MINIMUM LEARNING MATERIAL(MLM)

THE SOLID STATE

TERMS EXPLANATIONS
Amorphous and Crystalline Amorphous- short range order, Irregular shape eg-
Solids glass
Crystalline Solids- long range order, regular shape
eg : NaCl
Molecular solids Ar, CCl4, H2O (ice)Constituent particles are molecules
Covalent or Network solid SiO2 diamond Constituent particles are held
together by co-valent bonds.
No of lattice points per Simple cubic -8, BCC- 9, FCC – 14 , End-Centred- 10
unit cell
No of atoms per unit cell Simple cubic -1, BCC- 2, FCC – 4 , End-Centred- 2
(z )
Coordination Number FCC- 6:6 BCC- 8:8
Calculation of number of Let the number of close packed spheres be N, then:
voids The number of octahedral voids generated = N
The number of tetrahedral voids generated = 2N
Relation between r and a Simple Cubic 4r=2a , FCC 4r =√2 a BCC 4r
=√3 a
Packing Efficiency Simple Cubic52.4% , BCC 68% ,
FCC 74%
Calculations Involving Unit
Cell
M=molar mass (g/mol) a = edge
Dimensions
length in cm ,
NA = 6.023× 1023
Frenkel Defect: Cation is dislocated to an interstitial site. It does not
change the density of the solid. Frenkel defect is
shown by ionic substance in which there is a large
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 difference in the size of ions, for example, ZnS, AgCl,
AgBr and AgI due to small size of Zn2+ and Ag+ ions.
Schottky Defect A vacancy defect. The number of missing cations and
anions are equal. Schotky defect is shown by ionic
substance in which there is a small difference in the
size of ions.Density decreases. For example, NaCl,
KCl, CsCl and AgBr.
Metal excess defect due When NaCl heated in an atmosphere of Na vapour,
to anionic vacancies (F- the Na atoms deposited on the surface of the
centres ) crystal. The Cl– ions diffuse to the surface of the
crystal and combine with Na atoms to give NaCl. The
released electrons diffuse into the crystal and occupy
anionic sites The anionic sites occupied by unpaired
electrons are called F-centres They impart yellow
colour to the crystals of NaCl. Similarly, excess of
lithium makes LiCl crystals pink and excess of
potassium
makes KCl crystals violet (or lilac).
Doping The conductivity of intrinsic semiconductors is
increased by adding an appropriate amount of suitable
impurity. This process is called doping
n / p -type n- type : Si + As or Sb or Bi p-type: Si + B or
semiconductors Ga or In or Tl
13 –15 compounds &12–16 13 – 15 compounds: InSb, AlP and GaAs.
compounds 12 – 16 compounds :ZnS, CdS, CdSe and HgTe
Paramagnetic substances Weakly attracted by a magnetic field. Examples:
O2, Cu2+, Fe3+, Cr3+
Diamagnetic substances Weakly repelled by a magnetic field. Example: H2O,
NaCl and C6H6
Ferromagnetism: A few substances like iron, cobalt, nickel, gadolinium
and CrO2 are attracted very strongly by a magnetic
field.
Antiferromagnetism MnO. Domains oppositely oriented and cancel out
magnetic moment

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Ferrimagnetism: Domains aligned in parallel and anti-parallel directions
in unequal numbers. Example: Fe3O4 (magnetite)

SOLUTIONS

Gas in solid  Solution of hydrogen in palladium

Solid Solutions
Liquid in solid  Amalgam of mercury with sodium
Mass %, ppm, mole fraction and molality are independent of
Temp. Vs Conc. temperature, whereas molarity depends on temperature.
This is because volume depends on temperature.
At a constant temperature, the solubility of a gas in a liquid
is directly proportional to the pressure of the gas. p = KH .
Henry’s law. x
KH = Henry’s law constant ( greater the KH value
means lower the solubility.)
1.To increase the solubility of CO2 in soft drinks, the bottle
Application of is sealed under high pressure.
Henry’s law. 2. To avoid bends, the tanks used by scuba divers are filled
with air diluted with helium
Solubility of gas increases with decrease of temperature. It
Temp and Solubilty
is due to this reason that aquatic species are more
of gas
comfortable in cold waters rather than in warm waters.
The partial vapour pressure of each component in the
Raoult’s law for solution
volatile liquids is directly proportional to its mole fraction p1 α x1
p1 = p10 x 1
The solutions which obey Raoult’s law over the entire range
of concentration are known as ideal solutions. ( For ideal
Ideal Solutions
solution ΔmixH = 0, ΔmixV = 0)
Example : Solution of n-hexane and n-heptane,
Positive deviation : A-B interactions are weaker than
those between A-A or B-B,
Non-ideal Solutions
Example - Mixtures of ethanol and
acetone

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 Negative deviations : Forces between A-A and B-B are
weaker than those between A-B
Example- mixture of phenol + aniline. a
mixture of chloroform +acetone
Mixtures have same composition in liquid and vapour phase
and boil at a constant temp.
minimum boiling azeotrope(positive deviation) eg- 95% aq
Azeotropes
ethanol
maximum boiling azeotrope(negative deviation) eg- 68% aq
nitric acid
Colligative Depend on the number of solute particles not upon their
properties nature.
= XB
P0A = vapour pressure of solvent.
Relative Lowering
PA = vapour pressure of solution. = lowering of
of
vapour pressure
Vapour Pressure
XB = mole
fraction of solute.

ΔTb =Kb ΔTb = elevation in boiling point,

Elevation of Boiling
Kb = molal elevation constant
Point MB = molecular weight of solute, WB = weight of solute
WA = weight of solvent

ΔTf =Kf ΔTf = depression in freezing point,

Depression of Kf = molal depression constant
Freezing Point MB = molecular weight of solute, WB = weight of solute
WA = weight of solvent
Solvent flows through the semi permeable membrane from
Osmosis
pure solvent to the solution.
The extra pressure applied on the solution that just stops
Osmotic pressure
the flow of solvent is called osmotic pressure of the solution
Osmotic RT

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 pressure(π) R = gas constant
T = Temperature in Kelvin RT , RT where C is
concentration of solution.
Isotonic solutions Two solutions having same osmotic pressure
Hypertonic Higher osmotic pressure than a particular soln
Hypotonic Lower osmotic pressure than a particular soln
The direction of osmosis can be reversed if a pressure
larger than the osmotic pressure is applied to the solution
Reverse Osmosis
side. That is, now the pure solvent flows out of the solution
Application : Desalination of sea water
ratio of normal molar mass to experimentally determined
van’t Hoff factor ( molar mass or as the ratio of observed colligative property
i) to the calculated colligative property.
i= . i=
NaCl, KCl = 2 ; BaCl2 CaCl2 = 3 ; Na3PO4 = 4 ; Al2(SO4)3 ,
Value of van’t Hoff
K4[Fe(CN)6] = 5
factor(i)
CH3COOH ( in benzene) = ½

ELECTROCHEMISTRY

:Zn(s) | Zn2+ (aq) || Cu2+(aq)| Cu(s) ; LOAN : Left /

Cell Notation
Oxidation /Anode / Negative
EMn+/M = Eo Mn+ /M – log
Zn(s) | Zn2+ (aq) || Cu2+(aq)| Cu(s)
Nernst Eqn
Zn + Cu2+ → Zn2+ + Cu
Ecell = Eo cell – log
Store CuSO4 in No. because the following reaction takes place Zn(s) +
Zn pot? CuSO4(aq) → ZnSO4 (aq) + Cu(s) ;
F2(g) + 2e– → 2F– ; E0 = 2.87 F2(g) is the strongest
oxidizing element
Electrochemical
Li+ + e– → Li(s) ; E0 = –3.05 Li is the strongest
Series
reducing element
→

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 Relation ΔrG = – nFE(cell)
between ΔrG_ = –nFEo (cell)
E0 / Kc & ΔG ΔrG_ = –2.303RT log K.
R=ρ R = Resistance, ρ = resistivity l = length a = area
of cross section.

G= = =κ G = conductance
κ = conductivity
Units:- ρ(resistivity) = ohm metre (Ω
*
R, G, κ, G (Ω
1 Ωm = 100 Ω Ωcm = 0.01 Ω
G* = = R K G*= cell constant

K= =

Molar conductivity = Λm =

Molar
Conductivity
(Λm)

Limiting molar conductivity of an electrolyte can be

represented as the sum of the individual contributions of the
Kohlrausch
anion and cation of the electrolyte.
law

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 α & Ka
Where α is degree of dissociation.
The amount of chemical reaction which occurs at any electrode
Faraday’s 1st during electrolysis is proportional to the quantity of electricity
Laws passed through the electrolyte (solution or melt).

The amounts of different substances liberated by the same

quantity of electricity passing through the electrolytic solution
Faraday’s 2nd
are proportional to their chemical equivalent weights (Atomic
Laws
Mass of Metal ÷ Number of electrons required to reduce the
cation).
Electrolysis of
Cathode : Na+(l) + e– → Na(s) Anode : Cl–→
NaCl (molten)
½Cl2+e–
Cathode : H2O (l ) + e– → ½H2(g) + OH–
NaCl (aq)
Anode : Cl–→ ½Cl2+e–
Cathode : H+ + e-  ½ H2 Anode: 2H2O(l )→
H2SO4(dil)
O2(g) + 4H+(aq) + 4e–
Cathode : H+ + e-  ½ H2 Anode: 2SO4 2–
H2SO4(conc)
(aq) → S2O8 2– (aq) + 2e–
AgNO3(aq)-Ag Cathode : Ag+(aq) + e-  Ag(s) Anode: Ag(s) 
+ -
electrodes Ag (aq) + e
AgNO3(aq)- Pt Cathode : Ag+(aq) + e-  Ag(s) Anode: 2H2O(l
+ –
electrodes )→ O2(g) + 4H (aq) + 4e
CuCl(aq)- Pt Cathode : Cu+(aq) + e-  Cu(s) Anode: 2H2O(l )→
+ –
electrodes O2(g) + 4H (aq) + 4e
Pri & Sec In the primary batteries, the reaction occurs only once, and
Batteries cannot be reused again
Anode(Zn) : Zn(s) → Zn2+ + 2e–
Dry Cell Cathode(Graphite) : MnO2 + NH + + e– → MnO(OH) + NH
4 3
The emf = 1.5 V.
Anode(Zn-Hg) : Zn(Hg) + 2OH– → ZnO(s) + H2O +
Mercury Cell
2e– Cathode(HgO-C) : HgO + H2O + 2e– → Hg(l ) + 2OH–

