Chemistry (Study Package - XII)

[Study Package - Chemistry - Class XII]
STUDY PACKAGE
CHEMISTRY
CLASS XII
Brilliant
STUDY CENTRE
PALA
Mutholy Campus, Ph: 04822 - 206100, 206800
www.brilliantpala.org., email: admissions@brilliantpala.org.
1
Brilliant STUDY CENTRE
BLANK
2
CONTENTS
1. Solutions ------------------------------------------------------------------------------------- 05
2. Electrochemistry --------------------------------------------------------------------------- 29
3. Chemical Kinetics ------------------------------------------------------------------------- 54
4. The d-and f-block Elements ------------------------------------------------------------ 86
5. Co-ordination Compounds ----------------------------------------------------------- 111
6. Haloalkanes and Haloarenes -------------------------------------------------------- 140
7. Alcohols, Phenols and Ethers ------------------------------------------------------- 174
8. Aldehydes and Ketones --------------------------------------------------------------- 205
9. Carboxylic acids ------------------------------------------------------------------------- 233
10. Organic Compounds containing Nitrogen -------------------------------------- 254
11. Biomolecules ------------------------------------------------------------------------------ 277
12. The p-Block elements ------------------------------------------------------------------ 299
13. Principles Related To Practical Chemistry -------------------------------------- 322
3
4
CHAPTER - 01
SOLUTIONS
INTRODUCTION
A solution is a homogeneous mixture of two or more chemically non-reacting substances whose composi-
tion can be varied continuously up to what is called the limit of solubility. The term solution is commonly
applied to the liquid state of matter, but solutions of gases and solids are aplenty. Air, for example is a
solution of nitrogen and oxygen with trace amounts of many other gases and brass is a solution of copper
and zinc.
COMPONENTS OF A SOLUTION
Solutions are homogeneous mixtures; the substances that make the solution are called its components.
The major component is called solvent, and the minor component is called solute. Thus, solute is the
substance that dissolves, while solvent is the substance in which dissolution takes place.
A solution consisting of two components is called a binary solution. Similarly, a solution is called ternary or
quaternary when it is composed of three or four components, respectively.
METHODS OF EXPRESSING CONCENTRATION OF SOLUTIONS
The concentration of a solution is the amount of solute dissolved in a known quantity of solvent.
(i) Mass percentage (w/w): The number of parts (by mass) of solute per hundred parts by mass of
solution.
Mass of the component in solution

Mass % of a component (w/w) =  100
Mass of solution
x % by mass means 100 g solution contains x g solute and (100-x) g solvent.
(ii) Mass-volume percent (w/v): The mass of solute present in 100 cm3 of solution.
Mass of component in solution

Mass/volume percentage of a component (w/v ) =  100
Volume of solution
(iii) Volume percent (v/v): The number of parts by volume of solute (liquid) per hundred parts by volume
of solution.
Volume of the component in solution

Volume percentage of a component (w/v ) =  100
Volume of solution
5
(iv) Molarity (M): It is the number of moles of solute in 1L of the solution. It is the most widely used unit.
Number of moles of solute
Molarity (M) =
Volume of solution in litres
Mass of solute n w A / mA
= = 
Molar mass of solute  Volumeof solution (in litres) V V
mA is the molecular mass of solute and n is the number of moles of solute.
(v) Molality (m): Molality is defined as the number of moles of solute present in 1 kg of solvent.
Molality (m) =
Mass of solvent in kg
Mass of solute w B  1000
= =
Mol.mass of solute  Massof solvent(in kg) mB  w A
where wB = grams of solute, mB = molecular mass of solute, and wA = mass of solvent in g.
(vi) Mole Fraction (x) : It is the ratio of the number of moles of a particular component to the total number
of moles in the solution. It is denoted by the symbol x. If solute B dissolves in solvent A and their
number of moles are nB and nA, respectively, then their mole fractions, xA and xB are given as:
nA (w A / M A )
Mole fraction of solvent A, x A  
n A  nB (w A / M A )  (w B / M B )
nB (w B / M B )
Mole fraction of solute B, x B  
n A  nB (w A / M A )  (w B / M B )
or x B = (1- x A ) since, ( x A + x B =1)
ni n
For a solution containing ‘i’ components, xi   i
n1  n2  .....  ni  ni
Form a given solution, the sum of all the mole fractions is unity, i.e., x1  x 2  ......  x i  1
(vii) Mass Fraction (X) : It is the ratio of mass of a particular component to the total mass of the solution.
It is denoted by symbol (X). If a solute B of mass wB is dissolved in a solvent A of mass wA, then the
mass fraction of solvent (XA) and solute(XB) are given by:
wA wB
Mass fraction of solvent A ,(XA) = ; Mass fraction of solute B, (XB) =
wA  wB wA  wB
or XB = (1 – XA)
(viii) Parts per million (ppm) : Very low concentration of solute is expressed in parts per million (ppm).
Mass of solute
parts per million (ppm) =  106
Mass of solution
ppm = Mass fraction × 106 ; ppb (parts per billion) = Mass fraction × 109
VAPOUR PRESSURE OF LIQUID SOLUTIONS
A liquid solution is one in which the solvent is a liquid. Generally, the liquid solvent is more volatile and the
solute may or may not be volatile.
6
Vapour Pressure of Liquid-Liquid Solutions

When a binary solution of two volatile liquids A and B is taken in a closed vessel, both the liquids evaporate
and eventually establish an equilibrium between the vapour phase and the liquid phase. French chemist,
F M Raoult (1886) observed that for a solution of volatile liquids, the partial vapour pressure of each compo-
nent is directly proportional to its mole fraction in solution. Thus, for components A and B,
PA  x A and PB  x B
where PA and PB are the partial vapour pressures and xA and xB are the mole fractions of A and B respec-
tively.
PA  PA0 x A and PB  PB0 x B
where PA0 and PB0 are the vapour pressures of pure components A and B at the same temperature.
According to Dalton’s law of partial pressures, the total pressure inside the container will be the sum of the
partial pressures of the components of the solution,
Ptotal  PA  PB
Substituting the values of pA and pB,
Ptotal  x A PA0  x B PB0

 (1  x B )PA0  x B PB0
 PA0  (PB0  PA0 ) x B
Since PA0 and PB0 are constant at a given temperature, it is evident that the total vapour pressure is a linear
function of the mole fraction x B ( or x A as x A =1- x B ). Thus, a straight line is obtained on plotting ptotal against
x A or xB .
Figure - 01 Plot of vapour pressure and mole fraction of an ideal solution at constant temperature.
Lines I and II give the partial pressure vs composition of components A and B respectively and line III gives
the total vapour pressure vs mole fraction of solution. When x A =1(pure solvent A), Ptotal = PA0 and when
xB =1 (pure solvent B), Ptotal = PB0 .
(i) Raoults law is applicable only if the two components are completely miscible (homogeneous solu-
tion).
7
(ii) Solutions that obey Raoult’s law are called ideal solutions.
(iii) In case of ideal solutions, the vapour phase is richer in the more volatile component.
Relation between Dalton’s Law and Raoult’s Law. The composition of the vapour in equilibrium
with the solution can be calculated by applying Dalton’s law of partial pressures.
Let the mole fraction of A and B in vapours be yA and yB respectively. Let pA and pB be the partial
pressures of A and B respectively and Ptotal the total pressure.
PA = y A Ptotal
PB = y B Ptotal
In general, partial pressure of any component of a solution containing a number of volatile compo-
nents, Pi = y i Ptotal
Vapour Pressure of Solutions of Solids in Liquids. At a given temperature, the vapour pressure of a
solution of a non-volatile solute is lower than the vapour pressure of the pure solvent. This is because the
fraction of the solution surface covered by the solvent molecules gets reduced by the presence of solute
molecules. The decrease in vapour pressure depends only on the quantity of solute present in solution.
Raoult’s law states that the partial vapour pressure of each volatile component in a solution is directly
proportional to its mole fraction. Thus, when the solute is non-volatile, only the solvent molecules are present
in the vapour phase and contribute to vapour pressure.
If pA is the vapour pressure of the solvent and xA its mole fraction, then according to Raoult’s law,
PA  x A and PA  PA0 x A
where PA0 is its vapour pressure of the pure solvent. The proportionality constant is equal to the vapour
pressure of the pure solvent, PA0 . A plot of vapour pressure vs mole fraction of solvent is linear..
IDEAL AND NON-IDEAL SOLUTIONS
Binary solutions can be classified into ideal solutions and non-ideal solutions.
Ideal solution. A solution which obeys Raoult’s law at all temperatures and concentrations is known as
ideal solution. An ideal solution has the following characteristics :
(i) P = PA  PB  PA0 x A  PB0 x B , i.e., PA = PA0 x A and PB  PB0 x B .

(ii) Enthalpy of mixing is zero; H mix  0 . No heat is absorbed or evolved when components are mixed.
(iii) Volume change of mixing is always zero; Vmix  0 .
(iv) Entropy change of mixing is always positive; ΔSmix = + ve .
(v) Gibbs free energy change of mixing is always negative; ΔG mix = -ve .
(vi) A-A, B-B and A-B interactions are the same, i.e. A and B are identical in shape, size and character.
(vii) Escaping tendency of A and B are the same in pure liquids and in solution.
E.g., Dilute sloutions of (i) benzene + toluene, (ii) n-hexane + n-heptane, (iii) chlorobenzene +
bromobenzene, (iv) ethyl bromide + ethyl ioide, (v) CCl4 + SiCl4, (vi) C2H4Br2 + C2H4Cl2, (vii) C2H5Br +
C2H5Cl, , etc.
8
(i) (ii)
Figure - 02 Vapour pressure-composition curves: i. positive deviation, ii. negative deviation

Non-ideal solution : A solution which does not obey Raoult’s law is known as non-ideal solution.
PA  x A PA0 and PB  x B PB0

 mix H  O and  mix V  O . The vapour pressure of the solution will be either higher or lower than prdicted
by Raoult’s law. If the vapour pressure is higher, it is positive deviation and if lower, it is negative deviation.
a. Non-ideal solutions showing positive deviation from Raoult’s law. Characteristics:
(i) Endothermic dissolution, H mix  0 .
(ii) P A > P A0 x A ; P B  P B0 x B  PA  PB  PA0 x A  PB0 x B .
(iii) Volume increases on mixing, Vmix  0 .

(iv) A-B attractive forces should be weaker than A-A or B-B attractive forces. A and B have different size,
shape and character.
(v) A and B escape easily showing higher vapour pressure than the expected value.
Examples : (i) acetone + ethanol, (ii) acetone + CS2, (iii) water + methanol, (iv) water + ethanol,
(v) CCl4 + CHCl3, (vi) acetone + benzene, (vii) CCl4 + CH3OH, (viii) cyclohexane + ethanol, etc.
b. Non-ideal solutions showing negative deviation from Raoult’s law. Characteristics: (i) Exother-
mic dissolution, H mix  0 .
(ii) PA < PA0 x A ; PB  PB0 x B  p A  p B  p0A x A  p 0B x B .
(iii) Volume decreases on mixing, Vmix  0 .

(iv) A-B attractive forces should be stronger than A-A or B-B attractive forces. A and B have different
Escaping tendency of both components is lowered, resulting in lower vapour pressure than the ideal
value.
Examples : (i) acetone + aniline, (ii) acetone + chloroform, (iii) CH3OH + CH3COOH, (iv) H2O +
HNO3, (v) chloroform + diethyl ether, (vi) water + HCl, etc.
Azeotropic or Constant Boiling Mixtures. Binary mixtures that have the same compostion in liquid and
vapour phases and boil at a constant temperature are known as azeotropic mixtures or simply azeo-
tropes. In such cases, it is not possible to separate the components by fractional distillation.
There are two types of azeotropes; minimum boiling azeotropes and maximum boiling azeotropes.
9
1. Minimum boiling azeotropic mixtures. Non-ideal binary solutions which show very large positive
deviation from Raoult’s law form minimum boiling azeotropes at a constant composition.
A solution of ethanol and water shows a large positive deviation from Raoult’s law as can be seen
from the vapour pressure-composition curve. The solution at a particular composition has higher
vapour pressure (lower boiling point) than any of the components. At this point, composition of liquid
and vapour phases are the same and the liquid mixture boils at a constant temperature, which is
lower than the boiling temperature of either of the pure components. Fractional distillation will only give
any one of the components in the pure state (A or B) and azeotropic mixture.
E.g., Fractional distillation can concentrate ethyl alcohol to about 99.5% by volume beyond which the
azeotrope is obtained as distillate.Therefore, 100% alcohol cannot be obtained by fractional distillation.
Table - 01 Minimum and maximum boiling azeotropic mixtures.
Components Weight Boiling points

Type of Solution A B Percent of B A B Aze otrope
Minimum boiling H 2O C2H5OH 95.37 373.00 351.30 351.15
Azeotrope CHCl3 C2H5OH 6.8 334.20 351.30 332.30
Maximum boiling H 2O HCl 20.3 373.00 188.00 383.00
Azeotrope H 2O HNO3 68 373.00 359.00 393.50
2. Maximum boiling Azeotropic Mixtures. Non-ideal solutions which show negative deviation from
Raoult’s law form maximum boiling azeotropes.
From the vapour-pressure-composition diagram, it can seen that the solution has a minimum vapour
pressure at a particular composition, i.e., a maximum on the boiling point-composition diagram. At
this composition, the solution boils without change in composition, i.e., the liquid and vapour phases
have the same composition. E.g., a solution of HNO3 and H2O forms a maximum boiling azeotrope.
The composition of the azeotrope is 68% HNO3 and 32% water by mass, at 393.5 K.
COLLIGATIVE PROPERTIES
The properties of solutions which depend only on the number of solute particles (molecules or ions), but not
on their nature are called colligative properties. These are (i) relative lowering of vapour pressure ,(ii) eleva-
tion of boiling point, (iii) depression of freezing point and (iv) osmotic pressure.
Relative Lowering of Vapour Pressure
When a non-volatile solute, B is dissolved in a pure solvent, A, the vapour pressure of the solvent is lowered
due to lowering of escaping tendency of solvent molecules. If, at a certain temperature, P0 is the vapour
pressure of pure solvent and Ps is the vapour pressure of solution, then,
Lowering of vapour pressure = P0 – Ps
P0  Ps
Relative lowering of vapour pressure =
P0
P 0  Ps nB P nB
According to Raoult’s law,   x B or   xB
P 0
nA  nB P 0
nA  nB
10
For a dilute solution, nB being very small, nA + nB in the denominator can be replaced by nA. Therefore,
P0  Ps n B w B M A
  
P0 n A MB w A
where wA and wB are the masses and MA and MB are the molecular masses of of the solvent and solute
respectively (nA= wA/MA and nB= wB/MB).
Elevation of Boiling Point
A liquid boils at the temperature at which its vapour pressure becomes equal to the atmospheric pressure.
E.g., water boils at 373.15 K, when its vapour pressure becomes equal to 1.013 bar or 1 atmosphere.
Figure - 03 Elevation of boiling point.
When a non-volatile solute is dissolved in a solvent, the vapour pressure of the solution formed is lower than
that of the pure solvent. As a result, boiling point of the solution increases. If Tb0 is the boiling point of pure
solvent and Tb is the boiling point of the solution then, Tb > Tb0 and the elevation in boiling point,
Tb = Tb – Tb0
Over small ranges of concentration, the elevation in boiling point ( Tb ) is directly proportional to lowering
of vapour pressure of the solution.
Tb  P0  Ps or Tb   P
For a dilute solution, decrease in vapour pressure is proportional to molality (m) of the solution.
Tb  m or Tb  K b m or Tb  molality  K b

where Kb is the proportionality constant, called molal elevation constant or molal ebullioscopic con-
stant.
If m = 1, then Tb = Kb.
Determination of molecular mass of solute from elevation in boiling point. In order to determine the
molecular mass of an unknown solute, a known mass wB of the solute is dissolved in a known mass wA of
a suitable solvent and the elevation of boiling point is determined using a sensitive thermometer. If MB is the
molar mass of the solute, molality,
w B  1000
m
MB  w A
11
Substituting the value of m in equation, Tb  K b m
K b  w B  1000
Tb 
MB  w A
1000  K b  w B
Molar mass of solute, M B 
Tb  w A
Depression of Freezing Point
The freezing point of a liquid is the temperature at which the liquid and its solid state exist in equilibrium with
each other at one atmosphere pressure. It may also be defined as the temperature at which the liquid and
solid states of a substance have the same vapour pressure. When a non-volatile non-electrolyte is dis-
solved in a pure solvent, the vapour pressure of the solvent and the freezing temperature are lowered.
Figure - 04 Depression of freezing point.
In the figure, CB is the vapour pressure curve of the pure solvent in liquid state. It gives the vapour pressure
of the liquid at various temperatures. ED is the vapour pressure curve of the solution and AB is the vapour
pressure curve of the pure solvent in solid phase.
If Tf is the freezing point of pure solvent and (Tf) is the freezing point of its solution, then Tf  Tf . The
difference in the freezing point of the pure solvent and the solution is the depression in freezing point  Tf  .
Tf  Tf  Tf or Tf  m or Tf  K f m
where Kf is the proportionality constant called molal depression constant or molal cryoscopic constant.
If m =1, then, Tf  Kf .
The depression in freezing point is directly proportional to the lowering of vapour pressure of the solution.
Molal depression constant or molal cryoscopic constant. It is defined as the the depression of freezing
point when the molality of the solution is unity, i.e., when 1 mole of solute is dissolved in 1000g of solvent.
The units of Kf are K m-1 or K kg mol-1.
The value of Kf depends only on the solvent and not on the solute, e.g., Kf of water = 1.86 K m-1.
12
Determination of molecular mass of solute from depression of freezing point

The method of determining molecular mass of a solute from the depression of freezing point is called
cryoscopic method (Cryoscopy). In order to find out the molecular mass of an unknown non-volatile solute,
a known mass wB of solute is dissolved in a known mass wA of a suitable solvent and the depression of
freezing point is determined using a sensitive thermometer (e.g., Beckmann thermometer).
If MB is the molar mass of the solute, then molality of the solution is
w B  1000
m
MB  w A
Substituting the value of m in the equation, Tf  K f m
1000K f w B
Tf 
MB  w A
1000 K f w B
Molar mass of the solute, M B 
Tf w A
Table - 02 Molal elevation constant and freezing point depression constant for some common solvents.
Boiling point Molal elevation Freezing point Molal depression

Solvent o o
( C) constant (Kb) ( C) constant (Kf )
Water 273.2 0.52 273 1.86
Chloroform 354.4 3.63 209.6 4.79
Carbon tetrachloride 350 5.03 250.5 31.8
Benzene 353.3 2.53 278.6 5.12
Ethyl alcohol 351.5 1.20 155.7 1.99
Diethyl ether 307.8 2.02 156.9 1.79
Cyclohexane 353.74 2.79 279.55 20.2
Carbon disulphide 319.4 2.34 164.2 3.83
Acetic acid 391.1 2.93 290 3.9
Osmosis and Osmotic Pressure
1. Osmosis. Osmosis is the spontaneous flow of solvent molecules through a semipermeable membrane
(SPM) from a less concentrated to a more concentrated solution. The vapour pressure and the chemical
potential of pure solvent are greater than those of the solution, therefore, solvent molecules flow
through the SPM into the solution until the vapour pressures and the chemical potentials become
equal. Osmosis stops when the concentrations of the solutions on both sides of the SPM become
identical.
13
Semipermeable Membrane. A membrane that allows unrestricted movement of solvent molecules

through it, but does not allow the passage of solute molecules is called semipermeable membrane.
(i) Natural semipermeable membranes: Animal and vegetable membranes like egg membrane, gall
bladders, parchment, etc., are examples.
(ii) Artificial semipermeable membranes: Copper ferrocyanide, Cu2 [Fe (CN)6] deposited within the
walls of a porous pot is a perfect semipermeable membrane. Calcium phosphate supported on inert
material, Cellophane, collodion films, etc., are examples.
2. Osmotic Pressure. It is the excess of pressure that must be applied to a solution to prevent the
passage of solvent molecules into it through a semipermeable membrane. It may also be defined as
the hydrostatic pressure built up on the solution which just stops osmosis. The hydrostatic pressure
developed as a result of osmosis is a measure of osmotic pressure of the solution,
Osmotic pressure = hydrostatic pressure =   hdg
nST

V
where, V is the volume of solution containing one mole of the solute and S is the molar solution
constant. The value of S comes out to be 0.082 litre atm K–1 mol–1 which is in agreement with the
value of R, the molar gas constant.
In case, the solution contains n gram moles in V litre, the general equation would become :
V  nST or V  nRT
If wB g of solute of molecular mass MB is present in the solution, then nB = wB/ MB.
Substituting
w B RT wBRT
V  or MB 
MB V
Thus, knowing wB, T,  , and V, the molecular mass of solute can be calculated.
3. Isotonic, Hypertonic and Hypotonic solutions. Solutions having same osmotic pressure are termed
isotonic or iso-osmotic solutions.
1  2 or C1RT = C2RT or C1 = C2
When isotonic solutions are separated by a semipermeable membrane, no osmosis occurs.
A solution having higher osmotic pressure than another solution is called hypertonic solution, whereas
a solution having lower osmotic pressure relative to some other solution is called hypotonic solu-
tion.
4. Applications of osmotic pressure measurement.
Calculation of molecular mass of substances which are slightly soluble or having very high molar
masses (proteins, polymers, colloids, etc.).
14
5. Biological importance of osmosis. Absorption of water through the roots, movement of water inside
the body of the plants, germination of seeds and movements of plants such as stretching of leaves,
opening and closing of flowers.
Reverse Osmosis
If an external pressure greater than osmotic pressure is applied on the solution side, solvent molecules can
be made to flow from solution to pure solvent. This phenomenon is known as reverse osmosis.
A reverse osmosis (RO) system consists of a pressure vessel fitted with a suitable semipermeable
membrane. Under the influence of pressure, water from sea water passes through the SPM into pure water
in the adjoining compartment.
Figure - 05 Reverse osmosis (desalination of sea water).

Reverse osmosis is used for the desalination of sea water. Depending on salt concentration, osmotic pressure
of sea water vary between 4000 to 5500 kPa (1 kPa = 0.01 atm). For the purification of sea water by RO, the
pressure applied should be between 5400 to 6900 kPa (i.e., 1400 kPa more than the osmotic pressure of
sea water). Cellulose acetate membranes (called ‘skins’) supported by porous cellulose structures, Aramid
(aromatic polyamide) membranes, etc., act as SPM.
ABNORMAL COLLIGATIVE PROPERTIES
In many cases, the observed and the calculated molar masses of a solute differ appreciably. This is due to
association or dissociation of the solute molecules in solution.
Association of solute particles. The formation of a larger particle/molecule by the union of two or more
solute molecules is called association ; nX  (X)n . As a result of association, the total number of
particles in solution becomes less than the number of molecules initially dissolved and hence, colligative
properties will have lower values. As the molar mass of solute is inversely proportional to colligative properties,
the molar mass of solute will be greater than the theoretical value.
Acetic acid in benzene and chloroacetic acid in naphthalene are examples. Aacetic acid dimerises in benzene,
or
The molar mass of acetic acid, in benzene, as determined from freezing point depression, is 118 instead of
60. Molecules of acetic acid exist as dimers, (CH3COOH)2 when dissolved in benzene.
Dissociation of solute molecules : Electrolytes undergo ionisation or dissociation in ionising solvents to

give more number of particles in solution, e.g., one molecule of AB dissociates to give two ions in solution.
 A   B
AB 
15
Dissociation results in an increase in the total number of particles, therefore, the values of colligative properties
of such solutions will be higher. As colligative properties are inversely related to molecular mass, molecular
mass of an ionisable solute will be less than the theoretical value.
van’t Hoff factor (i) : In order to express the extent of association or dissociation which certain solutes
undergo in solution, van’t Hoff in 1886, introduced a relation, called Van’t Hoff factor (i),
Observed valueof colligative property Normal molecular mass

i 
Calculated valueof colligative property Observed molecular mass.
Tota l n umber of particles after association / dissociation

i
Tota l n umber of particles before association / dissociation
In case of association of solute particles in solution, the observed molecular weight of solute being more
than the normal, the value of factor ‘i’ is less than unity (i < 1), while for dissociation the value of its greater
than unity ( i > 1), because the observed molecular mass has lower value than normal molecular mass.
The equations for colligative properties can be modified by the inclusion of van’t Hoff factor as follows :
P 0  Ps n
Relative lowering of vapour pressure of solvent  0
=i 2
P n1
(i) Depression of freezing point, Tf  i K f m ; (ii) Elevation of boiling point, Tb  i Kb m ;
(iii) Osmotic pressure,   i n 2 RT / V
16
QUESTIONS
LEVEL - I
1. Which of the following is an example of gaseous solution?
1) Solution of hydrogen in palladium 2) Camphor in nitrogen gas
3) Chloroform in nitrogen gas 4) Both 2 and 3
2. Which one of the following is used as an antifreeze for the automobile engines?
1) Propyl alcohol 2) Ethanol 3) Methanol 4) Ethylene glycol
3. The concentration of pollutants in water or atmosphere is often expressed in
1) Mass % 2) Volume % 3) Parts per million 4) Mole fraction
4. Equal masses of NaCl, KCl, AgNO3 and CaCl2 are dissolved in 1 litre of solution. Molarity is highest for
[Atomic mass of Na = 23, K = 39, Ag = 108, Ca = 40, N = 14, O = 16]
1) NaCl 2) KCl 3) AgNO3 4) CaCl2
5. Which of the following concentration factors is affected by change in temperature?
1) Molarity 2) Molality 3) Mole fraction 4) Mass percentage
6. Unit of molality is
1) g lit –1 2) mol lit–1 3) lit kg–1 4) mol kg–1
7. The molality of 648 g of pure water is
1) 36 m 2) 3.6 m 3) 55.5 m 4) 5.55 m
8. How many grams of NaOH are present in 250mL of 0.5 N NaOH solution?
1) 5g 2) 0.5g 3) 4g 4) 0.4 g
9. Among the following substances the lowest vapour pressure is exerted by
1) water 2) alcohol 3) ether 4) mercury
10. Partial pressure of volatile component in a solution is directly proportional to its mole fraction is
1) Henry’s law 2) Dalton’s law 3) Raoult’s law 4) Van't Hoff law
11. If the total vapour pressure of the liquid mixture A and B is given by the equation : P  180 X A  90 ,
then the ratio of the vapour pressure of the pure liquids A and B is given by
1) 3 : 2 2) 4 : 1 3) 3 : 1 4) 6 : 4
12. A solution containing components A and B follows Raoult’s law, when
1) A –B attraction is less than A –A or B –B
2) A –B attraction is greater than A –A or B –B
3) Volume of the solution is different from sum of volume of solvent and solute.
4) A –B interactions remain same as A–A or B–B
13. Which one of the following solutions show nearly ideal behaviour?
1) Ethanol and acetone 2) Benzene and toluene
3) Water and ethanol 4) Chloroform and acetone
17
14. For an ideal solution, the correct option is
1)  mix G = 0 at constant T and P 2)  mix S = 0 at constant T and P
3)  mix V  0 at constant T and P 4)  mix H = 0 at constant T and P
15. Which liquid pairs show a negative deviation from Raoult’s law?
1) Ethanol and acetone 2) Phenol and aniline
3) Chloroform and acetone 4) Both 2 and 3
16. Azeotropic mixture of nitric acid and water has
1) 84% HNO3 2) 68% HNO3 3) 63% HNO3 4) 20.2% HNO3
17. The colligative properties of a solution depend on
1) Nature of solute particles present in it 2) Nature of solvent used
3) Number of solute particles present in it 4) Number of moles of solvent only
18. Which of the following is not a colligative property?
1) Relative lowering of vapour pressure 2) Osmotic pressure
3) Surface tension 4) Depression in freezing point
19. In an equimolar solution of NaCl, CaCl2 and AlCl3 in water have boiling points T1, T2 and T3 respec-
tively, then
1) T1 > T2 > T3 2) T3 > T2 > T1 3) T2 > T1 > T3 4) T1 = T2 = T3
20. The unit of ebullioscopic constant is
1) K kg mol -1 or K (molality) -1 2) mol kg K-1 or K-1 (molality)
3) kg mol-1 K-1 or K-1 (molality) -1 4) K mol kg-1 or K (molality)
21. The proportionality constant kf is
1) Molal depression constant 2) Cryoscopic constant
3) Ebullioscopic constant 4) Both 1 and 2
22. What weight of glucose [C6H12O6] should be added to 800 g of water in order to increase its boiling
point by 5 K? (Kf of water = 1.86 K kg mol–1)
1) 487.09 g 2) 387.09 g 3) 267.08 g 4) 287.09 g
23. The use of anhydrous NaCl to clear snow on the road. This causes
1) A lowering of melting point of ice
2) A lowering of freezing point of water
3) Melting of ice at the atmospheric temperature
4) All of these
18
24. The preservation of meat by salting and of fruits by adding sugar protects them from bacterial action
because
1) Bacteria die of eating sugar or salt
2) Due to osmosis bacteria lose water on salted meat or candid fruit and die
3) Due to osmosis bacteria gain water on salted meat or candid fruit and die
4) Bacteria get stuck to the salt and sugar layers and die
25. 3g of glucose [mol.wt 180] dissolved in 60g of water at 15oC. The osmotic pressure of the solution
will be
1) 5.57 atm 2) 0.657 atm 3) 6.57 atm 4) 0.557 atm
26. Two solutions having same osmotic pressure are
1) Hypertonic solutions 2) Hypotonic solutions
3) Isotonic solutions 4) Colloidal solutions
27. When placed in water containing more than 0.9% (m/V) salt, blood cells will collapse. This is because
1) Due to loss of water 2) This solution is hypertonic
3) The solution is hypotonic 4) Both 1 and 2
28. In reverse osmosis
1) Solvent molecules pass from dilute solution to concentrated solution.
2) Solute molecules pass from concentrated solution to dilute solution.
3) Solvent molecules pass from concentrated solution to dilute solution.
4) Solute molecules pass from dilute solution to concentrated solution.
29. When benzoic acid dissolves in benzene, the observed molecular mass is :
1) 244 2) 61 3) 366 4) 122
30. Which of the following will have same value of van’t Hoff factor as that of K 4  Fe  CN 6  ?
1) Al2  SO4 3 2) AlCl3 3) Al  NO3 3 4) Al  OH 3
LEVEL - II
1. On dissolving sugar in water at room temperature, solution feels cool to touch. Under which of the
following cases dissolution of sugar will be most rapid
1) Sugar crystals in cold water 2) Sugar crystals in hot water
3) Powdered sugar in cold water 4) Powdered sugar in hot water
19
2. Which of the following statement(s) is/are correct?

i) Sugar solution is a homogeneous mixture
ii) Amalgam is an example of liquid solution
iii) In a given solution, sum of all the mole fractions is unity
iv) 10% glucose solution contains 90 g water
1) i, ii and iii 2) i, iii and iv 3) ii, iii and iv 4) ii and iii
3. Molefraction of 80g NaOH in 72g H2O is
1) 0.33 2) 0.67 3) 1 4) 0.5
4. 6.022×1020 molecules of urea are present in 100ml of its solution. The concentration of urea solution
is
1) 0.02 M 2) 0.01 M 3) 0.001 M 4) 0.1 M
w
5. Calculate the molarity of 2.1%   H SO solution
v 2 4
1) 2.14 2) 4.28 3) 0.428 4) 0.214
6. If 9g of glucose (C6H12O6) is present in 2000 g of an aqueous solution of glucose, it is said to be
1) 0.05 molal 2) 0.01 molal 3) 0.025 molal 4) 1 molal
7. Solubility of a substance is its maximum amount that can be dissolved in a specified amount of
solvent. It depends upon
(i) Nature of solute (ii) Nature of solvent (iii) Temperature (iv) Pressure
1) Only i, ii and iii 2) Only i, iii and iv
3) Only i and iv 4) i, ii, iii and iv
8. The term like dissolves like means
1) Polar solutes dissolve in polar solvents 2) Non-polar solutes dissolve in polar solvents
3) Polar solutes dissolve in non-polar solvents 4) None of these
9. Which one of the following statements is correct?
1) Naphthalene and anthracene dissolve readily in benzene
2) Dissolution of gases decreases with increase in temperature
3) Sodium chloride is insoluble in benzene
4) All are correcct
10. The vapour pressure will be lowest for
1) 0.1 M sugar solution 2) 0.1 M KCl solution
3) 0.1 M Cu(NO3)2 solution 4) 0.1 M AgNO3 solution
20
11. Which of the following is not correct for an ideal solution?
1) Hmix  0 2) It obeys Raoult’s law
3) Smix  0 4) Vmix  0
12. When HNO3 is added to water, the solution

1) shows negative deviation from Raoult’s law 2) shows positive deviation from Raoult’s law
3) shows nearly ideal behaviour 4) do not dissolve
13. What are the conditions for an ideal solution which obeys Raoult’s law over the entire range of con-
centration?
1)  mix H  0,  mix V  0, PTotal  p 0A x A  p 0B x B
2)  mix H   ve,  mix V  0, PTotal  p 0A x A  p 0B x B
3)  mix H  0,  mix V   ve, PTotal  p 0A x A  p 0B x B
4)  mix H  0,  mix V  0, PTotal  p 0B x B
14. Which of the following binary mixtures will have same composition in liquid and vapour phase at
certain composition?
1) n-heptane and n-hexane 2) chloro ethane and bromo ethane
3) carbon disulphide and acetone 4) benzene and toluene
15. A binary liquid solution is prepared by mixing n-heptane and ethanol. Which one of the following
statements is correct regarding the behaviour of the solution?
1) The solution formed is an ideal solution
2) The solution is non-ideal, showing +ve deviation from Raoult’s Law
3) The solution is non-ideal, showing -ve deviation from Raoult’s Law
4) n-heptane shows +ve deviation while ethanol shows -ve deviation from Raoult’s Law
16. 50 mL of phenol and 50 mL of aniline are mixed, the volume of the resulting solution will be
1) > 100 mL 2) < 100 mL 3) 100 mL 4) Unpredictable
17. If two liquids A and B form minimum boiling azeotrope at some specific composition then
1) A-B interactions are stronger than those between A-A or B-B
2) Vapour pressure of solution increase because more number of molecules of liquids A and B can
escape from the solution
3) Vapour pressure of solution decreases because less number of molecules of only one of the liquids
escape from the solution
4) A-B interactions are weaker than those between A-A or B-B
21
18. The vapour pressure lowering caused by the addition of 100 g of sucrose (molecular mass = 342 g
mol–1) to 1000 g of water, if the vapour pressure of water at 25oC is 23.8 mm of Hg is
1) 1.12 mm Hg 2) 0.125 mm Hg 3) 1.15 mm Hg 4) 1.25 mm Hg
19. Elevation in the boiling point for 1 molal solution of glucose is 2 K. The depression in the freezing point
for 2 molal solution of glucose in the same solvent is 2 K. The relation between Kb and Kf is
1) Kb = 1.5 Kf 2) Kb = 0.5 Kf 3) Kb = 2 Kf 4) Kb = Kf
20. Equimolal solutions in the same solvent have
1) Same boiling point and same freezing point
2) Same boiling point and different freezing point
3) Same freezing point and different boiling point
4) Different boiling point and different freezing point
21. When a substance is dissolved in a solvent, the vapour pressure of the solvent is decreased. This
results in
1) An increase in the boiling point of the solution
2) A decrease in the boiling point of the solution
3) Freezing point of the solution is increased
4) Osmotic pressure of the solution is lowered
22. 5g of Na2SO4 was dissolved in x g of H2O. The change in freezing point was found to be 3.82oC. If
Na2SO4 is 81.5% ionised, the value of x (Kf for water = 1.86oC kg mol–1) is approximately
1) 15g 2) 45g 3) 25g 4) 65g
23. Mn  nCl  MCln . 0.1 molal aqueous solution of this compound shows a depression in freezing
point of 0.558 o C. Assuming 100% ionisation of the compound. The compound will be
[Kf of H2O = 1.86 K kg mol–1]
1) MCl 2) MCl3 3) MCl2 4) MCl4
24. A solution of urea (mol mass 60g mol–1) boils at 100.18oC at the atmospheric pressure. If Kf and Kb
for water are 1.86 and 0.512 K kg mol-1 respectively, the above solution will freeze at
1) –6.54oC 2) –0.654oC 3) 6.54oC 4) 0.654oC
25. Which colligative property is more useful to determine the molecular weight of the substance like
proteins and polymers?
1) Lowering of vapour pressure 2) Elevation in boiling point
3) Osmotic pressure 4) Depression in freezing point
22
26. If 6 g of glucose (molecular weight 180) is dissolved in 90 g of water at 27oC. The osmotic pressure of
the solution will be
1) 12.4 atm 2) 6.12 atm 3) 9.12 atm 4) 10.2 atm
27. 10% solution of urea is isotonic with 6% solution of a non-volatile solute X. What is the molecular
mass of solute X?
1) 6 g mol–1 2) 60 g mol–1 3) 36 g mol–1 4) 32 g mol–1
28. Which of the following statement is correct?
1) A saturated solution will remain saturated at all temperatures
2) A plant swells when placed in hypertonic solution
3) The depression in freezing point is directly proportional to molality of solution
4) Lowering of vapour pressure is a colligative property
29. Acetic acid dissolved in benzene shows a molecular mass of
1) 30 2) 120 3) 60 4) 180
30. The van’t Hoff factor ‘i’ for a compound which undergoes dissociation in one solvent and association
in other solvent is respectively
1) less than one and greater than one
2) less than one and less than one
3) greater than one and less than one
4) greater than one and greater than one
23
KEY WITH HINTS

LEVEL - I
1. 4
2. 4
3. 3
x x
4. 1 No of moles of NaCl  , No of moles of KCl 
58.5 74.5
x x
No of moles of AgNO3  , No of moles of CaCl2 
170 111
5. 1
no of moles of soute
6. 4 molality 
weight of solvent in kg
648
7. 3 No of moles of water   36 mol
18
No of moles of solute 36  1000

