highly reactive.
 Alky radicals are classified as 10, 20 or 30.
 The stability increases in the order.
2. HETEROLYTIC CLEAVAGE
 In heterolytic cleavage, the bond breaks in such a manner that the shared pair
of electrons remains with one of the fragments resulting in + vely and – vely
charged ions.
AB  A+
 + B–
CH3Br  CH3+
 + Br–
CARBOCATION
 A species having a carbon atom possessing sextet of electrons and a positive
charge is called a carbocation.
 Eg: Methyl Carbocation H3C+
 They are classified as 10, 20 or 30 depending on whether one, two or three

carbon atoms are directly attached to the positively charged carbon.
 They are highly unstable and reactive species.
 The order of stability of carbocation is
+
CH3 < CH3+CH2 < (CH3)2+CH < (CH3)3+C
STRUCTURE
 Carbocations have trigonal planar shape with + vely
charged carbon bearing sp2 hybridised.
TYPES OF ATTACKING SPECIES
1. ELECTROPHILES (E+)
 Electrophiles are neutral of +vely charged species.

 They are capable of accepting a pair of electrons from a substrate molecule.
 Electrophiles are electron deficient species.
 Eg: H+, H3O+, NO2+, NO+, Br+, Cl+, AlCl3, BF3 etc.
2. NUCLEOPHILES
 Nucleophiles are neutral of negatively charged species.
 They are capable of donating a pair of electrons to a substrate molecule.
 Nucleophiles are electron rich species.
 Eg: X, OH, NO2, CN, NH3, R-NH2, R2NH, R3N, R-OH, H2O etc.
3. FREE RADICALS
 Free radicals are neutral species containing an unpaired electron.
 They are highly reactive species.
QUESTION
1. Classify the following molecules/Ions as nucleophile or electrophile.
Nucleophiles: HS, C2H5O, (CH3)3N, H2N
Electrophiles: BF3, Cl+, CH3-C=O+, NO2+
ELECTRON MOVEMENT IN ORGANIC REACTIONS

 The movement of electrons in organic reactions can be shown by curved arrow
notations.
 It shows how changes in bonding occur due to electronic redistribution during
the reaction.
 To show the change in position of a pair of electrons, curved arrow starts from
the point from where an electron pair is shifted and it ends at a location to
which the pair of electrons may move.
 Three different possibilities of electron movements are as follows.
 Movement of a single electron is indicated by half headed curved arrows.
ELECTRON DISPLACEMENT EFFECTS IN COVALENT BONDS

 The partial or complete displacement of the bonding electrons resulting in the
development of polarity in a molecule is known as electron displacement effect.
POLAR COVALENT BOND
 When a covalent bond is formed between two atoms of different
electronegativities, the electron pair is unequally shared.
 The bond formed is called a polar covalent bond.
 The unequal sharing of electron pairs results in the origin of small fractional
charges on the constituent atoms.
INDUCTIVE EFFECT
 Inductive effect is a permanent effect.
 Here a polarity is induced on a carbon atom and the substituent attached to it.
 It is due to the minor displacement of bonding electron pair caused by the
difference in electronegativity.
 This effect propagates only through C – C σ bonds.

 This effect decreases rapidly as the number of C atoms increases.
 The polarization of sigma bond caused by the polarization of adjacent
sigma bond is referred to as Inductive Effect. OR Inductive Effect is
the induction of polarity in an otherwise non polar covalent bond.
 Eg: Chloroethane
-I EFFECT
 Atoms or groups having greater electron attracting power than hydrogen.
 They are also known as Electron Withdrawing Groups (EWG).
 Eg: -C6H5 , -OH, -OCH3 , -OC6H5 , -I, -Br, -Cl, -F, -COOH, -CN, -NO2 etc
+I EFFECT
 Atoms or groups having lesser electron attracting power than hydrogen.
 They are also known as Electron Donating Groups (EDG).
 Eg: -CH3 , -C2H5 etc.
QUESTIONS
1. Which bond is more polar in the following pairs of molecules:
(a) H3C-H, H3C-Br (b) H3C-NH2, H3C-OH (c) H3C-OH, H3C-SH
Answer (a) C–Br, since Br is more electronegative than H.