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 EMF= 1.35 V and remains constant during its life as the overall
reaction does not involve any ion in solution whose
concentration can change during its life time.
Anode : Pb Cathode : Pb packed with PbO2
Electrolyte : 38% H2SO4
Lead Storage Anode: Pb(s) + SO4 2–(aq) → PbSO4(s) + 2e–
Battery Cathode: PbO2(s) + SO4 2–(aq) + 4H+(aq) + 2e– → PbSO4 (s) +
2H2O (l )
On charging the battery the reaction is reversed
Anode&Cathode : Porous C Electrolyte : Aq NaOH
Cathode: O2(g) + 2H2O(l ) + 4e  4OH–(aq)
–

Anode: 2H2 (g) + 4OH–(aq)  4H2O(l) + 4e–

The cell runs continuously as long as the reactants are supplied.
Fuel Cells
Efficiency of about 70 %. Pollution free. The water vapours
produced during the reaction were condensed and added to the
drinking water supply for the astronauts (Apollo space
programme)
Oxidation: Fe (s)→ Fe2+ (aq) +2e–
Corrosion of
Reduction: O2 (g) + 4H+(aq) +4e– → 2H2O(l)
Iron
Atomospheric oxidation : 2Fe2+(aq) + 2H2O(l) + ½O2(g) →
(Rusting)
Fe2O3(s) + 4H+(aq)
By covering the surface with paint or by some chemicals (e.g.
bisphenol). / Cover the surface by other metals (Sn, Zn, etc.)
Prevention of
that are inert or react to save the object. An electrochemical
Corrosion
method (sacrificial electrode like Mg, Zn, etc.) which corrodes
itself but saves the object.

CHEMICAL KINETICS

Rate of a Chemical Change in concentration of a reactant or product in unit

Reaction time. Unit => mol L-1s–1
For RP

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 Average &
Instantaneous Rate

Rate of reaction =
For 2HI(g) →
H2(g) + I2(g)
Rate law is the expression in which reaction rate is given in
Rate law / Rate terms of molar concentration of reactants with each term
equation / raised to some power, which may
Rate expression or may not be same as the stoichiometric coefficient of
the reacting species in a balanced chemical equation.
The rate expression for this reaction is :
For aA + bB → cC +
Rate α [A]x [B]y => Rate = k [A]x [B]y k is the Rate
Dd
const. (x , y from expts)
The sum of powers of the concentration of the reactants in
the rate law expression is called the order of that chemical
Order of a Reaction reaction.
If Rate = k [A]x [B]y
Order = x + y
Elementary The reactions taking place in one step are called
reactions Elementary Reactions
For n th order reaction : mol1-n Ln-1 s-1

Unit of rate
constant

The number of reacting species taking part in an

Molecularity of a
elementary reaction, which must collide simultaneously in
Reaction
order to bring about a chemical reaction is called

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 molecularity of a reaction (values are limited from 1 to 3)
Rate Determining The overall rate of the reaction is controlled by the
Step slowest step in a reaction called the rate determining step
The half-life of a reaction is the time in which the
concentration of a reactant is reduced to one half of its
initial concentration. It is represented as t1/2.

Half-life (t1/2)

Zero Order
Reactions
(Integrated Rate
Equation)
First Order
Reactions
(Integrated Rate
Equation)
Dependence of t1/2 For zero order : t1/2 α [R]0. For first order reaction t1/2 is
on [R]0 independent of [R]0
Example of Zero The decomposition of gaseous ammonia on a hot platinum
Order surface is a zero order reaction at high pressure. Rate =
Reactions k [NH3]0 = k
All natural and artificial radioactive decay of unstable
Radioactive decay
nuclei take place by first order kinetics
When one of two reactants is present in large excess.
During the hydrolysis of 0.01 mol of ethyl acetate with
Pseudo First Order 10 mol of water The concentration of water does not get
Reaction altered much during the course of the reaction and the
reaction behaves as first order reaction. Such reactions
are called pseudo first order reactions.
Activation Energy Activation energy is given by the energy difference

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 between activated complex and the reactant molecules
k = A e -Ea /RT (exponential form)
ln k = – Ea/RT + ln A (logarithmic form)
Arrhenius equation
A is the Arrhenius factor or the frequency factor or pre-
exponential factor
-Ea /RT The factor e -Ea /RT corresponds to the fraction of
e
molecules that have kinetic energy greater than Ea
If k1 and k2 are rate
constants at T1 and
T2
Catalyst provides an alternate pathway or reaction
mechanism
Action of catalyst
by reducing the activation energy between reactants and
products and hence lowering the potential energy barrier
The number of collisions per second per unit volume of the
reaction mixture.
Collision frequency
For A + B → Products Rate = P.ZAB e−Ea/ RT P is
(Z)
probability or steric factor ZAB is collision frequency of
reactants, A and B

SURFACE CHEMISTRY

Adsorption Accumulation of molecular species at the

surface rather than in the bulk of a solid or
liquid.
Adsorbate & Adsorbent. The substance adsorbed is called adsorbate.
And the surface provider is called adsorbent.
Desorption. The process of removing an adsorbed
substance from a surface.
Adsorption and Absorption In adsorption, the substance is concentrated
only at the surface while in absorption, the
substance is uniformly distributed throughout
the bulk of the solid.
Sorption Both adsorption and absorption can take place
 simultaneously.
Enthalpy of adsorption Adsorption is exothermic ΔH is -ve. There is
decrease in entropy, ΔS is -ve. For a process
to be spontaneous, ΔG must be negative, so
ΔH should have sufficiently high-ve value.
Surface area & Adsorption Adsorption increases with the increase of
surface area of the adsorbent. Thus, finely
divided metals and porous substances having
large surface areas are good adsorbents.
Physisorption van der Waals’ forces / not specific
/reversible /easily liquefiable gases adsorbed
readily./ Enthalpy of adsorption is low/ Low
temperature is favourable / Multimolecular
layers.
Chemisorption chemical bond /highly specific /
irreversible/Enthalpy of adsorption high / High
temperature is favourable / / unimolecular
layer.
Adsorption Isotherm Variation of amount of gas adsorbed by the
adsorbent with pressure at constant
temperature can be expressed by means of a
curve termed as adsorption isotherm.
Freundlich isotherm X / m = k.P1/n (n > 1) log x/m = log k + 1/n
log P
Applications of Adsorption High vacuum/masks/Control of humidity/
Removal of colour/ catalysis/ curing diseases/
Homogeneous catalysis Reactants and the catalyst are in the same
phase.
Heterogeneous catalysis Reactants and the catalyst are in different
phases.
Activity of a solid catalyst Depends upon strength of chemisorption
.Reactants must get adsorbed reasonably
strongly.
Selectivity of a catalyst The selectivity of a catalyst is its ability to
 direct a reaction to yield a particular product.
Shape- Selective Catalysis by Depends upon the pore structure of the
Zeolites catalyst and the size of the reactant and
product molecules. Example:- ZSM-5 (a
zeolite) converts alcohols directly into gasoline
(petrol).
Characteristics of enzyme Highly efficient/ Highly specific / active under
catalysis optimum temperature& pH/ Increasing activity
in presence of activators and co-enzymes/
Influence of inhibitors and poisons
Catalysts used in industrial Haber’s process (NH3) Finely divided Fe, Mo
process. - promoter; Ostwald’s process(HNO3) Pt
Contact process(H2SO4) Pt or vanadium
pentoxide (V2O5);
Colloids Diameters of the particles is between 1 and
1000 nm.
Lyophilic colloids Liquid-loving/ can be reconstituted/
reversible/easily prepared/stable/ eg- gum,
starch.
Lyophobic colloids Liquid-hating/ not be reconstituted/
irreversible/ prepared by special methods/
precipitated on addition of
electrolytes/heating/shaking/ not stable./ eg –
metal sols , sulphide sols.
Multimolecular colloids Large number of atoms or molecules of a
substance aggregate eg- gold sol , sulphur sol.
Macromolecular colloids Macromolecules in suitable solvents. Eg-starch,
cellulose, proteins and enzymes; polythene.
Associated colloids Substances at low conc behave as strong
(Micelles) electrolytes, but at high conc exhibit colloidal
behaviour due to the formation of
aggregates(micelles.) eg- soaps and detergents.
Kraft Temperature (Tk) Formation of micelles takes place only above a
particular temperature.
CMC Formation of micelles takes place only above a
particular conc.
Cleansing action of soaps Soap molecules form micelle around the oil
droplet in such a way that hydrophobic part of
the stearate ions is in the oil droplet and
hydrophilic part projects out of the grease
droplet like the bristles . Since the polar
groups can interact with water, the oil droplet
surrounded by stearate ions is now pulled in
water and removed from the dirty surface.
Electrical disintegration or This process involves dispersion as well as
Bredig’s Arc method condensation. Colloidal sols of metals such as
gold, silver, platinum, etc., can be prepared.
Peptization Process of converting a ppt into colloid by
shaking it with dispersion medium in the
presence of a small amount of electrolyte. The
electrolyte used for this purpose is called
peptizing agent.
Dialysis: Removal of dissolved substance from colloidal
by diffusion through a suitable membrane.
Tyndall effect Colloidal particles scatter light in all directions.
Scattering of light illuminates the path of
beam of the light.
Conditions for Tyndall effect (i) Diameter of particles is not much
smaller than wavelength of the light
used;
(ii) Refractive indices of the phase and
medium differ greatly in magnitude
Charge on colloidal particles +ve charged sols  Hydrated metallic
oxides,/methylene blue sol. /Haemoglobin
(blood)
-ve charged sols  Metals,/ sulphides/ eosin,
congo red / starch, gum, gelatin, clay,charcoal.
Origin of charge on colloidal Preferential adsorption of ions . The sol
particles particles acquire positive or negative charge by
preferential adsorption of +ve or –ve ions.
When two or more ions are present in the
dispersion medium, preferential adsorption of
the ion common to the colloidal particle usually
takes place. AgI/I–
Zeta potential Potential difference between the fixed layer
and the diffused layer.
Electrophoresis The movement of colloidal particles under an
electric potential is called electrophoresis.
Electroosmosis If electrophoresis is prevented , it is
observed that the dispersion medium begins to
move in an electric field.
Coagulation(ppt) The process of settling of colloidal particles is
called coagulation or precipitation of the sol.
Reason of Coagulation Electrophoresis/mix oppositely charged
sols/boiling/persistent dialysis/addition of
electrolytes.
Hardy-Schulze rule The greater the valence of the flocculating ion
added, the greater is its power to cause
precipitation.
For coagulation of a negative sol, : Al3+>Ba2+>Na+
For coagulation of a negative sol :[Fe(CN)6]4– >
PO4 3– > SO4 2– > Cl–
Coagulating value Min. conc of an electrolyte in millimoles/L
required to cause precipitation of a sol in 2
hours
Emulsions Liquid-liquid colloida (i) Oil dispersed in water
(O/W type) - milk and vanishing cream .
(ii) Water dispersed in oil (W/O type).- butter
and cream.
Demulsification Emulsions can be broken into constituent
liquids by heating, freezing, centrifuging, etc.
Artificial Rain By throwing electrified sand , spraying a sol of
 opposite charge to the clouds from aeroplane
Formation of Delta River water is a colloidal solution of clay. Sea
water contains a number of electrolytes. When
river water meets the sea water, the
electrolytes present in sea water coagulate the
colloidal solution of clay resulting in its
deposition.
Electrical precipitation of The smoke, before it comes out from the
smoke(Cottrellppter) chimney, is led through a chamber containing
plates having a charge opposite to that carried
by smoke particles. The particles on coming in
contact with these plates lose their charge and
get precipitated.