Molality    55.5 m
Mass of solvent in kg 648
M  V inml 0.5  250

8. 1 No of moles of NaOH = =   0.125moles
1000 1000
Mass of NaOH = 0.125×40g = 5g
9 4 Mercury is non-volatile.
10. 3
11. 3 P  p10   p02  p10  x 2  p02  p10  180  p 02  180  90  270
Here p 2  p A and p1  p B p 0A : p 0B  270 : 90  3 :1

0 0 0 0
12. 4 Raoult’s law is valid for ideal solutions. For an ideal solution A–B interaction is same as A–A or
B–B. V  0 .
13. 2
24
14. 4 For an ideal solution
 mix G  0 at constant T and P ;  mix S  0 at constant T and P
 mix V  0 at constant T and P ;  mix H  0 at constant T and P
15. 4
16. 2 Azeotropic mixture of nitric acid and water has 68% nitric acid and 32% water by mass.
17. 3
18. 3
19. 2 Tb  iK b m i is greater for AlCl3
unit of Tb K K
20. 1 Unit of K b   ; 1
 K mol 1kg
unit of m molality mol kg
21. 4
K b  w 2  1000 Tb  M 2  w1 5  180  800

22 2 Tb  ; w2    387.09 g
M 2 .w 1 K b  1000 1.86  1000
23. 4
24. 2 Bacteria on salted meat or candid fruit loss water through osmosis shrink and die.
n 3 1000
25. 3 π = CRT = RT    0.0821 288  6.57 atm
V 180 60
26. 3
27. 4
28. 3
29. 1 Benzoic acid in benzene undergoes association through intermolecular hydgrogen bonding.
4
30. 1 K 4  Fe  CN 6   4K    Fe  CN 6  ; Al 2  SO4 3  2Al3  3SO24
LEVEL - II
1. 4 When powdered sugar is dissolved in hot water, powder form easily insert in the vacancies of
liquid particles. Further dissolution of sugar in water is an endothermic process.
2. 2
25
72g
3. 1 Molar mass of H2O = 18 gmol–1 ; No. of moles of H2O   4mol
18g
80g
Molar mass of NaOH = 40 g mol–1 ; No. of moles of NaOH   2 mol
40g
2 2
NaOH    0.33
24 6
6.022  1020
4. 2 No of moles of urea   10 3 moles
6.022  10 23
10 3  1000
Molarity   10 2  0.01M
100
w
  % 10 2.110
5. 4 M v    0.214
mol.wt 98
9
6. 3 9g glucose  mol  0.05 mol
180
n 0.05
Molality    0.025 molal
w1 2
7. 4
8. 1
9. 4
10. 3 Cu(NO3)2 give the maximum number of ions, so it causes the greatest lowering in vapour pres-
sure of water.
11. 3 For an ideal solution Smix is not equal to zero.
12. 1
13. 1
14. 3 Carbon disulphide and acetone show positive deviation and form azeotrope. 1,2 and 4 form
nearly ideal solution.
15. 2 n-heptane will decrease the inter-molecular forces between ethanol so it will increase the
vapour pressure than expected from Raoult’s law.
16. 2 Phenol and aniline show negative deviation.
17. 4 A-B attractive force should be weaker than A-A and B-B attractive forces. ‘A’ and ‘B’ can escape
easily from the solution, showing higher vapour pressure than expected value.
26
100
18. 2 Number of moles of sucrose   0.292 mol
342
1000
Number of moles of water   55.5 mol
18
Vapour pressure of pure water, po = 23.8 mm Hg
p n

p 0
nN
p 0.292

23.8 0.292  55.5
0.292  23.8
p   0.125 mm Hg
55.792
19. 3 Tb  2, m1  1, Tb  iK b m1

Tf  2, m 2  2, Tf  iK f m 2
Given, Tf  Tb ; iK f  2  iK b 1 K b  2K f

20. 1 Boiling point and freezing point depends on molality
1
21. 1 Boiling point of solution 
Vapour pressure
22. 2 Na 2SO 4  2Na   SO 42 
Initial : 1 mol 0 0
After ionisation 1  2 
Total no. of moles  1  2 ; i  1  2  1  2  0.815  2.63
1000  K f  w 2  i 1.86  2.63  5  1000

Tf  ;3.82 
M 2  w1 142  x
1.86  2.63  5000

 x  45g
142  3.82
23. 3 Tf  ik f m
Tf 0.558
i  3
k f m 1.86  0.1
The compound gives three ions.  The compound is MCl2
27
Tb 0.18
24. 2 Tb  K b  m m  
K b 0.512
0.18
Tf  K f  m  1.86   0.6540 C  Tf  0o  0.6540o  0.654o C
0.512
25. 3
n 6 1000
26. 3   CRT  RT    0.0821 300  9.12 atm
V 180 90
10 1 6
27. 3 No. of moles of urea =  ; Weight of solute, X = 6g ; No. of moles of X =
60 6 M
1 6
For isotonic solutions, n1 = n2 or  or M = 36 g mol–1
6 M
28. 3
29. 2 Acetic acid (CH3COOH) in benzene undergoes association and forms a dimer.
 Its molecular mass will be 2×60 =120
O H O
CH3 C C CH3
O H O
Dimer
30. 3 In case of dissociation, i is greater than1 and in case of association i is less than 1.
28
CHAPTER - 02
ELECTROCHEMISTRY
INTRODUCTION
Electrochemistry with chemical changes produced by electricity and the generation of electric current by
chemical changes. Electrochemical reactions involve electron transfer, and so they are redox reactions.
There are various extremely important electrochemical processes in both nature and in industry. The
transmission of sensory signals through neurons and communication between cells are known to be
electrochemical in nature. Electrochemical methods are employed in the extraction and refining of metals
and manufacture of chemicals. Batteries and fuel cells are extensively used in various systems and devices.
Coating of objects with metals and metal oxides by electrodeposition is important in protecting them from
corrosion.
ELECTROCHEMICAL CELLS
An electrochemical cell is a device which converts chemical energy into electrical energy and vice versa.
It is also called galvanic cell or voltaic cell after Luigi Galvani (1780) and Alessandro Volta (1800), who
made the basic discoveries. In an electrochemical cell, the decrease in free energy during an indirect
redox chemical reaction appears as electrical energy. In an indirect redox reaction, reduction and oxidation
are carried out in two separate vessels called half-cells or redox couples.
Figure - 01 Daniel cell.

Galvanic Cells
A galvanic cell consists of two half-cells or electrodes; a zinc electrode and a copper electrode. The electrodes
are connected using a metallic wire and the two solutions through a salt bridge. This setup is called Daniel
cell in which the following redox reaction occurs.
Zn(s) + Cu 2+ (aq) 
 Zn 2+ (aq) + Cu(s)
This reaction is a combination of two half reactions
Anode : Zn(s) 
 Zn2+(aq) + 2e- [Oxidation half-reaction]
Cathode : Cu2+(aq) + 2e- 
 Cu(s) [Reduction half-reaction]
29
Thus, in an electrochemical cell, the anode is the negative terminal and the cathode is the positive terminal.
By convention, the direction of flow of current is from positive terminal to the negative terminal, which is
opposite to the direction of flow of electrons.
Salt bridge. A salt bridge is an inverted U-tube filled with an aqueous solution of an inert electrolyte, such
as KCl, KNO3, NH4NO3 or K2SO4 mixed with agar-agar or gelatin to form a (semi-solid) jelly.
a. Requisites of the electrolyte used in salt bridge. (i) The electrolyte should be inert. (ii) The mobilities
of the cations and anions should be the same. (iii) The ions should not involve in any electrochemical
change.
b. Functions of salt bridge. (i) By completing the electrical circuit, it allows the flow of current. (ii) It
prevents intermixing of solutions and ions in the two half-cells. (iii) It helps to maintain electrical neutrality of
the solutions in the two half-cells. (iv) It eliminates liquid junction potential, which may decrease the e.m.f of
the cell.
Representation of electrochemical cell. A half cell is represented as M|Mn+ or Mn+|M where M stands for
the symbol of the metal and Mn+ for its cation. (i) A single vertical line represents the interface between the
two phases. (ii) The concentration of the electrolyte may be given in brackets. (iii) The two half cells are
separated by || (two vertical lines) which represents the salt bridge. The Daniel cell may be represented as :
Zn|Zn2+ (1.0 M)  Cu2+ (1.0 M)|Cu
By convention (IUPAC), anode or oxidation half cell is written on the left hand side and cathode or reduction
half cell is written on the right hand side.
STANDARD ELECTRODE POTENTIAL
Electrode potential depends on the concentration of the ions in solution and temperature. If the concentration
of every species taking part in the electrode reaction is unity and the reaction is carried out at 298K and 1 bar
pressure, the electrode potential is called standard electrode potential (E0).
1. Standard hydrogen electrode (SHE). The standard hydrogen electrode consists of a platinised platinum
electrode dipping in 1M solution of H+ ions (1M HCl) at 298K through which pure H2 gas at 1 bar is bubbled.
Pt, H2(g, 1bar), H+ (aq, conc = c) or Pt(s)|H2(g, 1bar)| H+ (aq, 1M)
By convention, the standard electrode potential (E0) of hydrogen electrode is taken as 0.00 volts.
Measurement of standard electrode potential
For measuring the electrode potential of an electrode, it is connected to SHE (anode) to form a cell.
Standard hydrogen electrode || Second half-cell
Since electrode potential of SHE is zero, the measured EMF is the electrode potential of the‘Second half-
cell’. The emf of the cell, E cell  E right  Eleft or E cell  E right  0 = E right
o o o o o o
Standard electrode potential is a measure of the tendency of the half cell reaction to occur in the forward
direction (reduction). The higher its positive value, the greater is the tendency of the oxidised form to get
reduced by accepting electrons.
Determination of standard electrode potential of Zn | Zn2+ electrode. For measuring the standard
electrode potential the zinc electrode is connected to SHE to form a cell and the emf is determined. The
measured emf is taken as the standard electrode potential of the zinc electrode.
Pt(s) H 2 (g,1bar) H  (aq,1M) Zn 2  aq,1M  Zn
 
0.76 V = 0.0 - E Zn 2+ (aq)| Zn(s) or E Zn 2+ (aq)| Zn(s) = - 0.76 V
E°cell = E°cathode – E°anode or
Thus, the standard EMF of the cell consisting of zinc half-cell (anode) and SHE (cathode) is 0.76V.
30
Electromotive Force (emf) or Cell Potential. It is defined as the difference between the electrode potentials
(reduction potentials) of the cathode and anode when no current is drawn through the cell.
Cell Potential, E cell  E cathode  E anode  E right  E left
EMF of the Daniel Cell. The EMF of the Daniel cell under standard conditions is given by

E°cell = E°cathode – E°anode = E Cu 2+ (aq) | Cu(s) – E  Zn 2+ /Zn = 0.34-(-0.76) = 1.1 V
Functioning of Daniell cell when external voltage opposing the cell potential is applied. If an opposite
external potential is applied on a galvanic cell, the reaction stops and no current flows from the cell when
the opposing voltage becomes equal to 1.1 V. Any further increase in external potential results in the reverse
reaction taking place in the half-cells, i.e., the cell starts to function as an electrolytic cell.
Electrochemical Series
It is also called Electromotive Series or Electrode Potential Series or Activity Series. The values of
standard electrode potentials arranged in the decreasing order is called electrochemical series. It is called
Activity Series since the relative activity of metals can be obtained by comparing their oxidation potentials.
Applications of Electrochemical Series. (i) Predicting spontaneity of a redox reaction:
(a) By calculating the standard EMF of the hypothetical redox reaction. If E°cell is positive, the reaction is
spontaneous in the given direction, otherwise not.
(b) Using the generalisation, “only those redox reactions are spontaneous in which the species with higher
reduction potential is reduced and the species with lower reduction potential is oxidised.”
(ii) To predict the reaction of a metal with dilute acids to liberate hydrogen : As SRP of hydrogen is
zero, metals having negative reduction potentials displace hydrogen from acids. For example,
Zn (E° = -0.76V) which is below hydrogen in the series displaces hydrogen from dilute acids, whereas Cu
(E0 = 0.34 V) which lies above hydrogen do not displace hydrogen from dilute acids.
Na  H 2SO 4   2 NaOH  H 2 ; Cu  H 2SO 4 
 Na 2SO 4  H 2 ; 2Na  2H 2 O   No reaction
(iii) Determination of EMF of a cell : Electrodes having low standard reduction potentials (SRP) act as
anodes while those having high reduction potentials act as cathodes.
Standard EMF of cell = Standard reduction potential of cathode - Standard reduction potential of anode.
E o cell  E o cathode  E o anode or E o cell  E o right  E o left or E°cell = E°(reduction) - E°(oxidation)
NERNST EQUATION
The electrode potential of an elecrode at a given concentration and temperature can be calculated from the
standard electrode potential using Nernst equation. For the electrode reaction,
 M(s) ,
M n  (aq)  ne  
RT [M] RT [M]
E (Mn  / M)  E (Mn  / M)  ln or E  E  ln
nF [M n+ ] nF [M n+ ]
where E is the electrode potential under given conditions of temperature and concentration, E° is the
standard electrode potential, R is Gas constant, T is the temperature (K), F is Faraday and n is the number
of electrons gained or lost according to the balanced equation.
Substituting the values of R (8.314 J K-1 mole-1), T (298K), and F(96487 coulomb mol–1).
2.303×8.314 J K-1 mol-1×298 K

 [M]
E=E - log
n  96500 C mol -1
[Mn+ ]
31
For pure solids, liquids and gases at one atmosphere, molar concentration, [M] is taken as unity, therefore,
0.0591 V 1
E  E  log
n [M n+ ]
where Q is the reaction coefficient of the electrode reaction.
Nernst equation for the Daniel cell (n = 2, both for Cu and Zn)
The electrode potential for any given concentration of Cu2+ and Zn2+ ions:
RT 1
For cathode: E (Cu 2+ | Cu) = E  (Cu 2+ | Cu)  ln
nF [Cu 2+ (aq)]
 RT 1
For anode: E (Zn 2+ | Zn) = E (Zn 2+ | Zn)  ln
nF [Zn 2+ (aq)]
 
Cell potential : E cell  E (Cu 2+ | Cu)  E (Zn 2+ | Zn)
 0.0591 1    0.0591 1 
= E (Cu 2+ | Cu)  log 2+   E (Zn2+ | Zn)  log 2+ 
 2 [Cu (aq)]   2 [Zn (aq)] 
  0.0591  Zn 2 (aq) 
E cell = E (Cu 2+ | Cu)  E (Zn 2+ | Zn)  log
2 [Cu 2+ (aq)]
0.0591 [Zn 2+ ] 0.0591 [Zn 2+ ]
E cell = 0.34  (  0.76)  log = 1.1  log
2 [Cu 2+ ] 2 [Cu 2+ ]
0.0591 [Zn 2+ ]
In general, E cell = E cell  log
2 [Cu 2+ ]
Equilibrium Constant from Nernst Equation
In a Daniel cell, with time, concentration of Zn2+ ions increases while concentration of Cu2+ ions
decreases.
Zn/Zn2+(aq)  Cu2+(aq)/Cu
After some time, there will be no change in the concentrations of Zn2+ and Cu2+ ions and an voltmeter gives
zero reading, indicating attainment of equilibrium.
 Zn2+(aq) + Cu(s)
Zn(s) + Cu2+(aq) 
Considering the concentrations of Zn(s) and Cu(s) to be unity, the equilibrium constant for the reaction is
[Zn2 (aq)]eqm
Kc 
[Cu2 (aq)]eqm
Nernst equation for the above reaction at equilibrium becomes
2.303RT [Zn2+ (aq)]
Ecell = Ecell  log
2F [Cu2+ (aq)]
Since Ecell at equilibrium is zero
2.303RT [Zn 2+ (aq)]eqm
0 = E ocell  log
2F [Cu 2+ (aq)]eqm
2.303RT [Zn 2+ (aq)]eqm
or E cell  log
2F [Cu 2+ (aq)]eqm
2.303RT
E  cell  log K c
2F
32
The value of Kc for the reaction is 2  1037 which indicates that the reaction proceeds almost to completion.
2.303RT
In general, E  cell  log K c
nF
where n is the number of electrons transferred during the reaction.
Substituting the values of R (8.314J K-1 mol-1), T (298K) and F (96500 C)
0.059 n
E  cell  log K c or log K c  E  cell
n 0.059
The equation gives a relationship between equilibrium constant for the reaction and standard potential of
the cell. Thus, the equilibrium constant can be calculated from the E° value of the cell.
Substituting the value of E0cell for Daniell cell = 1.1 V
0.059 (1.1  2)
1.1V  log K c or log K c  =37.2881
2 0.059
K c = 1.94  1037  2.0  1037 at 298 K
Electrochemical Cell and Gibbs Free Energy of Reaction

For a cell reaction to be spontaneous, DG° must be negative which means that E°cell must be positive. The
standard free energy change,
DrG° = –RT ln Kc or DrG° = –2.303 RT log Kc
where Kc is the equilibrium constant at T K.
Kc can be calculated from E°cell using the relation, n  E°cell = 0.0591 V  log Kc.
CONDUCTANCE OF ELECTROLYTIC SOLUTIONS

Resistivity or specific resistance,  . The resistance of a conductor is the ratio of the applied potential
difference V to the current I flowing through it. Electrical resistance is denoted by the symbol R and is
measured in ohm (W). In terms of SI base units, it is (kg m2)/(S3A3). The resistance R of a conductor of
uniform cross section is directly prportional to its length l and inversely proportional to its area of cross
section A.
l l A
R or R  or R
A A l
where  is a constant and called resistivity or specific resistance. Its SI unit is ohm metre (W m). Its
submultiple, ohm cm (W cm) is also used.
When l = 1 m and a = 1m2, then R=  . Thus, resistivity may be defined as the resistance of a conductor
of unit length (1 m) and unit area of cross section (1 m2).
Unit of resistivity = (ohm  m2 ) / m = ohm m or W m ; 1  m  100  cm or 1  cm  0.01  m.

Conductance, G. It is the reciprocal of resistance. Conductance is a measure of the ease with which
current flows through of a conductor.
1 A A
G  k
R l l
33
G is expressed in ohm-1 or mho, W -1. The SI unit of conductance is Siemens (S).
Conductivity or specific conductance (  )
The reciprocal of resistivity is called conductivity or specific conductance, denoted by the Greek letter k
(kappa). It may be defined as the conductance of 1m3 of the conductor (conductance of a solution of length
1m and area of cross section 1 m2).
1 1 l l
Conductivity,    or   G
 R A A
Units of conductivity : ohm-1 cm-1, W -1 cm-1 or S cm-1. SI unit of k : W -1 cm-1 or S m-1.
Measurement of Conductivity of Ionic Solutions
Resistance can be measured using Wheatstone bridge. However, measuring the resistance of an ionic
solution by passing a direct current (DC) changes the composition of the solution, therefore, an alternating
current (AC) source of power is used. The solution of the electrolyte is connected to the Wheatstone bridge
using a specially designed vessel called conductivity cell.
i.Conductivity cell. A conductivity cell is made up of pyrex glass and has two Pt electrodes of area of
cross section, A, fitted at a distance ‘l’ apart. The solution confined between the electrodes is a column of
area of cross section A and length l. The resistance of the column of solution is given by
l l
R  
A A
The quantity, l/A is called cell constant, denoted by G*. Once the cell constant is determined, it can be used
for measuring the resistance (or conductivity) of any solution.
l
G*   R
A
The cell constant is determined by measuring the resistance of a solution whose conductivity is known.
Generally, KCl solutions of known specific conductivities at different concentrations and temperatures are
used.
l l (cm) l (m)
Units of cell constant, G*   2
 cm 1 or  2
 m 1
A A(cm ) A(m )
(a)
Figure - 02 (a) Wheatstone bridge

ii. Wheatstone bridge. It consists of four arms containing resistances R1, R2, R3 and R4. R1 is a variable
resistance and R2 is the unknown resistance (conductivity cell). R1 is varied to obtain null point (no deflection
in the galvanometer, P). Knowing the values of R1, R3 and R4, R2 can be calculated.
34
R1 R 3 R 1R 4
 or R2 
R2 R4 R3
These days, conductivity meters are available which can directly read the conductance or resistance of the
solution in the conductivity cell. Knowing the cell constant and the resistance of the solution in the conductivity
cell, conductivity of the solution can be calculated.
cell constant G *
Conductivity,   
R R
Conductivity decreases with dilution. The conductivities of solutions of different electrolytes in the same
solvent at a given temperature may be different due to differences in charge and size of ions, concentration
of ions and ease with which ions move under a potential gradient. Therefore, a quantity called molar
conductivity,  m (Greek, lambda) , is calculated.
Molar conductivity ( Λm )
Molar conductivity is the conductance of volume, V, of solution containing one mole of electrolyte, kept
between two electrodes with area of cross section, A, kept unit distance apart. It is the product of
conductivity    and volume (V in mL) which contains one mole of the electrolyte.
  1000
m  = V or m  [M=Molarity]
c M
Units of molar conductivity: ohm–1 cm–2 mole-1 or S cm2 mol-1, S m2 mol–1 (SI unit).
Molar conductivity increases with dilution. When concentration approaches zero, the molar conductivity is
called limiting molar conductivity, om .
Variation of Conductivity and Molar Conductivity with Concentration
Both conductivity and molar conductivity vary with concentration of the electrolyte. Conductivity decreases
with dilution, both for weak and strong electrolytes. This because the number of ions per unit volume
decreases (conductivity of a solution at a given concentration is the conductance of unit volume of solution).
A
G  [both A and l are unity]
l
Molar conductivity increases with dilution. This is because the total volume, V, of the solution containing one
mole of electrolyte increases on dilution (molar conductivity of a solution at a given concentration is the
conductance of all the ions in volume V of solution).
A
m  =  or m  V [since l=1 and A=V]
l
The variation in  m with concentration is different for strong and weak electrolytes.
i. Conductance of Strong electrolytes. In case of strong electrolytes, molar conductivity varies with
concentration according to the equation,
 m   om  A c
where A is a constant depending on the type of electrolyte, nature of solvent, and temperature, and  om is
the molar conductivity at infinite dilution, called limiting molar conductivity. This equation is known as
Debye Huckel-Onsager Equation.
The value of A for a given solvent and temperature depends on the type of electrolyte. Depending on the
charges on cation and anion, NaCl, BaCl2 and MgSO4 are called 1-1, 2-1, and 2-2 electrolytes respectively.
35
For a given solvent and temperature, all electrolytes of a particular type have the same value for A.
When  m is plotted against c , a linear graph is obtained for low concentrations (with slope = –A) and a
non-linear graph for higher concentrations. The curve shows only a small increase in conductance with
dilution. This is because a strong electrolyte is completely dissociated in solution.
Figure - 03 Variation of molar conductivity of strong and weak electrolytes with concentration.
At higher concentrations, greater inter-ionic attractions retard the motion of ions, therefore, conductance
decreases with increase in concentration. Conductance increases with dilution (as ions move far apart )
and approaches a maximum limiting value at infinite dilution. The plot becomes linear at high dilutions.
Thus, it can be extrapolated to zero concentration to get the value of the molar conductivity at infinite
dilution,  om .
ii. Weak Electrolyte : A weak electrolyte does not dissociate appreciably, therefore, its conductance is
much lower than that of a strong electrolyte at the same concentration.  m increases steeply on dilution,
especially near low concentrations. Hence, extrapolation to zero concentration is not possible.
Kohlrausch’s Law of Independent Migration of Ions
Kohlrausch’s law states that the limiting molar conductivity of an electrolyte can be represented as the
sum of the individual contributions of the anion and cation of the electrolyte.
The individual contribution of an ion towards the total molar conductivity of the electrolyte is called molar
 xA + yB
ionic conductivity. For the reaction, AxBy 
Λ m(A x By ) = x λ (A y+ ) + y λ Bx-
 
 
where λ (A y+ ) and λ (Bx- ) are the molar conductivities of cations and anions respectively at infinite dilution
(limiting ionic conductivties). Subscripts x and y are the number of cations and anions furnished by one
formula unit of the electrolyte at infinite dilution.
Applications of Kohlarausch’s Law

(i) Calculation of molar conductivity at infinite dilution ( Λ  or Λ m ) for weak electrolytes. The molar
conductivity of a weak electrolyte at infinite dilution cannot be determined experimentally because (i) the
conductance of a very dilute solution is very low and (ii) dissociation of a weak electrolyte is not complete
even at very high dilutions.
(ii) Degree of dissociation of weak electrolytes.
 m Molar conductivity at a given concentration
Degree of dissociation,   
 om Molar conductivity at infinite dilution
iii) Dissociation constant of weak electrolyte. Degree of dissociation  at concentration c can be
calculated by measuring the molar conductivity at that dilution. The dissociation constant Kc for a weak
c 2 c2m
electrolyte of the type A B can be calculated as,
+ - Ka  
1   m (m m )
36
ELECTROLYTIC CELLS AND ELECTROLYSIS

The process of decomposition of an electrolyte by the passage of electricity is called electrolysis or
electrolytic dissociation. Electrolysis is carried out in an electrolytic cell, which consists of two electrodes
(metal strips) dipping in a solution or melt of a suitable electrolyte. For electrolysis, a direct current (DC) is
passed.
Factors which determine products of electrolysis: (i) Electrode potential of the reactions occuring at
the electrodes. (ii) Over potential of gases with respect to the electrode at which they are liberated. (iii)
Concentration of ions in solution. (iv) Type of electrodes, i.e., active and inactive electrodes.
a. Electrolysis of fused sodium chloride: When fused sodium chloride is electrolysed, Na+ ions move
towards the cathode and Cl- ions move towards the anode. At the cathode, Na+ ions accept electrons to
form sodium metal. At the anode, Cl- ions lose electrons and form Cl2 gas.
At anode : Cl- - e- 
 Cl (oxidation; primary change) ; Cl + Cl 
 Cl2 (secondary change)
At cathode : Na  (aq)  e  
 Na(s)
b. Electrolysis of aqueous solution of NaCl. Sodium chloride and water ionise as :
NaCl(aq)  Na+(aq) + Cl–(aq) (completely ionised) ; H2O(l) 
 H+(aq) + OH–(aq) (feebly ionised)
At the cathode, the following reduction reactions are possible :
Na  (aq)  e  
 Na(s) E cell  2.71 V (i)
H  (aq)  e  
 12 H 2 (g) E cell  0.00 V (ii)
The reaction with higher value of Eº is preferred, therefore, the reaction at the cathode is (ii).
However, H+(aq) is produced by the dissociation of H2O
H 2 O(l ) 
 H + (aq) + OH - (aq) (iii)
Therefore, the net reaction at the cathode may be written as the sum of Eqns. (ii) and (iii).
H 2 O(l ) +e - 
 1
2 H 2 (aq) + OH - (aq)
At the anode, the following oxidation reactions are possible :
Cl- (aq) 
 12 Cl 2 (g)+e- E cell  1.36 V (iv)
 O 2 (g)  4H  (aq) + 4e -
2H 2 O(l )  E cell  1.23 V (v)
The reaction at anode with lower Eº is preferred, therefore, water should get oxidised in preference to
Cl-(aq).
However due to over potential of oxygen, reaction (v) is preferred. The net reaction is:
NaCl(aq) + H 2 O(l) 
 Na + (aq) +OH - (aq) + 1
2 H 2 (g) + Cl- (aq)
c. Electrolysis of Sulphuric acid. The following processes are possible at the anode:
 O 2 (g)  4H  (aq) + 4e -
2H 2 O(l )  E cell  1.23 V (vi)
2SO 24 (aq) 

 S2 O82 (aq)  2e - E cell  1.96 V (vii)
For dilute H2SO4, reaction (vi) is preferred, but at higher concentrations of H2SO4, reaction (vii) is preferred.
Quantitative Electrolysis - Faraday’s laws
Michael Faraday (1833) deduced the relationship between the quantity of substances liberated at the
electrodes and the quantity of current passed through a solution of an electrolyte during electrolysis.
37
1. Faraday’s first law of electrolysis: The amount of substance deposited or liberated at an electrode is
directly proportional to the quantity of electricity passed through the electrolyte.
If a current of I amperes is passed for t seconds, the quantity of charge, Q = It.
If W gram of substance is deposited by Q coulombs of electricity, W  Q
W=ZQ or W  ZIt
where Z is a constant known as electrochemical equivalent. Its value is different for different species.
When Q = 1coulomb, W = Z
Thus, electrochemical equivalent may be defined as the weight in grams of an element liberated by the
passage of 1 coulomb of electricity.
Units of Z = gram/coulomb.
Faraday (F). It is the charge of 1 mole of electrons = 6.022×1023×1.6021×10-19 @ 96500 C.
Equivalent mass of subs tan ce in grams
Therefore, Z 
96500 Coulomb
If n electrons are involved in the electrode reaction, the passage of n Faradays will liberate n equivalents of
the substance. For example, Ag   e   Ag requires 1 Faraday of electricity to deposit 1 gram equivalent
(Avogadro’s number) of atoms of Ag (107.8682 g).
Cu 2  2e 
 Cu requires 2 Faradays of electricity to deposit 2 gram equivalents (Avogadro’s number) of
atoms of Cu (63.546 g).
Similarly, Al 3  3e  
 Al requires 3 Faradays of electricity to deposit 3 gram equivalents (Avogadro’ss
number) of atoms of Al (26.9815 g).
2. Faraday’s second law of electrolysis: When the same quantity of electricity is passed through solutions
of different electrolytes, the masses of different substances liberated at the electrodes are proportional to
their equivalent masses.
WE
where E is the equivalent mass. If W 1 and W 2 are the masses of two substances deposited at the electrodes
and E1 and E2 are their equivalent masses then, according to Faraday’s second law
W 1  E1 and W 2  E2
W1 E1
or 
W2 E 2
SOME COMMERCIAL CELLS (BATTERIES)

A cell is basically an electrochemical cell in which chemical energy is converted to electrical energy.
Types of commercial cells:
(i) Primary cells. Cells in which the redox reaction occurs only once and the cell becomes dead over a
period of time and cannot be used again, e.g., dry cell, and mercury cell.
(ii) Secondary cells. Secondary cells can be recharged by passing electric current through them so that
they can be used again and again, e.g., lead storage battery, and Ni-Cd storage cell.
(iii) Fuel cells. Cells in which energy produced by the combustion of fuels like H2, CO, CH4, etc., is directly
converted into electrical energy.
38
Primary Cells
1. Dry Cell. The dry cell is a compact Leclanche cell (discovered by G Leclanche in 1868). The anode
consists of a zinc container and the cathode is a graphite rod surrounded by powdered MnO2 and carbon.
The space between the electrodes is filled with a moist paste of NH4Cl and ZnCl2.
Figure - 04 (i) Commercial dry cell (ii) Mercury cell.

The electrode reactions can be written approximately as :
 Zn 2  2e  ; Cathode : MnO 2  NH 4  e  
Anode : Zn(s)   MnO(OH)  NH 3
In the cathode reaction, manganese is reduced from the +4 oxidation state to the +3 state. Ammonia is not
liberated as a gas but combines with Zn2+ to form [Zn(NH3)4]2+Cl22- [tetrammine zinc (II) chloride]. These
cells have voltage in the range 1.2 - 1.5V. However, they do not have long life because acidic NH4Cl corrodes
the zinc container even when the cell is not in use.
2. Mercury Cell. Mercury Cell (Discovered by Samuel Ruben) is used in small electrical devices like watches,
hearing aids, etc. It consists of a zinc container as anode, a carbon rod as cathode and moist mercuric
oxide mixed with KOH as electrolyte. A lining of porous paper keeps the electrolyte separated from the zinc
anode.
Anode: Zn(Hg) + 2OH- 
 ZnO(s) + H2O(l) + 2e-
Cathode: HgO(s) + H2O(l) + 2e- 
 Hg(l) + 2OH-
Overall reaction: Zn(Hg) + HgO(s) 
 ZnO(s) + Hg(l)
The overall reaction does not involve any ions whose concentration changes, therefore, the cell gives a
constant voltage (1.35V) throughout its life. However, the spent cells may cause severe environmental
pollution.
Secondary Cells
1. Lead Storage Battery. It is one of the most common batteries used in automobiles and inverters. It was
discovered by Gaston Plante. It consists of a lead anode and a grid of lead packed with lead dioxide as
cathode. A solution of sulphuric acid (38 percent by mass or having density 1.30 g cm–3) is used as electrolyte.
When the cell discharges, it operates as a voltaic cell.
At Anode : Pb(s)  SO 24 (aq) 
 PbSO 4 (s)  2e  (Precipitation)
At Cathode : PbO2 (s)  SO42 (aq)  4H (aq)  2e 
 PbSO4 (s)  2H2O(l )
 2
 2PbSO 4 (s)  2H 2O  l 
Over all reaction: Pb(s)  PbO 2 (s)  4H (aq)  2SO 4 (aq) 
39
A 12 V lead storage battery generally consists of 6 cells, each producing 2 volts.
(i) (ii)
Figure - 05 (i) Lead Storage Battery (ii) Nickel-Cadmium Cell

The concentration of H2SO4 decreases during discharge. When the concentration falls below 1.20 g cm-3,
the battery needs recharging. When a potential greater than the potential of the battery is applied, it can be
recharged. During recharging, the cell operates like an electrolytic cell. The electrode reactions are the
reverse of those that occur during discharge,
 Pb(s)  PbO 2 (s)  4H  (aq)  2SO 4  (aq)
2PbSO 4 (s)  2H 2 O 
2. Nickel-Cadmium Cell. Nickel-cadmium storage cell is extensively used in electronic equipments. It has
longer life than lead storage cell, but more expensive. It consists of a cadmium electrode (anode) and a
metal grid containing nickel(IV) oxide (cathode) immersed in KOH solution.
At Anode : Cd(s)  2OH  (aq) 
 Cd(OH) 2 (s)  2e 
At Cathode : NiO2 (s)  2H 2 O  l   2e 

 Ni(OH)2 (s)  2OH 
Over all reaction: Cd(s)  NiO 2 (s)  2H 2 O 
 Cd(OH) 2 (s)  Ni(OH) 2 (s)
The potential of Ni-Cd cell is 1.4V. As in a lead storage cell, the products of reaction adhere to the electrodes.
Hence, the reactions can be reversed by recharging.
As no gases are evolved, the battery can be sealed.
3. Lithium Ion Battery. Rechargeable battery used in cell phones, laptop computers, etc. They have still
higher voltage (3.6 - 3.7).
Fuel Cells. These are Galvanic cells that are designed to convert free energy of combustion of fuels
such as H2, CO, CH4, etc., directly into electrical energy.
Hydrogen-Oxygen Fuel Cell (Bacon cell) : It is a fuel cell that uses the reaction of hydrogen with oxygen
to form water.
Figure - 06 Hydrogen - oxygen fuel cell.
40
In the cell, H2 and O2 are bubbled through porous carbon electrodes containing suitable catalysts (finely
divided Pt or Pd) into concentrated aqueous KOH or NaOH solution.
Anode: 2H 2 (g)  4OH  (aq) 

 4H 2 O(l )  4e  ; Cathode : O 2 (g)  2H 2 O(l )  4e  
 4OH  (aq)
Overall reaction : 2H 2 (g) + O 2 (g) 

 2H 2 O(l )
This cell produces 0.9 V and works continuously as long as the reactants are supplied (efficiency : 60-70%).
The major difficulty is the storage of H2 and O2 which requires very low temperatures and very high pressures.
CORROSION
Corrosion is the wearing away of metal by the attack of atmospheric gases and mositure resulting in the
formation of oxides, sulphides, carbonates, sulphates, etc. It is basically an electrochemical phenomenon.
Rusting of iron, tarnishing of silver, development of green coating on copper and bronze, etc., are examples.
Mechanism of Corrosion
Electrochemical theory: This theory explains the formation of rust on the basis of formation of
electrochemical cells on the surface of the metal.
ii) Iron in contact with dissolved O2 and H+ ions undergoes oxidation (anode) to form Fe2+ ions.
 2Fe 2 (aq)  4e 
At anode : 2Fe(s)  ; E (Fe2 / Fe)  0.44 V
Figure -07 Corrosion.

iii) The electrons lost by iron migrate through the metal to other sites on the surface and reduce dissolved
oxygen in the presence of H+ ions (cathode).
 