(b) C–O (c) C–O
2. In which C–C bond of CH3CH2CH2Br, the inductive effect is expected to be the
least?
Answer: Magnitude of inductive effect diminishes as the number of intervening
bonds increases. Hence, the effect is least in the bond between carbon-3 and
hydrogen.
RESONANCE
 The concept of resonance was first introduced by Heisenberg.
 When a molecule cannot be represented by a single structure, but its
characteristic properties can be described by two or more structures, then the
actual structure is said to be a resonance hybrid of these structures.
 This phenomenon is called resonance.
 The different possible structures are called contributing structures or canonical
structures.
RESONANCE EFFECT
 It is defined as the polarity produced in the molecule by the interaction of the
two  bonds or between  bond and lone pair of electrons present on an

adjacent atom.
POSITIVE RESONANCE EFFECT (+R EFFECT)
 In this effect, the transfer of electrons is away from an atom or substituent
group attached to the conjugated system.
GROUPS HAVING +R EFFECT

 -X, -OH, -OR, -OCOR, -NH , -NHR, -NR 2 , -NHCOR
2
NEGATICE RESONANCE EFFFECT (-R EFFECT)

 In this effect, the transfer of electrons is towards the atom or substituent
group attached to the conjugated system.
GROUPS HAVING –R EFFECT

 -COOH, -CHO, =C==O, -CN, -NO2
ELECTROMERIC EFFECT
 The temporary effect which involves the complete transfer of a  electron pair
to one or other atoms joined by a multiple bond, under the influence of an
attacking reagent is called electromeric effect.
 A   B
Attacking reagent
A =B 
a) POSITIVE ELECTROMERIC EFFECT
 In this effect, the  electrons of the multiple bonds are transferred to the atom
to which the reagent gets attached.
b) NEGATIVE ELECTROMERIC EFFECT
 In this effect, the  electrons of the multiple bonds are transferred to that
atom to which the attacking reagent does not get attached.
HYPERCONJUGATION
 When a CH bond is attached to an unsaturated carbon atom,  electrons of
the CH bond enters into partial conjugation with the unsaturated system.
 The conjugation of electrons in a sigma bond with  electron system is known

as hyperconjugation.
 Hyperconjugation is also known as No Bond Resonance.
QUESTION
+ + +
1. Explain why (CH3 )3 C is more stable than CH3 C H2 and C H3 is least stable
cation.
+ +
 Hyperconjugation interaction in (CH3 )3 C is greater than in CH3 C H2 .
+
 The (CH3 )3 C has nine C-H bonds.
+
 In C H3 vacant p orbital is perpendicular to the plane in which C-H bonds lie.
 Hence cannot overlap with it.
+
 Thus, C H3 lacks hyperconjugative stability.
TYPES OF ORGANIC REACTIONS
1. SUBSTITUTION REACTIONS
 Reactions in which, an atom or a group of atoms is substituted by another
atom or a group of atoms to form a new substance.
2. ADDITION REACTIONS
 Reactions in which an atom or a group of atoms is added across CC multiple
bond.
3. ELIMINATION REACTIONS
 Reactions in which an atom or a group of atoms is eliminated from adjacent
carbon atoms.
 As a result of elimination, multiple bonds are formed.
4. REARRANGEMENT REACTIONS
 Reactions in which the carbon skeleton of a molecule is rearranged to give a
structural isomer of the original molecule.
 A substituent move from one atom to another atom in the same molecule.
METHODS OF PURIFICATION OF ORGANIC COMPOUNDS
1. FILTRATION
 This method is used for the separation of an insoluble solid component of the
mixture from the soluble component in a given solvent.
 Eg: A mixture of naphthalene and urea.
2. CRYSTALLISATION
 This method is used when the organic solid to be purified is highly soluble in a
solvent and the impurities are almost insoluble.
 Eg: A mixture of benzoic acid and naphthalene.
3. SUBLIMATION
 It is the process of conversion of a solid substance directly to vapour without
passing through the liquid state, by heating.
 It is used to separate sublimable compounds from non-sublimable impurities.
 Eg: Naphthalene, Camphor, Iodine etc.
4. DISTILLATION
 It is the process of conversion of a liquid into vapour, followed by the
condensation of the vapour.
 This method is applied for the purification of
 volatile liquids from non-volatile impurities.
 liquids having sufficient difference in their boiling points.
 The principle of this method is that liquids having different boiling points
vaporise at different temperatures.
 The vapours are cooled and the liquids so formed are collected separately.
Eg: 1) Ether and Toluene 2) Chloroform and Aniline
5. FRACTIONAL DISTILALTION
 This method is used
 to separate two or more liquids that are miscible.
 when two or more liquids have close boiling points.