GENERAL PRINCIPLES AND PROCESS OF EXTRACTION OF ELEMENTS

The most abundant elements in the earth’s crust: Oxygen > Silicon > Aluminum >
Iron > Calcium
Mineral: It is the combined state in which a metal occurs naturally in the crust of
the earth.
Ore: The mineral from which a metal can be profitably and conveniently extracted
is called ore.i.e. All ores are minerals but all minerals are not ores.
Gangue / Matrix: Earthly or undesired materials present in mineral are called
gangue.
Metallurgy:
The entire scientific and technological process used for isolation of the metal
from its ores is known as metallurgy.
 Conversion

Concentrated Ore
Concentration Refining
Reduction

Metal oxide

Crude metal
to oxide

Pure metal
of ore

Powdered Ore
Crushing -Hydraulic washing -Reduction with ' C ' - Liquation
Ore

and -Magnetic separatio n -Calcination -Reduction with ' CO ' -Distillation

grinding -Froth Floatation -Roasting -Reduction with ' Al ' - Electrolysis
-Leaching -Electolitic Reduction - Zone refining
- Vapour phase refining
- Chromatographic method

Reactivity Series
Reactivity decreases
Li K Ca Na Mg Al Mn Zn Fe Ni Pb Cu Ag Hg Au
Highly reactive elements Moderately reactive elements Least reactive elements
Ore Ore Ore
Ele tro me tallurgy Pyrometall urgy Thermometa llurgy

Crude metal Crude metal Crude metal

Electrometallurgy Electrolytic reduction (Reducing agent is electron, which is powerful reducing agent )
Pyrometallurgy Thermal reduction (Heating in presence of sutable reducing agent )
Thermometallurgy Simply heating ( In absence of reducing agent )

Hydraulic washing:
This method is used when the ore particles are heavier than the gangue particles.
E.g. Oxide ores
Magnetic separation
This is based on difference in magnetic properties of the ore component.
Froth floatation method
It is based on the difference in the wetting qualities of the gangue and sulfide
ore particles with water and oil. Where as the ore particles are wetted by oil, the
gangue particles are wetted by water.
Collectors enhance non-wet ability of the mineral particles. e.g. Pine oil, fatty
acid, xanthates, etc.
Froth stabilizers stabilizes the forth e.g. Cresol, aniline, etc.
Depressants are reagents used to suppress or depress the formation of forth.
For example, ZnS and PbS can be separated from each other in the forth
floatation process by the addition of small amounts of NaCN which act as
depresent.
NaCn selectively
4 NaCN + ZnS Na2 [ Zn ( CN )4 ] + Na2S
Depressant Ore Soluble complex
prevents ZnS from
coming to the froth by forming soluble
complex.
 But allows PbS to come with the froth.

Leaching of alumina from Bauxite

This process is followed if ore is soluble in suitable solvent. Bauxite contains
SiO2, TiO2 and iron oxide
Al2O3 + 2 NaOH + 3 H2O 2 Na [ Al (OH )4]
Alumia as impurities. When
Sodium meta aluminate
n
bauxite ore is treated with Conc . NaOH, alumina dissolves as
sodium meta aluminate and silica as sodium silicate leaving behind the impurities
i.e. Iron oxide.

SiO2 + 2 NaOH Na2SiO3 + H 2O

Silica Sodium silicate

The solution is filtred and neutralised by passing CO2 gas, when hydrated alumina gets precipitated
leaving sodium silicate in the solution. 2 Na [Al (OH) 4 ] + CO2 Al2O3.xH2O + 2 NaHCO3
Hydrated alumina
Hydrated alumina on heating give pure alumina.
Al2O3.xH2O Al2O3 + x H2O
Leaching of Ag and Au from their ore.
Silver and gold ores are treated with dilute solution of NaCN or KCN in presence of air to form soluble complex.
4 Au + 8 NaCN + 2 H2O + O2 4 Na [ Au (CN)2 ] + 4 NaOH
4 Ag + 8 NaCN + 2 H2O + O2 4 Na [ Ag (CN)2 ] + 4 NaOH
After filtration the solution treated with znic, which displace Ag and Au as precipitate.

2 Na [ Au (CN)2 ] + Zn Na 2[ Zn (CN)4 ] + 2 Au
2 Na [ Ag (CN)2 ] + Zn Na 2[ Zn (CN)4 ] + 2 Ag
( soluble complex ) ( Precipitate )

Calcination Roasting
The process of converting an ore into its oxide by The process of converting an ore into its oxide by
heating below its melting point in absence of air. heating below its melting point in presence of air.
CO2
ZnCO3 +ZnO 2 ZnS + 3O2 2 ZnO + 2SO2 Page 18
Slag : During metallurgy, ‘ flux ’ is added FeO + SiO2 FeSiO3 which
Impurity Flux Slag
combines with ‘ gangue ‘ to form ‘ slag ‘.
Slag separates more easily from the ore than the gangue.

Hydrometallurgy
The isolation of a metal present in the soluble complex by more reactive metal is
called hydrometallurgy.
Zinc is more reactive than
Zn (S) + Cu2+ (aq) Zn 2+ (aq) + Cu (S)
copper, So Zn can displace Cu
2+
from solution of Cu

To displace Zn from solution of Zn2+ ions, we need more reactive elements such as
Al, Mg, Ca and K.
But all these metals react with water forming their corresponding ions with the
evolution of H2 gas.
Thus Al, Mg, etc. can not be used to displace Zn from solution of Zn2+ ions. Thus,
copper can be extracted by hydrometallurgy but not zinc.
Electrometallurgy: [For highly reactive metals]
Highly reactive metals can be isolated from their ores by the process of
electrometallurgy.
The strongest possible reducing agent is an electron; any ionic material can be
Electrolytic reduction can be performed by applying a potential difference, E E ( applied ) ∆G
which is related to ∆G as follows: nF

reduce to their respective metal by electrolysis.

For a reaction having ∆G value 100 kj / mol, n= 1 and F = 96487 C Then E
(applied ) is nearly 1.03 V
But for this type of reduction, in terms of pyrometallurgy, require high
temperature, at which the ore become volatile.
Pyrometallurgy: ( Pyro means fire )- [For moderately reactive metals]
The process of converting metal oxide in to metallic form upon strong heating with a suitable reducing agent,
is known as pyrometallurgy.
Moderately reactive metals can be isolated from their ores by the process of pyrometallurgy.
[1] Thermite reaction: Reduction of metal oxide with aluminum. Cr O
2 3 +
2 Al Al2O3 2 Cr +
[2] Smelting : Reduction of metal oxide with help of coke.
Thermo metallurgy ( For least reactive metal )
The metals can be isolated by simply heating the oxide of the metals.
1 O
2 HgO 2 Hg + O2 Ag2O 2 Ag + 2 2

Distillation :
This method is employed for purification of volatile metals ( Zn, Hg, Cd ) by
heating the ore followed by condensation.
Liquation : This method is used when the M.P of the metals are lower than those
of the impurities.
e.g. low melting metal – Sn
Electrolytic refining ( Zn, Cu )
Anode : Impure metal ( Cu ) Cathode: Pure metal ( Cu )
Electrolyte : Soluble salt of same metal ( acidified CuSO4 solution )
The more basic metal remains in the solution and the less basic ones goes to the anode mud.
Anode: Cu Cu 2+ + 2e - ; Cathode: Cu 2+ + 2e - Cu
Antimony, Selenium, Tellurium, Silver, Gold and Platinum, which are less basic in nature present as
impurities in blister copper, collected as anode mud.
Zone refining ( Ge, Si, B, Ga, In )
This method is based upon the principle that the impurities are more soluble in the molten state ( melt )
than in the solid state of the metal. i.e. When a molten solution of the impure metal is allowed to cool, the
pure metal crystalises out while the impurities remain in the melt.
Vapour phase refining ( Ni, Zr, Ti )
In this method, the impure metal is converted into a volatile compound by suitable method leaving behind
the impurities. The volatile compound formed being unstable decomposes at an elevated temperature to give
pure metal.
330 - 350 K 450 - 470 K
Mond process Ni+ 4 CO Ni (CO)4 Ni 4 CO +
Impure Nickel Volatile Pure Nickel
( Nickel tetra carbonyl )