At cathode : O2 (g)  4H (aq)  4e  2H2O (l) (Ered  1.23V)
o
The overall reaction of the miniature cell will be
2Fe(s)  O 2 (g)  4H  (aq)  2Fe 2 (aq)  2H 2 O (l) ; E ocell  1.67 V

iv) The ferrous ions formed react with dissolved oxygen or oxygen from air to form ferric oxide with further
production of H+ ions.
2 
4Fe (aq )  O 2(g )  4H 2 O ( l )  2Fe 2 O 3(s )  8H (aq )
v) Ferric oxide then undergoes hydration to form hydrated ferric oxide (rust).
Fe2 O3  xH 2 O  Fe 2 O3 .xH 2 O
Rust peels off, exposing fresh iron surface for further rusting.
It is observed that iron in contact with a solution whose pH is above 9 - 10 does not corrode.
41
Prevention of Corrosion
1. Barrier Protection. The metal surface is prevented from coming into contact with moisture, oxygen, and
carbon dioxide by the following methods :
a) The metal surface is coated with paint.
b) Rusting of the surface of iron tools and machinery can be prevented by applying a film of oil or grease.
c) The iron surface is coated with non-corroding metals such as nickel, chromium, etc.
Protective coating can be applied by any of the following methods :
i) Electroplating: Iron article is coated with nickel, chromium, aluminimum, etc. by electrodeposition.
ii) Galvanisation. The process of coating an iron article with a protective layer of zinc by dipping it in molten
zinc is called galvanisation. The layer of Zn on the surface of iron, when comes in contact with mositure,
oxygen and carbon-dioxide in air, form a protective thin layer.
3. Electrical Protection (Cathodic Protection). The iron object to be protected is connected to a more
active metal, either directly or using a wire. The iron object acts as cathode and the protecting metal acts as
anode. The anode is gradually used up as a result of oxidation to its ions (due to loss of electrons). These
electrons are transferred through the wire to H+ ions present around the iron object and thus protects it from
rusting. As iron object acts as cathode, it is called cathodic protection. Metals used for protecting iron
objects from rusting are magnesium, zinc and aliminium which are called sacrificial anodes.
42
QUESTIONS
LEVEL - I
1. In an electrochemical cell, energy change is
1) Heat energy to electrical energy 2) Mechanical energy to electrical energy
3) Chemical energy to electrical energy 4) Electrical energy to chemical energy
2. Which of the following statements is not true for Daniel cell?
1) Electrons flow from zinc electrode to copper electrode
2) Current flows from copper electrode to zinc electrode
3) Cations move towards copper electrode which is cathode
4) Cations move towards zinc electrode which is anode
3. In a galvanic cell, the salt bridge :
1) separates cathode from anode
2) reduces the electrical resistance of the cell
3) completes the circuit
4) carry salts for the chemical reaction
4. The standard reduction potentials for Zn2+/Zn, Ni2+/Ni and Fe2+/Fe are –0.76, –0.23 and –0.44 V
respectively. The reaction: X  Y 2  
 X 2   Y will be spontaneous when :
1) X = Ni, Y = Fe 2) X = Ni, Y = Zn
3) X = Fe, Y = Zn 4) X = Zn, Y = Ni
5. The standard reduction potential, Eo for the half-reactions are as follows :
Zn  Zn 2  2e  ; E o   0.76 V
Fe  Fe2   2e  ; E o   0.44 V
The EMF for the cell reaction, Fe2   Zn 
 Zn 2   Fe is :
1) –0.32 V 2) + 0.32 V 3) + 1.20 V 4) –1.20 V
6. The standard reduction potential at 298 K for the following half cell reactions are given below.
Zn 2  2e  
 Zn (s) E o   0.76 V ;Cr3aq   3e 
 Cr(s) E o  0.74 V
2Haq   2e  
 H 2g  E o  0.00V ; Fe3 aq   1e  
 Fe2aq  E o  0.77 V
Which is the strongest reducing agent.
1) Zn(s) 2) H2(g) 3) Fe2+(aq) 4) Cr(s)
7. The position of some metals in the electrochemical series is given below.
Mg > Al > Zn > Cu
What will happen if a copper spoon is used to stir a solution of aluminium nitrate?
1) The spoon will get coated with Al
2) An alloy of copper and aluminium is formed
3) The solution becomes blue
4) There is no reaction
43
8. Daniell cell is shown as
1) Zn  s  / Zn 2aq  || Cu  s  / Cu 2aq  2) Zn  s  / Zn 2aq  || Cu 2aq  / Cu  s 
3) Zn  s  / Zn 2aq  || Cu  s  / Cu 2aq  4) Zn  s  / Cu 2aq  || Zn 2aq  / Cu  s 
9. Which of the following will turn blue when placed in copper vessel?
1) NaCl(aq) 2) MgSO4(aq) 3) AgNO3(aq) 4) ZnSO4(aq)
10. Out of Cu, Fe, Ag and Zn the metal which can displace all others from their salt solution is
1) Cu 2) Fe 3) Ag 4) Zn
11. Consider the following reduction processes :
(i) Zn 2   2e  
 Zn(s) ; E o   0.76 V ; (ii) Ca 2   2e 
 Ca(s) ; E o   2.87 V
(iii) Mg 2  2e 
 Mg(s) ; E o   2.36 V ; (iv) Ni 2   2e  
 Ni(s) ; E o   0.25 V
The reducing power of metals increases in the following order :
1) Ca < Mg < Zn < Ni 2) Ni < Zn < Mg < Ca 3) Ca < Zn < Mg < Ni 4) Zn < Mg < Ni < Ca
12. The difference between the electrode potential of two electrodes when no current is drawn through the
cell is called
1) cell potential 2) cell emf 3) potential difference 4) cell voltage
13. EMF of the cell Ni Ni 2   0.1M  Au 3 1.0 M  Au will be: (Given E Ni2 / Ni  0.25 V, E Au3 /Au  1.5 V )
o o
1) 1.75 V 2) +1.7795 V 3) +0.7795 V 4) –1.7795 V

14. The oxidation potential of hydrogen electrode at pH = 10 and p(H2) = 1 atm is
1) +0.59 V 2) –0.59 V 3) –0.118 V 4) +0.118 V
15. What is the potential of an electrode consisting of Zn metal in solution in which the zinc ion concentration
is 0.01M? (Zn 2  2e  
 Zn; E o  0.763V)
1) –0.781 V 2) –0.904 V 3) –0.863 V 4) –0.822 V
16. For a cell reaction involving a two-electron change, the standard emf of the cell is found to be 0.295 V
at 298K. The equilibrium constant for the reaction is :
1) 10 2) 1 × 1010 3) 29.5 × 10–2 4) 1 × 10–10
17. Cell reaction is spontaneous when
1) E ored is negative 2) G o is negative 3) E ooxid is positive 4) G o is positive
18. The equilibrium constant Kc for the reaction, Cu(s)  2 Ag  (aq) 

 Cu 2  (aq)  2 Ag(s) at 298 K is
101015 . E ocell for the reaction is :
1) 0.4728 mV 2) 0.04728 mV 3) 0.04728 V 4) 0.4728 V
44
19. The standard Gibbs energy for the cell reaction, Zn(s)  Cu 2 (aq) 
 Zn 2  (aq)  Cu(s) ; E o  2V,
at 298 K (in kJ mol–1) is : (Faraday’s constant, F = 96500 C mol–1)
1) –193 2) 193 3) –386 4) 386
20. Which of the following statement is not applicable to electrolytic conductors?
1) New products show up at the electrodes
2) Ions are responsible for carrying current
3) Show a positive temperature coefficient for conductance
4) A single stream electrons flow from cathode to anode
21. An increase in equivalent conductance of a strong electrolyte with dilution is mainly due to
1) increase in ionic mobility of ions
2) 100% ionisation of electrolyte at normal dilution
3) increase in both number of ions and ionic mobility
4) increase in number of ions
22. The molar conductance of NaCl, HCl and CH3COONa at infinite dilution are 126.45, 426.16 and
91 ohm–1 cm2 mol–1 respectively. The molar conductance of CH3COOH at infinite dilution is
1) 201.28 ohm–1 cm2 mol–1 2) 390.71 ohm–1 cm2 mol–1
3) 698.28 ohm–1 cm2 mol–1 4) 540.48 ohm–1 cm2 mol–1
23. Which one of the following statement is wrong?
1) Conductivity always decreases with decrease in conc.both for strong and weak electrolytes
2) Molar conductivity increases with decrease in concentration
3) For strong electrolytes molar conductivity increased steeply with dilution
4) At infinite dilution weak electrolytes dissociate completely
24. 1 Faraday is
1) 96500 C 2) 6.022 × 1023 C 3) 1.6 × 10–19 C 4) 9.1 × 10–31 C
25. The amount of electricity in Faraday required for the reduction of 1 mol of Cr2 O 72  ions to Cr3+ is
1) 1 F 2) 2 F 3) 6 F 4) 7 F
26. Electrolysis of water by 1F of electricity gives
1) 1 mole of oxygen 2) 1 gram equivalent of oxygen
3) 1 molecule of oxygen 4) 1 atom of oxygen
27. 4.5 g of aluminium (at mass 27 amu) is deposited at cathode from Al3+ solution by a certain quantity of
electric charge. The volume of hydrogen produced at STP from H+ ions in solution by the same
quantity of electric charge will be
1) 22.4 L 2) 44.8 L 3) 5.6 L 4) 11.2 L
28. Which one of the following metals could not be obtained on electrolysis of aqueous solution of its salt?
1) Ag 2) Mg 3) Cu 4) Au
45
29. The electrolyte used in Leclanche Cell is

1) paste of KOH and ZnO 2) 38% solution of H2SO4
3) moist paste of NH4Cl and ZnCl2 4) moist sodium hydroxide
30. When a lead storage battery is charged:
1) PbO2 dissolves
2) the lead electrode becomes coated with lead sulphate
3) sulphuric acid is regenerated
4) the amount of acid decreases
LEVEL - II
1. In a Daniell cell the half reaction takes place at cathode is
1) Zn 2aq   2e  
 Zn  s  2) Zn  s   Zn 2aq   2e 
2 
3) Cu  aq   2e 
 Cu  s   Cu 2aq   2e
4) Cu s  
2. If half cell reaction A aq   1e   A has a large –ve reduction potential, it follows that
1) A is readily reduced 2) A is readily oxidised
3) A is readily reduced
+
4) A+ is readily oxidised
3. Which of the following is/are extensively determined by using electrochemical cell?
1) Solubility product 2) Equilibrium constant
3) Potentiometric titrations 4) All of these
4. Electrode potential data for a few elements are given
Fe3 aq   1e  
 Fe2aq  E o  0.77 V
Al3 aq   3e 
 Al s  E o  1.66 V
Br2 aq   2e  
 2Braq  E o  1.08 V
Reducing power will increase in the order.
1) Br– < Fe2+ < Al 2) Fe2+ < Al < Br– 3) Al < Br– < Fe2+ 4) Al < Fe2+ < Br–
5. The standard reduction potential of four elements are given below. Which of the following will be the
most suitable oxidising agent?
A) –3.04 V B) –1.90 V C) 0.00 V D) +1.90 V
1) A 2) D 3) C 4) B

6. Standard electrode potential of Ag  aq  / Ag  s  is +0.80 and Cu 2aq  / Cu  s  is +0.34 V. These electrodes
are joined by salt bridge then :
1) Copper electrode works like cathode then E ocell  0.45 V
2) Silver electrode works like anode, E ocell  0.32 V
3) Silver electrode works like cathode, E ocell  0.46 V
4) Copper electrode works like anode, E ocell  0.34 V
46
7. The cell reaction of a cell is Mg s   Cu 2aq  

 Mg 2aq   Cu s 
E o Mg2 / Mg  s   2.36 V ; E o Cu 2 / Cu  s    0.34 V . The emf of the cell is

 aq   aq 
1) –2.70 V 2) +2.70 V 3) –2.02 V 4) +2.02 V
8. Determine the standard reduction potential of the half cell reaction Ag + + e 

 Ag (s) .
Given that Mgs  2Agaq 

 2Ags  Mg2aq ; E cell  3.16 V ; E oMg2 aq/ Mgs  2.36 V
 o
1) +0.80 V 2) –0.80 V 3) +5.52 V 4) –5.52 V
In a cell reaction, Cus  2Agaq 

 Cu2aq  2Ags ; E ocell  0.46 V . If the concentration of Cu2+

9.
ions is doubled than E ocell will be
1) doubled 2) Halved 3) Increased by four times 4) Unchanged
10. What will be the pH of the following half-cell : Pt, H 2 H 2SO 4
The oxidation potential is + 0.3005 V

1) 3.085 2) 4.085 3) 5.085 4) 6.085
11. The standard cell potential of Zn Zn 2aq  Cu 2aq  Cu cell is 1.10 V. The maximum work obtained by this
cell will be
1) 106.15 kJ 2) –212.30 kJ 3) –308.45 kJ 4) –424.60 kJ
1 1  1 Cu 2  Cl ,
12. What is the standard free energy change for the reaction, Cu(s)  Cl2 (g) 
2 2 2
taking place at 298 K in a cell whose standard e.m.f. is 1.02 V?
1) –49215 J 2) 98430 J 3) 96500 J 4) –98430 J
13. Which one of the following statements is correct?
1) Ecell and  r G of cell reaction both are intensive properties
2) Ecell and  r G of cell reaction both are extensive properties
3) Ecell is an intensive property while  r G of cell reaction is an extensive property
4) Ecell is an extensive property while  r G of cell reaction is an intensive property
14. Resistance of a conductivity cell filled with 0.1 mol L–1 KCl solution is 100 . The conductivity of
0.1 mol L–1 KCl solution is 1.29 S/m. Its cell constant is
1) 129 m–1 2) 12.9 m–1 3) 1.29 m–1 4) 0.129 m–1
15. The molar conductivity is maximum for the solution of concentration
1) 0.001 M 2) 0.005 M 3) 0.002 M 4) 0.004 M
47
16. Unit of m is
1) Sm2 mol–1 2) Mol lit–1 3) Scm2 mol–1 4) Both 1 and 3
17. The specific conductance of 0.1 M NaCl solution is 1.06 × 10 ohm cm–1. Its molar conductance in
–2 –1
ohm–1 cm2 mol–1 is

1) 1.06 × 102 2) 1.06 × 103 3) 1.06 × 104 4) 10.06 × 105
18. At infinite dilution, molar conductivity of Ba2+ and Cl– ions are 127.32 S cm2 mol–1 and 76.34 S cm2 mol–1
respectively. What is the molar conductivity of BaCl2 at the same dilution.
1) 330.98 S cm2 mol–1 2) 203.6 S cm2 mol–1 3) 280 S cm2 mol–1 4) 90.98 S cm2 mol–1
19. The increase in the value of molar conductivity of acetic acid with dilution is due to
1) increase in inter ionic forces 2) increase in degree of ionisation
3) increase in self ionisation of water 4) decreae in self ionisation of water
20. During the electrolysis of fused NaCl, which reaction occurs at anode
1) Chloride ions are oxidised 2) Chloride ions are reduced
3) Na ions are oxidised 4) Na ions are reduced
21. How many coulombs of electricity are required for the oxidation of 1 mole of H2O to O2?
1) 9.65 × 104 C 2) 4.825 × 105 C 3) 1.93 × 105 C 4) 1.93 × 104 C
22. If the aqueous solutions of the following salts are electrolysed for 1 hour with 10 ampere current,
which solution will deposit the maximum mass of the metal at the cathode (The atomic weights are,
Fe = 56, Zn = 65, Ag = 108 and Hf = 178).
1) ZnSO4 2) FeCl3 3) HfCl4 4) AgNO3
23. What is the volume of oxygen produced at 273K and 1 bar pressure by the same quantity of electricity
which deposits108 g of silver (atomic mass 108 amu) from AgNO3 solution?
1) 5.6 L 2) 11.21 L 3) 16.81 L 4) 22.41 L
24. Amount of eletricity that can deposite 108 g of silver from AgNO3 solution is
1) 1 ampere 2) 96500 C 3) 1 F 4) Both 2 and 3
25. The amount of chlorine evolved when 2 ampere of current is passed for 30 minutes in an aqueous
solution of NaCl is
1) 6.6 g 2) 1.32 g 3) 13.2 g 4) 9.98 g
26. In the electrolysis of aqueous solution of copper sulphate using copper strips as anode and cathode,
the anode reaction is
1) Cu 2  2e   Cu 2) Cu  Cu 2   2e 
1
3) 2HO   H 2  O 2  2e 4) SO 24   SO 4  2e 
2
27. A button cell used in watches function as following :
Zn 2  (aq)  2e 
 Zn  s  , E o  0.76 V ; Ag 2 O(s)  H 2 O(l)  2e  2Ag (s)  2OH (aq)

, E o  0.34 V
The cell potential will be
1) 0.84 V 2) 1.34 V 3) 1.10 V 4) 0.42 V
48
28. Assertion : The cell potential of mercury cell is 1.35V, which remains constant.
Reason : In mercury cell, the electrolyte is a paste of KOH and ZnO.
1) Both Assertion and Reason are true and Reason is the correct explanation of Assertion
2) Both Assertion and Reason are true but Reason is not the correct explanation of Assertion
3) Assertion is correct but reason is not correct.
4) Both Assertion and Reason are not correct.
29. The half-cell reaction for the corrosion,
1
2H   O 2  2e  
 H 2 O; E o  1.23V
2
 Fe  s  ;
Fe 2  2e  E o  0.44 V .
G o (in kJ) for the overall reaction is :
1) –76 kJ 2) –322 kJ 3) –161kJ 4) –152 kJ
30. The anodic half-cell of a lead - acid battery is recharged using 0.05 F of electricity. The quantity of
PbSO4 electrolysed (in g) during the process is : (mol mass of PbSO4 = 303.26)
1) 7.58 2) 11.6 3) 15.2 4) 22.8
49
KEY WITH HINTS

LEVEL - I
1. 3
2. 4
3. 3 Salt bridge is used to complete circuit.
4. 4 For spontaneous process, E  =E Reduced species -E Oxidised

species should be positive
E  =E Ni2+ /Ni -EZn 2+ /Zn  0.23  (0.76)  0.53 V

5. 2 For the cell reaction, Fe2   Zn 
 Zn 2   Fe ,
EMF  ECathode  E Anode  0.44  ( 0.76)  0.32V
6. 1 Zn has lowest standard reduction potential value and it will be easily oxidised. Zn act as strongest
reducing agent.
7. 4 Cu is less reactive than Al.
8. 2
9. 3 Cu is more reactive than Ag.
10. 4 Zn has lowest standard reduction potential among the given choices.
11. 2 Reducing nature increases as the value of standard reduction potential becomes more and
more negative.
12. 2
13. 2 Cell reaction : 3Ni  2Au 3  3Ni 2  2Au
3
0.0591  Ni 2   0.0591  0.1
3
2  1.5  0.25  
E cell  E cell  log 
log
6 1  1.7795 V
2
 Au 3  6
0.059  H  0.059 log1010

14. 1 E cell  E ocell  log  0  0.59 V
1 p  H2  1 1
15. 4 Concentration (activity) of pure Zn metal =1; Zn2+ concentration = 0.01
E  Eo 
0.059
log
 Zn  E  Eo 
0.059
log
1
n  Zn 
2  2 0.01
 0.059 
E  0.763     log100 = –0.763-0.059 = –0.822V
 2 
16. 2 G   nF E ocell
G   2.303 RT log K ;  nFE ocell  2.303 RT log K
2  96500  0.295
log K 
2.303  8.314  298
log K = 9.97 or K = 1 × 1010
50
17. 2
0.0591 0.0591
18. 4 E ocell  log K C  log (1.0 1016 )  0.4728 V
n 2
19. 3 G o   nF E cell
o
  2  96500  2.0 10 3   386 kJ mol 1
20. 4 No electron flow from cathode to anode.
21. 1 Strong electrolytes are completely ionised at all concentrations. On increasing dilution, the no.
of ions remains the same but the ionic mobility increases and the equivalent conductance
increases.
22. 2  CH 3COOaq   H aq 
CH 3COOH  aq  
 om  CH 3COOH   CH 3COO   Na   H   Cl    Na   Cl  
 91  426.16  126.45  390.71ohm 1cm 2 mol1
23. 3 For strong electrolytes conductivity increases slowly with dilution.
24. 1
+6
25. 3 Cr2 O 72  14H   6e   2Cr 3  7H 2 O
26. 2 1 F of electricity gives 1 gram equivalent of the substance.
27. 3 4.5g Al  0.5 F (1F  9 g  Eq.wt of Al) H 2 liberated by 0.5 F  0.5eqnt.of H 2  5.6 L
28. 2 Standard reduction potential of Mg is lower than that of hydrogen.
29. 3
30. 3
LEVEL - II
1. 3
2. 2
3. 4
4. 1 Lower the reduction potential more is the reducing power.
5. 2 Higher the standard reduction potential value more is the oxidising power.
6. 3 Cus  2Agaq 
 Cu 2aq  2Ag
Ag  Cathode
Cu = Anode
E ocell  E cathode
o
 E anode
o
0.80 – 0.34 = +0.46 V

7. 2 E ocell  E ocathode  E oanode  E oCu 2 /Cu  E oMg 2 /Mg  0.34  2.36  2.70 V
aq s aq s 
8. 1 E ocell  E oAg  / Ag  s   E oMg 2 / Mg s 

 aq   aq 
3.16  E oAg / Ags  2.36 ; E oAg / Ags  0.80

aq aq 
9. 4 E ocell  E cathode
o
 E anode
o
51
10. 3 Reduction reaction at Pt electrode :

H   e   1/ 2H 2
0.0591 1
Applying Nernst equation, E H  / H  E oH /H  log 
2 2
1  H 
0.0591 0.3005
0.3005  0  pH  pH   log  H     pH   5.085
1    0.0591
11. 2 Maximum work obtained  G  nFE cell
12. 4 G   nFE o ; G   1  96500 1.02   98430
13. 3 Ecell does not depend on mass where as r G depends on mass.
14. 1 Cell constant G* = Conductivity × resistance  1.29S / m 100   129 m1

15. 1 Molar conductivity is inversely proportional to molarity.
16. 4
K 1000 1.06102 1000

17. 1 m    1.06102 ohm1 cm 2 mol1
Molarity 0.1
18. 3 om BaCl 2  Ba

o o
 
2  2   127.32  2 76.34  280Scm mol
2 1
Cl
19. 2 For weak electrolytes degree of ionisation increases with dilution.

20. 1 2Cl  2e  Clo2 [At anode]
21. 3 2H 2 O 
 4H   O 2  4e
Oxidation of 2 mol water requires = 4 × 96500 C
 Oxidation of 1 mole water requires  96500 4  1.93105 C

2
22. 4 Solution Eq.wt.of deposit metal
ZnSO4 65/2
FeCl3 56/3
HfCl4 178/4
AgNO3 108/1
Hence maximum amount of silver will be deposited at cathode.
WAg 108
23. 1 Moles of Ag  = 1
M Ag 108
Ag  e  
 Ag [1F charge is required to deposit 1 mole of Ag]
1
 O2  2 H   2e 
H 2O  [2F charge is required to deposit (1/2) mole of O2]
2
 1F charge deposits (1/4) mole of O 2 .
nRT 0.0821 273
PV  nRT  Volume of O 2 produced =   5.6 L
P 4
52
Atomic mass 108

24. 4  Ags ; E Ag 
Ag   1e    108
Valency 1
WAg 108
No. of Faradays   1 (1 F = 96500 C)
E Ag 108
1
25. 2 At anode Cl  Cl 2  e ; Equivalent mass of chlorine = 35.5
2
E Cl2  I t 35.5 230 60

WCl2    1.32 g
96500 96500
26. 2 On electrolysis of CuSO4 solution using copper electrodes, CuSO4 ionises as :
Cu  s   Cu 2aq   2e  ; at anode (Oxidation)
Cu 2aq   2e  Cu  s  ; at cathode (Reduction)
The copper dissolves at the anode and is deposited at the cathode.
27. 3 E ocell  E cathode

o
 E anode
o
 0.34   0.76  1.1V
28. 2 The cell potential remains constant during its life as the overall reaction does not involve any ion
whose concentration changes during its life time.
29. 2 E.P of (cathode – anode) = Ecell = 1.67
G   nFE o  2  96500  1.67  322310 J  322 kJ
30. 1 PbSO 4 (s)  2 e  

 Pb(s)  SO 24
For 2 F current passed, PbSO4 electrolysed = 303.26 g
0.05  303.26
For 0.05 F, PbSO4 electrolysed =  7.58 g
2
53
CHAPTER - 03
CHEMICAL KINETICS
Chemical kinetics concerns itself with measurement of rates of reactions proceeding under given conditions
of temperature, pressure and concentration. It is highly useful in determining the factors which influence
rates of reactions as well as in understanding mechanisms of chemical reactions.
RATE OF A CHEMICAL REACTION

The speed or rate of a reaction can be defined as the change in concentration of a reactant or product in
unit time. It can be expressed in terms of
(i) the rate of decrease in concentration of any one of the reactants, or
(ii) the rate of increase in concentration of any one of the products.
AVERAGE RATE
Rate of a reaction is the change in concentration of any one of the reactants or products per unit time.
For the reaction, R 

 P, assuming that the volume remains constant
Decrease in concentration of R Increase in concentration of P

Rate of reaction  
Time taken Time taken
 R   P
Rate of reaction   
t t
where  [R] and  [P] are the change in molar concentrations of R and P, respectively during the time
interval  t. As the concentration of the reactant decreases with time,  [R] is negative. But rate of reaction
is a positive quantity. Hence, a negative sign is put before  [R]/  t to make it positive.
The rate of reaction in this case is the average rate of reaction (rav). This is because the rate of a reaction
depends on the molar concentration of the reactants (Law of Mass Action). As the molar concentration of
reactants decreases with time, the rate of reaction also decreases .
When the stoichiometric coefficients are different, the rates with respect to different species also will be
different. For the reaction, A  B 
 2C one mole of A reacts with one mole of B to form 2 moles of C.
The rates of disappearance of A and B are the same, but the rate of appearance of C is twice the rate of
disappearance of A and B.
Thus, 2 × Rate of disappearance of A = 2× Rate of disappearance of B = Rate of appearance of C.
54
To have a single value of the reaction rate (independent of the concentration term), we divide the reaction
rate defined with respect to any one of the reactants or products by the number of moles of that species in
the balanced chemical equation. Thus,
 A   B 1   C 
Rate of reaction    
t t 2 t
In general, for a reaction of the type : aA  bB 

 cC  dD
1   A 1   B 1   C  1   D 
Rate of reaction     
a t b t c t d t
Units of rate of reaction. When concentration of reactants and products are expressed in mol L–1, the
rate of reaction has units of mol L–1 min–1 or mol L–1 s–1.
For gaseous reactions, concentrations are expressed in terms of partial pressures. In this case, the rate of
reaction has units of atm min–1 or atm s–1.
INSTANTANEOUS RATE
The rate of a reaction at any instant of time is the rate of change of concentration of any one of the reactants
or products at that particular instant of time.
Let dt be a very small time  t  0  interval during which the concentration changes by dx. Then, the rate
of reaction at that instant (rinst) is given by dx/dt.
d  R  d  P 
For the reaction R  P , instantaneous rate, rinst  
dt dt
For a reaction of the type : aA  bB 

 cC  dD
1 d  A  1 d  B  1 d  C  1 d  D 
Instantaneous rate of reaction    
a dt b dt c dt d dt
Measurement of instantaneous rate of reaction
If the concentration of one of the reactants at different intervals of time are plotted against time, a graph of
the type shown in Fig.01(a) is obtained.
To find the rate of reaction with respect to that reactant, at any instant of time t, a tangent is drawn to the
curve at the point corresponding to time t which cuts the X and Y axes at points A and B respectively. The
slope of the tangent gives the rate of the reaction at that time.
In order to determine the rate of the reaction at t = 10 minutes, a tangent is drawn at point K on the curve,
corresponding to time = 10 minutes. The distance along the ordinate gives the fall of concentration  x
while that along the abscissa gives the time interval  t. The ratio  x/  t gives the slope of the tangent.
Change in concentration Δx OA
Rate of reaction = = = =  Slope of tangent
Time Δt OB
In Fig.01(a)  x = 0.030 mol L-1 and  t = 20 minutes (1200 seconds).
Thus, the rate of reaction at t = 10 mintues =  x/  t = 2.50 × 10–5 mol L-1 s–1.
Instantaneous rate of reaction at time t = – Slope of tangent at K =  tan 
55
(a) (b)
(c) (d)
Figure - 01 Instantaneous and average rate of reaction.

Calculation of Average Rate of Reaction. To calculate the average rate of reaction between any two
instants of time, t1 and t2, the corresponding concentrations x1 and x2 are noted from the graph as in
Fig.01(c).
[R] x  x1
Average rate of reaction    2
t t 2  t1
Calculation of rates from plot of concentration of a product vs time. If the concentration of one of the
products is plotted against time, a graph of the type shown in Fig.01(d) is obtained. To find the rate of
reaction at any instant of time t, a tangent is drawn to the curve at the point K corresponding to that instant
of time.
OA x
Rate    Slope of tangent
OB t
Also, instantaneous rate of reaction at time t = Slope of tangent at K = tan  , where  is the angle which the
tangent at K makes with the positive direction of X-axis. Here,  is acute, therefore, tan  will be positive.
Characteristics of Rates of Reactions
a) The rate of reaction is the change in concentration divided by the time taken for the change to take
place.
b) The rate of reaction can be expressed in terms of any reactant or product.
c) Rate of reaction is a positive quantity, therefore, a negative sign is used when rate is expressed in
terms of change in concentration of reactant (concentration of reactant decreases with time).
56
d) To make the different expressions for the rate equal, the rate expressions are divided by the
stoichiometric coefficients in the balanced chemical equation.
FACTORS INFLUENCING RATES OF REACTIONS
Rate of reaction depends on concentration of reactants (pressure in case of gases), temperature and
catalyst.
CONCENTRATION OF REACTANTS
The rate of a chemical reaction at a given temperature depends on the concentration of one or more
reactants or products. The representation of rate of reaction in terms of concentration of the reactants is
called rate law or rate equation or rate expression.
Rate Expression and Rate Constant
The rate of a reaction depends on the concentration of the reacting species. As the concentration of reactants
decrease with time, the rate of forward reaction decreases. The relationship between rate of reaction and
concentration of reacting substances is given by the law of mass action. For the reaction,
aA  bB 
 Products,
Rate   A   B 
x y
where x and y may or may not be the same as the stoichiometric coefficients a and b of the reactants and
the equation is called rate law or rate expression.
x y
Rate  k  A   B
where k is a constant called rate constant or velocity constant or specific reaction rate. The differential
form of this rate expression is given as
d[R]
 k  A   B
x y

dt
(i)  H 2 O  1 2O 2 ; Rate  k  H 2 O2  ,
H 2 O 2 
 H 2  I 2 ; Rate  k  HI
2
(ii) 2HI 
2NO  g   O2  g  
 2NO 2  g  ; Rate  k  NO2   O2 
2
(iii)
In the above reactions, the exponents of the concentration terms are the same as their stoichiometric
coefficients, but in the following reactions, the exponents are not the same as their stoichiometric coefficients.
(i) 2N 2O5 (g) 

 4NO2 (g)  O 2 (g) ; Rate  k  N 2 O5 
Rate  k  CHCl3   Cl 2 
1/ 2
(ii) CHCl3  Cl 2 
 CCl4  HCl ;
 CH 3COOH  C 2 H 5 OH ; Rate  k  CH 3COOC2 H 5   H 2 O 

1 0
(iii) CH 3COOC 2 H 5  H 2 O 
Thus, rate law for a reaction cannot be predicted by merely looking at the balanced chemical equation, but
must be determined experimentally.
57
Characteristics of Rate Constant

(i) Rate constant is a measure of the rate of reaction. Greater the value of rate constant, faster is the
reaction.
(ii) The value of rate constant changes with temperature.
(iii) The value of rate constant does not depend on the concentrations of the reactants.
(iv) The units of rate constant depends on the order of reaction.
ORDER OF REACTION
The order of a reaction is defined as the sum of the powers to which the concentration (or pressure) terms
are raised in the rate law expression. Order of reaction can be 0, 1, 2, 3 or even a fraction. It is an experimental
quantity.
For the reaction, aA  bB 

 cC  dD
Rate, r  k  A   B
x y
where x represents the order with respect to A, y represents the order with respect to B, (x+y) represents
overall order of the reaction, and k is the rate constant or velocity constant.
First order : r  k  A 
Second order : r  k  A  or r  k  A  B
2
r  k A or r  k  A   B or r  k  A  B r  k  A  B C
3 2 2
Third order : or
A, B and C stands for the various reactants.
Different reactions have different values of k at a particular temperature. When [A] = [B] = 1, then,
Rate, r = k
Thus, the rate constant of a reaction is defined as the rate of the reaction when the concentration of each
of the reacting species is unity.
A balanced chemical equation does not give a true picture of how a reaction takes place since a reaction
never gets completed in one step. A reaction taking place in one step is called elementary reaction. A
reaction taking place by a sequence of elementary reactions (called mechanism) is called complex reaction.
1. Reactions of zero order
A zero order reaction is one in which the rate of reaction is independent of the concentration of the
reactants, e.g., enzyme catalysed reactions and reactions occuring on metal surfaces
r  k  NH 3   k
o
i) Catalytic decomposition of NH3 : 2NH 3 
Mo or W
 N 2  3H 2
r  k  NH3   k
Pt / 1130K o
ii) Decomposition of NH3 on Pt : 2NH3   N 2  3H 2
Au / 
r  k  HI   k
o
iii) Thermal decomposition of HI on Ag : 2HI   H 2  I2
In these reactions, the concentration of the gaseous reactants on the metal surface remains constant
because more molecules of the reactant are adsorbed on the surface as the reactants react off forming
products. Hence, rate remains constant.
58
2. Reactions of first order

For a first order reaction, the concentration of the reactant decreases and that of the product increases
exponentially with time.
i) Decomposition of NH4NO2 : NH 4 NO2 
 N 2  2H 2 O r  k  NH 4 NO2 
ii) Decomposition of H2O2 : H2O2 

 H2O + ½O2 r  k  H2O2 
iii) Decomposition of N2O5 : N 2 O5 (g) 
 2NO2 (g)  1 2 O 2 (g) r  k  N 2 O5 
3. Reactions of second order
A reaction is said to be of the second order if r = k2[CA][CB] or k2[CA]2or = k2[CB]2. In some cases, both
the reaction terms may refer to the same reactant, i.e., two molecules of the same reactant.
r  k  HI 
2
i) Dissociation of HI : 2HI 
 H 2  I2
ii) Saponification of ethyl acetate :
CH3COOC2H5 + NaOH 
 CH3COONa + C2H5OH ; r  k  CH3COOC2 H5 ][NaOH 
iii) Reaction between NO and O3 : NO + O3 
 NO2 + O2
Units of Rate Constant
 cC  dD , rate, r  k  A   B
x y
In general, for a reaction, aA  bB 
where, x + y = n = order of the reaction
k
rate  mol L  s  mol L
1 1
  
A
x
B
y or k   1 1 n
s 1
 mol L  1 n
(i) Zero order (n = 0) :  mol L  s  mol L s

1 1 0 1 1 1
(ii) First order (n = 1) :  mol L  s  s

1 11 1 1
(iii) Second order (n = 2) :  mol L  s   mol L  s

1 1 2 1 1 1 1
 mol 1 L s 1  dm3 mol1 s 1
For gaseous reactions, the units are : (i) Zero order :  atm  s 1 (ii) First order : s  1
1
(iii) Second order : atm-1 s-1
MOLECULARITY OF A REACTION
According to kinetic molecular theory (collision theory), for a chemical reaction to take place, molecules
must collide with one another. The number of reacting species (atoms, ions or molecules) taking part in an
elementary reaction, that must collide simultaneously to bring about a chemical reaction is known as
molecularity of the reaction.
Reactions are classified as unimolecular, biomolecular, termolecular, depending on whether the number of
molecules taking part in collisions is one, two, or three respectively.
a) Unimolecular reaction : N 2O5  g  
 N 2 O 4  g   1/ 2 O2  g 
b) Bimolecular reaction : 2HI  g  
 H 2  g   I2  g 
c) Termolecular reaction : 2NO  g   O 2  g  
 2NO2  g 
59
Complex Reactions and Reaction Mechanism
The chances of simultaneous collision of molecules decrease with increase in the number of molecules
involved in the collision. Therefore, reactions involving three or more molecules should be rare. However, it
has been observed that some reactions involving more than three molecules are quite fast, e.g., oxidation
of ferrous sulphate to ferric sulphate in acidic medium.
KClO 3  6FeSO 4  3H 2SO 4 

 KCl  2Fe 2 (SO 4 )3  3H 2 O
This reaction which appears to be of tenth order is actually a second order reaction. This shows that such
reactions involve a series of steps and each step or elementary reaction has its own molecularity.
A complex reaction takes place through a sequence of elementary steps, which may be slow or fast. It is
the slowest step of the reaction that determines the rate of the overall reaction (rate-determining step).
The sequence of steps, proposed to account for the overall reaction is called mechanism of the reaction.
E.g., thermal decomposition of dinitrogen pentoxide
2N 2O5 (g) 
 4NO2 (g)  O 2 (g)
This reaction is first order with respect to N2O5, but evidence suggests that it takes place in two steps:
slow fast
N 2 O5 (g)   NO2 (g)  NO3 (g) ; N 2 O5 (g)  NO3 (g)    3NO 2 (g)+O2 (g)
The first step is unimolecular, whereas the second step is bimolecular. NO3 is an intermediate since it is
formed during the course of the reaction, but not in the overall balanced equation. The first step, being slow,
is the rate determining step. Thus, the rate of formation of intermediate will determine the rate of this
reaction.
Difference between Order and Molecularity
(i) Order of reaction is an experimental quantity. It can be zero and even a fraction, but molecularity
cannot be zero or a non integer.
(ii) Order is applicable to elementary as well as complex reactions, whereas molecularity is applicable
only to elementary reactions. For complex reactions, molecularity has no meaning.
(iii) For complex reactions, order is given by the slowest step and generally, molecularity of the slowest
step is the same as the order of the overall reaction.
Table - 01 Difference between order and molecularity of a reaction.
Order Molecularity
1 It is the sum of the powers of the It is the number of species undergoing simultaneous
concentration terms in the rate law expression. collision in the elementary or simplest reaction.
2 It is determined experimentally. Molecularity is a theoretical concept.
3 It need not be a whole number. It can be zero or It has only whole number values.
fractional.
4 Order of a reaction can be zero. Molecularity of a reaction cannot be zero.
60
INTEGRATED RATE EQUATIONS
The differential rate equation is integrated to obtain a relation between experimental data (concentrations at
various time intervals) and rate constant. Integrated rate equations are different for reactions of different
orders.
1. Intergrated Rate Law for Zero Order Reaction
Consider the following hypothetical reaction of zero order,
R 
P
If the molar concentration of R is [R] at a particular instant of time, then the instantaneous rate of
reaction at that instant of time is given by the expression,
d  R  d[R]
 k R  k or d  R   k dt
0
Rate  or
dt dt
where k is the rate constant. On integrating,
  d  R   k  dt or   R   kt  I ...(i)
where I is the constant of integration. The value of I can be calculated from the initial conditions.
When t = 0, [R] = [R]0, i.e., initial concentration of R. Thus (i) becomes,
  R 0  k  0  I or I    R 0
Substituting the value of I in Eq. (i), we get
  R   kt   R 0 or kt   R 0   R 
 R 0   R 
or k ...(ii)
t
Units of rate constant  mol L1 s 1
Variation of rate of a zero order reaction with concentration
For a zero order reaction,
rate = k[R]0 = k
In other words, for a zero order reaction, the rate of reaction does not vary with concentration of reactants.
Figure - 02 Zero order reaction : Plot of concentration vs time