 Eg: 1. Acetone and methyl alcohol
 Eg: 2. Separation of different fractions of crude oil.
6. DISTILLATION UNDER REDUCED PRESSURE
 This method is used to
 purify liquids having very high boiling points
 purify liquids which decompose at or below their boiling points.
 Such liquids are made to boil at a temperature lower than their normal boiling
points by reducing the pressure on their surface.
 Eg: Glycerol and Hydrogen Peroxide.
 Glycerol can be separated from spent-lye in soap industry.
7. STEAM DISTILLATION
 This method is used to
 To distill a liquid at a temperature much below its boiling point.
 separate organic compounds, which are steam volatile in steam and are
immiscible with water.
 Eg: 1. Aniline and Water 2. O-nitrophenol and p-nitrophenol
8. DIFFERENTIAL EXTRACTION OR SOLVENT EXTRACTION
 It is the process of separation of an organic compound from its aqueous
solution by shaking it with a suitable solvent such as ether, chloroform and
benzene.
 The solvent should be immiscible with water.
 So, they form two distinct layers which can be separated by separating funnel.
 The organic compound to be separated should be highly soluble in it.
 The organic solvent is later removed by distillation or by evaporation to get
back the compound.
9. CHROMATOGRAPHY
 Chromatography is a laboratory technique used for the separation of mixtures
into their components.
 The term chromatography is derived from the Greek word ‘chroma’ means
‘writing in colour’.
 The mixture to be separated is passed through a stationary phase, which may
be a solid or a liquid.
 A pure solvent or a mixture of solvents or a gas is allowed to move slowly over
the stationary phase.
 The moving phase is called the mobile phase.
 The components of the mixture get gradually separated from one another.
CLASSIFICATION OF CHROMATOGRAPHY
 Based on the principle involved, there are mainly 2 types of chromatography.
 Adsorption Chromatography
 Partition Chromatography
1. ADSORPTION CHROMATOGRAPHY
 It is based on the fact that different compounds are adsorbed on an
adsorbent in different degrees.
 Commonly used adsorbents are silica gel and alumina.
 Here a mobile phase is allowed to move over a stationary phase (adsorbent).
 Based on the adsorbing power, the components of the mixture are adsorbed at
different places over the stationary phase.
TYPES OF ADSORPTION CHROMATOGRAPHY
A. COLUMN CHROMATOGRAPHY
 It involves the separation of a mixture over a column of adsorbent (stationary
phase) packed in a glass tube.
 The column is fitted with a stopcock at its lower end.
 The mixture to be separated is passed through the column.
 Based on the adsorbing power, the components are adsorbed at different
places over the column.
 The most readily adsorbed substances are retained near the top and others
come down to various distances in the column.
 Then an appropriate eluant (solvent) is allowed to flow down the column
slowly.
 Different solvents are used to separate different components.
 So, the components can be collected separately and they can be separated.
B. THIN LAYER CHROMATOGRAPHY
 TLC involves the separation of substances of a mixture over a thin layer of an
adsorbent coated on a glass plate.
 A thin layer of an adsorbent (silica gel or alumina) is spread over a glass plate
of suitable size.
 The plate is known as thin layer chromatography plate or chromaplate.
 The solution of the mixture to be separated is applied as a small spot about 2
cm above one end of the TLC plate.
 The glass plate is then placed in a closed jar containing the eluant.
 As the eluant rises up the plate, the components of the mixture move up along
with the eluant to different distances depending on their degree of adsorption
and separation takes place.
 The relative adsorption of each component of the mixture is expressed in
terms of its retardation factor (Rf value).
Distance moved by the substance from the base line (x)