Van Arkel Method + ' W ' Filament

Zr
Impure Zirconium
2 I2 ZrI 4 Zr + 2 I2
Volatile 1800 K
Pure Zirconium
Ti + 2 I2 Ti I4 Ti + 2 I2
Impure Titanium Volatile Pure Titanium
Chromatographic Method
# This method is based upon the principle that different components of a mixture are differently adsorbed
on an adsorbent
# The zone thus formed due to adsorption is called chromatogram.
# The process of separation of the different components of the mixture from the adsorbent and their
recovery with the help of a suitable solvent ( eluant ), is called elution.
# The sample is dissolved in a mobile phase and then forced through the stationary phase, to form
chromatogram
# The stationary phase is selected in such a way that the impurities are more strongly adsorbed in the
stationary phase than element to be purified.
 Extraction of Znic
Ore Zinc blende / Sphalerite - ZnS; Calamine - ZnCO3 ; Zincite - ZnO
673 K
ZnO + C Zn + CO The metal is purified by fractional distillation.
Coke

Extraction of iron in the blast furnace

Ore Haematite Fe2O3 , Magnetite Fe3O4
Temperature 2170 K
Additive Coke (Reducing agent and fuel) and Lime stone (Basic Flux )
CO2
CaCO3 CaO +
CaO + SiO2
Impurity
CaSiO3
Flux Calcium silicate ( Slag )
C + O2 CO2 = - 393.3 Kj
Coke
CO2 + C 2 CO = + 163.2 Kj
3 Fe2O3 + CO 2 Fe3O4 + CO2
Fe3O4 + CO 3 FeO + CO 2
FeO + CO Fe + CO2
Pig iron
The iron obtained from Blast furnace ; Cuprite - Cu2O
contain about 4% carbon is known as pig
iron.
Cast iron contain about 3% carbon, obtained by melting pig iron with
scrap iron and coke using hot air blast.
Wrought iron the purest form, is prepared from cast iron by
oxidizing impurities with haematite. Haematite oxidises carbon to carbon
monoxide. Fe2O3 +
3 C --- 2 Fe 3 CO +

Extraction of Copper
Ore Copper pyrites- CuFeS2 ; Copper glance - Cu2S ; Malachite - CuCO3.Cu ( OH )2
Roasting
2 CuFeS2 + O2 Cu2S + 2 FeS + SO2

2 FeS + 3 O2 2 FeO + 2 SO2

FeO + Si O2 FeSi O3
Slag
Impurity Flux
Partial oxidation
2 Cu2S + 3 O2 2 Cu2O + 2 SO2
2 Cu2O + Cu2S 6 Cu + SO2
The solidified copper obtained has blistered appearance due to the evolution of SO2 and so it is called
blister copper
Extraction of Aluminium ( Hall - Heroult Process )
Ore Bauxite - Al2O3.x H2O Cryolite - Na3Al F6
Cathode -Steel; Anode - Graphite
Pure Al2O3 mixed with Cryolite ( Na3Al F6 ) or CaF2
To make alumina a good conductor of electricity.
To lowers the melting point of the mix.
3+ -
Al2O3 2 Al 3+ + 3 O 2- Cathode - Al + 3e Al ;
2- -
Anode - C + O CO + 2e
2- -
C + 2O CO2 + 4e
 The role of graphite as anode is to prevent the liberation of O2 which may other wise oxidise some of the
liberated Aluminium back to Al2O3
How is leaching carried out in case of low grade copper ores ?
Copper is leached out from the low grade ores by using acid or bacteria in presence of air.
2 Cu + 2 H2SO4 + O2 2 CuSO4 + 2 H2O
The solution containing Cu2+ is treated with scrap iron / H 2
to get pure copper.
+
Cu2+ (aq) + H2 Cu + 2H
2+
Cu (aq) + Fe Cu + 2 Fe2+
∆G = Ve ( Less )
Ellingham diagram
∆G Phase change
∆G = T ∆S
∆G = ∆S T + ∆G = Ve ( More )
A reaction that proceeds with decrease of entropy (∆S= Ve )
must have + ve slope. T
The slope becomes - ve for those reactions which proceed with increase of entropy ( ∆S = +Ve )
and ∆S of a reaction remain nearly constant, so the value of ∆G changes with temperature.

Defn- Ellingham diagrams are the graphs which represent the variation of standard free energy
change ( ∆G ) with temperature for the fomation of oxides of various elements.
Characteristics
[i] The curves always slope upwards because ∆G value for formation
of metal oxide increases with the rise in temperature.
[ii] The sudden change in the slope indicates the phase change.
This happens at the melting point and boiling point.
[iii] For the formation of CO the ∆G values gradually becomes more
∆G
negative with rise in temperature. i.e. the graph slopes downward.
[iv] Any metal oxide with lower ∆G is more stable than the metal
oxide with higher ∆G .
[v] The element involved in the formation of oxides placed lower in the
diagram can reduce the oxide of the element placed higher in the diagram T
i.e. Cr O
2 3 2 Al+ Al2 O3
+ Al O
2 Cr 2 3 + 2 Cr Cr2O 3
+ 2 Al

[vi] Ag2O and HgO, placed at the top of Ellingham diagram, are quite unstable and they decompose of their
own and no reducing agent equipped their reduction. Page 22
2 Ag2O 4 Ag + O2 2 HgO 2 Hg + O2
Limitation Ellingham diagram give no idea about the kinetics of reaction.
Explain overall reaction for extraction of aluminium by Hall-Heroults process is the carbon
reduction i.e. 2 Al2O3 + 3 C 4 Al + 3 CO2
3+
Al2O3 2 Al + 3 O2- ---------------[1]
Anode -(Graphite) O2- + C CO + 2e -

2- -
CO + O CO2 + 2e

2- -
C + 2O CO2 + 4e
3+ -
Cathode - [ Steel ] Al + 3e Al
[Anode reaction X 3 ] + [Cathode reaction X 4 ] = Cell reaction
2- -
C + 2O CO2 + 4e ]X 3
3+ -
Al + 3e Al ]X 4
3+ 2-
4 Al + 6O + 3C 4 Al + 3 CO 2 -------------------[2]
Adding eqn(1) with (2) by multiplying suitable integer.

Al2O3 2 Al3+ + 3 O2- ] X 2

3+ 2-
4 Al + 6O + 3C 4 Al + 3 CO 2

2 Al2O3 + 3C 4 Al + 3 CO2
Why is the reduction of a metal oxide easier if the metal formed is in liquid state at the temperature of
reduction ?
The value of entropy change ( ∆S ) of the reduction process is more on +ve side when the metal formed is in
liquid state and the metal oxide being reduced is in solid state. Thus the value of ∆G becomes more on
negative side and the reduction becomes easier.
Pyrometallurgical carbon reduction process is not applicable for the extraction of aluminium from bauxite
ore, explain.
4 Al + O 2 Al2 O3 ,
(S) 2 (g) 3
(S) ∆G1 ( ∆S = -ve since gas solid) ∆G1
3
2 C (s) + O2 (g) 2 CO (g), ∆G2 ( ∆S = + ve since 1 mol 2 mol gas) .

∆G2 ∆G1 ∆G1 ∆G2

.

--------------
For reduction of bauxite by carbon: .

∆G
.

2 C (s) 2+ O2 (g) 2 CO (g), ∆G21

Al O ∆G ∆G2
4
O2
3
2 Al O
2 3 3
Al
4
+ 2000 C
2 3 Al T
3 + 2C
.
3 + 2 CO ∆G = ∆G2 ∆G1
To get ∆G negative , ∆G1 ∆G2
.

i.e the reduction of bauxite by carbon will feasible above 2000 C . But at this temperature bauxite becomes
volatile. Therefore bauxite can not reduce by carbon.
Reducing nature of carbon ( coke )

[1] C C + O2 CO2
(S) + O2 ( g ) CO2 ( g ) ; ∆S = 0
------------------

n R =1 n =1
P
So ∆G remain same. ∆G
.

[2] 2 C (S) + O2 ( g ) 2 CO ( g ) ; ∆S .
0
n R =1 983 K
=2 n
P
So ∆G becomes increasingly negative. T
.

[3] 2 CO (g) + O2 ( g ) 2 CO2 ( g ) ; ∆S 0

.

n R =3 n P =2 So ∆G becomes positive.
So it is concluded that carbon ( coke ) act as reducing agent by changing to carbon monoxide above 983 k
Out of C and CO which is a better reducing agent for ZnO ?
Above 1073 K ∆G(CO,CO ) ∆G ( Zn, ZnO ) ∆G ( C, CO ) . .

2
Page 23
.

So, C can reduce ZnO to Zn but not CO

So, out of C and CO , C is the better reducing agent than CO for ZnO
Reduction of Zinc oxide
Zinc boils at 1180 K, so the curve ( Zn, ZnO ) increases rapidly
at this temperayure.

--------------------
Above 1270 K ∆G ( Zn, ZnO )
.

∆G ( C, CO )
.
∆G

------------
Thus zinc oxide is reduced by coke above 1270 K.

1270 K
C Above 1270 K.

1180 K
ZnO + Zn + CO
Explain the choice of reducing agent in a particular case depends
on thermodynamic factors. T
Only metal will reduce the oxides of other metal which lie above it in the Ellingham diagram because the
standard free energy change ( r G ) of the combined redox reaction will be - ve by an amount equal to
difference in f G of the two metal oxides. Thus both Al and Zn can reduce FeO to Fe, but Fe can not
reduce Al2O3 to Al and ZnO to Zn. Similarly C can reduce ZnO to Zn, but not CO.
Reduction of Haematite
.

[1] Below 1073 K, ∆G ( Fe, Fe2O3 ) ∆G ( CO, CO 2 )

.

-----------------
So Haematite is reduce by CO
Below 1073 K
Fe2O3 + 3 CO 2 Fe + 3 CO2 ∆G

1073 K
.

[2] Above 1073 K , ∆G ( Fe, Fe2O3 ) ∆G( C, CO )

.

So Haematite is reduce by coke.

Above 1073 K T
Fe2O3 + 3C 2 Fe + 3 CO
Out of C and CO , which is a better reducing agent at 673 K ?
.

AT 673 K ∆G ( c, co ) ∆G ( co, co2 ) So 'CO' is the better reducing agent.

.

Why is the extraction of copper from pyrites more difficult than that from its oxide ore through
reduction ?
CuFeS2 has to be converted into its oxide before reduction. .

∆G ( Cu ,Cu2S ) ∆G ( C, CS2 ) and ∆G ( H2 ,H2S )

.