61
Variation of concentration with time for a zero order reaction

On rearranging Eqn (ii), we get
 R   kt   R 0
This is an equation of the type, y = mx + c where m is the slope and c is the intercept on Y-axis.
Therefore, when a graph is plotted between concentration, [R] (along Y-axis) and time, t (along
X-axis), a straight line is obtained with slope equal to –k and Y-intercept equal to initial concentration,
 R 0 .
Characteristics of zero order reaction
i) Any zero order reaction obey the integrated rate law equation for the zero order. This can be treated
by substitution method or graphical method.
ii) The time required to reduce the concentration of the reactant to any fraction of initial concentration
depends on the initial concentration.
Suppose initial concentration, [R]0= a
Let t1/n is the time required to complete nth fraction of the reaction, then,
a
Final concentration, [R] = a 
n
1  a  a
t1/n   a   a   or t1/ n 
k  n  kn
Thus, t1/n depends on initial concentration, a.
Half-life period
It is the time required for the completion of half of the reaction or the time during which the concentration
of the reactants is reduced to half of the initial concentration. It is denoted by t1/2.
[R]0  [R]
For a zero order reaction, rate constant is given by, k 
t
At t  t1 2 , [R]  1 2[R]0
[R]0  1 2[R]0 [R]0
The rate constant at t1/2, k  or t1 2 
t1 2 2k
Thus, t1/2 for a zero order reaction is directly proportional to the initial concentration of the reactants
and inversely proportional to the rate constant.
a
Time of completion of a zero order reaction, t100% 
k
Integrated Rate Law for Zero Order Gas Phase Reaction
If the reactant is gaseous, pressure is measured instead of molar concentration; rate equation
becomes
 P 0   P  P0
k and t1/ 2 
t 2k
where, P0 is the initial pressure and P is the pressure after time t.
62
2. Integrated Rate Law for First Order Reaction
For a first order reaction, the concentration of the reactant decreases and that of the product increases
exponentially with time. For the reaction,
R 
P
If the concentration of R is [R] at a particular instant of time, the instantaneous rate of reaction at that instant
d R 
is given by the expression,   k R 
dt
where k is the rate constant. Rearranging the above equation
d R 
  k dt
R 
On intergrating the above equation;
d R 
  k  dt
R 
or – ln [R] = kt + I ...(i)
where I is the constant of integration. The value of I can be calculated from the initial conditions.
When t = 0, [R] = [R]0 i.e., initial concentration of R. Thus, Eqn (i) becomes
 ln  R 0  I ...(ii)
Substituting the value of I in Eqn (i), we get
 ln  R   kt  ln  R 0 or ln  R 0  ln  R   kt or ln
 R 0
 kt
R 
1  R 0
or k  ln ...(iii)
t R 
2.303  R 0
or k log ...(iv)
t R 
Eqn (iv) is called integrated rate equation for first order reaction.
When the initial concentration [R]0 = a and the concentration after time t is (a-x) then, Eqn (iv) becomes
2.303 a
k= log ...(v)
t ax
The rate constant for first order reaction from concentrations of reactants at two different times is given by
1 [R]1 2.303 [R]1
k= ln or k= log
(t 2  t1 ) [R]2 (t 2  t1 ) [R]2
where [R]1 and [R]2 are the molar concentrations at time t1 and t2 respectively.
Units of Rate Constant. The units of k are independent of the units in which the concentrations are
expressed. Depending on whether t is expressed in seconds, minutes, or hours, the units of rate constant k
would be in s–1, min–1 or hr–1 respectively.
63
Intergrated rate law equation for first order gas phase reaction
First order gas phase reaction : A(g) 
 B(g) + C(g)
Initial pressure : Pi atm 0 0
Pressure after time t : (Pi - x) atm x atm x atm
Total pressure of the reaction mixture after time t, Pt = (Pi - x) + x + x = (Pi + x) atm
x = Pt - P i
Pressure of A after time t, (PA) = (Pi - x) = Pi - (Pt - Pi) = 2 Pi - Pt
Substituting the values in Eq.(iv), k 

2.303 P 
log i , we get
t  PA 
2.303 Pi
k log
t  2Pi  Pt 
Exponential form of the intergrated rate law equation
 R 0  R 0 kt  R   ekt
From Eq.(iii), kt  ln or e or
R  R   R 0
 R    R 0 e kt ...(vi)
Characteristics of a first order reaction
First order reaction obey intergrated rate law equation of the first order. This may be tested as follows:
a) Substitution method. Starting with a known concentration of reactant, [R]0, the concentrations of the
reactant, [R], at different intervals of time may be found out experimentally. For each value of t, the
corresponding value of [R] may be substituted in the first order rate equation. If the value of rate constant,
k comes out to be nearly constant, the reaction is of first order.
b) Graphical method. Eqn (iv) may be written as;
k  R 0
 R   log  R 0  log  R 
t  log
2.303
k
or log  R    t  log  R 0 ...(vii)
2.303
When a graph is plotted between ln [R] (along Y-axis) and t (along X-axis), a straight line is obtained (Fig.03)
k
with slope   and Y - intercept = ln [R]0
2.303
(a) (b)
Figure - 03 First order reaction; (a) Plot of ln [R] vs time (b) Plot of log [R]0/[R] vs time.
64
Rate constant k can be calculated from the slope of the line so obtained.
Variation of concentration with time for first order reaction
The time required to reduce the concentration of the reactant to any fraction of the initial concentration is
independent of the initial concentration.
Suppose initial concentration, [R]0 = a
Let t1/n is the time required to complete nth fraction of the reaction, then
a  1 2.303 a
Final concentration [R] = a   a 1   or t1/ n  log
n  n k  1
a 1  
 n
2.303 n
or t1/ n  log
k n 1
Thus, t1/n is independent of a, i.e., the initial concentration.
Time taken for the reactant to reduce to the nth fraction. Here, (a-x) = (a/n), therefore,
2.303 a 2.303
t log or t log n
k a/n k
Time taken for the reactant to reduce to different fractions
t 3/4 or t 75%  2t1/2 , t 87.5%  3t1/2 , t 93.75%  4t1/2 , t 96.87%  5t1/2 , t 99.9%  10t1/2
Half -Life of a First Order Reaction
2.303  R 0 2.303  R 0
For a first order reaction, k log or t log
t R  k R 
 R 0
When,  R   , then t  t1/ 2
2
2.303  R 0 2.303 0.693
t1/ 2  log or t1/2  log 2 or t1/ 2 
k  R 0 / 2 k k
Half-life period of a first order reaction does not depend on the initial concentration of the reactant.
Amount of substance left after ‘n’ half-lives:
t t [R]0 t  2t1/2 1 [R]0 [R]0 t  3t1/2 1 [R]0 [R]0 t  nt1/2 [R]0

[R]0 
1/2
   2   2
 3  
2 2 2 2 2 2 2 2n
Average life
Average life (t) is the reciprocal of disintegration constant (k) for a first order reaction.
1 [R]o 1 1
t av  = ln e  ln e e 
k [R]o / e k k
Average life of a first order reaction (also called natural life-time) is the time in which the concentration of
the reactant reduces to 1/e of the original concentration.
1 [R]o 1 1
t av  = ln e  ln e e 
k [R]o / e k k
65
Life-time of the reaction. The time taken for the reaction to complete (usually 98%) is called life-time of
the reaction.
Table - 02 Integrated Rate Laws for the Reactions of Zero and First Order
Order Reaction Differential Integrate Straight Half- Units of k

type rate law rate law life life
0 RP d[R]/dt = -k kt = [R]0 - [R] [R] vs t [R]0/2k conc time-1 or mol L-1s-1
[R] = [R]0e-kt
1 RP d[R]/dt = -k[R] ln[R ]vs t ln 2/k time-1 or s-1
or kt = ln{[R]0/[R]}
PSEUDO FIRST ORDER REACTION
For simple reactions, order is the same as molecularity, but in several reactions, order is different from
molecularity. A second order reaction is considered as first order when one of the reactants is present in
such a large excess that its concentration remains practically constant, e.g., acid hydrolysis of ester.

CH3COOC2 H 5  l   H 2O  l  
H

 CH3COOH  aq   C 2 H 5OH  aq 
Ethyl acetate Water(excess) Aceticacid Ethyl alcohol
Such reactions which appear to be of higher order, but actually follow lower order kinetics are called pseudo
chemical reactions. The rate law expression for the reaction is
rate  k ' [CH 3COOC2 H 5 ][H 2O]

The term [H2O] can be taken as constant. The equation becomes
rate  k[CH3COOC 2 H 5 ]
where k  k ' [H 2 O]
Another example of pseudo first order reaction is the acid catalysed hydroysis of sucrose in presence of
large excess of water. It is also called inversion of cane sugar since the mixture of glucose and fructose
obtained on hydrolysis is laevorotatory, whereas sucrose is dextrorotatory.
H

C12 H 22O11  H 2O  excess   C6 H12O6  C6 H12O6
Sucrose Glucose Fructose
The rate law expression is, rate  k  C12 H 22 O11 
EFFECT OF TEMPERATURE ON REACTION RATES

It has been found that the rate of reaction nearly doubles for every 10 K rise in temperature. The ratio of the
velocity constants of a reaction at two temperatures differing by 10 K is known as the temperature
coefficient of the reaction.
Threshold energy. According to collision theory, only those collisions result in chemical reaction in which
the colliding molecules are associated with a certain amount of energy. The minimum energy that must be
possessed by molecules so that their mutual collisions result in chemical reaction is called threshold
energy.
66
Figure - 04 Energy vs progress of reaction curve showing the formation of activated complex.
Activation Energy. The minimum energy over and above the average energy which must be supplied to
the reactants to enable them to cross the energy barrier between reactants and products is called activation
energy. Activation energy = Thershold energy – Average energy of the reactants.
Ea  E t  E r
For fast reactions, activation energy is low and for slow reactions, activation energy is high.
Activated complex or Transition state. During a chemical reaction, existing bonds are broken and new
bonds are formed. The breaking of bonds requires energy, whereas formation of bonds results in the
release of energy.
Figure - 05 Formation of activated complex during the reaction of H2 and I2 to form HI.
In the beginning, breaking of bonds predominate. The energy of the system increases till it reaches a
maximum, corresponding to the thershold energy. Then, the energy decreases because bond formation
predominates. The arrangement of atoms corresponding to the energy maxima (threshold energy) is called
transition state or activated complex.
The effect of increase in temperature can be explained on the basis of effective collisions (collisions
which result in reaction). Fig.06 gives the Maxwell - Boltzmann energy distribution curves at temperatures
T1 and T2 where T2 = T1 + 10. The peak in Maxwell-Boltzmann distribution curve corresponds to the most
probable kinetic energy, which is the K.E. of maximum fraction of molecules at that temperature. With rise
in temperature, the kinetic energy of the molecules increases, the energy distribution curve is flattened and
the peak shifts towards the higher energy region. Increasing the temperature increases the fraction of
molecules which collide with energies greater than Ea.
Figure - 06 Distribution of molecular energies at temperature T1 and T2.
67
Molecules possessing energy greater than or equal to the threshold energy is almost double at T2 (area
abef) than at T1 (area abcd), which explains the increase in rate.
Arrhenius Equation
Arrhenius (1889) developed a mathematical relationship between temperature and the rate constant. (first
proposed by Dutch Chemist, J.H. van’t Hoff)
k  A e Ea /RT ...(1)
where, A is a constant called Arrhenius factor, frequency factor or pre-exponential factor. This is
related to the number of binary molecular collisions per second per litre. Ea is the activation energy
(J mol–1), R is gas constant and T is the absolute temperature.
Taking logarithm of both sides of the equation
Figure - 07 Plot of log k vs 1/T.
Ea
ln k  ln A 
RT
If k1 and k2 are the values of rate constants at temperatures T1 and T2, then,
Ea
ln k1  ln A  ...(2)
RT1
Ea
and ln k 2  ln A  ...(3)
RT2
Subtracting Eqn. (2) from Eqn. (3),
Ea  E a  Ea E k 2 Ea  1 1 
ln k 2  ln k1     or ln k 2  ln k 1   a or ln    
RT2  RT1  RT1 RT2 k1 R  T1 T2 
k2 E a  T2  T1 
or log   
k1 2.303R  T1 T2 
EFFECT OF CATALYST ON REACTION RATES

Substances which increase the rate of a reaction and can be recovered unchanged after the reaction are
called catalysts. A catalyst provides an alternate path for the reaction in which conversion of reactants into
products takes place quickly.
68
Intermediate complex formation theory
Figure - 08 Potential energy curves for catalysed and uncatalysed reactions.
Though the catalyst increases the rate of the reaction, it does not affect the state of equilibrium of reversible
reactions. This is because the activation energies for the forward as well as backward reactions are reduced
by the same extent. Thus, the amount of product formed remains the same whether a catalyst is used or
not.
i) A catalyst is highly specific in its action, i.e., a catalyst may increase the rate of one reaction, but may
be completely ineffective in another reaction.
ii) A catalyst may undergo intermediate physical change and may even form temporary chemical bonds
with the reactants but is recovered unchanged in mass and composition at the end of the reaction.
iii) A catalyst never starts a reaction which has no tendency to proceed.
iv) Since a catalyst does not alter the individual energies of reactants and products, H or U of the
reaction remains unaltered.
COLLISION THEORY OF CHEMICAL REACTIONS
Arrhenius equation satisfactorily explains the effect of temperature on the rate of reaction. The collision
theory of chemical reactions was developed by Max Trautz and William Lewis (1916-18) based on kinetic
theory of gases. According to this theory, for a reaction to occur, the reacting species (atoms, ions or
molecules) must undergo collisions with one another. The number of collisions per second per unit volume
of the reaction mixture is called collision frequency, Z.
In a gaseous mixture, under ordinary conditions of temperature and pressure, 1025 to 1028 binary collisions
occur, but all collisions are not effective in bringing about chemical reactions. Collisions which result in
chemical reaction are called effective collisions. There are two important barriers to a chemical reaction,
namely energy barrier and orientation barrier.
Energy factor (barrier). For effective collisions, the reacting species must have energy to cause breaking
of bonds. The minimum energy which the colliding molecules must posses in order to bring about a chemical
reaction is called threshold energy.
For the reaction, A + B  Products, if ZAB is the collision frquency and f is the fraction of molecules whose
collisions are effective, then,
Rate of reaction = -(dx/dt) = ZAB × f ...(i)
69
According to kinetic theory of gases, the fraction molecules having energy greater than E at temperature,
T is given by the Boltzmann factor, f = e-Ea/RT, where Ea is the activation energy. Substituting in Eqn. (i),
Rate = ZABe-Ea/RT
Since rate of reaction is directly related to rate constant, k
k = ZABe-Ea/RT ...(ii)
Orientation factor (barrier). In case of complex molecules, the colliding species must have proper
orientation so that old bonds break and new bonds form.
Thus, another factor called orientation factor or steric factor or probability factor, P also has to be
considered. Hence, Eqn. (ii) can be modified as
k = PZABe-Ea/RT ...(iii)
Thus, according to collision theory, activation energy and proper orientation of the molecules together
determine effective collision and hence rate of reaction.
Drawbacks of collision theory : It considers atoms and molecules to be hard spheres and does not take
into account their structural aspects.
70
QUESTIONS
LEVEL - I
1. Which of these does not influence the rate of reaction ?

1) Nature of the reactants 2) Concentration of the reactants
3) Temperature of the reaction 4) Molecularity of the reaction
2. According to the collision theory of chemical reactions:
1) A chemical reaction occurs with every molecular collision
2) Rate is directly proportional to the number of collisions per second
3) Reactions in the gas phase are always of zero order
4) Reaction rates are of the order of molecular speeds
3. For the reaction, 2H 2 (g) + 2NO(g)  N 2 (g) + 2H 2O(g), the observed rate expression is:
rate = k f [NO] 2 [H 2 ]. The rate expression for the reverse reaction is :
1) k b [N 2 ][H 2 O]2 /[H 2 ] 2) k b [N 2 ][H 2 O]
3) k b [N 2 ][H 2 O]2 4) k b [N 2 ][H 2 O]2 /[NO]
4. In the formation of sulphur trioxide by the contact process, 2SO 2  O 2  2SO3 , the rate of reaction
d  O 2 
was measured as  3.0  104 molL1s 1 . The rate of formation of SO3 will be
dt
1) 3.0  10 4 mol L1s 1 2) 6.0  104 mol L1s 1
3) 1.5  104 mol L1s 1 4) 4.5  104 mol L1s 1
d  H2  d  NH 3 
5.  2NH 3 , what is 
For the gaseous reaction, N 2  3H 2  if is 2  10 4 ?
dt dt
4 2 4
1) 3  10 2) 5  10 3) 3  10 4 4) 4  10
6. The differential rate law for the reaction, H 2 + I2 

 2HI is :
d H2  d  I2  d  HI d  H 2  d  I 2  1 d  HI 
1)    2)  
dt dt dt dt dt 2 dt
1 d  H 2  1 d  I2  d  HI d H2  d  I 2  d  HI

3)   4) 2  2 
2 dt 2 dt dt dt dt dt
71
2
7. For the reaction, A+2B  
 C , rate is given by R=[A][B] . Order of the reaction is :
1) 0 2) 1 3) 2 4) 3
8. For the non-stoichiometric reaction, 2A  B  C  D, the following kinetic data were obtained in three
separate experiments at 298K.
Initial Initial Initial rate of formation of C

concentration [A] concentration [B] (mol L-1 s-1 )
0.1M 0.1M 1.2×10-3
0.1M 0.2M 1.2×10-3
0.2M 0.1M 2.4×10-3
The rate law for the formation of C is :
dC dC dC dC
1) =k[A] 2) =k[A][B] 3) =k[A]2 [B] 4) =k[A][B]2
dt dt dt dt
9. Which of the following statements is incorrect?
1) Rate constant k is a measure of rate of reaction
2) Value of k is independent of concentration
3) Value of k is independent of temperature
4) At constant temperature, value of k is constant for a particular reaction
10. The unit of the rate of reaction is the same as that of the rate constant for
1) zero-order reaction 2) first-order reaction 3) second-order reaction 4) half-order reaction
11. For the reaction 2N 2 O 5 

 4NO 2  O 2 ; the rate is directly proportional to [N2O5]. At 45oC, 90% of
the N2O5 reacts in 3600 seconds. The value of the rate constant is
1) 3.2  10 4 s 1 2) 6.4  10 4 s 1 3) 8.5  10 4 s 1 4) 12.8  10 4 s 1

12. For a reaction of order n, the unit of the rate constant is
1) mol1-n L1-n s-1 2) mol1-n Ln-1 s-1 3) mol1-n Ln-1 s 4) mol1-n L2n s-1
13. The concentration of R in the reaction, R  P was measured as a function of time and the following
data was obtained :
[ R ] (molar ) 1.0 0.75 0.40 0.10

t (min) 0.0 0.05 0.12 0.18
The order of the reaction is:

1) 0 2) 2 3) 1 4) 3
14. Mechanism of a hypothetical reaction X 2  Y2  2XY , is given below :
i) X 2  X  X (fast) ii) X  Y2  XY  Y (slow) iii) X  Y  XY (fast)

The overall order of the reaction will be
1) 2 2) 0 3) 1.5 4) 1
72
15. Higher order (>3) reactions are rare due to

1) shifting of equilibrium towards reactants due to elastic collisions
2) loss of active species on collision
3) low probability of simultaneous collision of all the reacting species
4) increase in entropy and activation energy as more molecules are involved
16. Which of the following statements is incorrect about order of a reaction?
1) Order of a reaction can never be equal to zero or fractional value
2) It is always determined experimentally
3) It is equal to the molecularity of an elementary reaction
4) It is sum of the powers of concentration terms in the differential rate law of a reaction.
17. A substance having initial concentration ‘a’ reacts according to zero-order kinetics. The time it takes
for the completion of the reaction is
1) a/k 2) a/2k 3) k/a 4) 2k/a
18. The half-life of a reaction A  B varies as the inverse of concentration of A. The order of the reaction
would be:
1) zero 2) first 3) second 4) third
19. For a Ist order reaction, which one is not correct?
1) The concentration of product increases linearly with time
2) The concentration of product increases exponentially with time
3) The degree of dissociation ‘  ’ is given by 1  e  kt
4) The reaction never goes for completion
20. It takes 1h for a first order reaction to go to 50% completion. The total time required for the same
reaction to reach 87.5% completion will be
1) 1.75 h 2) 6.00 h 3) 3.50 h 4) 3.00 h
21. The half life period of a first order chemical reaction is 6.93 minutes. The time required for the comple-
tion of 99% of the chemical reaction will be (log 2 = 0.301)
1) 230.3 min 2) 23.03 min 3) 46.06 min 4) 460.6 min
22. For a first order reaction, A  2B, one mole of reactant gives 0.2 moles of B after 100 minutes. What
is the half-life of the reaction ?
1) 450 min 2) 540 min 3) 589 min 4) 660 min
23. The half-life for the thermal decomposition of acetone is 80 s and is independent of initial concentration
of acetone. The time required for the reaction to go to 80% decomposition is (log 2 = 0.30)
1) 186.1 s 2) 206.1 s 3) 150.1 s 4) 226.1 s
24. In a zero-order reaction for every 10o rise of temperature, the rate is doubled. If the temperature is
increased from 10oC to 100oC, the rate of the reaction will become
1) 64 times 2) 512 times 3) 256 times 4) 128 times
73
25. An example of a pseudo – first order reaction is:
1) Dissociation of hydrogen iodide
2) Hydrolysis of methyl acetate in dilute solution in presence of mineral acid
3) Dissociation of phosphorus pentachloride
4) Decomposition of hydrogen peroxide

26. According to Arrhenius theory, the activation energy is :
1) The energy it should posses so that it can enter into an effective collision
2) The energy which the molecule should possess in order to undergo reaction
3) The energy it has to acquire further so that it can enter into effective collision
4) The energy gained by the molecules on colliding with another molecule

27. The activation energy of a reaction is zero. The rate constant of this reaction:
1) Increases with increase of temperature 2) Decreases with an increase of temperature
3) Decreases with decrease of temperature 4) Is independent of temperature
28. For the equilibrium, A  g   B  g  , H is – 40 kJ mol–1. If the ratio of the activation energies of the
forward (Ef) and reverse (Eb) reaction is (2/3) then:
1) E f  60 kJ mol 1 ; E b  100 kJ mol 1 2) E f  30 kJ mol 1 ; E b  70 kJ mol1
3) E f  80 kJ mol 1 ; E b  120 kJ mol1 4) E f  70 kJ mol 1 ; E b  30 kJ mol1
29. The main function of a catalyst in speeding up a reaction is:
1) To increase the rate of the forward reaction
2) To change the reaction path so as to decrease the energy of activation for the reaction
3) To reduce the temperature at which the reaction can occur
4) To increase the energy of the molecules of the reactants
30. What is the activation energy for a reaction if its rate doubles when the temperature is raised from
 1
20oC to 35oC? R  8.314 J mol K
1

1) 34.7 kJ mol 1 2) 15.1kJ mol 1 3) 342 kJ mol1 4) 269 kJ mol1
LEVEL - II
3
1. The rate of disappearance of SO2 in the reaction 2SO 2  O 2  2SO3 is 1.28  10 g / sec . The rate of
formation of SO3 is
1) 0.64  103 g / sec 2) 0.80  103 g / sec 3) 1.28  103 g / sec 4) 1.60 10 3 g / sec
74
2. For the reaction, 2A + 3B + (3/2)C  3P,
dn A 3 dn B 3 dn C dn A dn B dn C
1) = = 2) = =
dt 2 dt 4 dt dt dt dt
dn A 2 dn B 4 dn C dn A 2 dn B 3 dn C
3) = = 4) = =
dt 3 dt 3 dt dt 3 dt 4 dt
3. During the decomposition of H2O2 to give oxygen, 48 g O2 is formed per minute at a certain point of
time. The rate of formation of water at this point is
1) 0.75 mol min–1 2) 1.5 mol min–1 3) 2.25 mol min–1 4) 3.0 mol min–1
4. During the kinetic study of the reaction, 2A  B  C  D , following results were obtained
Expt.
A  B Initial rate of formation of D
mol L -1
mol L -1
mol L-1 min -1
1 0.1 0.1 6.0×10-3
2 0.3 0.2 7.2×10-2
3 0.3 0.4 2.88×10-1
4 0.4 0.1 2.40×10-2
The rate constant of the above reaction is
2 2 1
1) 4.5 mol2 L2 min 1 2) 12 mol 2 L2 min 1 3) 8 mol2 L2 min 1 4) 6 mol L min
d  A
5. 
For a chemical reaction, A 2 
1
 K
 2A , the expression for is :
K 1 dt
1) 2k1  A 2   k 1  A  2) k 1  A 2   k 1  A  3) k 1  A 2   k  1  A  4) 2k1  A 2   2k 1  A 
2 2 2 2
6. In a gaseous reaction, A 2  g   B  g   1/ 2  C  g  . The increase in pressure from 100 mm to 120

mm is noticed in 5 minutes. The rate of disappearance of A2 in mm min–1 is :
1) 4 2) 8 3) 16 4) 2
7. For the first order reaction, PCl5 (g)  PCl3 (g)  Cl2 (g) , the concentration of PCl5 reduces from
50 mol L-1 to 10 mol L-1 in 120 minutes at 300K.The rate constant for the reaction is :
1) 1.34  10 2 min 1 2) 1.55  10 2 min 1 3) 1.07  10 2 min 1 4) 1.87  10 2 min 1

8. For a first-order reaction, A  Products, the concentration of A changes from 0.1 M to 0.025 M in 40
min. The rate of the reaction when the concentration of A is 0.01 M is:
1) 1.73 × 10–5 M min–1 2) 3.47 × 10–4 M min–1 3) 3.47 × 10–5 M min–1 4) 1.73 × 10–4 M min–1
d  NH3  d  N2  d H2 
9. For the reaction 2NH3  N 2  3H 2 , if  k1  NH 3  ,  k 2  NH 3  ,  k 3  NH 3 
dt dt dt
then the relation between k1, k2 and k3 is
1) k1= k2 = k3 2) k1= 3k2 = 2k3 3) 1.5 k1= 3k2 = k3 4) 2k1= k2 = 3k3
75
10. A first order reaction is 20% complete in 10 min. The rate constant of the reaction A  B is:
1) 0.223 min–1 2) 0.0223 min–1 3) 2.23 min–1 4) 22.3 min–1
11. For the reaction, 2NO  g   O 2  g   2NO 2  g  , the volume is suddenly reduced to half its value by
increasing the pressure on it. If the reaction is of first-order with respect to O2 and second-order with
respect to NO, the rate of reaction will be:
1) diminished to one-fourth of its initial value 2) diminished to one-eighth of its initial value
3) increased to eight times of its initial value 4) increased to four times of its initial value
12. The rate of a gaseous reaction is given by the expression R  k  A  B . If the volume of the vessel is
suddenly reduced to 1/4 of initial volume, new rate relating to original rate will be
1) 1/10 2) 1/8 3) 8 4) 16
13. The initial rates of reaction for the equation, 2A  B 

 Products were determined under various
initial concentration of reactants.
 A 0  B0 -d  B /dt
0.20 M 0.20 M 0.50 M s -1
0.10 M 0.20 M 0.25 M s -1
0.10 M 0.10 M 0.25 M s -1
The rate law is equal to:
1) k  A  B 2) k  B 3) k  A  B 4) k  A 
2
14. The rate constant for the reaction, 2N 2 O5  4NO 2  O 2 is 3.0 × 10 –5 s –1 . If the rate is
2.40 × 10–5 mol L–1 s–1, then the concentration of N2O5 (in mol L–1) is:
1) 1.4 2) 1.2 3) 0.04 4) 0.8
15. For the first-order decomposition reaction of N2O5, it is found that
1 d  N 2 O5 
2N 2 O5  g   4NO2  g   O2  g  ;   k  N 2 O5 
2 dt
d  N 2 O5 
N 2O5  g   2NO2  g   ½O2  g  ;   k   N 2 O5 
dt
which of the following facts is true?
1) k = k' 2) k > 2k' 3) k > k' 4) 2k = k'
16. A reaction that is of the first order with respect to reactant A has a rate constant 6 min–1. If we start with
[A] = 0.5 mol L–1, when would [A] reach the value 0.05 mol L–1
1) 0.384 min 2) 0.15 min 3) 3 min 4) 3.84 min
76
17. At 500 K, the half life period of a gaseous reaction at an initial pressure of 80 kPa is 350 sec. When
the pressure is 40 kPa, the half life period is 175 sec; the order of the reaction is:
1) zero 2) one 3) two 4) three
18. For a reaction between A and B the order with respect to A is 2 and the order with respect to B is 3. If
the concentrations of both A and B are doubled, the rate will increase by a factor of
1) 12 2) 16 3) 32 4) 10
19. When the concentration of a reactant in reaction A  B is increased by 8 times but rate increases
only 2 times, the order of the reaction would be:
1) 2 2) 1/3 3) 4 4) 1/2
20. The half-life period of a certain reaction, A  Products is 1 h, when the initial concentration of the
reactant A, is 2.0 mol L–1. How much time does it take for its concentration to come from 0.50 mol L–1 to
0.25 mol L–1, if it is a zero-order reaction?
1) 1 h 2) 4 h 3) 0.5 h 4) 0.25 h
21. The t1/2 for a zero order reaction at the initial concentration of 6  103 M is one minute at 27oC. The
rate constant at 27oC in mol dm–3 s–1 is
1) 3  10 4 2) 6  10 4 3) 5  10 5 4) 5  10 4
22. If a first order reaction takes 40 minutes for 75% completion, then the time required for 90% completion
is
1) 66.6 min 2) 80 min 3) 90 min 4) 78.6 min
23. For a first order reaction A  P , concentration of reactant ‘A’ changes from 2 mol/L to 0.125 mol/L in
36 minutes. The t1/ 2 of the reaction is
1) 12 min 2) 18 min 3) 9 min 4) 7.2 min
24. Which one of the following is wrongly matched?
1) Saponification of CH3COOC2H5 – Second order reaction
2) Acid hydrolysis of CH3COOCH3 – Pseudo first order reaction
3) Decomposition of H2O2 – First order reaction
4) Combination H2 and Br2 to give HBr – Zero order reaction
25. A first order reaction which is 30% complete in 30 minutes has a half-life period of
1) 24.2 min 2) 58.2 min 3) 102.2 min 4) 120.2 min

26. In a particular reaction, the time required to complete half of the reaction was found to increase 16
times when the initial concentration of the reactant was reduced to one-fourth. What is the order of
the reaction?
1) 1 2) 4 3) 2 4) 3
77
27. For a reaction, consider the plot of lnk versus 1/T given in the figure. If the rate constant of this reaction
at 400 K is 10–5 s–1, then the rate constant at 500 K
Slope = –4606 K
1/T
1) 10–4 s–1 2) 4 × 10–4 s–1 3) 10–6 s–1 4) 2 × 10–4 s–1
1
28. A plot of vs ln k for a reaction, gives the slope 1 10 4 K . The energy of activation for the reaction
T
is (Given : R  8.314 J K 1mol1 )
1) 8314 J mol 1 2) 1.202 kJ mol1 3) 12.02 J mol1 4) 83.14 kJ mol 1

29. Which of the following statements is not correct?
1) The efficiency of a solid catalyst depends upon its surface area
2) Catalyst operates by providing alternate path for the reaction that involves a lower activation energy
3) Catalyst lowers the energy of activation of the forward direction without affecting the energy of
activation of the backward direction
4) Catalyst does not affect the overall enthalpy change of the reaction.
30. If the activation energy of a reaction is 80.9 kJ mol–1, what is the fraction of molecules having enough
energy to react to form products at 700K ? (R=8.31 J K-1 mol-1)
1) 13.9 2) 21.3 3) 28.7 4) 35.1
78
KEY WITH HINTS

LEVEL - I
1. 4 Molecularity of the reaction does not influence the rate of reaction.
2. 2 The increase in collision frequency brings in an increase in effective collisions and thus rate of
reaction increases.
For the reaction, 2H 2 (g) + 2NO(g)  N 2 (g) + 2H 2O(g), rate = k f [NO] [H 2 ]. 2NO and 1 H2 get
2
3. 1
reacted and 1 H2 will be left on the reactant side so that the rate for the reverse reaction will be
[N 2 ][H 2O]2
Rate = k b
[H 2 ]
d  O 2  1 d SO3  3  104  1 d SO3  d SO3   6  104 mol L1 s 1
4. 2  ; ;
dt 2 dt 2 dt dt
5. 1  2NH 3
N 2  3H 2 
d  N 2  1 d  H 2  1 d  NH 3  d  H 2  3 d  NH3  3
   So,      2  104  3  104
dt 3 dt 2 dt dt 2 dt 2
6. 4 H 2 +I 2  2HI . When 1 mole of H2 reacts with 1 mole of I2, 2 moles of HI are formed in the
d H2  d  I2  1 d  HI
same time interval. Thus, rate may be expressd as :   
dt dt 2 dt
The negative sign signifies the decrease in concentration of the reactant with time.
7. 4 Order is the sum of the powers of the concentration terms in the rate law expression,
R  [ A][ B ]2 . Order of the reaction = 1 + 2 = 3.
8. 1 For the reaction, 2A  B  C  D
1 d A d  B d  C  d  D 
Rate of reaction =    
2 dt dt dt dt
d[C]
Rate of reaction =k[A]x [B]y
dt
From table,
1.2  103  k  0.1  0.1
x y
...(1)
1.2 10 3  k  0.1  0.2

x y
...(2)
2.4 10 3  k  0.2  0.1

x y
...(3)
y
1.2 103 k(0.1) x (0.1) y 1
Dividing equation (i) by (ii), we get 3
 y 1     y=0
1.2 10 x
k(0.1) (0.2) 2
1 x
1.2  103 k(0.1) x (0.1) y 1 1
Dividing equation (i) by (iii), we get 3
        x 1
2.4 10 x
k(0.2) (0.1) y
2 2
d[C]
Hence, =k[A]1[B]0  k[A]
dt
79
9. 3 Value of k increases with increase in temperature.