R =
f Distance moved by the solvent from the base line(y)
2. PARTITION CHROMATOGRAPHY
 It is based on continuous differential partitioning of components of a mixture
between stationary and mobile phases.
 Paper chromatography is a type of partition chromatography.
PAPER CHROMATOGRAPHY
 In paper chromatography, a special quality paper known as
chromatography paper is used.
 Chromatography paper contains water trapped in it, which acts as the
stationary phase.
 A strip of chromatography paper, spotted at the base with the solution of
the mixture, is suspended in a suitable solvent or a mixture of solvents.
 This solvent acts as the mobile phase.
 The solvent rises up the paper by capillary action and flows over the spot.
 The paper selectively retains different components according to their
differing partition in the two phases.
 The paper strip is known as a chromatogram.
 The spots of the separated coloured compounds are visible at different
heights from the position of initial spot on the chromatogram.
 These spots can be visible by UV light or by spraying suitable reagents.
QUATITATIVE ANALYSIS
 The qualitative analysis of an organic compound involves the detection of
elements.
 The elements commonly present in organic compounds are Carbon, Hydrogen,
Oxygen, Nitrogen, Halogens, Sulphur and Phosphorous.
1. DETECTION OF CARBON AND HYDROGEN
 The Organic compound is heated with excess of copper (II) oxide [CuO].
 Carbon present in the compound is oxidised to carbon dioxide.
 Hydrogen present in the organic compound is oxidised to water.
 CO2 turns lime water milky.

 Water turns anhydrous copper sulphate blue.
C + 2CuO 
 2Cu + CO2
Ca(OH)2 + CO2 
 CaCO3 + H2O
2H + CuO 
 Cu + H2O
CuSO4 + 5H2O 
 CuSO4.5H2O
2. DETECTION OF NITROGEN, SULPHUR AND HALOGENS

LASSAIGNE’S TEST
PREPARATION OF SODIUM FUSION EXTRACT
 A small quantity of the organic substance is fused with metallic sodium in an
ignition tube.
 When it becomes red hot, it is plunged into distilled water taken in a China
dish,
 The contents are boiled, cooled and filtered.
 The filtrate is known as Lassaigne’s Extract or Sodium Fusion Extract.
A. DETECTION OF NITROGEN
 A small quantity of the extract is boiled with ferrous sulphate solution and
acidified with dilute H2SO4.
 A Prussian blue precipitate of Ferric ferrocyanide confirms the presence of

nitrogen.
Na + C + N 
 NaCN
6NaCN + FeSO 
 Na [Fe(CN) ] + Na SO
4 4 6 2 4
3Na [Fe(CN) ] + 2Fe (SO ) 
 Fe [Fe(CN) ] + 6Na SO
4 6 2 4 3 4 63 2 4
B. DETECTION OF SULPHUR
 A little of the sodium fusion extract is acidified with acetic acid and then lead
acetate is added.
 A black precipitate of lead sulphate indicates the presence of Sulphur.
Na S + (CH COO) Pb 
 PbS + 2CH COONa
2 3 2 3
2Na + S 
 Na2S
C. SODIUM NITROPRUSSIDE TEST

 A little of the sodium fusion extract is treated with sodium nitroprusside
solution.
 A deep violet colour confirms the presence of Sulphur.
Na S + Na [Fe(CN) NO] 
 Na [Fe(CN) NOS]
2 2 5 4 5
3. DETECTION OF HALOGENS
 A little of the sodium fusion extract is boiled with dilute Nitric acid to
decompose NaCN, Na2S etc.
 The solution is cooled and AgNO3 solution is added.
 A white curdy precipitate soluble in NH4OH indicates the presence of Chlorine.
 A pale yellow precipitate partially soluble in NH4OH indicates the presence of
Bromine.
 An yellow precipitate insoluble in NH4OH indicates the presence of Iodine.
A g NO + NaCl 
 AgCl + NaNO
3 3
AgNO3 + NaBr 
 AgBr + NaNO3
AgNO3 + NaI 
 AgI + NaNO3
4. DETECTION OF PHOSPHOROUS
 The organic compound is heated with an oxidising agent like sodium peroxide.
 The phosphorus present in the compound is oxidised to phosphate.
 The solution is boiled with Conc. Nitric acid and then treated with ammonium
molybdate.
 An yellow precipitate indicates the presence of phosphorus.
Na3PO4 + 3HNO3 
 H3PO4 + 3NaNO3
H PO4 + 12(NH4 )2 MoO4 + 21HNO3 
 (NH4 )3 PO4.12MoO3 + 21NH4NO3 + 12H2O
3
QUANTITATIVE ANALYSIS
The percentage composition of elements present in an organic compound is
determined by the following methods:
1. ESTIMATION OF CARBON AND HYDROGEN
 A known mass of an organic compound is burnt in the presence of excess of
oxygen and copper (II) oxide.
 Carbon is oxidised to carbon dioxide.
 Hydrogen is oxidised to water respectively.
 x+y  y
CxHy +   O2 
 xCO + H O
 4  2 2 2
 The mass of water produced is determined by passing the mixture through a