.
So Cu2S can not be reduced by C or H2
In contrast, ∆G ( Cu, Cu2O ) ∆G ( C , CO ) So Cu 2 O can be easily reduced by coke.
.

Cu2O + C 2 Cu + CO
Predict conditions under which Al will reduce MgO
.

Below 1350 C, ∆G( Al, Al2O3 ) ∆G( Mg, MgO )

---------------

So Mg can reduce Al2O3

1350 C

2 Mg + 2Al O
2 M gO + 4 Al ∆G
3 2 3 3
But Mg is much costlier than Al, hence the process will
uneconomical. T
.

Above 1350 C , ∆G ( Mg, MgO ) ∆G( Al, Al 2O 3 ) So 'Al' can reduce MgO 4 Al
+ 2 M gO 2 Al O
2 3 +2 M g
.
3 3
The value of ∆G for formation of Cr2O3 is – 540 kJ/mol and that of Al2O3 is – 827 kJ/mol.Is the
reduction of Cr2O3 possible with Al ? Since ∆G4( Cr, Cr O ) ∆G( Al, Al O )
.

2 Cr O 2 3 2 3
.

So 'Al ' Can reduce Cr2O3 4 3 2 3 2 3 Cr + O2 ∆G = + 540 KJ / mol

3 Al 3 Al2O3 ∆G = - 827 KJ / mol

4 +2 Cr
O2
2O3
4 Cr
3 + 2 Al O
3 ∆G = - 287 KJ / mol
3 Al +3 2 3

Since ∆G of combine reaction is - ve , therefore reduction of Cr2O3 by Al is possible.

Name the process from which Cl2 is obtained as by-product. What will happen if an aqueous solution of
NaCl is subjected to electrolysis? Down's process , for extraction of sodium metal by electrolysis of
fused mixture of NaCl and CaCl2 at 873 K NaCl Na+ + Cl-
Cathode: Na+ + e- Na Anode : 2 Cl - Cl + 2 e-
2

IncaseofaqueousNaCl. NaCl Na+ +

-
Cl- Page 24
- -
Cathode: 2 H2O + 2 e H2 + 2 OH Anode : 2 Cl - Cl2 + 2 e

NaOH will obtain in the solution

 THE P-BLOCK ELEMENTS

N exhibits +5 oxidation state, but It does not have d orbitals to expand its
not form NCl5 covalence beyond 4
PH3 has lower boiling point than NH3. Due to high electronegativty of N, NH3
Why? forms H-bonding
Pentahalides more covalent than High +ve oxidation state, more polarizing
trihalides power, so covalent
BiH3 is strongest reducing agent Because BiH3 is the least stable hydrides
amongst the hydrides of Group 15.
Reaction of thermal decomposition of 2NaN →2Na+3N2
sodium azide.
Why is N2 less reactive at room Strong pπ–pπ overlap resulting into the
temperature? triple bond, N≡N.
Why does NH3 act as a Lewis base ? Nitrogen atom in NH3 has one lone pair of
electrons
Conditions required to maximise the P = 200atm, T=700 K catalyst such as
yield of ammonia. iron oxide.
How does ammonia react with a Cu2+ (blue) + 4 NH3(aq)  [Cu(NH3)4]2+(aq)
solution of Cu2+? (deep blue)
Why does NO2 dimerise ? It has odd electrons. On dimerisation,
converted to N2O4
What is the covalence of nitrogen in 4
N2O5 ?
Prove that PH3 is basic in nature? Reacts with acids like HI .
PH3+HI→PH4I
Bond angle in PH + is higher than that in PH3 there is lone pair-bond pair
4
in PH3. Why? repulsion
white P is heated with conc NaOH P4+3NaOH+3H2O PH3+3NaH2PO2 sodium
solution in CO2 ? hypophosphite
Why does PCl3 fume in moisture ? PCl3 +3H2O→H3PO3 +3HCl (fumes)
Are all the five bonds in PCl5 Two axial bonds are longer than equatorial
molecule equivalent? bonds due to repulsion
What happens when PCl5 is heated? PCl5 → PCl3 + Cl2

Page 25
 Hydrolytic reaction of PCl5 in heavy PCl5 + D2O → POCl3 + 2DCl
water.
Account for the reducing behaviour Two H are bonded directly to P giving
of H3PO2 reducing character
What is the basicity of H3PO4? 3
What happens when H3PO3 is heated? 4H3PO3 → 3H3PO4 + PH3
(disproportionation)
The HNH angle is higher than HPH, sp3 hybridisation in NH3
HAsH angles.
Why does R3P = O exist but R3N = O Nitrogen cannot form dπ –pπ bond
does not
Why NH3 is basic while BiH3 is only Small size and hence high electron density
feebly basic. on N
Nitrogen as diatomic molecule and Due to small size N form pπ–pπ bond
phosphorus as P4. resulting into N≡N.
Differences between white P and White P: white waxy/poisonous/ soluble
red P in CS2/ reactive
Red P : grey /nonpoisonous/insoluble in
CS2/less reactive
N show catenation properties less N-N single bond is weaker than P-P single
than phosphorus? bond.
Can PCl5 act as an oxidising & P is in highest oxidation state +5. So it is
reducing agent? Justify. only oxidizing agent
Elements of Gr- 16 show lower value Due to extra stable half-filled p orbitals
of first IE compared to the electronic configurations of Group 15
corresponding periods of group 15. elements
Why?
H2S is less acidic than H2Te. Why? Due to the decrease in bond (Te–H)
dissociation enthalpy
Order of thermal stability of the H2O>H2S>H2Se>H2Te>H2Po
hydrides of Group-16
Why is H2O a liquid and H2S a gas ? Due to intermolecular H-bonding in H2O
Why does O3 act as a powerful Due to the ease with which it liberates
oxidising agent atoms of nascent oxygen

Page 26
How is O3 estimated quantitatively When ozone reacts with an excess of
potassium iodide solution.
iodine is liberated which can be titrated
against a standard solution of sodium
thiosulphate
Which form of sulphur shows In vapour state sulphur partly exists as S2
paramagnetic behaviour ? molecule which has two

orbitals like O2 and, hence, exhibits

paramagnetism.
What happens when sulphur dioxide 2Fe3+ + SO2 + H2O  2Fe2+ + SO 2- + 4H+
4
is passed through an aqueous solution
of Fe(III) salt?
Comment on the nature of two S–O Both the S–O bonds are covalent and have
bonds formed in SO2 equal strength
How is the presence of SO2 detected It decolourises acidified potassium
? permanganate(VII) solution
Write the conditions to maximise the Low temperature and high pressure
yield of H2SO4
Why is Ka2 << Ka1 for H2SO4 in water H2SO4 is largely dissociated into H+ and
? HSO4-
Why is dioxygen a gas but sulphur a O can form pi bond,exists as discrete O2
solid? molecule, so it is gas.
Knowing the electron gain enthalpy Oxides having O2– have high negative
values for O → O– and O → O2– as – lattice enthalpy.
141 and 702 kJ mol–1 respectively,
how can you account for the
formation of a large number of
oxides having O2– species and not O–?
Which aerosols deplete ozone? Freons
How is SO2 an air pollutant? It causes acid rain
Halogens have maximum negative Halogens have the smallest size in their
electron gain enthalpy respective periods

Page 27
Although electron gain enthalpy of It is due to
fluorine is less negative as compared (i) low enthalpy of dissociation of F-F bond
to chlorine, fluorine is a stronger (ii) high hydration enthalpy of F–
oxidising agent than chlorine. Why?
Fluorine exhibits only –1 oxidation Fluorine is the most electronegative
state whereas other halogens exhibit element and cannot exhibit any positive
+ 1, + 3, + 5 and + 7 oxidation states oxidation state. Other halogens have d
also. Explain. orbitals and therefore, can expand their
octets and show + 1, + 3, + 5 and + 7
Considering the parameters such as Electrode potential of F2 is higher than Cl2
bond dissociation enthalpy, electron so F2 is stronger oxidizing agent than Cl2
gain enthalpy and hydration enthalpy,
compare the oxidising power of F2
and Cl2.
Two examples to show the anomalous F forms only one oxo acid , HF is liquid
behaviour of F but others are gas
Write the balanced chemical equation 3Cl2 + 6NaOH → 5NaCl + NaClO3 + 3H2O
for the reaction of Cl2 with hot and Yes, chlorine from zero oxidation state is
concentrated NaOH. Is this reaction changed to –1 and +5
a disproportionation reaction? oxidation states.
Justify.
Give the reason for bleaching action Cl2 + H2O  2HCl +O , Coloured substance
of Cl2. + O  Colourless
Name two poisonous gases prepared Phosgene gas (COCl2) , mustard gas
from chlorine gas.
When HCl reacts with finely Its reaction with iron produces H2. 2
powdered iron, it forms ferrous Fe+2HCl→FeCl +H2
chloride and not ferric chloride. Liberation of H2 prevents the formation of
Why? ferric chloride.
Deduce the molecular shape of BrF3 There are three bond pairs and two lone
on the basis of VSEPR theory. pairs. The two lone pairs will occupy the
equatorial positions of aTBP The shape
would be that of a slightly bent ‘T’.
Why is ICl more reactive than I2? I-Cl bond is weaker than I-I bond

Page 28
Why are halogens strong oxidising Due to low bond dissociation energy, high
agents? electronegativity and large negative
electron gain enthalpy
Explain why fluorine forms only one Due to high electronegativity and absence
oxoacid, HOF. of d-orbitals
Oxygen forms hydrogen bonding Due to large size of Cl
while chlorine does not.
Write two uses of ClO2. It is powerful oxidizing agent and
chlorinationg agent
Why are halogens coloured? Their molecules absorb light in visible
region
What happens when NaCl is heated 4NaCl +MnO2 + 4H2SO4  MnCl2 +
with sulphuric acid in the presence of 4NaHSO4 + Cl2 + H2O
MnO2.
Noble gases have very low boiling Noble gases being monoatomic have no
points. Why? interatomic forces except weak dispersion