10. 1
11. 2 Rate of reaction is directly proportional to [N2O5]. Therefore it is a first order reaction.
2.303  A o 2.303 100

k log  log  6.39 104 s 1
t  A  3600 10
12. 2 For nth order reaction, Rate = k[a]n
Rate mol L-1 s-1 mol L-1 s -1
k= n
= -1 n
= n -n
 mol1-n Ln-1 s-1
[a] (mol L ) (mol L )
d [ R ] 1  0.75 0.25
13. 1 For the given reaction,   5
dt 0.05  0 0.05
d[R] 0.75  0.40 0.35
  5
dt 0.12  0.05 0.07
d[R]
Thus, the value of  k is constant, and the reaction follows zero order kinetics.
dt
14. 3 Rate = k[X] [Y2] .............(i)
Slow step is the rate determining step.
 X  , [X] 
2
Equilibrium constant for fast step, K  K[X 2 ]

X2 
By substituting [X] in equation (i) we get
1 3
Rate  k K[X 2 ] [Y2 ]  k [X 2 ]1/ 2 [Y2 ]  Order of reaction   1   1.5
2 2
15. 3
16. 1 Order of a reaction may have zero, fractional, positive or negative value.
17. 1 For a zero-order kinetics, the time of completion is [A]0/k or a/k
18. 3 For second order reaction A  B, t1/ 2  1/ k  A 0
19. 1 X  a 1  e  kt  ;
20. 4 100 
t1/2
 50 
t1/2
 75 
t1/2
 87.5
t 87.5%  3 t1/2
0.693 0.693 2.303 a 2.303

21. 3    0.1 ; t  log  log100
t1 6.93  ax 0.1
2
t = 46.06
80
22. 4 A  2B
Initial 1 0
At time t 1-x 2x
1 a 1 1 1 1 1
k= ln  ln  (ln1  ln 0.9)  (0  (0.105))  k   0.105
t a  x t 0.9 t t 100
ln 2 0.693
t1 2    100  660 min
k 0.105
0.693 2.303 100
23. 1 k ,t  log
t1/ 2 k 20
24. 2 Initial rate = r1 , Final rate = r2

r2 = 29 r1 = 512 r1

25. 2 CH 3COOCH 3  H 2 O 
H
 CH 3COOH  CH 3OH
26. 3
27. 4 When Ea = 0, the rate of reaction becomes independent of temperature. (Ea = Energy of
activation).
28. 3 A g  Bg H  40 kJ

Ef 2
Since,   x where ‘x’ is the activation energy of forward reaction.
E b 3 x  40
29. 2 Catalyst decreases energy of activation.
k2 Ea  1 1 
30. 1 log    
k1 2.303R  T1 T2 
k 2  2k1 , T1  20  273  293K or T2  35  273  308 K ; R  8.314 J mol 1 K 1

Ea  1 1  Ea 15
log 2      0.3010  
2.303  8.314  293 308  19.147 293  308
E a  34673J mol 1 or 34.7 kJ mol1
LEVEL - II
1 d SO2  1 d SO3  d SO 2  d SO3 

1. 4   ;  
2 dt 2 dt dt dt
d SO 2  1.28  103
   0.02  103 mol / sec
dt 64
d SO3 
 0.02  103  80  1.6  103 g / sec
dt
81
2. 3 2A + 3B + (3/2)C  3P
1 dA 1 dB 2 dC 1 d[P] dn A 2 dn B 4 dn C
Rate=  = = = or  
2 dt 3 dt 3 dt 3 dt dt 3 dt 3 dt
3. 4 2H 2 O 2  2H 2 O  O 2
1 d[H 2 O 2 ] 1 d[H 2 O] d[O 2 ]
Rate    
2 dt 2 dt dt
48
Rate of formation of oxygen = 48 g min–1  mol min 1  1.5 mol min 1
32
1 d  H 2O d O 2  d  H 2 O d O2 
 Rate of formation of H2O   ;  2  2  1.5  3mol min 1
2 dt dt dt dt
Let the rate of reaction be given by : rate  k  A   B

a b
4. 4
Consider II and III, where [A] is constant.
7.2  102  0.3  0.2 1  1 

a b b
 ;    b2
2.88  101  0.3a 0.4b 4  2 
Consider I and IV
6.0  103  0.1  0.2 1  1 

a b a
 ;    a 1
2.4 102  0.4a  0.1b 4  4 
rate 6 103
Rate  k  A  B ; k 
2
   6 mol2 L2 min 1
 A  B 0.1 (0.1) 2
2
d A
 2k1  A 2   2k 1  A 
2
5. 4
dt
rf  k1  A 2  rb  k 1  A  ; Net rate  k1  A 2   k 1  A 
2 2
1 d A d A
 k 1  A 2   k 1  A  ;  2k1  A 2   2k 1  A 
2 2
2 dt dt
1
6. 2 A2 g   Bg  Cg
2
t=0 100 mm 0 0
x
t = 5 min (100 – x) x
2
x
Total pressure 100  x  x   120  x  40 
2
d  A 2  40
Rate of disappearance of A 2    8
dt 5
82
7. 1 For first order reaction,
1  a  2.303 50 2.303  0.6989

k  ln   log   0.0134 min 1 or 1.34  102 min 1
t  a  x  120 10 120
0.693
8. 2 0.1 
t1/2
 0.05 
t1/2
 0.025; 2t1/2  40, t1/ 2  20; k
t1/ 2
Rate = k[A] (for first-order reaction) = 0.03465 × 0.01 = 3.47 × 10–4 M min–1.
9. 3 2NH3  N2  3H2
1 d  NH 3  d  N 2  1 d  H 2 
Rate    
2 dt dt 3 dt
1 1
k1  NH 3   k 2  NH 3   k 3  NH 3 
2 3
1.5k1  3k 2  k 3
 A t k 100

k
 10, k  0.0223 min 1
10. 2 log  t ; log
 A 0 2.303 80 2.303
11. 3 The rate law for the reaction is Rate = k[O2] [NO]2.
When volume is redued to half, concentration becomes double the initial concentration, so the
rate law becomes rate  k  2O 2  2NO   rate  8k  O 2  NO  .
2 2
1
12. 4 If volume is decreased by of initial then conc. of A and B both are increased by 4 times of
4
initial so rate increased 16 times.
13. 4 Let order w.r.t. A = a, order w.r.t B = b
d  B
 k  A   B
a b

dt
0.5  k  0.2   0.2 

a b
.......(i)
0.25  k  0.1  0.2  .......(ii)

a b
0.25  k  0.1  0.1

a b
.......(iii)
From equations (i) and (ii), 2 = (2)a a=1

From equations (ii) and (iii), 1 = (2)b  (2)0 = (2)b  b = 0
Thus, rate law  k  A  B  k  A 

0
83
14. 4 [N2O5] = r/k  0.8 molL1 .
15. 1 Rate of disappearance of N2O5 does not depend upon the way a chemical reaction is formulated.
Hence, k = k'.
2.303 a
16. 1 For first order kinetics, k  log
t ax
2.303 0.5 2.303 0.5 2.303

 a  x   0.05 mol L1 , 6  log or t  log   0.384 min
t 0.05 6 0.05 6
 t1/2 1
n 1 n 1
p  350  40   1
n1
17. 1  2  ,   2   1 n  1  n  0
 t1/ 2 2  p1  175  80   2 
Rate1  k  A   B ; Rate 2  k  2A   2B

2 3 2 3
18. 3
Rate 2  32k  A   B
2 3
 Rate 2  32 (Rate)1
2r
r1  k  A  , r2  2r1  k 8A   1   8 
n nn
19. 2
r1
20. 4 For a zero-order reaction, t1/2 = [A]/2k where [A] is the initial concentration.
x  0.50  0.25  0.25 h

So, k = [A]/2t1/2 = 2/2 × 1 = 1. Also for zero-order reaction, k  t
t 1
21. 3 For a zero order reaction, A  product, rate = k
 A 0
t1/ 2 
2k
 A 0 6  103
k   5  105 mol dm 3 s 1
2  t1/ 2 2  60
40
22. 1 t 75%  2 t1/ 2  40 ; t 1/2  20min
2
t 90%  3.33t1/ 2  3.33  20  66.6 min
23. 3 2 mol 
t1/2
1mol 
t1/2
 0.5mol 
t1/2
 0.25 mol 
t1/2
 0.125 mol
36
4t1/ 2  36 ; t1/ 2   9 min
4
24. 4  2HBr is a 1.5 order reaction, i.e., k   H 2  Br2 
H 2  Br2 
1/ 2
2.303 a 0.693 2.303 100

25. 2 k log ;  log  t1/ 2  58.2 min
t ax t1/2 t 100  30
84
1
26. 4 We know that t1/ 2  .
a n 1
Ea
27. 1 From Arrhenius equation, ln k  ln A 
RT
E a k E T T 
Slope   4606 K or, ln 2  a  2 1 
R k1 R  T1T2 
k2  500  400 
ln 5
 4606  
10  500  400 
k2 k
ln 5
 2.303; 25  antiln  2.303
10 10
k 2  1 104 s 1
28. 4 Plot of ln k vs 1/ T gives
Ea Ea
Slope   1104  
R 8.314
E a  8.314  104 J mol 1  83.14  103 J mol1 or E a  83.14 kJ mol 1
29. 3 A catalyst lowers the energy of activation of both forward and backward reactions.
30. 1 Fraction of molecules having enough energy to react  e  Ea / RT
Comparing with e x ,
Ea 80.9  103
x=   13.9
RT 8.31  700
85
CHAPTER - 04
The d- AND f-BLOCK ELEMENTS
INTRODUCTION
The d- block consists of four periods of 10 elements each belonging to groups 3 to 12 in which the d-
orbitals are progressively filled. The f- block consists of two long periods of 14 elements each in which the
4f and 5f orbitals are filled. These elements are formal members of group 3 from which they have been
taken out to form separate blocks. The 4f series and 5f series are known as lanthanoids (Lanthanones) and
actinoids (Actinons) respectively. All elements belonging to the d and f-blocks are metals. The names
transition metals and inner transition metals are often used to refer to the elements of d-and f-blocks
respectively.
Precious metals such as silver, gold and platinum and industrially important metals like iron, copper, titanium,
etc., form part of the transition metals. Pt, Pd, Ru, Rh, etc., are important catalysts. Elements such as Th,
Pa and U are sources of nuclear energy. Besides these, many useful chemicals such as KMnO4, K2Cr2O7,
etc., are compounds of transition metals.
THE TRANSITION (d-BLOCK) ELEMENTS
A transition element may be defined as one which has incompletely filled d- orbitals in its ground state or in
any of its oxidation states. Zinc, cadmium and mercury of group 12 which have d10 configuration in their
ground states as well as common oxidation states are not regarded as transition metals. However, being
the last members of the transition series, their chemistry is studied along with the transition metals.
Classification of d-Block Elements
Unlike s and p-block elements which are usually discussed as groups (columns), the d-block elements are
discussed as series (rows). In the periodic table, there are four transition series of elements corresponding
to filling of 3d, 4d, 5d and 6d sublevels in periods 4, 5, 6, and 7.
The first transition series (3d series) consists of 10 elements from 21Sc to 30 Zn in the 4th period.
The second transition series (4d series) consists of elements from 39Y to 48Cd in the 5th period. The
third transition series (4d series) consists of 10 elements including 57La and elements 72Hf to 80 Hg in the
6th period. The fourth transition series (4d series) consists of elements including 89Ac and elements
104
Rf to 112Cn in the 7th period.
Electronic Configuration of d-Block Elements

1. General electronic configuration. General electronic configuration is [Inert gas] (n-1)d1–10 ns1–2.
(i) First transition series: [Ar]18 3d1-10 4s1-2. (ii) Second transition series: [Kr]36 4d1-10 5s1-2. (iii) Third
transition series: [Xe]54 4f14 5d1-10 6s1-2. (iv) Fourth transition series: [Rn]86 5f14 6d1-10 7s1-2.
86
Exceptional behaviour of Zn, Cd, and Hg. Due to d10 configuration, Zn, Cd and Hg show exceptional
behaviour in their respective series. In the first transition series, Zn differs from the other members: (i) It has
much higher atomic radius and ionisation enthalpies. (ii) It does not exhibit variable oxidation states. (iii)
Compounds are colourless except when anions are coloured. (iv) Compounds are diamagnetic. (iv) Forms
lesser number of complexes.
PROPERTIES OF TRANSITION ELEMENTS .
1. Metallic character. Transition elements except Zn, Cd, Hg and Mn have one or more typical metallic
structures at normal temperature. They exhibit all the characteristics of metals.
Table - 02 Lattice Structures of Transition Elements.
They have relatively low ionisation energies and have one or two electrons in their outermost energy level
(ns1 or ns2). The unpaired d-electrons can also form metallic bonds. Thus ns as well as (n-1) d-electrons
participate in metallic bonding. Both metallic and covalent bonding exist in transition elements. Hardness
and brittleness are associated with covalent bonding. Cr, Mo and W are very hard metals as they have high
strength of covalent bonding due to the presence of maximum number of unpaired d-orbitals. Zn, Cd and
Hg are soft in nature as they do not have unpaired d-electrons.
In any group, metallic character increases. Heavier transition metals form M-M bonds.
(a) (b)
Figure - 01 Trends in (a) melting points (b) enthalpies of atomisation of transition elements.
87
2. Melting and Boiling Points. Transition metals have very high melting and boiling points. The melting
points rise to a maximum at d5 and then decreases with increase in atomic number. Manganese and
technetium have abnormally low melting points while tungsten has the highest melting point among
transition elements.
The high melting points of these metals is due to the involvement of greater number of electrons from
(n-1)d in addition to the ns electrons in metallic bonding; greater the number of unpaired electrons,
stronger the metallic bonding. This is evident from their high enthalpies of atomisation. Since enthalpy
of atomisation is an important factor in determining the standard electrode potential, metals with very
high enthalpy of atomisation (i.e., high b.p.) tend to be noble.
3. Atomic radii. The atomic radii of transition metals are intermediate between those of s- and
p-block elements. In a series, the atomic radii generally decrease with increase in atomic number, but
the decrease is small after midway. In the first transition series, the atomic radii decrease from scandium
to chromium and thereafter remains almost the same. The atomic radius first decreases because of
poor shielding effect of d-electrons. After midway, with increase in the number of d-electrons, screening
effect increases. This counterbalances the increased nuclear charge. As a result, the atomic radii
remain practically the same after chromium. E.g., in Fe, the two opposing tendencies almost
counterbalance and there is no change in the size from Mn to Fe. The same behaviour is observed in
the case of the second and third transition series.
Towards the end of a period, there is a slight increase in the atomic radii because the increased
electron-electron repulsions are greater than the attractive forces due to increased nuclear charge.
This results in expansion of the electron cloud and therefore, increase in atomic radius.
The atomic radii increases down the group. The atomic radii of of the second transition series is
greater than those of the first series, but the atomic radii of the second and third transition series are
similar.
Since in atoms of the second transition series, the number of shells increases, their atomic radii are
greater than those of the first transition series. The atomic radii of the second and third transition
series are nearly the same because of lanthanide (lanthanoid) contraction.
Figure - 02 Trends in atomic radii of transition elements.

The filling of 4f before 5d orbitals results in a regular decrease in atomic radii called Lanthanoid
contraction which compensates for the expected increase in atomic size with increasing atomic
number. The net result of lanthanoid contraction is that the second and the third d-series exhibit
similar radii (e.g., Zr 160 pm, Hf 159 pm) and have very similar physical and chemical properties.
Lanthanoid contraction is caused by the imperfect shielding of 4f electrons.
88
4. Ionisation Enthalpy. The first ionisation enthalpies of d-block elements are higher than s-block
elements and lower than p-block elements. Ionisation enthalpies increase gradually with increase in
atomic number in a given transition series though some irregularities are observed. This is due to
increase in nuclear charge with increase in atomic number, which reduces the size of the atom,
making removal of electrons difficult.
The irregular trend in the first ionisation enthalpy of 3d metals is because the removal of an electron
alters the relative energies of 4s and 3d orbitals. There is thus, a reorganisation energy accompanying
ionisation. with increase in exchange energy as the number of electrons increases and from
transference of s- electrons into d- orbitals. There is increase in the values as the effective nuclear
charge increases. However, the value for Cr is lower because of the absence of any change in the
d-configuration (3d5 4s1). The value for Zn is higher because ionisation takes place from the 4s level of
a stable configuration (3d10 4s2).
Table - 03 Ionisation Enthalpies (kJ mol –1) of First Transition Series.
Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
1st I.E. 631 656 650 652 717 762 758 736 745 906
2nd I.E. 1235 1309 1414 1592 1509 1561 1644 1752 1958 1734
3rd I.E. 2393 2657 2833 2990 3260 2962 3243 3402 3556 3829
In a given series, the difference in ionisation enthalpies between successive members is much less
than the difference in case of successive members of s-block or p- block. This is due to shielding
effect of d-electrons.
The first ionisation enthalpy of Zn, Cd and Hg are very high due to fully filled, (n-1)d10, ns2, configuration.
The second and third ionisation enthalpies also increase along a period, but the magnitude of increase
among successive members is much higher. The second ionisation enthalpy which shows unusually
high values for Cr and Cu where the d5 and d10 configurations of the M+ ions are disrupted, with
considerable loss of exchange energy. The value for Zn is low because the removal of an electron
results in stable d10 configuration.
The third ionisation enthalpies are quite high and are not complicated by the 4s orbital factor. There is
a marked break between the values for Mn2+ and Fe2+. The third ionisation enthalpy of Mn is very high
because the third electron has to be removed from the stable, half-filled 3d orbital (3d5 4s2). The third
ionisation enthalpy for Fe2+ to Fe3+ is very small because loss of the third electron gives a stable, half-
filled 3d5 configuration.
Cu, Ni and Zn exhibit a maximum oxidation state of +2 due to high values of third ionisation enthalpies.
The first ionisation enthalpies of 5d elements are higher than those of 3d and 4d elements. This is
because the weak shielding effect of 4f electrons results in greater effective nuclear charge acting on
the outer electrons.
Figure - 03 Ionisation Enthalpies of transition series

89
5. Oxidation States. Transition elements exhibit a great variety of oxidation states in their compounds.
This is due to the participation of ns and (n-1)d electrons in bonding, their energies being almost
equal. In general, lower oxidation state is exhibited when ns electrons participate in bonding and higher
oxidation states are shown when ns as well as (n-1)d electrons take part in bonding.
The most common oxidation state of the first row transition metals +2, except for Sc (+3). This indicates
that d-orbitals are more stable than s-orbital after scandium.
Mostly ionic bonds are formed in +2 and +3 oxidation states. In compounds having higher oxidation
states, the bonds are mostly covalent, formed by the sharing of d-electrons.
The maximum number of oxidation states of reasonable stability corresponds to the sum of the s and
d electrons up to manganese (TiIVO2, VVO2+, CrV1O42–, MnVIIO4–) followed by a rather abrupt decrease
in stability of higher oxidation states (FeII,III, CoII,III, NiII, CuI,II, ZnII).
Table - 04 Oxidation States of First Transition Series (most common ones in bold type and very rare
and unstable in parentheses).
Sc Ti V Cr Mn Fe Co Ni Cu Zn
+3 (+2) +2 +2 +2 +1
+3 +3 +3 (+3) +2 +2 +2 +2 +2
+4 +4 (+4) +4 +3 +3 (+3)
+5 (+5) (+5) (+4) (+4) (+4)
+6 (+6) (+6)
+7
The variability of oxidation states arises out of incomplete filling of d-orbitals in such a way that their
oxidation states differ from each other by unity, e.g., VII, VIII, VIV, VV. This is in contrast with the variability
of oxidation states of non-transition elements, where oxidation states normally differ by a unit of two,
e.g., PbII, PbIV.
Although in the p-block the lower oxidation states are favoured by the heavier members (due to inert
pair effect), the opposite is true in the groups of d-block, e.g., in group 6, Mo(VI) and W(VI) are found
to be more stable than Cr(VI). Thus Cr(VI) in the form of dichromate in acidic medium is a strong
oxidising agent, whereas MoO3 and WO3 are not.
Low oxidation states are found when a complex compound has ligands of p-acceptor character in
addition to s-bonding. For example, in Ni(CO)4 and Fe(CO)5, the oxidation state of nickel and iron is
zero.
The oxidation state of a metal in a solvent depends on the nature of the solvent, e.g., Cu+ is unstable
in water as it may undergo oxidation to Cu2+. Similarly, Fe2+ in water changes to Fe3+.
6. Trends in the stability of higher oxidation states of transition metal halides (3d-series). The
highest oxidation numbers along the series vary from +4 for Ti in TiX4, +5 for V in VF5, +6 for Cr in CrF6
and +7 for Mn in MnO3F. Beyond Mn, no other metal in the series show oxidation number greater than
+3. The highest oxidation state is generally more stable with fluorine. This may be due to the higher
lattice energy or the higher bond enthalpies for the higher covalent compounds, e.g., VF5 and CoF6.
Vanadium shows +5 oxidation state in VF5 only. Other halides undergo hydrolysis to give oxohalides,
VOX3, in which the oxidation state of V is +5.
In the lower oxidation states, fluorides are unstable, e.g., in TiX2, VX2, CuX (X = Cl-, Br- and I-). However
Cu(II) halides except iodides are known. They oxidise iodide to iodine.
2Cu 2   4I  
 Cu 2 I 2 (s)  I 2
90
Many Cu(I) compounds are unstable in aqueous solution and undergo disproportionation.
2Cu  
 Cu 2   Cu
The greater stability of Cu2+(aq) than Cu+(aq) is due to greater negative enthalpy of hydration of Cu2+(aq).
7. Trends in the stability of higher oxidation states of transition metal Oxides (3d-series).
The highest oxidation state in the oxides is the same as the group number upto group 7 (Sc2O3 to
Mn2O7).
Beyond group 7, the maximum oxidation state is +3 (in Fe2O3), although in ferrates, (FeO4)2-, formed
in alkaline medium, Fe has oxidation number +6. But these readiy decompose to Fe2O3 and O2.
Higher oxidation states are also found in oxo cations, e.g., V(V) in VO2+, V(IV) in VO2+ and Ti(IV) in
TiO2+.
Oxygen stabilises the highest oxidation state more than fluorine, e.g., the highest fluoride of Mn is
MnF4, whereas the highest oxide is Mn2O7. This is due to the ability of oxygen to form multiple bonds
with metal ions. In Mn2O7, each Mn is tetrahedrally surrounded by four O-atoms including an Mn-O-Mn
bridge. Similarly, [MO4]n- ions exist having a tetrahedral structure where M=V(V), Cr(VI), Mn(V), Mn(VI)
and Mn(VII).
8. Standard Electrode Potentials. Electrode potential depends on factors such as enthalpy of
atomisation/sublimation of the metal, the ionisation enthalpy and the hydration enthalpy. The total
energy,  TH for the process is the sum of the three types of enthalpies
 M  (aq)  e  ;  T H   a H   i H   hyd H
M(s) 
Thus,  TH is the total enthalpy change when solid metal, M is brought into aqueous medium as
monovalent ion, M+(aq). The electrode potential is a measure of  TH.
Table - 07 Thermochemical data (kJ mol-1) for the first row Transition Elements and the
Standard Electrode Potentials for the Reduction of MII to M.
2+
Element [M]  a H° [M]  iH° 1 [M]  i H°2 [M]  hydH° [M ] E°/V
Ti 469 661 1310 -1866 -1.63
V 515 648 1370 -1895 -1.18
Cr 398 653 1590 -1925 -0.90
Mn 279 716 1510 -1862 -1.18
Fe 418 762 1560 -1998 -0.44
Co 427 757 1640 -2079 -0.28
Ni 431 736 1750 -2121 -0.25
Cu 339 745 1960 -2121 0.34
Zn 130 908 1730 -2059 -0.76
9. Trends in the M3+/M2+ Standard Electrode Potential. The low value for E° (Sc3+/Sc2+) is due to the
stability of Sc3+, which has noble gas configuration. The highest value for Zn is because the third
electron has to be removed from the stable d10 configuration of Zn2+. Therefore, it is difficult to remove
an electron to convert it into +3 state. The comparatively high value for Mn shows that Mn2+(d5) is
particularly stable. The comparatively low value for Fe shows the extra stability of Fe3+ (d5). The
comparatively low value for V is related to the stability of V2+ (half-filled t2g level).
91
10. Chemical Reactivity and E° Values. Transition metals vary widely in chemical reactivity. Many of
them are sufficiently electropositive to dissolve in mineral acids, whereas a few are unaffected. (i) The
metals of the first series except Cu are relatively more reactive and are oxidised by 1M H+, though the
rate is slow. E.g., Ti and V, in practice, are passive to dilute non oxidising acids at room temperature.
(ii) The E° values for M2+/M indicate a decreasing tendency in forming divalent cations across the
series. The less negative E° values is related to the increase in the sum of the first and second
ionisation enthalpies. (iii) The E° values for Mn, Ni and Zn are more negative than the general trend.
Whereas the stabilities of half-filled d subshell (d5) in Mn2+ and completely filled d -subshell (d10) in zinc
are related to their E° values; for nickel, E° value is related to the highest negative enthalpy of hydration.
(iv) The E° values for the redox couple M3+/M2+ shows that Mn3+ and Co3+ ions are the strongest
oxidising agents in aqueous solution. Ti2+, V2+ and Cr2+ are strong reducing agents and can liberate
hydrogen from dilute acid.
11. Magnetic Properties. Many of the transition metals and ther compounds are paramagnetic.
Paramagnetism arises due to the presence of unpaired electrons in atoms, ions, complex ions or
molecules. When the number of unpaired electrons increases, the magnetic moment and hence
paramagnetic character also increases.
Each electron has a magnetic moment associated with its spin angular momentum and orbital angular
momentum. The orbital motion of unpaired electrons is severely disturbed by the electrons of the
surrounding ligands thereby ‘quenching’ the orbital angular momentum in transition metal compounds.
For the compounds of the first series, the contribution of the orbital angular momentum is effectively
quenched and hence is of no significance. Therefore, in such cases the spin contribution becomes
more significant. The magnetic moment is calculated using the ‘spin-only’ formula,   n(n  2) B.M.
Where n is the number of unpaired electrons and µ is the magnetic moment in units of Bohr magneton
(BM).
Table - 08 Calculated and observed magnetic moments (BM) for first row transition elements.
Electronic No. of unpaired Magnetic moment (B. M.)

Ion
configuration electrons Calculated Observed
3+ 0
Sc 3d 0 0 0
3+ 1
Ti 3d 1 1.73 1.75
2+ 2
Ti 3d 2 2.84 2.76
2+ 3
V 3d 3 3.87 3.86
2+ 4
Cr 3d 4 4.9 4.8
2+ 5
Mn 3d 5 5.92 5.96
2+ 6
Fe 3d 4 4.9 5.3 - 5.5
2+ 7
Co 3d 3 3.87 4.4 - 5.2
2+ 8
Ni 3d 2 2.84 2.9 - 3.4
2+ 9
Cu 3d 1 1.73 1.8 - 2.2
2+ 10
Zn 3d 0 0 0
12. Formation of Coloured Ions. Most transition metal compounds, ionic as well as covalent, are coloured
both in the solid state and in aqueous solution. This is due to the presence of unpaired electrons.
92
When an electron in a lower energy d-orbital is excited to a higher energy d-orbital, the energy of
excitation corresponds to the frequency of light absorbed. The colour observed is the complementary
colour of the light absorbed. In case of complexes, the frequency of the light absorbed is determined
by the nature of the ligand.
A few of the transition metal ions such as Sc(III), Ti(IV), Cu(I) and Zn(II) are colourless. In these ions
the (n-1) d- subshell is either empty or completely filled. Other ions such as Cu(II), Ti(III), Co(II), Fe(III),
etc., with one to nine electrons in the (n-1)d- subshell are coloured.
Table - 09 Colour of some of the first row (aquated) Transition Metal ions.
Ion Configuration Colour Ion Configuration Colour

3+ 0 2+ 4
Sc 3d Colourless Cr 3d Blue
4+ 0 3+ 5
Ti 3d Colourless Fe 3d Yellow
3+ 1 2+ 6
Ti 3d Purple Fe 3d Green
4+ 1 3+ 6
V 3d Blue Co 3d Blue
3+ 2 2+ 7
V 3d Green Co 3d Pink
2+ 3 2+ 8
V 3d Violet Ni 3d Green
3+ 3 2+ 9
Cr 3d Violet Cu 3d Blue
3+ 4 2+ 10
Mn 3d Violet Zn 3d Colourless
2+ 5
Mn 3d Pink
13. Formation of Complexes. Transition metals form a large number of complex compounds or
complexes. These are compounds in which the metal ions bind a number of anions or neutral molecules
giving complex species with characteristic properties. These ions or molecules, called ligands, donate
lone pairs of electrons to the central metal ion forming coordinate bonds, e.g., [Fe(CN)6]3–, [Cu(NH3)4]2+
and [PtCl4]2–.
Formation of complexes is due to (i) comparatively smaller size of the metal ions, (ii) high ionic charge
on the metal ions (they have large charge/size ratio) and (iii) availability of vacant d- orbitals (to accept
lone pairs) for bond formation.
14. Catalytic Properties. Transition metals and their compounds are extensively used as catalysts due
to the presence of unpaired electrons in their incomplete d-orbitals and their ability to adopt multiple
oxidation states and form complexes. (i) Vanadium (V) oxide in Contact Process for the manufacture
of H2SO4. (ii) Finely divided iron (catalyst) and molybdenum (promoter) in Haber’s Process for the
manufacture of ammonia. (iii) Finely divided nickel in catalytic hydrogenation of oils. Iron (III) catalyses
the reaction between iodide and persulphate ions.
2I   S2 O8 2 
 I 2  2SO 4 2 
The catalytic action is explained as: 2Fe3  2I  

 2Fe 2   I 2 ; 2Fe 2  S2 O8 2  
 2Fe3  2SO 4 2 .
15. Interstitial Compounds. Compounds formed when small atoms like H, C or N are trapped inside the
crystal lattices (interstitial sites) of metals are called interstitial compounds. They are usually non-
stoichiometric and are neither typically ionic nor covalent, e.g., TiC, Mn4N, Fe3H, Fe3C, VH0.56, TiH1.7,
etc. The formulae do not correspond to normal oxidation state of the metal.
Characteristics: (i) These are very hard (some borides are as hard as diamond). (ii) They have high
melting points (higher than those of pure metals). (iii) They have metallic conductivity. (iv) They are
chemically inert.
93
16. Alloy Formation. Alloys are homogeneous solid solutions in which the atoms of one metal are
distributed randomly among the atoms of the other. These are obtained by melting the component
metals and then cooling the melt. Alloys are formed by atoms with metallic radii that are within about
15 percent of each other. Because of similar radii, atoms of one metal can easily take up the positions
in the crystal lattice of another.
Alloys are generally harder and have often high melting points. They are more resistant to corrosion
than individual metals.
Some Important Compounds of Transition Elements

1. Oxides and Oxoanions of Metals. Since the transition metals exhibit variable oxidation states, a
large variety of oxides are formed.
i. The oxides are generally formed by the reaction of metals with oxygen at high temperatures.
ii. The highest oxidation number of the oxides coincides with the group number in case of Sc2O3 to
Mn2O7. Beyond group 7, no higher oxides of iron above Fe2O3 are known.
iii. All transition metals except Sc form MO oxides which are ionic. As the oxidation number of the
metal increases, ionic character decreases. Thus, Mn2O7 is a covalent green oil. CrO3 and V2O5 have
low melting points.
iv. In the higher oxides, acidic character is predominant. Thus, Mn2O7 gives HMnO4 and CrO3 gives
H2CrO4 and H2Cr2O7.
2 8/3 3 4 7
Mn O  Mn 3 O 4  Mn 2 O3  Mn O 2  Mn 2 O7
Basic Amphoteric Amphoteric Amphoteric Acidic
v. Certain metals in their higher oxidation states stabilise by forming oxocations, e.g., VV as VO2+, VIV
as VO2+ and TiIV as TiO2+.
In case of vanadium, there is gradual change from basic V2O3 to less basic V2O4 and to amphoteric
V2O5. V2O4 dissolves in acids to give VO2+ salts. V2O5 is amphoteric though mainly acidic and gives
VO43– as well as VO 2 salts.
CrO is basic, Cr2O3 is amphoteric and CrO3 is acidic. Thus, CrO3 dissolves in water to give acids
H2CrO4 and H2Cr2O7.
A few of the oxides dissolve in acids and bases to form oxometallic salts, e.g., potassium chromate,
potassium dichromate, potassium permanganate etc.
2. Potassium dichromate K2Cr2O7
a. Preparation. Dichromates are prepared from chromates which are obtained by the fusion of chromite
ore (FeCr2O4) with sodium or potassium carbonate in free access of air.
4FeCr2 O 4 + 8Na 2 CO3 + 7 O 2 

 8Na 2 CrO 4 + 2Fe 2 O3 + 8CO 2
The yellow solution of sodium chromate is acidified with sulphuric acid to get a solution from which
sodium dichromate, Na2Cr2O7. 2H2O is crystallised.
2Na 2 CrO 4 + 2H + 
 Na 2 Cr2O 7 + 2Na + + H 2 O
Sodium dichromate is more soluble than potassium dichromate, therefore, the latter is prepared by
treating sodium dichromate solution with potassium chloride.
94
Na 2 Cr2 O 7 + 2KCl 
 K 2 Cr2 O 7 + 2NaCl
The chromates and dichromates are interconvertible in aqueous solution depending on the pH. The
oxidation state of chromium in chromate and dichromate is the same (+6).
2 CrO 4 2  + 2H + 
 Cr2 O 7 2 + H 2 O ; Cr2 O 7 2 + 2OH  
 2CrO 4 2  + H 2 O
b. Structure of chromate and dichromate ions. The chromium atom in chromate ion is sp3 hybridised.
The four oxygen atoms around the central chromium atom are oriented in tetrahedral arrangement.
The chromate ion is tetrahedral, whereas the dichromate ion consists of two tetrahedra sharing one
corner with Cr–O–Cr bond angle of 126°.
(a) (b)
Figure - 04 Structure of (a) chromate ion (b) dichromate ion

c. Colour of chromate and dichromate ions. In both chromate and dichromate ions, Cr(VI) has d0
configuration. The yellow colour of CrO42- and orange colour of Cr2O72- are not due to d-d-transition but
due to charge transfer, i.e., the momentary transfer of charge from oxygen atom to metal atom thereby
changing O2- ion momentarily to O- ion and reducing the oxidation state of Cr from +6 to +5.
d. Properties. Potassium dichromate forms orange red crystals which melts at 669K. It is moderately
soluble in cold water, but freely soluble in hot water.
i. Action of alkalies. When alkali is added to an orange red solution of dichromate ions, a yellow
solution of chromate ions is obtained.
K Cr O + 2KOH 
2 2 7  2K 2CrO4 + H 2O
Pot. dichromate Pot. chromate
ii. Action of concentrated sulphuric acid. In the cold, red crystals of chromic anhydride (chromium
trioxide) are formed.
K 2 Cr2 O 7 + 2H 2SO 4 
 2CrO3  2KHSO 4  H 2 O
On heating the mixture, oxygen is evolved.
2K 2 Cr2 O 7 + 8H 2SO 4 
 2K 2SO 4  2Cr2 (SO 4 )3  8H 2 O  3O 2
iii. Oxidising properties. Dichromates are strong oxidising agents. In acidic solution,
Cr2 O7 2 + 14H + + 6e  
 2Cr 3+ + 7H 2 O (E = +1.33V)
It oxidises iodides to iodine, sulphides to sulphur, iron (II) to iron (III) and tin(II) to tin(IV).
Cr2 O 7 2 + 14H + + 6I  
 2Cr 3+ + 7H 2 O + 3I 2
Cr2 O 7 2 + 3H 2S + 8H  
 2Cr 3+ + 3S + 7H 2 O
Cr2 O 7 2  + 6Fe2+ + 14H  

 2Cr 3+ + 6Fe3 + 7H 2 O
Cr2 O 7 2 + 3Sn 2+ + 14H  

 2Cr 3+ + 3Sn 4 + 7H 2 O
95
3. Potassium permanganate KMnO4

a. Preparation. (i) Potassium permanganate is prepared by the fusion of MnO2 (pyrolusite) with KOH or
K2CO3 in presence of air or an oxidising agent such as KNO3 or KClO3. This gives dark green K2MnO4
which disproportionates in neutral or acidic solution to give permanganate.

2MnO 2 + 4KOH + O 2   2K MnO2 4 + 2H 2 O
Potassium manganate
3MnO 4 2  + 4H + 
 2MnO 4  + MnO 2 + 2H 2O (Disproportionation)
Manganate ion Permanganate ion
(ii) Commercial Preparation. KMnO4 is prepared by the alkaline oxidative fusion of MnO2 followed by
electrolytic oxidation of manganate (Vl) in alkaline solution.
MnO 2 
Fused with KOH, oxidised with air or KNO3
MnO 4 2 ; MnO 24 
Electrolysis in alkaline solution
 MnO 4  e 
manganate ion
(iii) In the laboratory, a manganese (II) ion salt is oxidised by peroxodisulphate to permanganate.
2Mn 2+ + 5S2 O82  + 8H 2 O 
 2MnO 4  + 10SO4 2 + 16H +
Peroxodisulphate Permanganate
b. Properties. It forms dark purple crystals with greenish metallic lustre. It is moderately soluble in
water at room temperature (6.4 g/100 g of water at 293 K).
(i) Action of heat. When heated, it decomposes at 513 K giving oxygen.
2KMnO 4 
513K
 K 2 MnO 4 + MnO 2 + O 2
(ii) Oxidising nature. Potassium permanganate is a powerful oxidising agent in neutral, alkaline and
acidic media. Oxidation reactions of KMnO4 in acidic medium:
(i) It oxidises sulphur dioxide to sulphuric acid.
2MnO 4  + 2H 2 O + 5SO 2 
 2Mn 2+ + 5SO 4 2- + 4H +
(ii) Hydrogen sulphide is oxidised to sulphur.
2MnO 4  + 16H + + 5S 2   
 2Mn 2+ + 8H 2 O + 5S
(iii) It oxidises nitrites to nitrates.
2MnO4  + 6H + + 5NO2  
 2Mn 2+ + 3H 2O + 5NO3
(iv) Sulphurous acid or sulphite is oxidised to a sulphate or sulphuric acid.
5SO32  + 2MnO 4  + 6H + 
 2Mn 2+ + 3H 2 O + 5SO 4 2 
(v) Iodine is liberated from potassium iodide .
10 I  + 2MnO 4  + 16H + 
 2Mn 2+ + 8H 2 O + 5I 2
(vi) Fe2+ ion (green) is converted to Fe3+ (yellow).
2MnO 4  + 16H + + 10Fe 2+ 

 2Mn 2+ + 8H 2 O + 10Fe3+
(vii) Oxalate ion or oxalic acid is oxidised at 333 K.
5C 2 O 4 2 + 2MnO 4  + 16H + 
 2Mn 2+ + 8H 2 O + 10CO 2
96
Permanganate titrations in presence of HCl are unsatisfactory since HCl is oxidised to chlorine.
2MnO 4  + 16H + + 10Cl- 
 2Mn 2+ + 8H 2 O + 5Cl 2
The reduction of permanganate to manganate, manganese dioxide and manganese(II) salt by half-
reactions can be represened as.
MnO 4  + e  
 MnO 4 2 (E = + 0.56 V) (ii)
MnO 4  + 4H + + 3e  
 MnO 2 + 2H 2 O (E = + 1.69 V) (iii)
MnO4  + 8H + + 5e 
 Mn 2+ + 4H2O (E = + 1.52 V) (iv)
The hydrogen ion concentration of the solution influences the reaction. Although many reactions can
be understood on the basis of redox potential, kinetics of the reaction is also an important factor.
Permanganate at [H+] = 1 should oxidise water (E°ox = -1.23 V) but in practice the reaction is extremely
slow unless either Mn2+ ions are present or the temperature is high.
c. Structure of permanganate ion. Manganese in MnO4- is sp3 hybridised and hence four oxygen atoms
are arranged tetrahedrally around manganese.
(a) (b)
Figure - 05 Structure of tetrahedral (a) manganate (green) ion (b) permanganate (purple) ion.
It has intense colour and diamagnetism along with temperature-dependent weak paramagnetism.
These can be explained using molecular orbital theory. The manganate and permanganate ions are
tetrahedral; the pi-bonding takes place by overlap of p-orbitals of oxygen with d-orbitals of manganese.
The green manganate is paramagnetic because of one unpaired electron but the permanganate is
diamagnetic due to the absence of unpaired electrons.
d. Uses of Potassium permanganate. (i) As an oxidising agent in the laboratory and in industry. (ii) In
volumetric analysis for the estimation of oxalates, ferrous salts, iodides, H2O2 etc. (iii) As a favourite
oxidant in preparative organic chemistry. (iv) To disinfect water in wells and tanks. (v) Due to oxidising
action, it is used for bleaching wool, cotton, silk and other textile fibres and for the decolourisation of
oils.
THE INNER TRANSITION (f-BLOCK) ELEMENTS
The elements in which the last or differentiating electron enters the f-orbital of the anti-penultimate
(n-2) f-orbitals are called f-block elements. They are also called inner transition elements because
they form transition series within transition series (d-block elements). Their general electronic
configuration is (n-2)f1-14(n-1)d0-1 ns2. Thus, they have three incomplete shells, viz., (n-2), (n-1), and n.
THE LANTHANOIDS
The elements in which the last electron enters the 4f-orbitals are called 4f-block elements or first
inner transition series. These 14 elements, earlier called rare earths, are now called lanthanides,
lanthanons or lanthanoids because they come after lanthanum in the Periodic Table. Lanthanum,
though a d-block element is included in the lanthanoid series because it closely resembles the
lanthanoids. The general symbol for lanthanoids is Ln.
1. Abundance. Lanthanoids has an abundance of only 0.2 ppm on the earth’s crust. The most abundant
lanthanoid is cerium. The most common mineral containing lanthanoids is monazite. It is mainly
lanthanoid orthophosphate.
97
2. Electronic Configuration. Lanthanoids have electronic configurations with 6s2 common and variable
occupancy of 4f level. The electronic configurations of all the tripositive ions (most stable oxidation
state) are of the form 4fn ( n  1 to 14) with increasing atomic number..
Thus, the general electronic configuration of lanthanoids is [Xe] 4f 1-14 5d 0-1 6s2.
Table - 10 Electronic Configurations of Lanthanum and Lanthanoids.
Atomic Electronic configuration Oxidation Radii (pm)