weighed U-tube containing anhydrous calcium chloride.
 Carbon dioxide is absorbed in another U-tube containing concentrated
solution of potassium hydroxide.

 These tubes are connected in series.
 The increase in masses of calcium chloride and potassium hydroxide gives the
amounts of water and carbon dioxide.
 From these, the percentage of carbon and hydrogen are calculated.
12 x m2 x 100
Percentage of Carbon in the compound =
44 x m
2 x m1 x 100
Percentage of Hydrogen in the compound =
18 x m
Where ‘m’ is the mass of the organic compound.
Where ‘m1’ is the mass of H2O produced.
Where ‘m2’ is the mass of CO2 produced.
2. ESTIMATION OF NITROGEN
A. DUMAS METHOD
 A known mass of the organic compound is heated with cupric oxide in an
atmosphere of carbon dioxide.
 The carbon and hydrogen are oxidized to CO2 and H2O respectively.
 Nitrogen is set free.

 If any oxide of nitrogen is formed, it is reduced to nitrogen by passing over red
hot copper.
 The gaseous mixture is collected over KOH solution.
 All the gases except nitrogen are absorbed.
 The volume of nitrogen collected is measured.
 This volume is reduced to volume at STP.
 The percentage of nitrogen is calculated.
28 x V0 x 100
Percentage of Nitrogen in the compound =
22400 x m
‘V0’ is the volume of N2 at STP.
B. KJELDAHL’S METHOD
 A known mass of the organic compound is heated with Conc. Sulphuric acid.
 The nitrogen present in the organic compound is converted to ammonium
sulphate.
 The solution is heated with excess of NaOH.
 The liberated NH3 is absorbed in a known mass of a standard solution of an
acid.
 The amount of acid neutralized is determined by titrating the solution against a
standard alkalie solution.
 This corresponds to the amount of ammonia produced.
 From this, the percentage of Nitrogen can be calculated.
14 x V1 x N1 x100
Percentage of Nitrogen in the compound =
1000 x m
‘V1’ is the volume of the acid.
‘N1’ is the normality of the acid.
3. ESTIMATION OF HALOGENS [CARIUS METHOD]

 A known mass of an organic compound is heated with fuming nitric acid in the
presence of silver nitrate in a Carius tube in a furnace.
 Carbon and hydrogen present in the compound are oxidised to carbon dioxide
and water.
 The halogen present in the compound is converted to sillver halide (AgX).
 It is filtered, washed, dried and weighed.
Atomic mass of X x m1 x 100
Percentage of halogen =
Molecular Mass of AgX x m
‘m1’ is the mass of AgX formed.
4. ESTIMATION OF SULPHUR [CARIUS METHOD]

 A known mass of an organic compound is heated in a Carius tube with sodium
peroxide or fuming nitric acid.
 Sulphur present in the compound is oxidised to sulphuric acid.
 It is precipitated as barium sulphate by adding excess of barium chloride
solution in water.
 The precipitate is filtered, washed, dried and weighed.
 The percentage of sulphur can be calculated from the mass of barium sulphate.
32 x m1 x 100
Percentage of Sulphur =
233 x m
Where ‘m’ is the mass of the organic compound
‘m1’ is the mass of barium sulphate formed
5. ESTIMATION OF PHOSPHOROUS
 A known mass of an organic compound is heated with fuming nitric acid.