Does the hydrolysis of XeF6 lead to a No, the products of hydrolysis are XeOF4
redox reaction? and XeO2F2 where the oxidation states of
all the elements remain the same
Why is helium used in diving Due to its low solubility in blood
apparatus?
Why has it been difficult to study Due to its very short half life
the chemistry of radon?
With what neutral molecule is ClO– ClF, Yes it is a Lewis base
isoelectronic? Is that molecule a
Lewis base?
Why do noble gases have large They have onle van der Waals radii which
atomic sizes? is longer
List the uses of neon and argon Neon- in discharge tube. Ar – to make an
gases. inert atmosphere
F2, Cl2, Br2, I2 - increasing bond I2< F2 <Br2 <Cl2,
dissociation enthalpy.
HF, HCl, HBr, HI - increasing acid HF<HCl<HBr<HI

Page 29
strength.
NH3, PH3, AsH3, SbH3, BiH3 – BiH3 < SbH3< AsH3,< PH3,< NH3,
increasing base strength.
Which one of the following does not NeF2
exist?
(i) XeOF4 (ii) NeF2 (iii) XeF2 (iv) XeF6

The d & f BLOCK ELEMENTS

Scandium (Z = 21) is a transition Incompletely filled 3d orbitals in case of

element but Zinc (Z = 30) is scandium
not? Zn & Zn2+ have completely filled d orbitals
(3d10)
Ag (4d10) but it is a transition Ag has +2 oxidation state having incompletely
element? filled d-orbital
Transition elements exhibit Because of large number of unpaired electrons
higher enthalpies of in their atoms they have stronger interatomic
atomisation? interaction
Enthalpy of atomization of zinc In the formation of metallic bonds, no electrons
is low from 3d-orbitals are involved in case of
zinc(3d10)
Having no variable oxidation Scandium (Z = 21)
states.
Largest number of oxidation Mn(+2 to +7) Because it has largest number of
states. unpaired electrons
Why is Cr2+ reducing and Mn3+ Cr2+ changes from d4 to d3(stable).On the other
oxidising when both have d4 hand, the change from Mn2+ to Mn3+ results in
configuration. the half-filled (d5)
The E0(M2+/M) value for copper Due to its high ΔaH0 and low ΔhydH0)
is +ve
Oxidising power:VO + < Cr O 2– < This is due to the increasing stability of the
2 2 7
MnO – lower species
4

Page 30
Account for the irregular Due to varying degree of stability of different
variation of IE 3d-configurations
The E0 (M2+/M) values are not Due to the irregular variation of IE ,
regular sublimation enthalpies
E0 of Mn3+/Mn2+ is more Much larger third IE of Mn (where the required
positive than that for Cr3+/Cr2+ change
or Fe3+/Fe2+? Explain. is d5 to d4) is mainly responsible for this.
Highest oxidation state of a Small size and high electronegativity O or F can
metal exhibited in its oxide or oxidise the metal to its highest oxidation state.
fluoride
Which is a stronger reducing Cr2+ is stronger reducing agent than Fe2+
agent Cr2+ or Fe2+ and why ? Reason: d4 → d3 occurs in case of Cr2+ to Cr3+,
d3 is stable
But d6 → d5 occurs in case of Fe2+ to Fe3+
Magnetic moment of a divalent d5 Configuration (five unpaired electrons). The
ion in aqueous solution if its magnetic moment, μ is μ = √5(5+2) = 5.92BM
atomic number is 25.
Calculate the ‘spin only’ M2+ (aq) ion (Z = 27)  d7  3 unpaired
magnetic moment of M2+ (aq) ion electrons
(Z = 27). μ = √3(3+2) = 3.87BM
What is meant by When a particular oxidation state becomes less
‘disproportionation’ of an stable relative to other oxidation states, one
oxidation state? Give an lower, one higher, it is said to undergo
example. disproportionation. For example, Mn (VI)
becomes unstable relative to Mn(VII) and Mn
(IV) in acidic solution.
3 MnO4 2– + 4 H+ → 2 MnO4- + MnO2 + 2H2O
Explain why Cu+ ion is not stable Cu+ in aqueous solution undergoes
in aqueous solutions? disproportionation,
2Cu+(aq) → Cu2+(aq) + Cu(s) The E0 is favourable
for this
Lanthanoids to exhibit +4 Cerium (Z = 58)
oxidation state.
Actinoid contraction is greater 5f electrons themselves provide poor shielding

Page 31
than from element to
lanthanoid contraction. Why? element in the actinoid series.
Mn2+ more stable than Fe2+ It is because Mn2+ has 3d5 configuration which
is stability.
Stable oxidation state for : 3d3 (V): (+2), +3, +4, and +5 ; 3d5 (Cr): +3, +4,
3d3, 3d5, 3d8 and 3d4? +6
3d5 (Mn): +2, +4, +6, +7 ; 3d8 (Co): +2, +3
(in complexes)
3d4 There is no d4 configuration in the ground
state.
Oxometal anions in which the Vanadate VO −, Chromate Cr O − ,
metal exhibits the oxidation Permanganate MnO −
state equal to its group number.
What is lanthanoid contraction? Gradual decrease of atomic radii form La to Lu
What are the consequences of Consequences : similar properties of 2nd and 3rd
lanthanoid contraction? rows transition elements

In what way is the electronic In transition elements the last electron goes
configuration of the transition into penultimate shell
elements different
from that of the non transition
elements?

Oxidation states of the +3 is the common oxidation lso +3, oxidation

lanthanoids? states +2 and +4
Transition metals are For having unpaired electrons
paramagnetic
Enthalpies of atomisation of Due to strong metallic bonding
the transition metals are high.

Transition metal form coloured Due to incompletely filled d-orbital there is d-d
compounds electron transition
Transition metals and their Because they can adopt variable oxidation

Page 32
many compounds act as good states to form different intermediate
catalyst.
How is the variability in In transition elements the oxidation states vary
oxidation states of transition by one
metals different from For example, for Mn it may vary as +2, +3, +4,
that of the non transition +5, +6, +7.
metals? Illustrate with In the nontransition elements the variation is
examples. selective, always differing by 2, e.g. +2, +4, or
+3, +5 or +4, +6 etc.
Which of the following will be Except Sc3+, all others will be coloured due to
coloured Ti3+,V3+,Cu+,Sc3+,Mn2+, incompletely filled 3d-orbitals, will give rise to
Fe3+ & Co2+. d-d transitions.
Of the d4 species, Cr2+ is Cr2+ is reducing as it change from d4 to d3, the
reducing while Mn(III) is latter is more stable Mn(III) to Mn(II) is from
strongly oxidising. 3d4 to 3d5 again 3d5 is stable
Co(II) is stable in aq sol but in Due to CFSE, which more than compensates the
the presence of complexing 3rd IE.
reagents it easily oxidised.
The d1 configuration is The hydration or lattice energy more than
unstable in ions. compensates the ionisation enthalpy involved in
removing electron from d1.
Which transition metal has +1 Cu, because with +1 oxidation state an stable
oxidation state most frequently configuration, 3d10
and why?
Calculate the number of Unpaired electrons Mn3+ = 4, Cr3+ = 3, V3+ = 2,
unpaired electrons in the Ti3+ = 1. Most stable Cr3+
following gaseous ions: Mn3+,
Cr3+, V3+ and Ti3+. Which one of
these is the most stable in
aqueous solution?
The lowest oxide of transition In lowest oxidation state ionic bond is formed
metal is basic, the highest is but in highest oxidation state covalent bond is
amphoteric/acidic. formed

Page 33
A transition metal exhibits O and F are strong oxidizing agents and can
highest oxidation state in excite electrons
oxides
and fluorides.

The highest oxidation state is Oxygen is strong oxidizing agent

exhibited in oxoanions of a
metal.

Which is the last element in the Lawrencium(103)

series of the actinoids? Write
the electronic 5f 146d17s2
configuration of this element.
Comment on the possible +3
oxidation state of
this element.

BIOMOLECULES

KEY POINTS EXPLANATIONS

Monosaccharides Cannot be hydrolyzed further . eg- glucose, fructose,
ribose
Disaccharides Sucrose (α-D- glucose + β-D-fructose) , Maltose(α-D-
glucose + α-D- glucose)
Lactose(β-D-galactose + β-D-glucose )
Polysaccharides Starch (two components—Amylose and Amylopectin) polymer of
α-D- glucose
Amylose Water soluble , 15-20% of starch., unbranched chain ,
C1– C4 glycosidic linkage.
Amylopectin Water insoluble , 80-85% of starch., branched chain polymer,
C1–C4 & C1–C6 glycosidic linkage
Cellulose Straight chain polysaccharide of β -D-glucose units/ joined by
C1-C4glycosidic linkage (β-link), not digestible by human /

Page 34
 constituent of cell wall of plant cells
Glycogen Highly branched polymer of α-D- glucose .found in liver,
muscles and brain.
reducing sugars Aldehydic/ ketonic groups free so reduce Fehling’s/ Tollens
solution and. Eg- maltose and lactose
Non reducing Aldehydic/ ketonic groups are bonded so can not reduce
sugars Fehling’s solution and Tollens’ reagent. Eg- Sucrose
Anomers. The two cyclic hemiacetal forms of glucose differ only in the
configuration of the hydroxyl group at C1, called anomeric
carbon Such isomers, i.e., α –form and β -form, are called
anomers.
Invert sugar Sucrose is dextrorotatory but after hydrolysis gives
dextrorotatory glucose and laevorotatory fructose. Since the
laevorotation of fructose (–92.4°) is more than dextrorotation
of glucose (+ 52.5°), the mixture is laevorotatory. Thus,
hydrolysis of sucrose brings about a change in the sign of
rotation, from dextro (+) to laevo (–) and the product is named
as invert sugar
Glycosidic Linkage between two mono saccharide
linkage
Importance of Major portion of our food. / used as storage molecules as
Carbohydrates starch in plants and glycogen in animals/.
Cell wall of bacteria and plants is made up of cellulose./wood
and cloth are cellulose /
provide raw materials for many important industries like
textiles, paper, lacquers and breweries.
essential amino which cannot be synthesised in the body and must be obtained
acids through diet, eg- Valine, Leucine
Nonessential which can be synthesised in the body, eg - Glycine,
amino acids Alanine
zwitter ion. In aqueous solution, amino acids exist as a dipolar ion known as
zwitter ion.
peptide linkage peptide linkage is an amide formed between –COOH group and –
NH2 group of two successive amino acids in peptide chain.