Name Symbol 2+ 3+ 4+ 3+
Number Ln Ln Ln Ln states Ln Ln
57 Lanthanum La 1 2 1 0 +3 187 106
[Xe] 5d 6s 5d 4f
58 Cerium Ce 1 1 2 2 1 0 +3, +4 183 103
[Xe] 4f 5d 6s 4f 4f 4f
59 Praseodymium Pr 3 2 3 2 1 +3, +4 182 101
[Xe] 4f 6s 4f 4f 4f
60 Neodymium Nd 4 2 4 3 2 +2, +3, +4 181 99
[Xe] 4f 6s 4f 4f 4f
61 Promethium Pm 5 2 5 4 +3 181 98
[Xe] 4f 6s 4f 4f
62 Samarium Sm 6 2 6 5 +2, +3 180 96
[Xe] 4f 6s 4f 4f
63 Europium Eu 7 2 7 6 +2, +3 199 95
[Xe] 4f 6s 4f 4f
64 Gadolinium Gd 8 2 7 1 7 +3 180 94
[Xe] 4f 6s 4f 5d 4f
65 Terbium Tb 9 2 9 8 7 +3, +4 178 92
[Xe] 4f 6s 4f 4f 4f
66 Dysprosium Dy 10 2 10 9 8 +3, +4 177 91
[Xe] 4f 6s 4f 4f 4f
67 Holmium Ho 11 2 11 10 +3 176 90
[Xe] 4f 6s 4f 4f
68 Erbium Er 12 2 12 11 +3 175 89
[Xe] 4f 6s 4f 4f
69 Thulium Tm 13 2 13 12 +2, +3 174 88
[Xe] 4f 6s 4f 4f
70 Ytterbium Yb 14 2 14 13 +2, +3 173 87
[Xe] 4f 6s 4f 4f
14 1 2 14 1 14
71 Lutetium Lu [Xe] 4f 5d 6s 4f 5d 4f +3 172 86
3. Atomic and Ionic Radii (Lanthanoid Contraction). The regular decrease in the atomic and ionic
radii of lanthanoids with increasing atomic number is called lanthanoid contraction. This contraction is
attributed to imperfect shielding of one electron by another in the same sub-shell. Thus, there is
decrease in the size with increasing atomic number.
Figure - 06 Ionic radii of Lanthanoids (4f-series).
The decrease in size, although continuous is not regular. The decrease is much more in case of the
first 6 elements than the subsequent elements.
98
Consequences of Lanthanoid Contraction. (i) Similarity of second and third transition series.
Lanthanoid contraction causes the radii of the members of the third transition series to be very similar
to those of the corresponding members of the second series. The almost identical radii of Zr (160 pm)
and Hf (159 pm) is a consequence of lanthanoid contraction. This accounts for their occurrence
together in nature and for the difficulty faced in their separation.
2. Oxidation States. The lanthanoids show only limited number of oxidation states because the energy
gap between 4f and 5d subshells is very large. Among lanthanoids, Ln(III) compounds are predominant
species. However, +2 and +4 ions in solution or in solid compounds also exist. This irregularity, as in
ionisation enthalpies, arises mainly from the extra stability of empty, half-filled or fully-filled f-subshell.
La forms only the La3+ ion because removal of three electrons gives it noble gas configuration (of
xenon).
The formation of CeIV ion is favoured by its noble gas configuration, but being a strong oxidant reverts
to the common +3 state. The Eo value for Ce4+/ Ce3+ is + 1.74 V which indicates that it can oxidise
water. However, the reaction rate is very slow and hence Ce(IV) is a good analytical reagent.
Pr, Nd, Tb and Dy exhibit +4 state in their oxides, MO2.
Eu2+ is formed by losing the ‘s’ electrons and its f 7 configuration accounts for its formation. However,
Eu2+ is a strong reducing agent changing to the common +3 state.
Similarly Yb2+ which has [Xe] 4f 14 configuration is a reductant.
TbIV has half-filled f-orbitals and is an oxidant. The behaviour of samarium is very much like europium,
exhibiting both +2 and +3 oxidation states.
The reason for lanthanoids showing limited number of oxidation states when compared to transition
elements is that the (n-1) d-orbitals in transition elements can easily participate in bond formation but
the (n-2) f-orbitals in lanthanoids are deep within, and therefore, could not.
3. Atomic and Physical Properties. Lanthanoids are silvery white soft metals which tarnish rapidly in
air. They have typical metallic structure and are good conductors of heat and electricity. Their m.p.
and b.p. increase with increase in atomic number. Melting points range between 1000 to 1200 K, but
samarium melts at 1623 K. Hardness increases with increase in atomic number; samarium is as
hard as steel. Densities range between 6.77 and 9.74 g cm-3.
4. Coloured ions. Many trivalent ions are coloured both in the solid state and in aqueous solution. This
may be attributed to f-f transitions in partially filled f-orbitals. La3+ or Lu3+ ions do not show any colour
but the rest do so. However, absorption bands are narrow, probably because the excitation is within f-
level. It has been observed that the colour of the ion containing nf-electrons is the same as those with
(14-n)f-electrons.
5. Magnetic properties. The lanthanoid ions other than the f 0 type (La3+ and Ce4+) and the f 14 type (Yb2+
and Lu3+) are all paramagnetic. Paramagnetism is maximum for neodymium.
Ionisation enthalpy. The first and second ionisation enthalpies are around 600 kJ mol–1 and
1200 kJ mol–1. The third ionisation enthalpies will be low if it leads to empty, half-filled or completely
filled configurations. This is indicated by the abnormally low values of third ionisation enthalpy of La,
Gd and Lu.
6. Electropositive character. Due to low ionisation enthalpies, they are highly electropositive.
Electropositive character decreases with increase in atomic number.
7. Standard electrode potentials. E° values for the half-reaction, Ln 3+ (aq) + 3e   Ln(s) are in
the range of –2.2 to –2.4 V, except for Eu for which the value is –2.0 V. Thus, they are good reducing
agents.
99
8. Basic character. Their hydroxides, M(OH)3, are ionic and basic in character. They are stronger bases
than Al(OH)3 but weaker than Ca(OH)2. La(OH)3 is the strongest and Lu(OH)3 is the weakest base.
9. Complex formation. Lanthanoids, in spite of high charge (+3), have only weak tendency to form
complexes. This is because of low charge density due to large size. The tendency to form complexes
increases with increase in atomic number.
10. Chemical reactivity :
Uses of lanthanoids. (i) They are used for the production of alloy steels for plates and pipes. (ii)
Mischmetal consists of a lanthanoid metals (~ 95%) and iron (~ 5%) and traces of S, C, Ca and Al.
(iii) Magnesium mixed with 3% mischmetal is a pyrophoric alloy (which produces spark when struck
or rubbed) is used for making bullets, shells and lighter flints. (iv) Mixed oxides of lanthanoids are
employed as catalysts in petroleum cracking. (v) Because of paramagnetic and ferromagnetic
properties, their compounds are used for making magnetic and electronic devices. (vi) Some individual
Ln oxides are used as phosphors in television screens and similar fluorescing surfaces.
THE ACTINOIDS
The actinoids, actinides or actinones include the fourteen elements from thorium to lawrencium.
Although actinium does not belong to the 5f - series, it is also included because of its close resemblence
with the actinoids. Since in these elements, the number of electrons in the outermost as well as the
penultimate shell remains the same, all the actinides resemble one another very closely.
All actinoids are radioactive. The earlier members have relatively long half-lives, but the latter elements
have half-lives ranging from a day to 3 minutes for lawrencium. Elements beyond uranium (Z = 92) are
man made. These elements do not occur in nature because their half-life periods are so short that
they ceased to exist on earth. The chief source of thorium is monazite sands while uranium is obtained
from pitchblende and carnotite. Actinium and protactinium occur in all uranium ores as decay products
of 238U.
100
1. Electronic Configuration. The actinoids have 7s2 electronic configuration with variable occupancy
of the 5f and 6d subshells. The fourteen electrons are added to 5f from Pa to Lr. The irregularities in
the electronic configurations of the actinoids, like those in the lanthanoids are related to the stabilities
of the f0, f7 and f 14 occupancies of the 5f orbitals. Thus, the configurations of Am and Cm are [Rn] 5f
7
7s2 and [Rn] 5f 76d17s2. Berkelium (Bk, Z = 97) shows exceptional configuration of [Rn] 5f 96d07s2
which is neither half-filled nor completely filled. 5f orbitals resemble 4f orbitals in the angular part of the
wave-function, but they are not as buried as 4f orbitals and hence they participate in bonding to a
greater extent.
Table - 11 Properties of Actinium and Actinoids
Atomic Electronic configuration Radii /pm)

Name Symbol 3+ 4+ Oxidation states 3+ 4+
Number M M M M M
1 2 0
89 Actinium Ac [Rn] 6d 7s 5f 3 111
2 2 1 0
90 Thorium Th [Rn] 6d 7s 5f 5f (+3), +4 99
2 1 2 2 1
91 Protactinium Pa [Rn] 5f 6d 7s 5f 5f +3, +4, +5 96
3 1 2 3 2
92 Uranium U [Rn] 5f 6d 7s 5f 5f +3, +4, +5, +6 103 93
4 1 2 4 3
93 Neptunium Np [Rn] 5f 6d 7s 5f 5f +3, +4, +5, +6, +7 101 92
6 2 5 4
94 Plutonium Pu [Rn] 5f 7s 5f 5f +3, +4, +5, +6, +7 100 90
7 2 6 5
95 Americium Am [Rn] 5f 7s 5f 5f +3, +4, +5, +6 99 89
7 1 2 7 6
96 Curium Cm [Rn] 5f 6d 7s 5f 5f +3, (+4) 99 88
9 2 8 7
97 Berkelium Bk [Rn] 5f 7s 5f 5f +3, +4 98 87
10 2 9 8
98 californium Cf [Rn] 5f 7s 5f 5f 3 98 86
11 2 10 9
99 Einsteinium Es [Rn] 5f 7s 5f 5f 3
12 2 11 10
100 Fermium Fm [Rn] 5f 7s 5f 5f 3
13 2 12 11
101 Mendelevium Md [Rn] 5f 7s 5f 5f 3
14 2 13 12
102 Nobelium No [Rn] 5f 7s 5f 5f 3
14 1 2 14 13
103 Lawrencium Lr [Rn] 5f 6d 7s 5f 5f 3
2. Ionic Sizes. The general trend in actinoids is similar to those of lanthanoids; there is a gradual decrease
in the size of the atoms and the M3+ ions across the series. Thus, on moving from Ac3+ to Cm3+, the
ionic radius decreases from 111 to 99 pm. This steady decrease in the ionic radii with increase in
atomic number is called actinoid contraction. This is greater than lanthanoid contraction due to poor
shielding of 5f electrons.
3. Oxidation States. There is a greater range of oxidation states because the 5f, 6d and 7s levels are of
comparable energies. The actinoids in general show +3 oxidation state. The elements, in the first half
of the series exhibit higher oxidation states. E.g., the maximum oxidation state increases from +4 in
Th to +5, +6 and +7 respectively in Pa, U and Np, but decreases in succeeding elements. Actinoids
resemble lanthanoids in having more compounds in +3 state than in the +4 state. However, +3 and +4
ions tend to hydrolyse.
4. General Characteristics. The actinoids are silvery white metals having a variety of structures. This
is due to irregularities in metallic radii, which are far greater than in lanthanoids. All actinoids except
thorium and americium have high densities. Actinoids, like lanthanoids have high melting and boiling
points. However they do not show any regular trend with increase in atomic number.
5. Magnetic properties. Actinoids are strongly paramagnetic. The variation in magnetic susceptibility
of actinoids is roughly parallel to the corresponding values for lanthanoids, the latter having higher
values.
101
6. Ionisation enthalpy. The ionisation enthalpies of the early actinoids, are lower than lanthanoids because
the 5f orbitals are less penetrating than 4f and hence more effectively shielded from the nuclear
charge.
7. Coloured ions. Cations with two or more unpaired 5f electrons are coloured both in the crystalline
state as well as in their aqueous solutions, e.g., U4+ is green and U3+ is red. The colours arise out of
electronic transitions (f - f transitions) within the 5f-subshell. Cations containing f 0 and f 7 configurations
are colourless.
8. Chemical reactivity. They are highly electropositive and as such they act as strong reducing agents.
They are highly reactive, especially when finely divided. (i) They react with boiling water to give a
mixture of oxide and hydride. (ii) Hydrochloric acid attacks all metals but most are slightly affected by
nitric acid owing to the formation of protective oxide layers. (iii) Alkalies have no action.
9. Comparison of actinoids with the lanthanoids. Both lanthanoids and actinoids exhibit similarities
in many respects. (i) Both lanthanoids and actinoids show a dominant oxidation state of +3. (ii) Both
lanthanoids and actinoids are electropositive metals and act as strong reducing agents. (iii) Cations
with unpaired electrons in both the series exhibit paramagnetism. (iv) Most of the cations of lanthanoids
and actinoids are coloured. (v) Both series show a steady decrease in their ionic radii. Thus lanthanoids
show lanthanoid contraction and actinoids show actinoid contraction.
Table - 12 Differences between lanthanoids and actinoids.
Lanthanoids Actinoids
Besides +3, some of them show +2 and +4 Besides +3, they show +4, +5 and +6 , +7 oxidation
oxidation states states.
They have less tendency to form complexes. They have stronger tendency to form complexes.
Except promethium, all are non-radioactive. All are radioactive.
Do not form oxocations. 2+ 2+ +
Form oxocations like UO2 , PuO2 , UO2 etc.
Oxides and hydroxides are less basic. Oxides and hydroxides are more basic.
Most ions are colourless. Ions are coloured.
Magnetic properties can be easily explained. Magnetic properties are not easy to explain.
Uses of D and F block Elements

 Iron and steels are the most important construction materials. Their production is based on the reduction
of iron oxide, removal of impurities and addition of carbon and alloying metals such as Cr, Mn and Ni.
 TiO are manufactured for pigment industry and dry battery cell use MnO2.
 UK copper coins are ‘copper’ coated steel and ‘silver’ UK coins are a Cu/Ni alloy.
 V2O5 catalyses oxidation of SO2 in the manufacture of H2SO4.
 Haber process uses iron catalyst.
 Ni catalysts enable the hydrogenation of fats.
 TiCl4 with Al(CH3)3 forms the basis of the Ziegler catalysts used in the manufacture of polyethene.
 Wacker process uses PdCl2 as catalyst in the conversion of ethyne to ethanal.
 Photographic industry uses light sensitive property of AgBr.
102
QUESTIONS
LEVEL - I
1. Which one of the following is a transition metal?
1) Mg 2) Fe 3) Al 4) Ge
2. The general electronic configuration of Zn. Cd and Hg are represented by
1) (n – 1)d10 (n – 1)s2 2) (n – 1)d9 ns2 3) (n – 1)d10 ns1 4) (n – 1)d10 ns2
3. Which one of the following elements is not a transition element?
1) Fe 2) Cu 3) Mn 4) Zn
4. Hg is not considered as a transition element because
1) It is a liquid at room temperature 2) Melting point is very low
3) Completely filled d10 configuration 4) (n – 1) d shell is incomplete
5. The correct electronic configuration of chromium is [Z = 24]
1) [Ar] 3d4 4s2 2) [Ar] 3d4 3) [Ar] 3d5 4s1 4) [Ar] 3d6
6. Valence shell electronic configuration of Fe3+ is [Z = 26]
1) [Ar] 3d6 2) [Ar] 3d5 3) [Ar] 3d4 4) [Ar] 3d4 4s1
7. Which one of the following ions has maximum unpaired electrons?
1) Fe2+ 2) Cu2+ 3) Ni2+ 4) Zn2+
8. Among the following configuration of transition metals which one show the highest oxidation state?
1) [Ar] 3d2 4d2 2) [Ar] 3d6 4s2 3) [Ar] 3d5 4s2 4) [Ar] 3d5 4s1
9. Which of the following ions have noble gas configuration?
1) Cr3+ 2) Ti3+ 3) Sc3+ 4) V3+
10. Most of the transition metals exihibit
1) Paramagnetic behaviour 2) Variable oxidation states
3) Formation of coloured ions 4) All of these
11. Identify the correct statement about transition metals.
1) They show horizontal similarity 2) They show variable valency
3) They are all metals 4) All statements are correct
12. Which one of the following statements is not true for transition elements?
1) Transition metals show variable valency
2) Transition metals form coloured ions
3) Transition metals do not form coordination compounds
4) Transition metals form coordination compounds
13. Which one of the following metals show variable oxidation state?
1) Zn 2) Ca 3) Cu 4) Mg
14. Fe compounds are more stable than Fe compounds because
3+ 2+
1) Fe3+ has higher oxidation state 2) Fe3+ has 3d5 configuration

3) Fe3+ has 3d5 configuration state 4) Fe3+ is paramagnetic in nature
103
15. Paramagnetism of transition metals is due to

1) Variable valency
2) Presence of unpaired electrons
3) High standard electrode potential
4) High hardness
16. The metal which show diamagnetism is
1) Fe 2) Mn 3) Cr 4) Zn
17. Magnetic moment can be determined by spin only formula n  n  2  n stands for
1) Total number of electrons
2) Total number of valence electrons
3) Total number of unpaired electrons
4) Total number of paired electrons
18. Magnetic moment of Mn2+ is
1) 4.89 BM 2) 5.91 BM 3) 3.9 BM 4) 2. 82 BM
19. Colour of transition metal ions are due to the absorption of some wavelength. This results in
1) d - d transition 2) s - s transition 3) d - s transition 4) s - p transition
20. Which one of the following ions form coloured compounds?
1) Mg2+ 2) Fe2+ 3) Zn2+ 4) Na+
21. Colour of CuSO4 solution is
1) Green 2) Blue 3) Purple 4) Red
22. Catalyst used for the hydrogenation of fats is
1) Fe 2) Mn 3) Ni 4) Cr
23. Given below are two statements : one is labelled as Assertion (A) and the other is labelled as
Reason (R).
Assertion A : Transition metals show variable valency.
Reason R : A very small energy difference between the ns2 and (n – 1) d electrons.
In the light of the above statements choose the correct answer from the options given below.
1) Both A and R are true and reason is the correct explanation of A
2) Both A and R are true but R is not the correct explanation of A
3) A is true but R is false
4) A is false but R is true
24. Catalytic property of transition metals is due to
1) High hardness 2) High melting point
3) Ability to adopt multiple oxidation states 4) Paramagnetic behaviour
25. In which of the following compounds ionic radii of chromium is smallest?
1) CrCl2 2) K2Cr2O7 3) CrF2 4) Cr2O3
104
26. Alloys are readily formed by transition metals, because

1) Show variable valency 2) High hardness
3) Similar radii 4) Similar density
27. Which one of the following is incorrect for interstitial compounds?
1) They retain metallic conductivity
2) Their melting points are lower than those of pure metals
3) They are chemically inert
4) They are very hard
28. Acidified potassium permanganate solution oxidises oxalates to
1) Carbon dioxide 2) Carbon 3) Oxalic acid 4) Oxygen
29. How many elements are present in Lanthanides?
1) 10 2) 12 3) 18 4) 14
30. Which one of the following is an actinoid metal?
1) Thorium 2) Platinum 3) Palladium 4) Gold
LEVEL - II
1. Which of the following is a d-block element?
1) Ni 2) Mg 3) Ca 4) Ga
2. Elements with incomplete d-orbitals are called
1) d-block elements 2) Representative elements
3) f-block elements 4) Transition elements
3. From the following pair if ions, identify the same electronic configuration.
1) Sc3+, Cr3+ 2) Co3+, Ni2+ 3) Cu2+, Cr2+ 4) Fe3+, Mn2+
4. Electronic configuration of a transition element ‘X’ in +3 oxidation state is [Ar] 3d5. Its atomic number is
1) 23 2) 24 3) 26 4) 25
5. Which one of the following has electronic configuration [Ar]3d . 6
1) Fe3+ 2) Mn3+ 3) Co3+ 4) Ni3+

6. Which one of the pair of ions do not have same magnetic moment?
1) Fe3+, Mn2+ 2) Cu1+, Zn2+ 3) Ti2+, Co3+ 4) V2+, Cr3+
7. How many unpaired electrons are present in Cu+1.
1) 1 2) 3 3) 2 4) 0
8. Lattice structures of CO, Ni and Cu respectively are
1) ccp, bcc, ccp 2) ccp, ccp, ccp 3) bcc, ccp, ccp 4) hcp, ccp, bcc
9. In the first transition series, the element with highest melting point is
1) Mn 2) Fe 3) Cr 4) Cu
10. Which of the following order of size is correct?
1) Mn2+ < Mn3+ 2) Fe2+ < Fe3+ 3) Cr3+ < Cr2+ 4) Cu1+ < Cu2+
11. In which of the following ions the stability of two oxidation states is correctly represent?
1) Mn2+ > Mn3+ 2) Ti3+ > Ti4+ 3) Cu1+ > Cu2+ 4) Fe2+ > Fe3+
105
12. Identify the incorrect statement from the following

1) Mn show all the oxidation states from +2 to +7
2) Actinoids are radio active elements
3) Potassium permaganate oxidises hydrogen sulphide to sulphur
4) All d-block elements show paramagnetism
13. The spin only formula is
1) n  n  1 2) n  n  2 3) n  n  2  4) n  n  2 
14. Magnetic moment of a metal ion is 1.73 BM. No. of unpaired electrons is
1) 4 2) 3 3) 2 4) 1
15. The increasing order of paramagnetic behaviour of the following transition metals is
1) Sc < Ti < V < Cr 2) Cr < V < Ti < Sc 3) Ti < Sc < V < Cr 4) Sc < V < Ti < Cr
16. Correct increasing order of magnetic moment given below is
1) Cu2+ > Ni2+ > Co3+ > Mn2+ 2) Mn2+ > Co3+ > Ni2+ > Cu2+
3) Ni2+ > Co3+ > Cu2+ > Mn2+ 4) Co3+ > Mn2+ > Ni2+ > Cu2+
17. Which of the following d-subshell configuration shows highest magnetic moment?
1) 3d3 2) 3d7 3) 3d9 4) 3d5
18. Which one of the following ions are coloured?
1) Zn2+ 2) Sc3+ 3) Ti4+ 4) V4+
19. Which one of the following transition metal ions are colourless in water?
1) Ti3+ 2) V3+ 3) Cu2+ 4) Sc3+
20. Select the incorrect statement from the following
1) Mn2O7 is a covalent green oil
2) Cr2O3 is amphoteric
3) Ionic character increases with increase in oxidation state
4) Oxidation state of Mn in Mn2O7 is +7
21. Identify the correct statement about catalytic activity of transition metals?
1) Transition metal ions can change their oxidation states
2) First raw transition metals utilize 3d and 4s electrons for bonding
3) Weakening of the bonds in the reacting molecules
4) All are correct
22. Interstitial compounds of transition metals with H, C and N are
1) Stoichiometric compounds 2) Non-stoichiometric compounds
3) Ionic compounds 4) Covalent compounds
23. KMnO4 is isostructural with
1) KClO3 2) KCl 3) KClO4 4) Na2CO3
106
24. Na 2 Cr2 O 7  xKCl 

 K 2 Cr2 O 7  2NaCl . Identify the value of ‘x’
1) 2 2) 1 3) 4 4) 3
25. 5C 2 O 24   2MnO 4  16H  

 2Mn 2   8H 2 O  xCO 2 . X the value of x in the given reaction is
1) 8 2) 10 3) 12 4) 6
26. In acidic medium potassium permanganate oxidises I to –
1) IO 3 2) IO 2 3) I 2 4) HI
27. When MnO2 is fused with KOH in the presence of air a coloured compound is formed. The product
and its colour is
1) K2MnO4, dark green 2) Mn3O4 black 3) KMnO4, purple 4) Mn2O3 brown
28. In the dichromate anion. Which one of the following is correct?
1) All Cr – O bonds are equivalents
2) Six Cr – O bonds are equivalent
3) Four Cr – O bonds are equivalent
4) All Cr – O bonds are not equivalent
29. Lanthanoids and actinoids are together called
1) Main transition elements 2) Inner transition elements
3) Long period elements 4) Representative elements
30. Lanthanoid contraction is due to
1) Atomic radius 2) Increase in effective nuclear charge
3) Poor shielding effect of 4f electrons 4) Both 2 and 3
107
KEY WITH HINTS

LEVEL - I
1. 2
2. 4
3. 4
4. 3
5. 3
3d5
6. 2 Fe3+ = Ar
7. 1 Fe2+ [Ar]3d6 - 4 unpaired electrons.

Cu2+ [Ar]3d9 - 1 unpaired electrons.
Ni2+ [Ar]3d8 - 2 unpaired electrons.
Zn2+ [Ar]3d10 - 0 unpaired electrons.
8. 3 Maximum oxidation state is +7.
9. 3 Sc Atomic no = 21
Sc = [Ar] 3d1 4s2
Sc3+ = [Ar]
10. 4
11. 4
12. 3
13. 3
14. 2
15. 2
16. 4 All the orbitals of Zn are completely filled.
17. 3
3d5
18. 2 Mn 2+  Ar 
No of unpaired electrons is 5
Magnetic moment μ = n  n  2   5  5  2   5  5  2   5.91
108
19. 1
20. 2 Transition metal ions form coloured compounds.
21. 2
22. 3
23. 1
24. 3
25. 2
26. 3
27. 2 Their melting points are higher than those of pure metals.
28. 1 5C 2 O 24   2MnO 4  16H   2Mn 2   8H 2 O  10 CO 2

29. 1
30. 1
LEVEL - II
1. 1
2. 4
3. 4 Fe3+ [Ar] 3d5
Mn2+ [Ar] 3d5
4. 3 X3+ = [Ar] 3d5 23 electrons.
 Atomic number is 26
5. 3 Co3+ = [Ar] 3d6
2
3d
6. 3 Ti2+ [Ar] 3d2
Co3+ [Ar] 3d6
7. 4 Cu+1 = [Ar] 3d10

8. 2
9. 3
10. 3 Greater the +ve charge of the same atom, smaller is its size.
11. 1 In Mn2+ 3d orbitals are half filled [Ar] 3d5.
12. 4
13. 2
14. 4 n  n  2   1.73
11  2   3  1.73
n=1
109
15. 1 Paramagnetism increases with increase in number of unpaired electrons.
Sc  [Ar]3d1 4s 2 , Ti[Ar]3d 2 4s 2
V  [Ar]3d 3 4s 2 , Cr[Ar]3d5 4s1
16. 2 Ni 2   Ar  3d8  n  2
M  2  2  2   2.82
Mn 2  Ar  3d5  n  5
M  n  n  2   5  5  2   5.83
Co3  Ar  3d 6  n  4
4  4  2   4.89
Cu 2    Ar  3d 9  n  1  11  2   1.73
17. 4 In 3d5 five unpaired electrons.
18. 4 V4+ - Blue
19. 4 Sc3   Ar  3d 0
20. 3 As the oxidation state increases ionic character decreases.
21. 4
22. 2 Interstitial compounds of transition metals are non-stioichiometric.
23. 3 Two crystals are said to be iso structural, if they have the same structure, but not necessarily
the same cell dimensions.
24. 1
25. 2
26. 3 KMnO4 oxidised I– to iodine.
27. 1 2MnO 2  4KOH 

 2K 2 MnO 4  2H 2 O
O O
179
28. 2 O Cr pm Cr O
pm 16
3 O 3p O
O 16 m
29. 2
30. 4
110
CHAPTER - 05
COORDINATION COMPOUNDS
Compounds in which metal atoms are linked to a number of ions or neutral molecules through coordinate
bonds are called complex compounds.
WERNER’S THEORY OF COORDINATION COMPOUNDS
Postulates of Werner’s theory (Swiss chemist, Alfred Werner,1892)
(i) In coordination compounds, metals show two types of valencies (linkages); primary and secondary.
(ii) The primary valencies are ionisable and are satisfied by negative ions. These valencies are also referred
to as oxidation state of the metal.
(iii)The secondary valencies are non ionisable and are satisfied by neutral molecules or negative ions. The
secondary valence is equal to the coordination number and is fixed for a metal.
(iv)The ions or groups bound by secondary linkages to the metal have characteristic spatial arrangements
corresponding to different coordination numbers.
These spatial arrangements are called coordination polyhedra. In [Co(NH3)6]3+3Cl-, [CoCl(NH3)5]2+2Cl-,
[CoCl2(NH3)4]+Cl-, etc., the species within square brackets are coordination entities or complexes and
the ions outside square brackets are called counter ions.
He further postulated that octahedral, tetrahedral and square planar shapes are more common among
coordination compounds of transition metals. Thus, [Co(NH3)6]3+, [CoCl(NH3)5]2+ and [CoCl2(NH3)4]+ are
octahedral, [Ni(CO)4] is tetrahedral and [PtCl4]2–is square planar.
Types of complexes
(i) Cationic complexes. Complexes in which the complex ion carries a net positive charge are called cationic
complexes, e.g., [Cr(NH3)6]3+, [Co(NH3)6]3+, [Ni(NH3)6]2+, etc.
(ii) Anionic complexes. Complexes in which the complex ion carries a net negative charge are called
anionic complexes, e.g., [Fe(CN)6]3-, [Fe(CN)6]4-, [Ag(CN)2]-, etc.
(iii) Neutral complexes. Complexes in which the complex ion carries no net charge are called neutral
complexes or simply complexes, e.g., [Co(NH3)3Cl3], [Ni(CO)4], etc.
Difference between double salt and complex
Both double salts and complexes are formed by the combination of two or more stable compounds in
stoichiometric ratio. However, double salts exist only in crystal lattices and break down into their constituents
in solution. Coordination compounds exist in the solid state as well as in solution.
111
The properties of a double salt are the same as those of the constituent compounds, e.g., Mohr’s salt,
FeSO4.(NH4)2SO4.6H2O, dissolved in water gives all the properties of its components, FeSO4 and (NH4)2SO4.
On the other hand, components of a complex ion lose their identity on the formation of the complex and their
properties are entirely different from the constituents. E.g., [Fe(CN)6]3– does not give the properties of Fe3+
and CN– ions and exist as a single entity in solution.
In a double salt, metal ions exhibit their normal valency, whereas in a complex ion, the metal ion is surrounded
by oppositively charged ions or neutral molecules which are more in number than its normal valency.
Important Terms Pertaining to Coordination Compounds
(a) Coordination entity or Complex ion, [MLn]±. The coordination entity consists of the central metal
atom/ion bonded to a fixed number of oppositely charged ions or neutral molecules through coordinate
bonds. E.g., [CoCl3(NH3)3] is a coordination entity in which the cobalt ion is surrounded by three ammonia
molecules and three chloride ions.
Co-ordination sphere : The central atom/ion and the ligands attached, enclosed in square brackets is
termed co-ordination sphere.
(b) Central atom/ion. In a coordination entity, the atom/ion to which a fixed number of ions/groups are
attached in a definite geometrical arrangement is called the central atom or ion. The central atom/ion in the
coordination entities, [NiCl2(H2O)4], [CoCl(NH3)5]2+ and [Fe(CN)6]3– are Ni2+, Co3+ and Fe3+, respectively.
The central atom/ion may be referred to as a Lewis acid.
(c) Ligands. The ions or molecules bound to the central atom/ion in a coordination entity are called ligands
or coordinating groups. Ligands may be simple ions (Cl–, CN-, NO2_ SO42–, etc), small molecules (H2O,
NH3, etc), larger molecules (H2NCH2CH2NH2, N(CH2CH2NH2)3, etc) or even macromolecules (proteins,
etc). The atom in the ligand which donates the electron pair is called donor atom. In [Co(NH3)6]Cl3, the six
NH3 molecules are the ligands and N atom in NH3 is the donor atom. Thus ligands are Lewis bases.
(d) Charge on the complex ion. The charge carried by a complex ion is the algebraic sum of the charges
of the central metal ion and the ligands coordinated to it. E.g., in the complex ion [Cu(NH3)4]2+, Cu2+ ion
carries a charge equal to +2 and as NH3 ligands are neutral, therefore, the net charge on the complex ion is
+2. In [Fe(CN)6]3–, the net charge on the complex ion is –3, which is the difference between Fe3+ and 6CN–.
(e) Counter ions. The ionisable groups/atoms written outside the square brackets are called counter ions.
The counter ions exactly balance the charge on the complex ion and renders the complex as a whole
neutral. E.g., in [Co(NH3)6]Cl3, the charge on [Co(NH3)6]3+ is balanced by three Cl– ions and in K3[Fe(CN)6],
the charge on [Fe(CN)6]3–, is balanced by three K+ ions.
(f) Coordination number. The coordination number (CN) of a metal ion in a complex is the number of
ligand donor atoms to which the metal is directly bonded. For example, in the complex ions, [Ni(NH3)4]2+,
and [PtCl6]2– the coordination number of Ni and Pt are 4 and 6 respectively. Similarly, in the complex ions,
[Fe(ox)3]3–, and [Co(en)3]3+, the coordination number of both, Fe and Co, is 6 because ox (oxalato) and en
(ethane-1,2 -diamine) are didentate ligands. In [Co(edta)]–, the coordination number of Co is six because
edta is hexadentate ligand.
(g) Coordination polyhedron. The spatial arrangement of the ligand atoms which are directly attached to
the central metal atom/ion defines a coordination polyhedron about the central atom. The most common
coordination polyhedra are octahedral, tetrahedral and square planar. For example, [Co(NH3)6]3+, [Cu(NH3)6]2+,
and [FeF6]3– are octahedral, [MnCl4]2–, [Cd(CN)4]2–, [ZnCl4]2–, and [Ni(CO)4] are tetrahedral and [PtCl4]2–,
[Ni(CN)4]2–, [Cu(NH3)4]2+, and [PdCl4]2– are square planar.
112
Figure - 01 Shapes of different coordination polyhedra (M = central atom/ion and L = unidentate ligand)
(h) Oxidation number of central atom. The oxidation number of the central atom in a complex is defined
as the charge carried by it if all the ligands, along with their shared electron pairs are removed from it.
Oxidation number is represented by a Roman numeral in parenthesis following the name of the coordination
entity. For example, oxidation number of copper in [Cu(CN)4]3– is +1 and it is written as Cu(I). Oxidation
number of central metal atom/ion (x) can be calculated as:
x + (Number of ligands × Charge on ligand)] = Charge on coordination sphere.
E.g., oxidation number of Co in [Co(NH3)5Cl]2+ : x +1(–1) + 5(0) = +2 or x = +3.
(i) Homoleptic and Heteroleptic Complexes. A complex in which the metal atom/ion is bound to only one
kind of donor group is known as homoleptic complex, e.g., [Co(NH3)6]3+and [CuCl5]3–. Complexes in which
the metal is bound to more than one kind of donor groups are known as heteroleptic complexes, e.g.,
[Co(NH3)4Cl2]+ and [Fe(H2O)5NO]2+.
CLASSIFICATION OF LIGANDS
Ligands may be classified on the basis of denticity, i.e., the number of donor atoms which form coordinate
bond(s) with the central metal atom/ion as (i) Unidentate ligands and (ii) Polydentate or chelating ligands.
1. Unidentate or monodentate ligands. Ligands containing only one donor atom are called unidentate
ligands, e.g., Cl–, H2O, NH3, OH–, O22–, N3–, CN-, NO2–, C5H5N (pyridine), (C6H5)3P, etc.
Ambidentate ligand. Ligands which can bind through two different atoms are called ambidentate ligands,
e.g., NO2– and SCN– ions. For example, NO2– ion can coordinate to a central metal atom/ion either through
nitrogen or through oxygen. Similarly, SCN– ion can coordinate through sulphur or nitrogen.
2. Bidentate or didentate ligands. When a ligand can bind through two donor atoms as in H2NCH2CH2NH2
(ethylene-diamine, ethane-1, 2-diamine or en) or C2O42– (oxalato or ox), the ligand is said to be didentate.
Symmetrical and unsymmetrical bidentate ligands. Bidentate ligands in which the two coordinating
groups are the same (e.g., oxalate ion) are called symmetrical ligands.
When the coordinating groups are different (e.g., glycinato, H2NCH2COO-), they are called unsymmetrical
bidentate ligands.
113
3. Polydentate ligands. When several donor atoms are present in a single ligand it is said to be polydentate.
The number of such ligating groups is called the denticity of the ligand. Depending on the number of donor
sites, ligands may be termed as bidentate, tridentate (e.g. diethylenediamine or dien), tetradentate (e.g.
triethylenetetraamine or trien), pentadentate (e.g. ethylenediamine-triacetato ion, edta3-) and hexadentate
(e.g. ethylenediamine-tetracetato ion, edta4-). EDTA4– is an important hexadentate ligand. It can bind through
two nitrogen and four oxygen atoms to the central metal ion.
4. Chelating ligands and Chelates. When a di- or polydentate ligand uses its two or more donor atoms to
bind to a single metal ion, it is called chelate ligand; the complex is called chelate and the process is
called chelation. Chelate complexes tend to be more stable than similar complexes containing unidentate
ligands. This effect is called chelate effect. E.g., [Cu(en2)]2+ is more stable than Cu(NH3)42+.
(a) (b) (c)
Figure - 02 Chelation of Pt with (a) ethylene diamine, (b) diethylene triamine, (c) triethylene tetramine.
NOMENCLATURE OF COORDINATION COMPOUNDS
In IUPAC system, the additive principle is followed for formulation as well as naming, i.e., while writing the
formula, ligands are added after the central metal atom/ion and while naming, the names of the ligands are
added before the name of the central metal atom/ion.
Formulas of Mononuclear Coordination Entities
Mononuclear coordination entities contain a single central metal atom. The following rules are applied :
(i) The central atom is listed first.
(ii) Ligands are listed in alphabetical order. The placement of a ligand does not depend on its charge. In
case of ligands with special names, e.g., aqua for water, the first letter of the special name is considerd.
(iii) Polydentate ligands are also listed alphabetically. In case of abbreviated ligand, the first letter of the
abbreviation is used to determine the position of the ligand in the alphabetical order.
(iv)The formula for the entire coordination entity, whether charged or not, is enclosed in square brackets.
Formulas of polyatomic ligands and ligand abbreviations are enclosed in parentheses.
(v) No space is left between the ligands and the metal within a coordination sphere.
(vi)The formula of a charged coordination entity is written (without that of the counter ion) with the charge
indicated outside the square brackets as a right superscript with the number before the sign. For example,
[Fe(CN)6]3–, [Co(CN)6]3–, [Cr(H2O)6]3+, etc.
(vii)The charge of the cation(s) is exactly balanced by the charge of the anion(s).
114
Naming of Mononuclear Coordination Compounds