 Phosphorus present in the compound is oxidised to phosphoric acid.
 It is precipitated as ammonium phosphomolybdate, (NH 4)3PO4.12MoO3, by
adding ammonia and ammonium molybdate.

31 x m1 x 100
Percentage of Phosphorous =
1877 x m
Where ‘m’ is the mass of the organic compound
‘m1’ is the mass of ammonium phosphomolybdate formed
If Phosphorous is estimated as Mg2P2O7,

62 x m1 x 100
Percentage of Phosphorous =
222 x m
‘m1’ is the mass of Mg2P2O7 formed.

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 Organic chemistry is defined as the chemistry of carbon compounds.

 Urea is prepared by heating ammonium cyanate (NH 4CNO).

2. What is the type of hybridization of each carbon in the following compounds?

a) CH3Cl (b) (CH3)2CO (c) CH3CN (d) HCONH2 (e) CH3CH=CHCN

3. Write the state of hybridization of carbon in the following compounds and

(a) H2C=O (b) CH3F (c) HCN

(a) SP2 hybridised carbon, trigonal planar

(b) SP3 hybridised carbon, tetrahedral

(c) SP hybridised carbon, linear

STRUCTURAL REPRESENTATIONS OF ORGANIC COMPOUNDS

2. CONDENSED STRUCTURAL FORMULA

3. BOND LINE STRUCTURAL FORMULA

a) 3-methyl octane b) 2-bromo butane c) Chlorocyclo hexane

Bond line formula

THREE DIMENSIONAL REPRESENTATION OF ORGANIC MOLECULES

2. CLOSED CHAIN OR CYCLIC OR RING COMPOUNDS

CLASSIFICATION OF HOMOCYCLIC COMPOUNDS

NON BENZENOID AROMATIC COMPOUNDS

HETEROCYCLIC AROMATIC COMPOUNDS

Ethane C2H6 Octane C8H18

Propane C3H8 Nonane C9H20

Butane C4H10 Decane C10H22

Pentane C4H12 Icosane C20H42

Hexane C6H14 Triacontane C30H62

BRANCHED CHAIN HYDROCARBONS

CH4 Methane -CH3 Methyl

C2H6 Ethane CH2  CH3 Ethyl

C3H8 Propane CH2  CH2  CH3 Proplyl

C4H10 Butane CH2  (CH2 )2  CH3 Butyl

C4H12 Pentane CH2  (CH2 )3  CH3 Pentyl

C6H14 Hexane CH2  (CH2 )4  CH3 Hexyl

C7H16 Heptane CH2  (CH2 )5  CH3 Heptyl

C8H18 Octane CH2  (CH2 )6  CH3 Octyl

C9H20 Nonane CH2  (CH2 )7  CH3 Nonyl

C10H22 Decane CH2  (CH2 )8  CH3 Decyl

 Abbreviations are used for some alkyl groups.

RULES FOR THE NOMENCLATURE OF BRANCHED CHAIN ALKANES

c) 3-Ethyl-4,4-Dimethyl heptane d) 3-Ethyl-6-methyl octane

2. Write the IUPAC names of the following organic compounds.

 COOH, SO3H, COOR, COCl, CONH2, CN, CHO, =C=O, OH,

NH2, =C=C=, CC

Hexane-2,4-dione 5-oxohexanoic acid

2. Derive the structure of the following compounds

NOMENCLATURE OF SUBSTITUTED BENZENE COMPOUNDS

 If the benzene ring is di-substituted, the position of the substituents is defined

 Isomerism can be classified into two types.

C. FUNCTIONAL GROUP ISOMERISM

Ethoxy Ethane Methoxy Propane

 The phenomenon is called stereoisomerism.

ORGANIC REACTION MECHANISM

 Each fragment formed as a result of homolysis carries one unpaired electron

 Eg: Methyl Carbocation H3C+

 They are classified as 10, 20 or 30 depending on whether one, two or three

charged carbon bearing sp2 hybridised.

TYPES OF ATTACKING SPECIES

 Electrophiles are neutral of +vely charged species.

Nucleophiles: HS, C2H5O, (CH3)3N, H2N

Electrophiles: BF3, Cl+, CH3-C=O+, NO2+