Page 35
10- str. of sequence of amino acids that is said to be the primary
proteins: structure of protein
20- str. of secondary structure of protein refers to the shape in which a
proteins: long polypeptide chain can exist.
They are found to exist in two types of structures viz. α -helix
and β -pleated sheet structure.
Tertiary further folding of the secondary structure. It gives rise to two
structure of major molecular shapes viz. fibrous and globular.
proteins:
Fibrous proteins Polypeptide chains run parallel, held together by hydrogen and
disulphide bonds, fibre– like structure. Water insoluble . Eg-
are keratin(in hair, wool, silk) and myosin (present in muscles).
Globular chains of polypeptides coil around to give a spherical shape.
proteins water soluble. Eg-Insulin and albumins
Stab.forces 2°& hydrogen bonds, disulphide linkages, van der Waals and
3° electrostatic forces of attraction.
Denaturation of When a protein is subjected to physical change like change in
Proteins temperature or chemical change like change in pH, the
hydrogen bonds are disturbed. Due to this, globules unfold and
helix get uncoiled and protein loses its biological activity. This
is called denaturation of protein.
(During denaturation 2° and 3° structures are destroyed but 1º
structure remains intact.)
eg- The coagulation of egg white on boiling, curdling of milk
Fat soluble vit These are vitamins A, D, E and K. They are stored in liver and
adipose (fat storing) tissues
Water soluble B , C . these vitamins must be supplied regularly in diet because
vit they are readily excreted in urine
Vitamins – Vit- A (Fish liver oil, carrots)- Night blindness /
sources- Vitamin B1 (Yeast, milk,)- Beri beri
Deficiency Vit-B2 (Milk, eggwhite)- Cheilosis
diseases Vit- B6 (Yeast, milk,)- Convulsions
Vit- B12 (Meat, fish,)- anaemia
Vit C(Citrus fruits)- Scurvy, Vit D(Exposure to sunlight,

Page 36
 fish and egg yolk)- Rickets, osteomalacia
Vit E(wheat oil, sunflower oil)- fragility of RBCs / Vit
K(leafy vegetables)- Increased blood clotting time
DNA pentose sugar (D-2-deoxyribose) + phosphoric acid +
nitrogenous bases
( A , G , C, T )
RNA pentose sugar (ribose) + phosphoric acid +
nitrogenous bases
(A , G , C, U )
Nucleoside / Nucleoside  sugar + base Nucleotides  sugar + base +
tides phosphate
Phosphodiester Linkage between two nucleotides in polynucleotides
link
Functions of DNA reserve genetic information, maintain the identity of
Nucleic Acids different species , is capable of self duplication during cell
division, synthesizes protein in the cell.

POLYMERS

POLYMER MONOMER(Name & USES

Structure)
Addition or Chain Growth Polymer
Polythene Ethene CH2=CH2 Insulator, ,Packing material,
Teflon Lubricant, Insulator and
(Poly Tetrfluoroethene CF2=CF2 making non-stick cooking ware.
tetrfluoroethene
Poly acrylonitrile Acrylonitrile CH2=CH-CN For synthetic fibres and
synthetic wool.
Buta-1,3-diene + Automobile tyres and Foot
Styrene wears
Buna S
CH2=CH-CH=CH2
C6H5CH=CH2
Buta-1,3-diene + Oil seals, Tank lining
Buna N
Acrylonitrile

Page 37
 CH2=CH-CH=CH2 CH2=CH-
CN
2-Methylbuta-1,3-diene Used for tyres after
Natural Rubber
(Isoprene) vulcanization
Synthetic 2-Chlorobuta-1,3-diene Insulator, making conveyor
Rubber(Neoprene) (Chloroprene) belts and printing rollers
Polypropene Propene CH3-CH=CH2 Ropes, toys, pipes and fibres
Insulator, Wrapping
Polystyrene Styrene C6H5CH=CH2 material,toys, Radio and
television cabinets.
Polyvinyl chloride Rain coats, Hand bags, Vinyl
Vinyl Chloride CH2=CH-Cl
(PVC) flooring and water pipe.
Condensation or Step Growth Polymers
Ethane-1,2-diol + Benzene- Used for making fibres,
Terylene(Dacron) 1,4-dicarboxylic acid safety belts, tents

Hexamethylene diamine + For making brushes,paratutes

Adipic acid and ropes
Nylon 66
NH2(CH2)6NH2
HOOC(CH2)4COOH
Nylon 6 Caprolactum Tyres cords,fabrics and ropes
Combs,electrical
Bakelite Phenol + Methanal switches,handles of utensiles
and computer discs
Melamine Melamine + Methanal Unbreakable crockery
PHBV 3-Hydroxybutanoic acid + Specialty packaging,
biodegradable 3-Hydroxypentanoic acid orthopedic devices, In
controlled drug release
Nylon 2 – Nylon 6 Glycine + Amino
biodegradable caproic acid
H2N-CH2-COOH H2N
(CH2)5-COOH
Urea- Unbreakable cups , laminated
Urea + Formaldehyde
formaldehyde sheet

Page 38
resin
Ethane1,2-diol + Benzene- Binding material
Glyptal 1,2-dicarboxylic acid in preparation of mixed
plastics and paints

Semi-synthetic
Cellulose Acetate (Rayon)
poly
Thermoplastic Linear or slightly branched / capable of repeatedly softening
polymers on heating and hardening on cooling. Example : Polythene,
Polystyrene, Polyvinyls, etc.
Thermosetting Cross linked or heavily branched molecules, / on heating
polymers undergo extensive cross linking in moulds and again become
infusible. These cannot be reused. Examples : Bakelite, Urea-
formaldelyde resins.
Homo-polymer & Homo-polymer  Polymer of a single monomeric species.
Co-polymer Example : Polythene , PVC
Co-polymer Polymer of more than one monomer .Example :
Nylon66, Bakelite
Initiators Benzoyl Peroxide [ C6H5CO-O-O-CO-C6H5 ] (in free radical
addition polymerization)
Vulcanisation of Natural rubber is soft at high temp and brittle at low temp
Rubber. and absorbs water. To improve these physical properties, it is
heated with sulphur and an appropriate additive at a
temperature range between 373 K to 415 K. On vulcanisation,
sulphur forms cross links at the reactive sites of double
bonds and thus the rubber gets stiffened.

CHEMISTRY IN EVERYDAY LIFE

THERAPEUTIC ACTION OF DIFFERENT DRUGS

Drugs Action Example
Analgesics Relieving pain Aspirin Analgin, Seridon, Anacine,
Analgesics Reduce tension and pain. Opium, Heroin , Pethidine , Codeine,
Narcotic produce unconsciouness. Morphine

Page 39
Antibiotics Produced by micro – Penicillin G(Narrow Spectrum)
organism, that can inhibit Streptomycin, Ampicillin ,
the growth or destroy Amoxycillin Chloramphenicol
other micro-organism. Vancomycin, ofloxacin ,
Ampicillin and Amoxycillin
are synthetic
modifications of
penicillins. These have
broad spectrum.
Antiseptics Prevent the growth of Dettol, Bithional(in soap)
micro-organism or kill Tincture iodine, 0.2% phenol,
them but not harmful to
the living tissues.
Disinfectants Kills micro-organisms, not 1% phenol,
safe for living tissues. It chlorine (Cl2) ,
is used for toilets, Sulphurdioxide ( SO2)
instruments.
Antacids Reduce or neutralise the NaHCO3 Al(OH)3 gel MgCO3
Mg(OH)2
acidity.
AlPO4

Antihistamines Reduce release of acid. Cimetidine(Tegamet), Ranitidine

(Zantac),
It is also used to treat
allergy Brompheniramine ( Dimetapp)
Terfenadine ( Seldane)
Tranquilizers Reduce the mental Valium, Serotonin, Veronal,
anxiety, stress, (sleeping Equanil,Amytal,Nembutal,Luminal,
pill) Seconal
Antipyretics Reduce body temperature Aspirin, Paracetamol, Analgin,
Phenacetin.
Antifertility These are the steroids Norethindrone, Ethynylestradiol
drugs used to control the (novestrol )
pregnancy
CHEMICALS IN FOOD
Sweetening Saccharine, Aspartame(for cold foods)
Agent Alitame
Sucrolose(stable at cooking temp)
Food Salt, sugar, veg. oils, sodium benzoate
Preservative
CLEANSING AGENTS
Soap Na / K –salt of long chain Not work in hard water becoz with
fatty acids Ca and Mg salt soap produce
insoluble scum
Anaionic Sodium laurylsulphate Used in household work / in tooth
detergen paste
Cationic Cetyltrimethyl ammonium Hair conditioner / germicidal
detergent bromide properties
Non ionic Ester of stearic acid and Liquid dishwashing
detergent polyethylene glycol
Detergents with highly branched hydrocarbon parts are non biodegradable and
hence water pollutants so branching is minimized which are degradable and
pollution is prevented.