The names of coordination compounds are derived from the principles of additive nomenclature. The groups
that surround the central atom must be identified in the name. They are listed as prefixes to the name of the
central atom along with any appropriate multipliers. Ligands should be sorted alphabetically, irrespective of
charge. The following rules are applied:
(i) The cation is named first in both positively and negatively charged coordination entities.
The name starts in small letter with the complex part written as one word, e.g., [Co(HN3)6]Cl3 as
hexamminecobalt (III) chloride and K3[Fe(CN)6] as potassium hexacyanoferrate (III). Non-ionic and molecular
complexes are given one word names, e.g., [Pt(NH3)2Cl4] as diamminetetrachloroplatinum (IV), and
[Co(NH3)3(NO2)3] as triamminetrinitrocobalt (III).
(ii) The ligands are listed in alphabetical order before the name of the central atom/ion. (This is
the reverse of the procedure followed for writing the formula). The prefixes di, tri, tetrakis, etc.
should not be considered while determining the alphabetical order.
E.g., the complex, [Pt(NH3)4Cl(NO2)]SO4, is named tetraamminechloridonitroplatinum(IV) sulphate.
(iii) Names of the anionic ligands end in -o, those of neutral and cationic ligands are the same
except aqua for H2O, ammine for NH3, carbonyl for CO, thiocarbonyl for CS, and nitrosyl for NO.
These are placed within enclosing marks ( ) when written in the formula of coordination entity.
In the name of the anionic ligands ending in -ide, -ite or -ate, the last alphabet, ‘e’, is replaced by ‘o’. Thus,
-ide becomes -ido, -ite becomes -ito and -ate becomes -ato. SO42– (sulphato), C2O42– (oxalato), NH2–
(amido), NH2– (imido), ONO – (nitrito), NO 3–(nitrato), SCN– (thiocyanato), NCS– (isothiocyanato),
CH2(NH2)COO– (glycinato), etc.
Cl –, Br –, I – and F – end in -ide, therefore, they should be named as chlorido, bromido, etc. CN– should be
named as cyanido though the name cyano is still used. Hydrogen as ligand is always considered as anionic
(hydride) and is named as hydrido.
Positive ligands are very few and end in -ium, e.g., NH2– NH3+ (hydrazinium), NO+ (nitrosonium), and NO2+
(nitronium).
Organic free radicals are given their own names. E.g., CH3 (methyl), C2H5 (ethyl), C6H5 (phenyl), C5H5
(cyclopentadieneyl), etc.
For neutral organic molecules, their names are used, e.g., CH 3NH 2 (methylamine), C 5H 5 N
(pyridine or py), P(C 6H 5) 3 (triphenylphosphine), H 2NCH 2NH 2 (thiourea or tu), H 2NCH 2CH 2NH 2
(ethylenediamine or ethane –1, 2–diamine or en), CH3C(NOH)C(NOH)CH3 (dimethylglyoxime or dmg), etc.
Small (lower case) letters are used in abbreviations.
In case of ambidentate ligands, the point of attachment is indicated by placing the symbol of the donor atom
after the name of the group, separated by hyphen. E.g., in thiocyanate and nitrite, there are two options
each: –SCN (thiocyanato) and –NCS (isothiocyanato) and –NO2 (nitro) and –ONO (nitrito) respectively.
(NH4)3[Cr(SCN)6] is named as ammonium hexathiocyanato-S-chromate (III). (NH4)2[Pt(NCS)6] is named as
ammonium hexaisothiocyanato-N-platinate(IV). [Co(NO2)6]3- is named as hexanitrito-N-cobaltate (III) ion.
[Co(ONO)6]3- is named as hexanitro-O-cobaltate (III) ion.
(iv) Prefixes mono, di, tri, etc., are used to indicate the number of individual ligands in the
coordination entity. When the names of the ligands include a numerical prefix (dipyridyl, ethylene
diamine, triphenylphosphine, etc), then the terms, bis, tris, tetrakis are used, the ligand to which
they refer being placed in parentheses.
115
(v) Oxidation state of the metal in cation, anion or neutral coordination entity is indicated by Roman
numeral in parenthesis.
(vi) If the complex ion is a cation, the metal is named the same as the element. If the complex ion
is an anion, the name of the metal ends with the suffix -ate. When the complex is an acid, the name
of the metal ends in ‘-ic acid.’ For some metals, the Latin names are used in the complex anions.
(vii) A neutral complex molecule is named similar to that of the complex cation.
Table - 01 Common name and IUPAC name of some complexes.
Complex Commonly used name IUPAC name

K4 [Fe(CN)6 ] Potassium ferrocyanide potassiumhexacyanoferrate (II)
K3 [Fe(CN)6 ] Potassium ferricyanide potassiumhexacyanoferrate (III)
3-
Na3 [Co(ONO)6 ] Sodium cobaltinitrite sodiumhexanitritocobaltate (III)
Na2 [Fe(CN)5 NO] Sodium nitroprusside sodiumnitrosoniumpentacyanoferrate (II)
ISOMERISM IN COORDINATION COMPOUNDS
The principal types of isomerism among coordination compounds are structural isomerism and stereo
isomerism.
Structural isomerism
This type of isomerism arises due to difference in structure of coordination compounds.
(a) Linkage Isomerism. Linkage isomerism arises in complexes containing ambidentate ligands. In case
of NO2–, either N or an O atom can act as donor giving two different isomers. The complex [Co(NH3)5(NO2)]Cl2,
obtained as the red form, contains nitrite ligand bound through oxygen (–ONO), and the yellow form, has
the nitrite ligand bound through nitrogen (–NO2). The red form is easily decomposed by acids to give nitrous
acid, while the yellow form is stable to acids.
Complexes containing the thiocyanate ligand, NCS–, may bind through the nitrogen to give M – NCS or
through sulphur to give M – SCN, e.g., [Cr(H2O)5(SCN)]2+ and [Cr(H2O)5(NCS)]2+.
[Co(NH3)2(NO2)2(Py)2]NO3 and [Co(NH3)2(ONO)2(Py)2]NO3 also exhibit linkage isomerim.
(b) Coordination Isomerism. This type of isomerism arises from the interchange of ligands between
cationic and anionic entities of different metal ions present in a complex. For example, the coordination
isomer of [Co(NH3)6][Cr(CN)6], in which the NH3 ligands are bound to Co3+ and the CN– ligands to Cr3+ is
[Cr(NH3)6][Co(CN)6], in which the NH3 ligands are bound to Cr3+ and the CN– ligands to Co3+.
Other examples: (i) [Cr(NH3)6][Co(C2O4)3] and [Cr(C2O4)3][Co(NH3)6] and (ii) [Co(en)3][Cr(CN)6] and
[Cr(en)3][Co(CN)6]
116
(c) Ionisation Isomerism. Compounds which give different ions in solution even when they have the same
composition are called ionisation isomers. This form of isomerism arises when the counter ion in a complex
salt is itself a potential ligand and can displace a ligand which can then become the counter ion, e.g.,
pentaamminesulphatocobalt(III)bromide [Co(NH3)5(SO4)]Br and pentaamminebromidocobalt(III)sulphate,
[Co(NH3)5Br]SO4. Whereas [Co(NH3)5Br]SO4, red violet in solution, gives a precipitate of BaSO4 with BaCl2
solution (test for sulphate), [Co(NH3)5(SO4)]Br, red in solution, does not give a precipitate with BaCl2. Instead,
it gives a precipitate of AgBr with AgNO3 solution (test for bromide).
Other examples: (i) [Pt(NH3)4(OH)2]SO4 and [Pt(NH3)4SO4](OH)2 (ii) [Pt(NH3)4Cl2]Br2 and [Pt(NH3)4Br2]Cl2
(d) Solvate Isomerism. Compounds which have the same composition but differ in the number of solvent
molecules present as ligands (inside coordination sphere) and as free solvent molecules in the crystal
lattice are called solvate isomers. This is known as ‘hydrate isomerism’ when water is the solvent.
Solvate isomers differ by whether or not a solvent molecule is directly bonded to the metal ion or merely
present as free solvent molecules in the crystal lattice, e.g., the aqua complex [Cr(H2O)6]Cl3 (violet) and its
solvate isomers [Cr(H2O)5Cl]Cl2.H2O (grey-green) and [Cr(H2O)4Cl2]Cl.2H2O (dark-green).
Stereoisomerism
Coordination compounds exhibit (i) geometrical isomerism and (ii) optical isomerism.
1. Geometrical Isomerism or Cis-trans isomerism
Geometrical isomerism arises in heteroleptic complexes due to different geometrical arrangements of the
ligands around the central metal atom. In cis isomers, two identical ligands occupy positions adjacent to
each other. In trans isomers, two identical ligands occupy positions diagonal to each other. This behaviour
is observed in complexes of coordination numbers 4 and 6, i.e., square planar and octahedral complexes.
(a) Square planar complexes. Complex of the type MX2L2 and MABXL, can exist in cis and trans forms
MX2L2 type. The two X ligands are arranged adjacent to each other in the cis isomer or opposite to each
other in the trans isomer, e.g., diamminedichloridoplatinum (II), [Pt(NH3)2Cl2].
(iv) For MABXL type (A, B, X, L are unidentate) complex three isomers, one trans and two cis are possible.
The position of one ligand, say A, is fixed while other ligands, B, X, and L are placed trans to it, e.g.,
amminehydroxylamine-pyridinenitroplatinum (I), [Pt(NH3)(NH2OH)(C5H5N)(NO2)].
Geometrical isomerism is not possible for tetrahedral geometry because all the four coordination positions
are adjacent to each other.
(b) Octahedral complexes. Cis-trans isomerism is possible in octahedral complexes. Any complex of
type MX2L4, MA3B3 and MX2(L - L)2 exist in cis and trans forms.
(i) MX2L4 type. Complexes in which the two X ligands may be oriented cis or trans to each other, e.g.,
[Cr(NH3)4Cl2]+ ion, [Co(NH3)4Cl2]+ ion, etc.
117
(ii) MA3B3 type. This type of geometrical isomerism occurs in octahedral coordination entities like
[Co(NH3)3(NO2)3], [RhCl3(py)3], [Co(NH3)3Cl3], etc. If three ligands of the same type occupy the corners of
a face of the octahedron, we have the facial (fac) isomer. When the positions are around the meridian of
the octahedron, we get the meridional (mer) isomer.
(ii) MX2(L - L)2 type. This type of isomerism arises in complexes like [CoCl2(en)2] in which didentate ligands
are present.
2. Optical Isomerism
Optical isomerism is the phenomenon by which isomers of certain compounds rotate the plane of polarised
light. Optical isomers are mirror images that are not superimposable on one another. These are called
enantiomers or enantiomorphs. The molecules or ions that cannot be superimposed are said to be
chiral. The two forms are called dextro (d) and laevo (l) depending on the direction in which they rotate the
plane of polarised light (d rotates to the right and l to the left).
(a) Coordination number 4. Complexes with coordination number four are either tetrahedral or square
planar. Square planar complexes do not show optical isomerism because they have a plane of symmetry.
Tetrahedral complexes which contain unsymmetrical bidentate ligands show optical activity, e.g.,
bis(glycinato)nickel(II), [Ni(CH2NH2COO)2]. Tetrahedral complexes containing four different groups do not
exhibit optical activity because they are very much labile and cannot be isolated.
(b) Coordination number 6. In octahedral complexes, optical isomerism is possible if there are six different
unidentate ligands, e.g., [(Pt IV)(Br)(Cl)(I)(NO2)(C2H5)(NH3)]. Optical isomerism is common in octahedral
complexes involving 1, 2, or 3 symmetrical didentate ligands.
(i) [M(AA)3] type. Coordination entities of the type [Co(en)3]3+ or [Cr(ox)3]3–, shows optical activity.
118
(ii) [M(AA)2B2] or [M(AA)2BC] type. In a coordination entity of the type [PtCl2(en)2]2+, or [CoCl2(en)2]+, only the
cis-isomer shows optical activity. This is because it is unsymmetrical. The trans isomer does not exhibit
optical isomerism since it is symmetrical. (This type of complexes show geometrical isomerism.)
BONDING IN COORDINATION COMPOUNDS

Werner’s theory could not explain why only certain elements form coordination compounds, bonds in
coordination compounds have directional properties and coordination compounds have characteristic optical
and magnetic properties. Many theories have been put forth to explain the nature of bonding in coordination
compounds viz. Valence Bond Theory (VBT), Crystal Field Theory (CFT), Ligand Field Theory (LFT) and
Molecular Orbital Theory (MOT).
VALENCE BOND THEORY (VBT)
Pauling (1931) extended Valence Bond Theory to coordination compounds. According to this theory, the
metal atom or ion, under the influence of ligands, use its (n-1)d, ns, np or ns, np, nd orbitals for hybridisation
to yield a set of equivalent orbitals of definite geometry such as octahedral, tetrahedral, square planar, etc.
These hybridised orbitals overlap with ligand orbitals which donate electron pairs for bonding.
Table - 02 Number of orbitals and types of Hybridisations.
Coordination No. Hybridisation Geometry Examples

+ -
2 sp Linear [Ag(NH3)2] , [Ag(CN)2]
2 -
3 sp Trigonal planar [HgI3]
3 2+
4 sp Tetrahedral [Zn(NH3)4] , [Ni(CO)4]
2 2- 2+
4 dsp Square planar [Ni(CN)4] , [Pt(NH3)4]
3 3-
5 sp d Trigonal bipyramidal Fe(CO)5, [Cu(Cl)5]
3 2 2+ 2+
6 sp d Octahedral [Zn(NH3)6] , [Ni(H2O)6]
2 3 3+ 3-
6 d sp Octahedral [Co(NH3)6] , [Fe(CN)6]
119
Inner Orbital and Outer Orbital Complexes

A complex in which, the central metal atom/ion uses inner (n-1)d-orbitals for hybridisation (e.g., d2sp3) is
called inner orbital complex. Electrons of the metal pair up so that the complex will be either diamagnetic or
having lesser number of unpaired electrons. This type of complex is called Low Spin Complex. [Co(NH3)6]3+,
[Mn(CN)6]3–, [Co(CN)6]3–, [Co(CN)6]4–, [Co(C2O4)3]3–, [Cr(ox)3]3–, etc., are examples.
In an outer orbital complex, the central metal atom/ion uses its outer nd orbitals for hybridisation (e.g.,
sp3d2). As the configuration of the metal remains unchanged, the complex will have large number of unpaired
electrons (paramagnetic), e.g., [Mn(Cl)6]3–, [Fe(H2O)6]2+, [Fe(H2O)6]3+, [FeF6]3–, [CoF6]3–, [Ni(NH3)6]2+,
[Ni(H2O)6]2+, etc. This type of complex is called High Spin Complex.
1. Octahedral Complexes. Complexes are formed by d2sp3 (inner orbital) or sp3d2 (outer orbital)
hybridisation.
(i) Formation of [Co(NH3)6]3+. In the diamagnetic octahedral complex, [Co(NH3)6]3+, the cobalt ion is in the
+3 oxidation state. The outer electronic configuration of Co is 3d6 4s2 and that of Co3+ is 3d6. The electrons
in the 3d-orbitals pair up in order to make six vacant orbitals available.
Six pairs of electrons from NH3 molecules, occupy the six hybrid orbitals. Thus, the complex has octahedral
geometry. It is diamagnetic due to the absence of unpaired electrons. Since the inner d orbitals (3d) are
used in hybridisation, the complex, [Co(NH3)6]3+ is an inner orbital or low spin or spin paired complex.
(ii) Formation of [CoF6]3–. In the octahedral complex, [CoF6]3–, the outer d-orbital (4d) of cobalt is used in
hybridisation (sp3d2). F- is a weak ligand and cannot force the electrons to pair up in the 3d-orbital. Thus, 4s,
three 4p and two 4d-orbitals mix up to form six sp3d2 hybridised orbitals F- ions.
Since the outer 4d-orbitals are used for hybridisation, it is called outer orbital or high spin or spin free
complex. The molecule is highly paramagnetic due to the presence of four unpaired electrons (magnetic
moment corresponds to four unpaired electrons).
2. Tetrahedral Complexes. In tetrahedral complexes, one s- and three p-orbitals of the metal hybridise to
form four equivalent orbitals oriented tetrahedrally.
(i) Formation of [NiCl4]2–. In [NiCl4]2-, nickel is in +2 oxidation state and the ion has 3d8 electronic configuration.
The 4s and three 4p-orbitals hybridise to form four sp3 hybrid orbitals.
120
Each Cl– ion donates a pair of electrons. Since it contains two unpaired electrons, the compound is
paramagnetic (magnetic moment corresponds to two unpaired electrons).
3. Square planar Complexes. In square planar complexes, the hybridisation is dsp2.
(i) Formation of [Ni(CN)4]2–. In [Ni(CN)4]2-, nickel is in +2 oxidation state and has 3d8 electronic configuration.
The two unpaired electrons in Ni2+ are forced to pair up because CN– are strong ligands. Each of the dsp3
hybridised orbitals receives a pair of electrons from a cyanide ion. The compound is diamagnetic due the
absence of unpaired electron(s).
Magnetic Properties of Coordination Compounds.

Predicting type of hybridisation from magnetic behaviour. Magnetic moment measurement helps in
determining the number of unpaired electrons and hence, the structure of complexes. Metal ions containing
upto three unpaired electrons in the d-orbitals have two vacant d-orbitals available for octahedral hybridisation
with 4s and 4p-orbitals. The magnetic behaviour of free ions and their coordination entities is similar. Thus,
the magnetic moments for Ti3+ (d1), V3+ (d2), and Cr3+ (d3) correspond to 1, 2, 3, unpaired electrons
respectively.
When more than three 3d electrons are present, the required number of 3d-orbitals for octahedral hybridisation
is not directly available as a consequence of the Hund’s rule. Thus, for Cr 2+ and Mn 3+
(d 4), Mn2+ and Fe3+ (d 5), Fe2+, Co3+ (d 6), a pair of vacant d orbitals are formed by the pairing of 3d electrons
which leaves two, one and zero unpaired electrons, respectively.
The magnetic data agree with maximum spin pairing, especially with complexes containing d6 ions, but
there are complications with species containing d 4 and d 5 ions. [Mn(CN)6]3– has magnetic moment of two
unpaired electrons while [MnCl6]3– has a paramagnetic moment of four unpaired electrons. [Fe(CN)6]3– has
magnetic moment of a single unpaired electron while [FeF6]3– has a paramagnetic moment of five unpaired
electrons. [CoF6]3– is paramagnetic with magnetic moment of four unpaired electrons while [Co(C2O4)3]3– is
diamagnetic.
VB theory explains these anomalies in terms of formation of outer orbital and inner orbital coordination
entities.[Mn(CN)6]3–, [Fe(CN)6]3– and [Co(C2O4)3]3– are inner orbital complexes involving d2sp3 hybridisation;
the first two are paramagnetic while the latter is diamagnetic. [MnCl6]3–, [FeF6]3– and [CoF6-]3– are outer
orbital complexes having sp3d2 hybridisation and paramagnetic moment corresponding to 4, 5 and 4 unpaired
electrons.
121
Limitations of Valence Bond Theory

(i) It is based on a number of assumptions.
(ii) It does not give quantitative interpretation of magnetic data.
(iii) It does not explain the spectra of complexes.
(iv) It could not explain the the distortion in the geometry of molecules.
(v) It does not explain the colour of coordination compounds.
(vi) It does not give quantitative interpretation of the thermodynamic or kinetic stabilities of complexes.
(vii) It does not make exact predictions regarding the structures of 4-coordinate complexes.
(viii) It does not distinguish between weak and strong ligands.
CRYSTAL FIELD THEORY

The crystal field theory (CFT), developed by Hans Bethe and John Van Vleck (1929) is an electrostatic
model which considers the metal-ligand bond to be ionic, arising from electrostatic interactions between
the metal ion and the ligand. The properties of complexes like magnetic character, colour, etc., which are
not explained by VB theory have been explained by crystal field theory.
Salient features of Crystal Field Theory
(i) Transition metal acts as central cation and ligands donate lone pair of electrons to its vacant orbitals.
(ii) Ligands are considered as point charges in case of anions and dipoles in case of neutral molecules
(either anions or the negative ends of dipolar molecules like NH3, H2O, etc.).
(iii) The metal-ligand bond is ionic, arising purely from electrostatic interactions.
(iv)The electrostatic interactions may be ion-ion attraction between positive and negative ions or ion-dipole
attraction if the ligand is a neutral molecule.
(v) The negatively charged electron cloud of the ligands repel the valence electrons of the cation. This
results in the valence electrons occupying those d-orbitals which are not in the direction of the attacking
ligand. Thus, the degeneracy of the the d-orbitals is lost and they attain different energies.
(vi)The magnetic character depends on the extent of splitting of d-orbitals by a ligand. Greater the splitting
of d-orbitals lesser will be the number of unpaired electrons and hence lesser will be the magnetic character.
(vii) The colour/spectra of complexes is due to electronic transitions between various d-orbitals.
(viii) The shape of complexes can be explained on the basis of crystal field stabilisation energy (i.e., gain in
energy achieved by preferential filling of stable orbital).
Orientation of d-orbitals and Crystal field splitting of energy levels
Three d-orbitals having orientations in regions in between the coordinate axes (dxy, dxz, dyz) are called t2g
orbitals (three-fold degenerate) and the two orbitals ( d x2  y 2 , d z 2 ), oriented along the axes are called eg
orbitals (two-fold degenerate).
The five d-orbitals in an isolated gaseous metal atom/ion are degenerate. The degeneracy is maintained if
a spherically symmetrical field of negative charges surrounds the metal atom/ion. However, when the
negative field is due to ligands in a complex, it becomes asymmetrical and the degeneracy of the d-orbitals
is lifted. It results in splitting of the d-orbitals into two sets having different energies. The conversion of the
five degenerate d-orbitals of the metal ion into two sets of orbitals having different energies is called crystal
field splitting.
122
Crystal field splitting in octahedral coordination entities

In an octahedral coordination entity with six ligands surrounding the metal atom/ion, there will be repulsion
between the electrons in metal d-orbitals and the electrons of the ligands. This repulsion is more when the
metal d-orbital is directed towards the ligand. Thus, the d x 2  y2 and d z2 orbitals which point towards the axes
along the direction of the ligand will experience greater repulsion and will be raised in energy while the dxy,
dyz and dxz orbitals which are directed between the axes will be lowered in energy relative to the average
energy in the spherical crystal field.
Thus, degeneracy of the d-orbitals has been removed due to ligand electron-metal electron repulsions in
the octahedral complex to yield three orbitals of lower energy, t2g set and two orbitals of higher energy, eg
set.
This splitting of the degenerate levels due to the presence of ligands in a definite geometry is termed as
crystal field splitting and the energy separation is denoted by  0 (subscript ‘o’ for octahedral). Crystal
field splitting energy (CFSE) is measured in terms of a parameter called Dq (Differential of quanta). By
convention,  0 is taken to be equal to 10 Dq. Thus, the energy of the two eg orbitals will increase by (3/5)
 0 or (+0.6  0 ) and that of the three t2g will decrease by (2/5)  0 or (–0.4  0 ).
Figure -03 d-orbital splitting in an octahedral crystal field.
In fig.03, state-I represents degeneracy of all the five d-orbitals in the isolated central ion. State-II represents
hypothetical degeneracy of all the orbitals at a higher energy level since the negative charge of all the
ligands is assumed to be uniformly affecting the electrons in the d-orbitals of the metal ion. State-III represents
crystal field splitting.
On assigning electrons to the d-orbitals of the metal ion, it has been observed that:
(i) The single d-electron (d1) occupies one of the lower energy t2g orbitals.
(ii) In d2 and d3 coordination entities, d-electrons occupy the t2g orbitals singly in accordance with Hund’s
rule.
(iii)For d4 ions, the fourth electron could either enter the t2g level and pair with an existing electron or avoid
pairing energy by occupying the eg level. The choice depends on the relative magnitude of the crystal field
splitting,  0 and the pairing energy, P (energy required for electron pairing in a single orbital).
(iv) If  0 < P, the fourth electron enters one of the eg orbitals giving the configuration (t2g)3 (eg)1.
123
Ligands for which  0 < P are known as weak field ligands and form high spin complexes. If a complex
has maximum number of unpaired electrons, it is called high spin complex or weak field complex.
(v) If  0 > P, it is energetically favourable for the fourth electron to occupy a t2g orbital with configuration
(t2g)4 (eg)0. Ligands which produce this effect are known as strong field ligands and form low spin
complexes.
If a complex has less number of unpaired electrons, it is called low spin complex or strong field complex.
Calculations show that d4 to d7 coordination entities are more stable for strong field as compared to weak
field entities.
Crystal field splitting in tetrahedral coordination entities
In case of tetrahedral structure, none of the d-orbitals point exactly towards the ligands. The three t2g
orbitals point close to the direction in which the ligands approach while the two eg orbitals lie in between the
ligands.
Figure - 04 d-orbital splitting in a tetrahedral crystal field.

In the formation of tetrahedral coordination entity, the splitting of d-orbital is inverted and is smaller as
compared to octahedral field splitting. For the same metal, the same ligands and metal-ligand distances,
 t = (4/9)  0 (subscript ‘t’ indicating tetrahedral complex). The orbital splitting energies are not sufficiently
large to force pairing, and therefore, low spin configurations are rare.
The subscript ‘g’ is used for octahedral and square planar complexes which have centre of symmetry.
Since tetrehedral complexes lack symmetry, subscript, ‘g’ is not used with energy levels.
Factors Influencing the Magnitude of Crystal Field Splitting
Nature of ligands (Spectrochemical series). The crystal field splitting,  0 , depends on the field produced
by the ligand and charge on the metal ion. Some ligands produce strong fields in which case, the splitting
will be large, whereas others produce weak fields and consequently result in small splitting of d-orbitals.
Ligands with small value of  0 are called weak field ligands and ligands with large value of  0 are called
strong field ligands. Ligands arranged in the order of increasing field strength is known as spectrochemical
series.
I– < Br– < SCN– < Cl– < S2– < F– < OH– < C2O42– < H2O < NCS– < edta4– < NH3 < en < NO2– < CN– < CO.
It is an experimentally determined series based on the absorption of light by complexes.
124
Crystal Field Stabilisation Energy (CFSE)

The difference in energy between the two sets of d-orbitals is called crystal field splitting energy or crystal
field stabilisation energy. Each electron occupying t2g orbital results in lowering of energy by (2/5)  0 or
(–0.4  0 ). Each electron occupying eg orbital results in increase in energy by (3/5)  0 or (+0.6  0 ). Thus, if
x is the number of electrons in t2g orbitals and y is the number of electrons in eg orbitals,
CFSE = (–0.4x + 0.6y)  0

A negative value of CFSE indicates net lowering of energy or gain in stability while a positive value indicates
increase in energy or decrease in stability.
Explanation of the Properties of the complexes by Crystal field theory
(a) Electronic configuration (High spin and low spin states). In d1, d2 and d3 configurations, electrons
enter the lower energy t2g orbitals with parallel spins. For d4, d5,d6, d7, etc. configurations, electrons may
either enter t2g level and become paired or enter the higher energy eg orbitals with parallel spins giving rise
to low spin complex in the former case and high-spin complex in the latter. d8 to d10 configurations can have
only one possible arrangement and hence fixed  0 value.
(b) Magnetism. Using the principle that strong fields cause low spin states to be more stable, and weak
field ligands cause high spin states to be more stable, we can determine whether the electrons are paired
up or not and hence predict the paramagnetism or diamagnetism of a complex.
(c) Colour in Coordination Compounds. Transition metal complexes exhibit a wide range of colours.
This is because the complex absorbs certain wavelengths from white light. The observed colour corresponds
to the complimentary colour of the light absorbed.
Table - 03 Wavelength of light absorbed and the colour of coordination entities.
Wavelength of light Colour of light Colour of coordination
Coordination entity
absorbed (nm) absorbed entity
2+
[CoCl(NH3 ) 5 ] 535 Yellow Violet
3+
[Co(NH3 )5 (H2 O)] 500 Blue Green Red
3+
[Co(NH3 )6 ] 475 Blue Yellow Orange
3-
[Co(CN)6 ] 310 Ultraviolet Pale Yellow
2+
[Cu(H2 O)4 ] 600 Red Blue
3+
[Ti(H2 O)6 ] 498 Blue green Violet
Colour of coordination compounds is due to d-d transition of electrons. The CFSE (  0 ) for most complexes
is of the same order of magnitude as the energy of a photon of visible light. It is therefore possible for a
complex to absorb visible light which excites electrons from the lower d-levels to higher energy ones. E.g.,
the complex [Ti(H2O)6]3+, is violet in colour. It is an octahedral complex where the single electron (Ti3+ is a
3d1 system) in the metal, d-orbital is in the t2g level in the ground state. The next higher state available for
the electron is the empty eg level. When the complex absorbs light corresponding to energy of blue-green
region, it excites the electron from t2g level to eg level (t2g1eg0  t2g0 eg1) and the complex appears violet in
colour.
In the absence of ligands, crystal field splitting does not occur and hence the substance is colourless, e.g.,
removal of water from [Ti(H2O)6]Cl3 by heating renders it colourless. Similarly, anhydrous CuSO4 is white,
but CuSO4.5H2O is blue in colour.
125
The influence of ligands on the colour of complexes may be illustrated in case of green coloured [Ni(H2O)6]2+,
nickel(II) chloride solution in water. When the didentate ligand, ethane-1,2-diamine (en) is progressively
added in molar ratios (1:1, 1:2 and 1:3), the following reactions and associated colour changes occur :
[Ni(H 2 O)6 ]2+ 

en
 [Ni(H 2 O)4 (en)]2+ 
en
[Ni(H 2 O) 2 (en) 2 ]2+ 
en
 [Ni(en)3 ]2+
Green Pale Blue Blue/Purple Violet
Colour of Some Gem Stones. Ruby is aluminium oxide (Al2O3) containing 0.5 – 1% Cr3+ ions (d3), distributed
in positions normally occupied by Al3+. These Cr(III) species may be considered as octahedral chromium(III)
complexes incorporated into the alumina lattice; d–d transitions at these centres give rise to red colour. In
emerald, Cr3+ ions occupy octahedral sites in the mineral beryl (Be3Al2Si6O18). The absorption bands shift to
longer wavelength, namely yellow-red and blue, causing emerald to transmit light in the green region.
Limitations of Crystal Field Theory
(i) As ligands are considered as point charges, anionic ligands should exert the greatest splitting effect but
actually they are found at the low end of the spectrochemical series.
(ii) It does not take into account the covalent character of bonding between the ligand and the central atom.
BONDING IN METAL CARBONYLS
Metal carbonyls are organometallic compounds in which carbon monoxide (CO) acts as the ligand, e.g.,
[Ni(CO)4], [Fe(CO)5], [Cr(CO)6], [V(CO)6], [Mo(CO)6], [W(CO)6], [Co2(CO)8], [Mn2(CO)10], etc.
Homoleptic carbonyls have simple, well defined structures. Tetracarbonylnickel (0) is tetrahedral,
pentacarbonyliron (0) is trigonal bipyramidal and hexacarbonyl chromium (0) is octahedral.
Decacarbonyldimanganese (0) is made up of two square pyramidal Mn(CO)5 units joined by a Mn – Mn
bond. Octacarbonyldicobalt (0) has a Co – Co bond bridged by two CO groups.
Figure - 05 Structures of some representative homoleptic metal carbonyls.
Bonding in Metal Carbonyls.The M – C sigma-bond is formed by the donation of lone pair of electrons on
the carbonyl carbon into the vacant orbital of the metal. The M – C pi-bond is formed by the donation of a
lone pair of electrons from a filled d-orbital of metal into a vacant antibonding pi-molecular orbital (  *) of
CO. This is called synergic effect. As a result of synergic effect, the bond between CO and metal is
strenghtened.
126
Ligands such as CO, NO+, and CN- which are capable of accepting appreciable amount of electron density
from the metal atom into empty p or p* orbital of their own are called p-acceptor or p-acid ligands. This
type of interaction increases the value of  0 and explains why they are strong ligands.
APPLICATIONS OF COORDINATION COMPOUNDS

Analytical Chemistry. Coordination compounds are used in qualitative and quantitative chemical analysis.
The colour reactions given by metal ions such as Ni2+, Co2+, Fe3+, Zn2+, Ca2+, Mg2+, etc., with ligands (especially
chelating ligands) is the basis for their detection and estimation. EDTA (C10H16N2O8), DMG (C4H8N2O2),
a-nitroso-b-naphthol, cupron, etc are examples of such reagents.
Hardness of water can be estimated by titration with EDTA. Ca2+ and Mg2+ ions form stable complexes with
EDTA. Selective estimation of these ions is possible due to difference in the stability constants of the
complexes.
Metallurgy. Extraction of metals like silver and gold make use of complex formation. Silver, is extracted by
dissolving its ore in NaCN solution and then precipitating the metal by adding Zn. Gold, combines with
cyanide ions in presence of oxygen and water to form [Au(CN)2]–, which is precipitated by the addition of
zinc. Similarly, metals can be purified by formation and subsequent decomposition of their coordination
compounds, e.g., in Mond’s process, impure nickel is converted to [Ni(CO)4] and then decomposed to get
pure nickel.
Biological systems. (i) Chlorophyll, is a complex of magnesium. (ii) Haemoglobin is a complex of iron. (iii)
Vitamin B12, cyanocobalamine, is a complex of cobalt (Co3+). (iv) Many enzymes like, carboxypeptidase A
and carbonic anhydrase (catalysts of biological systems) are complexes of Zinc.
Industry. Complexes are used as catalysts. (i) The rhodium complex, [(Ph3P)3RhCl], a Wilkinson catalyst,
is used for the hydrogenation of alkenes.(ii) Complexes of Ru catalyse the decomposition of water.
Electroplating. Articles can be electroplated with Ag and Au more smoothly and evenly from solutions of the
complexes, [Ag(CN)2]– and [Au(CN)2]– than in a solution of simple metal ions.
Photography. In black and white photography, the developed film is fixed by washing with hypo solution
which dissolves the undecomposed AgBr to form a complex ion, [Ag(S2O3)2]3–.
Dyes or pigments. Phthalocyanin blue which is a blue complex of Cu(II) is used as a dye.
Medicine. (i) In chelate therapy for treatment of problems caused by the presence of metals in toxic
proportions in plant/animal systems. Thus, excess of copper and iron can be removed by the chelating
ligands, D-penicillamine and desferrioxime B. (ii) EDTA is used in the treatment of lead poisoning. (iii) The
platinum complex, cisplatin, [Pt(NH3)2Cl2] and related compounds effectively inhibit the growth of tumours.
(iv) British anti-Lewisite (BAL) containing the chelating ligand (HS)CH2CH(SH)CH2OH, is used as antidote
for arsenic poisoning.
127
QUESTIONS
LEVEL - I
1. According to Werner’s theory of coordination compounds
1) Primary valency is ionisable
2) Secondary valency is ionisable
3) Primary and secondary valencies are ionisable
4) Neither primary nor secondary valency is ionisable
2. Which is the metal present in the coordination compound chlorophyll?
1) Ca 2) Mg 3) K 4) Na
3. The complex [Pt(NH3)6]Cl4 gives
1) 4 ions 2) 3 ions 3) 2 ions 4) 5 ions
4. Which one is ambidentate ligand?
1) SO32  2) CN– 3) NH3 4) H2O

5. Ethane-1,2-diamine is an example of
1) Monodentate ligands 2) Bidentate ligands
3) Tridentate ligands 4) Hexadentate ligands
6. The secondary valency of platinum in tetrammine dichloroplatinum (IV) chloride is :
1) +4 2) +2 3) 3 4) 6
7. Which of the following is a negatively charged bidentate ligand?
1) Dimethyl glyoximato 2) Cyano 3) Ethylene diamine 4) Acetato
8. Which of the following is a neutral complex?
1) [Pt(NH3)2Cl2] 2) [Co(NH3)6]Cl3 3) [Ni(NH3)6]Cl2 4) K4[Fe(CN)6]
9. The coordination number of Cu in complex [Cu(H2O)4]2+ is :
1) 4 2) 3 3) 2 4) 1
10. The oxidation number, d-orbital occupation and coordination number of Cr in the complex
cis[Cr(en)2Cl2]Cl are respectively
1) +3, 3d and 4 2) +3, 4d and 6 3) +3, 3d and 6 4) +2, 3d and 6
11. Which one among the following is a homoleptic complex?
1) Tris(ethane-1,2-diamine)cobalt (III) chloride
2) Triamminetriaquachromium(III) chloride
3) Diamminechloridonitrito-N-platinum (II)
4) Dichlorodobis (ethane-1,2-diamine) cobalt (III) chloride
12. The IUPAC name of [Ni(CO)4] is :
1) Tetracarbonyl nickel (II) 2) Tetracarbonylnickel (0)
3) Tetracarbonyl nickelate (II) 4) Tetracarbonylnickelate (0)
13. Which among the following will be named as dibromidobis (ethylene diamine) chromium (III) bromide
1) [Cr(en)3]Br3 2) [Cr(en)2Br2]Br 3) [Cr(en)Br4 ] 4) [Cr(en)Br2]Br

128
14. As per IUPAC norms, the name of the complex [Co(en)2(ONO)Cl]Cl is :

1) Chloridobis (ethane-1, 2-diamine) nitrito-O-cobalt (III) chloride
2) Chlorobis (ethylenediamine) nitro-O-cobalt (III) chloride
3) Chloridodi (ethylene diamine) nitrocobalt (III) chloride
4) Chloroethylenediaminenitro-O-cobalt (III) chloride
15. [Co(NH3)5NO2]Cl2 and [Co(NH3)5(ONO)]Cl2 are related to each other as :
1) Geometrical isomers 2) Optical isomers
3) Linkage isomers 4) Coordination isomers
16. The number of geometrical isomers of the complex [Pt(NO2)2(NH3)2] is :
1) 2 2) 3 3) 4 4) 0
17. Geometrical isomerism in coordination compounds is exhibited by
1) Square planar and tetrahedral complexes
2) Square planar and octahedral complexes
3) Tetrahedral and octahedral complexes
4) Square planar, tetrahedral and octahedral complexes
18. Match the Column I with Column II and mark the appropriate choice
Column I Column II
(Complex) (Isomerism)
A. [Co(NH3)6][Cr(CN)6] i. Geometrical isomerism
B. [Co(en)2(NO2)Cl]Br ii. Optical isomerism
C. [Pt(en)2Cl2] iii. Coordination isomerism
D. [Cr(CN)2(NH3)4] 2+
iv. Linkage isomerism
1) A-iv, B-ii, C-iii, D-i 2) A-ii, B-iii, C-i, D-iv 3) A-iii, B-iv, C-ii, D-i 3) A-i, B-iii, C-iv, D-ii
19. Which one has largest number of isomers?
1) [Co(en)2Cl2]+ 2) [Co(NH3)5Cl]2+ 3) [Ir(PR3)2(H2O)2]2+ 4) [Ru(NH3)4Cl2]+
20. What type of hybridization is involved in [Fe(CN)6]3–
1) d2sp3 2) dsp2 3) sp3d2 4) dsp3
21. Which one of the following is wrongly matched?
1) [Cu(NH3)4]2+ - square planar 2) [Ni(CO)4] - neutral ligand
3) [Fe(CN)6] - sp d
3– 3 2
4) cis-[CrCl2(ox)2]3– - optically active
22. Which of the following statements is correct about [Co(H2O)6]2+ complex?
1) Electronic configuration = 3d  t 2g eg , no. of unpaired electrons = 3,   3.87 B.M.