NAME REACTIONS

1. Finkelstein CH3Br + NaI CH3-I + NaBr

2. Swarts CH3Br + AgF CH3F + AgBr
CH3

Friedel-Crafts Anhydrous AlCl3

Alkylation
3.
COCH3
Friedel-Crafts CH3COCl

Acylation
4. Anhydrous AlCl3

2Na
Wurtz +
5. H3C Cl + Cl CH3 H3C CH3 Na Cl

Cl Cl

Fittig
2Na
+ + Na Cl
6. Dry ether
 Cl

Wurtz-Fittig +
2Na
Cl CH3 CH3 + Na Cl
7. Dry ether
OH OH
ONa
Na OH i) CO2 COOH
Kolbe
ii) H+
8.
OH
ONa OH
Reimer- CH3Cl + Na OH CHO H+ CHO
Tiemann
9.
10 Williamson CH3-Br + CH3-ONa CH3-O- CH3 + NaBr
H O+
Stephen H3C H3C CH NH
3
H3C CHO
11
CN + SnCl2 + HCl
CH3 CHO

CrO2Cl2
Etard
H3O+
12
CHO

Gatterman – CO / HCl
Koch Anhydrous AlCl3
13
O H2 O
Rosenmund C C

14 reduction
H3C Cl Pd / BaSO4 H3C H

O
Clemmensen Zn - Hg
C H3C CH2 CH3
15 Reduction H3C CH3 Conc. HCl
-
O NH
Wolff-Kishner i) NH2 2
C H3C CH2 CH3
ii) KOH / Ethylene glycol / ∆
16 reduction
H3C CH3

Tollens’ test R-CHO + 2 [Ag(NH3)2]+ + 3 OH- R-COO- + 2Ag +

17 2H2O + 4 NH3
18 Fehling’s test R-CHO + 2 Cu2+ + 5 OH- R-COO- + Cu2O + 3H2O
 O
I / NaOH
Iodoform
2
C CHI3 + CH3COONa
19 H3C CH3 OR, NaOI
OH
∆
Aldol
dil NaOH
2 H3C CHO H3C CH CH2 CHO H3C CH C
condensation
2
Conc. NaOH
Cannizzaro
21 HCHO
+ HCHO HCOONa + H3C OH

Hell-Volhard- i) Cl2 / Red Phosphorus

Zelinsky H3C COOH H2C COOH
2 (HVZ) ii) H2O
Cl
O
Hoffmann Br
2
bromamide H3C C NH2
NaOH
H3C NH2

2 degradation
∆
2 Carbylamine R-NH2 + CHCl3 + 3 KOH R-NC + 3 KCl + 3 H2O
NH2 + -
N Cl
2

Diazo
NaNO2 + dil HCl

2
273 - 278 K
+ -
N2 Cl Cl

Sandmeyer. CuCl / HCl

+ N2
2
+ -
N2 Cl Cl

Gatterman Cu / HCl
+ N2
2
+ - OH-
Coupling N2 Cl + H OH N N OH
2

DISTINGUISH BY A SINGLE CHEMICAL TEST

1. All aldehydes ( R-CHO) give Tollens’ Test and produce silver mirror.

RCHO + 2 [Ag(NH3)2]+ + 3 OH-  RCOO- + 2 Ag + 2H2O + 4 NH3

 Tollens’ Reagent silver
ppt
Note: HCOOH(methanoic acid ) also gives this test, ketones(RCOR) do not
give this test

2. All aldehydes (R-CHO) and ketones(RCOR) give 2,4-DNP test

RCOR + 2,4-DNP  Orange ppt
R-CHO + 2,4-DNP  Orange ppt

3. Aldehydes and ketones having CH3CO- (keto methyl) group give Iodoform
Test. Alcohols having CH3CH- group also give Iodoform Test.
|
OH
CH3CHO + 3I2 + 4 NaOH  CHI3 + HCOONa + 3 NaI + 3H2O
Yellow ppt
The following compounds give Iodoform Test: ethanol (C2H5OH), propan-
2-ol (CH3CH(OH)CH3), ethanal(CH3CHO), propanone(CH3COCH3), butanone
( CH3COCH2CH3) , pentan-2-one (CH3COCH2 CH2CH3) , acetophenone ( PhCOCH3 )

4. All carboxylic acids ( R-COOH) give Bicarbonate Test

RCOOH + NaHCO3  RCOONa + CO2 + H2 O
effervescence

5. Phenol gives FeCl3 Test

C6H5OH + FeCl3  (C6H5O)3Fe + 3 HCl
(neutral) (violet color)

6. All primary amines (R/Ar -NH2) give Carbyl Amine Test

R-NH2 + CHCl3 + KOH(alc)  R-NC + KCl + H2O
offensive smell

7. Aniline gives Azo Dye Test ( Only for aromatic amines)

C6H5NH2 + NaNO2 + HCl  C6H5N 2+Cl- ; then add β-naphthol 
orange dye
 8. All alcohols (ROH) give Na-metal test
R-OH + Na  R-ONa + H2
bubbles

9. For esters (RCOOR) : Hydrolyses first. Then see the products ( acid &
alcohol) and give a test to identify
them

10. All alkenes (C=C) and alkynes (C≡C) decolorizes Br2 – water from red to
colorless

11. Lucas Test to distinguish primary, secondary and tertiary alcohols

Lucas reagent: ZnCl2/HCl
0
3 -alcohol + Lucas reagent  immediate turbidity
20-alcohol + Lucas reagent  turbidity after sometime 10-
alcohol + Lucas reagent  no turbidity

KEY FOR CONVERSIONS

Sl Reagent Group Out Group In Remark

No
1 KMnO4 / H+ -CH2OH -COOH Strong Oxidation (20
alc ketone)
2 LiAlH4 -COOH -CH2OH Strong Reduction
(ketone  20 alc)
3 Cu / 573 K or -CH2OH -CHO Dehydrogenation
CrO3
4 PCl5 or SOCl2 -OH -Cl
5 Cl2 / Δ or Cl2 / -H -Cl Free radical
UV substitution
6 Aq NaOH / KOH -X -OH Nucleophilic
substitution
7 KCN -X -CN Step Up
8 AgCN -X -NC
9 Alcoholic KOH -HX = Dehydrohalogenation
(Stzf)
10 Mg / dry ether Mg R-X  R-MgX
11 HBr >=< H, Br Merkovnikov
12 H2 / Pd-BaSO4 -COCl -CHO Rosenmund Reduction
13 Zn-Hg / HCl >C=O -CH2- Clemmension
Reduction
14 NH3 / Δ -COOH -CONH2 -COOH + NH3  -
COONH4
15 Br2 / NaOH or -CONH2 -NH2 Step Down (
NaOBr Hoffmann)
16 HNO2 or -NH2 -OH HONO
NaNO2/HCl
17 CHCl3 / alc KOH -NH2 -NC Carbyl amine
18 P2O5 -CONH2 -CN Dehydration
19 H3O+ -CN -COOH Hydrolysis
20 OH- -CN -CONH2
21 LiAlH4 -CN -CH2NH2 Reduction
22 Red P / Cl2 α-H of acid -Cl HVZ Reaction

In benzene ring
23 Fe / X2 /dark -H -X Halogination
24 CH3Cl / AlCl3(anhyd) -H -CH3 Friedel Craft
alkylation
25 CH3COCl / -H -COCH3 Friedel Craft
AlCl3(anhyd) acylation
26 Conc.HNO3/con.H2SO4 -H -NO2 Nitration
27 Conc H2SO4 -H -SO3H Sulphonation
28 KMnO4 / H+ -R -COOH Oxidation
29 CrO2Cl2 / H+ -CH3 -CHO Mild oxidation(Etard
Reaction)
30 Sn / HCl or Fe/HCl -NO2 -NH2 Reduction
31 NaOH / 623K / 300 -Cl -OH
atm
32 Zn dust / Δ -OH -H
33 NaNO2 / dil HCl / -NH2 -N2+Cl- Diazo reaction
273-278 K
34 CuCl / HCl or Cu/HCl -N2+Cl- -Cl Sanmeyer or
Gattermann
35 CuBr / HBr or -N2+Cl- -Br Sanmeyer or
Cu/HBr Gattermann
36 CuCN / KCN -N2+Cl- -CN Sanmeyer
37 KI -N2+Cl- -I
38 HBF4 / Δ -N2+Cl- -F
39 H3PO2 or -N2+Cl- -H
CH3CH2OH
40 H2O / 283 K -N2+Cl- -OH
41 HBF4/ NaNO2, Cu / Δ -N2+Cl- -NO2
42 C6H5-OH -N2+Cl- -N=N-C6H5-OH Coupling ( p-hydroxy)
43 C6H5-NH2 -N2+Cl- -N=N-C6H5-NH2 Coupling ( p-amino)

Reactions of Grignard Reagent

Any one below + H2O Product

Grignard reagent +

H2O or ROH or RNH2 R-H
H-CHO R-CH2-OH (10 alc)
R-CHO R-CH(OH)-R (20 alc)
R-CO-R R2C(OH)-R (30 alc)
R-MgX
CO2 R-COOH
R-CN R-CO-R
HCOOR Aldehyde
RCOOR Ketone

NB: i) During reaction generally changes take place in the functional group only so
see the functional group very carefully.
 ii) Remember structural formula of all the common organic compounds ( with
their IUPAC and common
names)
iii) Wurtz Reaction and Aldol Condensation are not included in the table
although they are
very important for conversions so study them .
iv) By taking examples practice all the above cases ( from 1 to 43 and
Grignards reaction.)

vi) Start practicing NOW !

Directional Properties of groups in benzene ring for electrophilic substitution

Ortho-para directing group: -R , -OH, -NH2, -X, -OR, -NHR, -NR2, -

NHCOCH3, -CH2Cl, -SH, - Ph

Meta-directing group: -NO2 , -CHO , -COOH , COOR , -CN , -SO3H , -

+
COCH3 , -CCl3 , -NH3 ,
ELECTRON DISPLACEMENT EFFECTS

+ I : O- , COO- , (CH3)3C , (CH3)2CH , CH3CH2 , CH3

(electron donating)

- I : NR3+ , SR2+ , NH3+, NO2 , SO2R , CN , COOH , F , Cl , Br , I , OR , OH, NH 2

(withdrawing)

+ R (+M) : OH , NH2 , OR , NHR , X

(electron donating)

- R (-M) : NO2 , CN , CHO , COOH , COCH3

(electron withdrawing)

DIRECTIVE INFLUENCE OF SUBSTITUENTS IN BENZENE RING

(for electrophilic substitution reactions)

EFFECT OF THE DIRECTING ACTIVATING /

GROUP DEACTIVATING

+I Ortho / Activating

Para

+I,+R Ortho / Activating

Para

-I<+R Ortho / Activating

Para

- I > + R Ortho / Deactivating

 Para

-I Meta Deactivating

-I, -R Meta Deactivating

Example: -I > +R : - X , - CH=CH2 , -CH=CH-COOH , -CH2-Cl

These groups are deactivating but exceptionally o / p directing due to +E effect

by the attacking reagents electron density increases at ortho and para position .

If two groups are present initially

1. When both the groups present in benzene ring are o/p directing than the

order of influence

O- > NH2 > NR2 > OH > OCH3 > NHCOCH3 > CH3 > X

2. When both the groups present in benzene ring are meta directing than the

order of influence :

(CH3)3N+ > NO2 > CN > SO3H > CHO > COCH3 > COOH

3. When one group is o/p and another is m – directing than o/p directing group

takes priority

…………………………………………………