7 5 2

6 4 2

7 6 1

7 3 4
129
23. Mark the correct statements regarding the geometry of complex ions
i. The geometry of the complex ion depends upon the coordination number
ii. If coordination number is 6, the complex is octahedral
iii. If coordination number is 4, the geometry of the complex may be tetrahedral or square planar
1) i, ii and iii 2) i and ii only 3) i and iii only 4) ii and iii only
24. Which of the following sequences is correct regarding field strength of ligands as per spectrochemi-
cal series
1) SCN– < F– < CN– < CO 2) F– < SCN– < CN– < CO
3) CN– < F– < CO– < SCN– 4) SCN– < CO– < F– < CN–
25. What is the correct electronic configuration of the central atom in K4[Fe(CN)6] based on crystal field
theory?
4 2 4 2 6 0 3 3
1) eg t 2 2) t 2g eg 3) t 2g eg 4) eg t 2g
26. The magnitude of CFSE (crystal field splitting energy,  0 ) can be related to the configuration of d-
orbitals in a coordination entity as
3 1
1) If  0 < P, the configuration is t 2g eg = weak field ligand and high spin complex
3 1
2) If  0 > P, the configuration is t 2g eg = strong field ligand and low spin complex
4 0
3) If  0 > P, the configuration is t 2g eg = strong field ligand and high spin complex
4) If  0 = P, the configuration is t 2g eg = strong field ligand and high spin complex

4 0
27. Which of the following metal ion forms unstable complex with CN–?
1) Ag (I) 2) Zn (II) 3) Cu (II) 4) Cr (II)
28. The terminal and bridged CO ligands in the compound [Co2(CO)8] are respectively
1) 0, 2 2) 6, 1 3) 5, 2 4) 6, 2
29. Cr–C bond in the compound [Cr(CO)6] shows  -character due to
1) Covalent bonding 2) Coordinate bonding 3) Synergic bonding 4) Ionic bonding
30. The complex used as an anticancer agent is :
1) trans –[Co(NH3)3Cl3] 2) cis –[PtCl2(NH3)2]
3) cis –K2[PtCl2Br2] 4) Na2CO3
LEVEL - II
1. Which of the following will not give a precipitate with AgNO3
1) [Co(NH3)3Cl3] 2) [Co(NH3)4Cl2]Cl 3) [Co(NH3)5Cl]Cl2 4) [Co(NH3)6]Cl3
130
2. The number of ions formed when cuprammonium sulphate is dissolved in water is :

1) 1 2) 2 3) 4 4) Zero
3. Arrange the following complexes in increasing order of conductivity of their solutions
i) [Co(NH3)3Cl3] ii) [Co(NH3)4Cl2]Cl iii) [Co(NH3)6]Cl3 iv) [Co(NH3)5Cl]Cl2
1) i < ii < iv < iii 2) ii < i < iii < iv 3) i < iii < ii < iv 4) iv < i < ii < iii
4. One mole of the complex compound Co(NH3)5Cl3, gives 3 moles of ions on dissolution in water. One
mole of the same complex reacts with two moles of AgNO3 solution to yield two moles of AgCl(s). The
structure of the complex is :
1) [Co(NH3)5Cl]Cl2 2) [Co(NH3)3Cl3].2NH3
3) [Co(NH3)4Cl2]Cl.NH3 4) [Co(NH3)4Cl]Cl2.NH3
5. A chelating agent has two or more than two donor atoms to bind to a single metal ion. Which of the
following is not a chelating agent?
1) Thiosulphato 2) Oxalato 3) Glycinato 4) Ethane-1,2-diamine
6. The sum of coordination number and oxidation number of the metal M in the complex [M(en)2(C2O4)]Cl
(where en is ethylenediamine) is :
1) 9 2) 6 3) 7 4) 8
7. Select the pair in which the first compound is heteroleptic and the second compound is homoleptic
1) [Co(NH3)6]3+, [Co(NH3)4Cl2]+ 2) [Co(NH3)6]3+, [Co(NH3)5Cl]2+
3) [Co(NH3)4Cl2]+, [Co(NH3)6]3+ 4) [Co(NH3)4Cl2]+, [Co(NH3)5Cl]2+
8. IUPAC name of [Pt(NH3)3(Br) (NO2)Cl]Cl is :
1) Triamminechlorobromonitroplatinum (IV) chloride
2) Triamminebromonitrochloroplatinum (IV) chloride
3) Triammine bromido chlorido nitro-N platinum (IV) chloride
4) Triamminenitrochlorobromoplatinum (IV) chloride
9. The IUPAC name of [Co(NH3)6] [Cr(C2O4)3] is :
1) Hexa-ammine cobalt (III) tri oxalato chromium
2) Hexa-ammine cobalt (III) tri oxalato chromate (III)
3) Hexa-ammine cobalt tri oxalato chromium (III)
4) Hexa-ammine cobalt (III) chromium (III) oxalate
10. The complexes [Co(NH3)6] [Cr(CN)6] and [Cr(NH3)6] [Co(CN)6] are the examples of which type of
isomerism
1) Geometrical isomerism 2) Linkage isomerism
3) Ionization isomerism 4) Coordination isomerism
11. Which kind of isomerism is exhibited by octahedral [Co(NH3)4Br2]Cl?
1) Geometrical and ionisation 2) Geometrical and optical
3) Optical and ionisation 4) Geometrical only
131
12. The ionization isomer of [Cr(H2O)4 Cl(NO2)]Cl is :

1) [Cr(H2O)4(O2N)]Cl2 2) [Cr(H2O)4Cl2]NO2
3) [Cr(H2O)4Cl(ONO)]Cl 4) [Cr(H2O)4Cl2(NO2)]H2O
13. Which one of the following will not show geomterical isomerism
1) [Cr(NH3)4Cl2]Cl 2) [Co(en2)Cl2]Cl 3) [Co(NH3)5NO2]Cl2 4) [Pt(NH3)2Cl2]
14. Both geometrical and optical isomerism are exhibited by
1) Dichlorobis (ethylenediamine) cobalt (III) ion 2) Pentaamminechlorocobalt (III)
3) Triamminotrichlorocobalt (III) ion 4) Tetraamminedichlorocobalt (III) ion
15. [Co(NH3)Cl(en)2]2+ shows two geometrical isomers cis and trans. Which of the following statements
is correct?
1) trans-isomer will show optical isomerism
2) cis-isomer will show optical isomerism
3) Both trans and cis-isomers will show optical isomerism
4) Neither cis nor trans-isomer will show optical isomerism
16. Which one of the following coordination entity is chiral?
1) trans-[CrCl2(ox)2]3– 2) cis-[Co(NH3)4Cl2]+ 3) cis-[CrCl2(ox)2]3– 4) trans-[Co(NH3)4Cl2]+
17. [CoF6]3– is
1) Paramagnetic and undergoes sp3d2 hybridisation
2) Diamagnetic and undergoes d2sp3 hybridisation
3) Paramagnetic and undergoes sp3d hybridisation
4) Diamagnetic and undergoes sp3 hybridisation
18. Which of the following is a pair of diamagnetic complexes?
1) [CO(NH3)6]3+, [Fe(CN)6]4– 2) [CO(OX)3]3–, [FeF6]3–
3) [Fe(OX3)3]3–, [FeF6]3– 4) [Fe(CN)6]3–, [COF6]3–
19. Match the Column I with Column II and mark the appropriate choice
Column I Column II
A. [Ag(NH3)2]+ i. d2sp3, octahedral
B. [Ni(CN)4]2– ii. dsp2, square planar
C.[Ni(CO)4] iii. sp, linear
D. [Fe(CN)6]3– iv. sp3, tetrahedral
1) A-i, B-ii, C-iii, D-iv 2) A-iii, B-ii, C-iv, D-i
3) A-iv, B-iii, C-ii, D-i 4) A-ii, B-i, C-iii, D-iv
132
20. Geometrical shapes of the complexes formed by the reaction of Ni2+ with Cl–, CN– and H2O, respec-
tively, are
1) Octahedral, tetrahedral and square planar 2) Tetrahedral, square planar and octahedral
3) Square planar, tetrahedral and octahedral 4) Octahedral, square planar and tetrahedral
21. Which of these statements about [Co(CN)6]3– is true
1) [Co(CN)6]3– has four unpaired electrons and will be in a low-spin configuration
2) [Co(CN)6]3– has four unpaired electrons and will be in a high-spin configuration
3) [Co(CN)6]3– has no unpaired electrons and will be in a high-spin configuration
4) [Co(CN)6]3– has no unpaired electrons and will be in a low-spin configuration
22. The d-electron configuration of Cr2+, Mn2+, Fe2+ and Co2+ are d4, d5, d6 and d7 respectively. Which one
of the following will exhibit minimum paramagnetic behaviour?
1) [Mn(H2O)6]2+ 2) [Fe(H2O)6]2+ 3) [Co(H2O)6]2+ 4) [Cr(H2O)6]2+
23. Electronic configuration of [Cu(NH3)6]2+ on the basis of crystal field splitting theory is :
4 5 6 3 9 0 5 4
1) t 2g eg 2) t 2g eg 3) t 2g eg 4) t 2g eg
(  0 = Crystal Field Splitting Energy in an octahedral field.

24. [FeF6]3– is paramagnetic due to presence of unpaired electrons in the complex. The five electrons
remain unpaired because
1) Fluorine is the most electronegative element
2) F– is a weak field ligand hence does not cause pairing of electrons
3) F– is a strong field ligand hence does not cause pairing of electrons
4) Pairing does not take place in iron complexes
25. Low spin tetrahedral complexes are not formed because
1) For tetrahedral complexes, the CFSE is lower than pairing energy
2) For tetrahedral complexes, the CFSE is higher than pairing energy
3) Electrons do not go to eg in case of tetrahedral complexes
4) Tetrahedral complexes are formed by weak field ligands only
26. CrCl3.6H2O exist in different isomeric forms which show different colours like violet and green. This is
due to
1) Ionisation isomerism 2) Coordination isomerism
3) Optical isomerism 4) Hydrate isomerism
27. The complex [Ti(H2O)6]3+ appears violet in colour due to absorption of energy in ‘x’ region due to the
excitation electron from ‘y’ to ‘z’. x, y and z are respectively
1) violet, eg, t2g 2) blue green eg, t2g
3) violet, t2g, eg 4) blue green, t2g, eg
133
28. The tetrahedral crystal field splitting is only _______ of the octahedral splitting
1 2 3 4
1) 2) 3) 4)
9 9 9 9
29. Correct increasing order for the wavelengths of absorption in the visible region for the complexes of
Co3+ is
1) [Co(H2O)6]3+, [Co(en)3]3+, [Co(NH3)6]3+
2) [Co(H2O)6]3+, [Co(NH3)6]3+, [Co(en)3]3+
3) [Co(NH3)6]3+, [Co(en)3]3+, [Co(H2O)6]3+
4) [Co(en)3]3+, [Co(NH3)6]3+, [Co(H2O)6]3+
30. Which of the following statements is incorrect regarding the importance of coordination compounds
in biological systems?
1) Vitamin B12 used to prevent anaemia is a complex compound of zinc
2) Haemoglobin is the red pigment of blood and contains iron
3) Chlorophyll is the green pigment of plants and contains magnesium
4) Potassium dicyanoargentate is used in metallurgy
134
KEY WITH HINTS

LEVEL - I
1. 1
2. 2
3. 4 [Pt(NH3)6]Cl4 complex gives 5 ions in the solution.
[Pt(NH3)6]Cl4 [Pt(NH3)6]4+ + 4Cl– ; 1 cation + 4 anions = 5 ions
4. 2 Ambidentate ligands have two or more donor atoms but in forming complexes only one donor
atom is attached to metal ion. M 
 :CN:  :NC 
M 
Cyano Isocyano
5. 2 CH2 NH2
CH2 NH2
Ethane-1,2-diamine is an example of bidentate ligands.

6. 4
7. 1
8. 1 [Pt(NH3)2Cl2] complex has no charge present on coordination sphere.
9. 1 The coordination no. = no. of ligands attached.
10. 3 Oxidation state of Cr = x + 2(–1) = +1  x   3
Cr3+ occupies 3d orbitals and its coordination number in the given complex is 6.
11. 1 Complexes in which the metal atom or ion is linked to only one type of ligands are called homoleptic
12. 2
13. 2
14. 1
15. 3 Here more than one atom function as donor, as oxygen in first one and nitrogen in second, so
they show linkage isomerism.
O2N NH3 O2N NH3

16. 1 Pt and Pt
O2N NH3
Cis H3N Trans NO2
17. 2 Geometrical isomerism is shown by square planar and octahedral complexes.

18. 3
19. 1 [Co(en)2Cl2]+ shows geometrical as well as optical isomerism.
135
20. 1 [Fe(CN)6]3–
Fe (26)  3d6 4s2
Oxidation state of Fe in complex is +3

Fe 3  3d5 4s2 4p0
As CN– is strong ligand

[Fe(CN) 6 ]3  ×× ×× ×× ×× ×× ××

d2sp3
21. 3 [Fe(CN)6]3– is an inner orbital octahedral complex.

22. 1 In [Co(H2O)6]2+, oxidation state of Co = +2, Co2+ = 3d7
eg t 52g eg2 [ n  3]
  3(3  2)  15  3.87 BM
3d
t 2g
23. 1
24. 1
25. 3 In K4[Fe(CN)6] complex, Fe is in +2 oxidation state.
3d 4s
Fe : 2+
As CN– is a strong field ligand, it causes pairing of electrons therefore, electronic configuration
6 0
of Fe2+ in K4[Fe(CN)6] is t 2g eg .
26. 1 If CFSE ( 0 ) < P (Energy required for pairing), the electrons do not pair up and fourth electron
goes to eg of higher energy. Hence, high spin complex is formed. Pairing of electrons does not
take place in case of weak field ligands.
27. 3 CN– form the complex [Cu(CN)4]3– with Cu (II) ion.
O
OC C CO
28. 4 The structure of [Co2(CO)8] is : OC Co Co CO
OC C CO
29. 3
Cr–C  bond is formed by the donation of a pair of electrons from a filled d-orbital of Cr into the
vacant antibonding * orbital of CO. This is synergic bonding due to which both  and 
character are shown by Cr–C bond.
136
30. 2 Cis-platin is used to inhibit the growth of tumours.

LEVEL - II
1. 1 As [Co(NH3)3Cl3] does not loses any Cl– ions in the solution so it will not give ppt. with AgNO3.
2. 2 Cuprammonium salt - [Cu(NH3)4]SO4
[Cu(NH3 ) 4 ]SO 4 [Cu(NH3)4]2+ + SO 24 
3. 1 Higher the number of ions in the solution, higher is the conductivity.
No. of ions : [Co(NH3)3Cl3] = 0 ; [Co(NH3)4Cl2]Cl = 2
[Co(NH3)5Cl]Cl2 = 3 ; [Co(NH3)6]Cl3 = 4
4. 1 2Cl– ions are ionizable [Co(NH3 )5 Cl]Cl2 [Co(NH3 )5 Cl]2   2Cl

  
3 ions
2Cl   2AgNO3  2AgCl  2NO3
5. 1 Thiosulphato (S2 O32 ) is not a chelating ligand because geometrically it is not favourable for
S2 O 32  to chelate a metal ion.
6. 1 (en) and (C 2 O 42 ) are bidentate. So coordination no. of M = (2 × 2) + (1 × 2) = 6

If oxidation no. of M in [M(en)2(C2O4)]+1Cl–1 is x, then : x + 2(0) + (–2) = + 1
x = 3; Sum = 6 + 3 = 9
7. 3 The complexes in which the metal is bound to more than one kind of donor groups are called
heteroleptic complexes i.e. [Co(NH3)4Cl2]+ is heteroleptic and the complexes in which the metal
is bound to only one type of donor groups are called homoletpic complexes i.e. [Co(NH3)6]3+ is
homoleptic.
8. 3
(3) (0) ( 3) ( 2)
3 3
9. 2 Oxidation number of cobalt is +3 in this complex. Complex [Co(NH 3 ) 6 ] [Cr(C 2 O 4 ) 3 ]
10. 4
11. 1
[Co(NH3)4Br2]Cl also exhibits ionization isomerism giving [Co(NH3)4BrCl]Br.

137
11. 2 The ionisation isomer for the given compound will be obtained by exchanging ligand with counter
ion as : [Cr(H2O)4Cl2]NO2.
12. 3 As it is a type [MA5B]. The position of all NH3 ligands will be same with respect to NO2 ligand.
13. 1 Complex of the type [M(AA)2X2] or [M(AA)2XY] exhibit optical activity. [CoCl2(en)2]+ forms geo-
metrical isomers (cis and trans form). Trans form does not show optical isomerism, i.e., it
cannot be resolved into optical isomers. The reason is that the molecule has plane of symme-
try. On the other hand, the cis-isomer is unsymmetrical and can be resolved into optical
isomers.
14. 2 Trans-[Co(NH3)Cl(en)2]2+ has a plane of symmetry and hence it is
optically inactive.
15. 3 Octahedral complex of general formula [M(AA)2a2]n+ show optical isomerism. Trans from of
[M(AA)2a2]n+ does not show optical isomerism due to symmetry.
cis-[Co(NH3)4Cl2]+ and trans-[Co(NH3)4Cl2]+ do not show optical isomerism due to symmetry.

16. 1
17. 1 [Co(NH3)6]3+ and [Fe(CN)6]4– are diamagnetic complexes.
18. 2 [NiCl4]2– = 3d8 configuration with Nickel in +2 oxidation state. Cl– being weak field ligand does not
compel for pairing of electrons.
. Hence, complex has tetrahedral geometry..
[Ni(CN)4]2– = 3d8 configuration with nickel in +2 oxidation state CN– being strong field ligand
which complex for pairing of electrons.
. Hence, complex has square planar geometry..
[Ni(H2O)6] = 3d8 configuration with nickel in +2 oxidation state. As with 3d8 configuration two
d-orbitals are not available for d2sp3 hybridisation. So, hybridisation of Ni(II) is sp3d2 and Ni(II)
with six coordination will have octahedral geometry.
138
19. 2
20. 4 In [Co(CN)6]3–, O.N. of Co = +3
Co3+ = 4s03d6
CN– is strong field ligand so hybridisation is d2sp3 and has no unpaired electrons.
21. 3 [Mn(H2O)6]2+ : Mn2+ = 3d5  Number of unpaired electron = 5
[Fe(H2O)6]2+ : Fe2+ = 3d6  Number of unpaired electron = 4
[Co(H2O)6]2+ : Co2+ = 3d7  Number of unpaired electron = 3
[Cr(H2O)6]2+ : Cr2+ = 3d4  Number of unpaired electron = 4
22. 2 In [Cu(NH3)6]2+, oxidation state of Cu = +2, Cu2+= 3d9
3d9  t 62g e3g
23. 2 F– is a weak field ligand hence it does not cause pairing of electrons
[FeF6]3– :
24. 1 Crystal field stabilisation energy for tetrahedral complexes is less than pairing energy hence
they do not pair up to form low spin complexes.
25. 4 [Cr(H2O)6]Cl3 - Violet, [Cr(H2O)5Cl]Cl2.H2O - Green, [Cr(H2O)4Cl2]Cl.2H2O-Green
26. 4 Due to excitation of electron from t2g level to eg level absorbing energy in blue green region
[Ti(H2O)6]3+ is violet in colour.
4
27. 4 t  0
9
28. 4 Increasing order of crystal field splitting energy is H2O < NH3 < en
Thus, increasing order of energy for the given complexes is : [Co(H2O)6]3+ < [Co(NH3O)6]3+
< [Co(en)3]3+
hc
As, E 
λ
Thus, increasing order of wavelength of absorption is :
[Co(en)3]3+ < [Co(NH3)6]3+ < [Co(H2O)6]3+
30. 1 Vitamin B12 used to prevent anaemia is a complex compound of cobalt.
139
CHAPTER - 06
HALOALKANES AND HALOARENES
INTRODUCTION
Haloalkanes and haloarenes are two classes of organic compounds containing one or more halogen atoms
attached to carbon atoms of alkyl and aryl groups respectively. They differ widely in chemical reactivity
depending on the halogen and the class to which they belong and may even differ within a class. They have
applications in industry as well as in day-to-day life. They are used as solvents for relatively non-polar
compounds and as starting materials for the synthesis of organic compounds. Many organohalogen
compounds occur in nature.Chloramphenicol, a chlorine containing antibiotic, is used in the treatment of
typhoid fever. The human body produces thyroxine, an iodine containing hormone. Chloroquine is used in
the treatment of malaria. Halothane is used as anaesthetic. Certain fully fluorinated compounds are being
considered as potential blood substitutes in surgery. Many synthetic organic halogen compounds are used
in agriculture.
Halogenated compounds persist in the environment due to resistance to breakdown by soil microorganisms,
therefore, halocarbons, including those that might not be hazardous can cause waste disposal issues.
CLASSIFICATION OF HALOGEN COMPOUNDS
The halogen derivatives of hydrocarbons can be broadly classified into (i) aliphatic halogen compounds and
(ii) aromatic halogen compounds.
Classification based on the Number of Halogen Atoms
On the basis of number of halogen atoms, these may be classified as mono-, di- or polyhalogen compounds,
depending on whether they contain one, two or more halogen atoms.
Classification based on the type of hybridization of the carbon bonded to the halogen atom
On the basis of type of hybridization of the carbon to which the halogen is attached, halogen derivatives of
hydrocarbons are classified into three types
140
(a) Compounds containing Csp3  X bond
(i) Haloalkanes or alkyl halides (R-X). Alkyl halides form a homologous series with the general formula,
CnH2n+1 X. They are further classified as primary, secondary or tertiary according as the halogen is
linked to primary, secondary or tertiary carbon atom.
(ii) Allylic halides. In these halides, the halogen is attached to an sp3-hybridised carbon atom next to a
carbon-carbon double bond, i.e., an allylic carbon. These may be further classified as 10, 20 or 30.
(iii) Benzylic halides. In these compounds, the halogen is attached to an sp3-hybridized carbon atom
next to an aromatic ring, i.e., to a benzylic carbon. These may be further classified as 10, 20 or 30.
(b) Compounds containing C sp 2  X bond
(i) Vinylic halides. In these halides, halogen is attached to a carbon atom of the carbon-carbon double
bond.
(ii) Aryl halides. In these halides, the halogen is directly attached to the aromatic ring.
141
NOMENCLATURE OF HALOGEN COMPOUNDS

Nomenclature of Haloalkanes
(a) Monohalogen derivatives. In the common or trivial system, the monohalogen derivatives of alkanes
are named as alkyl halides. Their names are derived by naming the alkyl group followed by the name
of the halogen as halide. The name of an alkyl halide is written as two separate words, e.g., CH3Br as
methyl bromide. In the IUPAC system, alkyl halides are considered as derivatives of the corresponding
alkanes and are named as haloalkanes. The name is written as one word, e.g., CH3Br as
bromomethane.
(b) Dihalogen derivatives
(i) Alkylidene dihalides. In the common system, dihaloalkanes in which halogen atoms of the same
type are present on the same carbon atom are called alkylidene dihalides (geminal dihalides or
gem-dihalides).
In the IUPAC system, they are named as dihaloalkanes. The position or the locant for the halogen,
being repeated twice, is prefixed to the name of the dihaloalkane (for dihalomethanes locants are not
used).
CH 2Cl2 CH 3CHBr2 CH3CH 2 CHCl2 CH 3CCl2CH3

Dichloromethane 1, 1 Dibromoethane 1, 1 Dichloropropane 2, 2Dichloropropane
(Methylene dichloride) (Ethylidene dibromide) (Propylidene dichloride) (Isopropylidene dichloride)
(ii) Alkylene dihalides. Dihalogen derivatives of alkanes in which two halogen atoms of the same type
are present on adjacent carbon atoms are called alkylene dihalides (vicinal dihalides or vic-dihalides).
In the IUPAC system, the locants for the two halogen atoms are prefixed to the name of the dihaloalkane.
ClCH 2CH 2Cl CH3CHBr2 CH3  CHCl  CH 2Cl

1, 2-Dichloroethane 1, 1-Dibromoethane 1, 2 Dichloropropane
(Ethylene dichloride) (Ethylidene dibromide) (Pr opylene dichloride)
142
Table - 01 Common and IUPAC Names of Haloalkanes.
Nomenclature of Haloarenes (Aryl Halides)

i. The common as well as IUPAC name of aryl halide is Haloarene, e.g., chlorobenzene.
ii. For dihalogen derivatives, the preifixes o, m-, p- are used in the common system. In the IUPAC system,
numerical prefixes 1, 2; 1, 3 and 1, 4 are used.
iii. If the aromatic hydrocarbon carries a side chain or a substituent, numbering of the carbon atoms of the
ring begins with the substituent and if the hydrocarbon is benzene, numbering begins with the halogen
atom.
143
iv. Polyhalogen derivatives do not have common names but only IUPAC names in which the position of
halogens are indicated by arabic numerals.
iv. Aralkyl halides are aromatic halogen compounds in which halogen is attached to one of the carbon
atoms of the side chain carrying the aryl group. The following aryl groups have special names:
NATURE OF THE CARBON - HALOGEN (C-X) BOND

The C–X bond is a polar covalent bond. As the size of halogen atom increases from fluorine to iodine, the C-
X bond length increases and bond enthalpy decreases.
Table - 02 Carbon-Halogen Bond Lengths, Bond Enthalpies and Dipole Moments.
Halomethane C-X bond length(pm) C-X bond enthalpy (k J mol-1 ) Dipole moment (Debye)
CH3 F 139 452 1.847
CH3 Cl 178 351 1.86
CH3 Br 193 293 1.83
CH3 l 214 234 1.636
Electronegativity decreases from F to I, therefore, polarity of the C–X bond and hence dipole moment should
decrease accordingly, but the dipole moment of CH3F is lower than that of CH3Cl. This is due to small size
of fluorine atom as compared to chlorine. Thus, the order of dipole moments is: C-F < C-Cl > C-Br > C-I.
METHODS OF PREPARATION OF HALOALKANES
1. From alcohols. (i) By the action of halogen acids (nucleophilic substitution reaction).
R  OH  HX 
 R  X  H 2O
Alcohol Haloalkane
As nucleophilicity of the halide ions decreases in the order, I   Br   Cl  , the reactivity of the halogen
acids decreases in the same order: HI > HBr > HCl. Since the stability of the carbocations decreases
in the order 3o  2 o  1o , the order of reactivity of the alcohols for a given haloacid decreases in the
same order.
(a) Chloroalkanes or Alkyl Chlorides. Primary and secondary chloroalkanes are prepared by passing
HCl gas through a suitable alcohol in presence of anhydrous zinc chloride.
144
Anhyd.ZnCl2
CH3CH2  OH  HCl(g)   CH3CH2  Cl  H2O
Anhyd.ZnCl2
CH3  CHOH  CH3  HCl(g)   CH3  CHCl  CH3  H2O
Pr opan  2ol 2Chloropropane
Tertiary alcohols react with conc. HCl even in the absence of zinc chloride.
(b) Bromoalkanes or Alkyl Bromides. Bromoalkanes are pepared by refluxing alcohols with constant
boiling HBr (48%) in presence of a little conc. H2SO4 as catalyst or a mixture of conc. H2SO4 and KBr.

ROH  KBr  H 2SO4 
 R  Br  KHSO4  H 2O
(c) Iodoalkanes or alkyl iodides. Iodoalkanes are prepared by refluxing alcohols with constant boiling
hydroiodic acid (57%). HI may also be prepared by the action of 95% phosphoric acid on KI.
Re flux
CH3CH 2OH  HI 
 CH 3CH 2 I  H 2O

CH3OH  KI  H3PO 4 
 CH3  I  KH 2PO 4  H 2O
Methanol Iodomethane
(d) Action of phosphorus halides. Phosphorus halides react with alcohols to form haloalkanes.
ROH  PCl5 
 R  Cl  POCl3  HCl
3ROH  PX 3 
 3R  X  H3 PO3 ; (X  Cl, Br, I)
Since PBr3 and PI3 are not very stable, these are generally prepared in situ by the action of red
phosphorus on bromine and iodine respectively.
redP/X
ROH 
2
R  X ; (X = Br, I)
(e) Action of thionyl chloride. Chloroalkanes are conveniently prepared by refluxing alcohols with thionyl
chloride (SOCl2) in presence of pyridine (C5H5N).
ROH  SOCl 2 
 RCl  SO 2  HCl
The byproducts in this reaction, being gases, escape leaving behind the chloroalkanes in almost
pure state.
2. From Alkanes
(a) Free radical halogenation of alkanes. Halogenation of alkanes with Cl2 or Br2 in presence of heat or
light gives a mixture of mono-, di-, and polyhaloalkanes.
Cl /hv
CH 4 2
or 520 670 K
 CH 3Cl  CH 2 Cl 2  CHCl3  CCl 4
Methane Chloromethane Dichloromethane Trichloromethane Tetrachloromethane
Substitution beyond monohalogenation can be suppressed by controlling the ratio of halogen to alkane.
In case of higher alkanes, even monohalogenation gives a mixture of all possible isomeric haloalkanes.
Cl ,h
CH3  CH 2  CH3 
2
298K
CH3  CH 2  CH  Cl CH3  CHCl  CH3
Pr opane 1Chloropropane (45%) 2Chloropropane (55%)
3. From Alkenes
(i) Addition of halogen acids. Alkenes react with halogen acids to form haloalkanes. The order of reactivity
being HI > HBr > HCl > HF.
CH 2  CH 2  HI 
 CH3  CH 2  I
Ethene (Ethylene) Iodoethane (Ethyl iodide)
Mark.addn.
CH3  CH 2  CH 2  HBr 
 CH 3  CH 2 Br  CH3
Pr opene 2 bromopropane
145
The addition of hydrogen halides to unsymmetrical alkenes takes place according to Markovnikov’s
rule.
However, in presence of peroxides like benzoyl peroxide (C6H5COOOCOC6H5), addition of HBr (not
HCl or HI) to unsymmetrical alkenes takes place against Markonikov’s rule. This is known as Kharasch
effect.
Peroxide
CH3  CH 2  CH 2  HBr  CH 3  CH 2  CH 2  Br
(ii) Addition of halogens to alkenes. vic-Dibromides can be prepared by addition of Br2 in CCl4 to
alkenes.
CCl
CH2  CH2  Br2 
4
 BrCH 2  CH2Br
Ethene 1, 2 Dibromoethane ( vic dibromide)
The reddish brown colour of bromine is discharged due to the formation of colourless vic-dibromide,
therefore, this reaction is used as a test for detection of unsaturation in organic molecules.
4. Halogen exchange
(i) Finkelstein reaction Iodoalkanes can be prepared from chloroalkanes or bromoalkanes by heating
with sodium iodide in acetone or methanol.
Acetone, 
R  X  NaI 
 R  I  NaX (X = Cl, Br)
ii. Swarts reaction. Alkyl fluorides can be prepared indirectly by heating suitable chloro- or bromoalkanes
with inorganic fluorides, such as AsF3, SbF3, CoF2, AgF, Hg2F2, etc.
CH3Br  AgF 
 CH3F  AgBr
Bromomethane Fluoromethane
METHODS OF PREPARATION OF HALOARENES

Haloarenes cannot be prepared from phenols because it is difficult to replace the hydroxyl group by
halogen. This is because the carbon-oxygen bond in phenol has partial double bond character due to
resonance.
1. Electrophilic substitution reaction. Haloarenes (chloroarenes and bromoarenes) can be prepared
by direct halogenation of aromatic hydrocarbons at low temperature (310-320 K), absence of sunlight
and the presence of Lewis acid catalysts such as iron or iron(III)chloride .
Reactions with iodine are reversible and require the presence of an oxidising agent like HNO3, HIO4,
etc., to oxidise the HI formed. Fluoro compounds cannot be prepared by this method due to high
reactivity of fluorine.
2. From diazonium salts
i) Sandmeyer reaction. Chloroarenes and bromoarenes are prepared by treating diazonium salts
with CuCl dissolved in HCl or CuBr dissolved in HBr respectively.
146
Benzenediazonium chloride is obtained by treating aniline in dil. HCl with aqueous NaNO2 at
273-278 K.
ii) Iodoarenes are prepared by warming diazonium salt solution with aqueous KI solution.
PHYSICAL PROPERTIES OF HALOALKANES AND HALOARENES

1. Physical state, colour, odour, etc. Alkyl halides are colourless when pure, but bromides and iodides
develop colour when exposed to light. Methyl chloride, methyl bromide, ethyl chloride and some chlo-
rofluoromethanes are gases at room temperature. Higher chloro, bromo, iodo compounds are either
liquids or solids. Many volatile halogen compounds have sweet smell.
2. Melting points and boiling points
(a) Haloalkanes. (i) Due to greater polarity and higher molecular mass, dipole-dipole and van der
Waals forces are stronger in halogen compounds. Thus, boiling points of chlorides, bromides and
iodides are
considerably higher than those of hydrocarbons of comparable molecular mass.
(ii) For the same alkyl group, the b.p. of haloalkanes decrease in the order: RI > RBr > RCl > RF. This
is because the magnitude of van der Waal forces increases with increase in size and mass of halogen
atom.
(iii) For the same halogen atom, b.p. increases with increase in size of the alkyl group :
CH3Cl < CH3CH2Cl < CH3(CH2)2Cl < CH3(CH2)3Cl.
(iv) For isomeric alkyl halides, b.p. decrease with branching (surface area and hence van der Waals
forces decreases with branching) : CH 3CH 2 CH 2 CH 2 Br > CH 3CH 2CHBrCH3 > (CH3 )CBr.
(v) Generally, the b.p. of chloro, bromo and iodo compounds increase as the number of halogen atoms
increases: CH 3Cl  CH 2 Cl2  CHCl3  CCl 4 .
(b) Haloarenes. (i) The boiling points of haloarenes are nearly the same as those of haloalkanes with
the same number of carbon atoms.
(ii) For the same aryl group, the melting and boiling points increase as the size of the halogen atom
increases: C6H5I > C6H5Br > C6H5Cl > C6H5F > C6H6’
(iii) For the same halogen atom, the melting and boiling points increase as the size of the aryl group
increases.
(iv) The boiling points of isomeric dihalobenzenes are nearly the same, but their melting points are
quite different. Generally, the melting point of the p-isomer is higher than that of the o-or the
m-isomer. This is because the p-isomer is more symmetrical and hence its molecules pack closely in
the crystal lattice. As a result, intermolecular forces of attraction are stronger and hence the p-isomer
melts at a higher temperature.
147
3. Density. Alkyl fluorides and chlorides are generally lighter than water, whereas alkyl bromides, iodides,
and polyhalides are heavier. Their relative densities follow the order: RI > RBr > RCl.
Compound Density (g/mL) Compound Density (g/mL) Compound Density (g/mL)
n-C3 H7 Cl 0.89 CH3 I 2.279 CH2 Cl2 1.336
n-C3 H7 Br 1.335 C2 H5 I 1.933 CHCl3 1.489
n-C3 H7 I 1.747 n-C3 H7 I 1.747 CCl4 1.595
Among the alkyl halides, methyl iodide has the highest density. As the size of the alkyl group increases,
the densitiy of alkyl halide decreases: CH3I > CH3CH2I > n-C3H7I. Density increases with increasing
number of halogen atoms : CCl4 > CHCl3 > CH2Cl2.
4. Solubility. Even though haloalkanes and haloarenes are polar they are insoluble in water. This is
because haloalkanes can neither form hydrogen bonds with water nor break the hydrogen bonds
between water molecules. However, they are quite soluble in organic solvents of low polarity such as
petroleum ether, benzene, ether, chloroform, carbon tetrachloride, etc.
CHEMICAL REACTIONS OF HALOALKANES
The reactions of haloalkanes may be divided into three categories; (i) Nucleophilic substitution reactions
(iii) Elimination reactions and (iii) Reactions with metals.
Nucleophilic substitution Reactions
In this type of reaction, a nucleophile reacts with haloalkane (substrate) having a partial positive charge
on the carbon atom bonded to halogen and the halogen atom (leaving group) departs as a halide ion.
Since substitution reaction is initiated by a nucleophile, it is called nucleophilic substitution reaction.
The leaving group such as X– (Cl–, Br–, I–, etc.) which leaves with an electron pair is called a nucleophile.
The order in which the leaving groups depart follows the sequence : I– > Br– > Cl– > F–.
The order of reactivity of haloalkanes is : iodoalkanes > bromoalkanes > chloroalkanes > fluoroalkanes
Table - 03 Nucleophilic Substitution Reactions of Alkyl Halides (Nu- + R–X ® R–Nu + X–).
Substitution Class of the main

Reagent Nucleophile (Nu- )
product (R-Nu) product
NaOH, KOH HO- R-OH Alcohol
H2O H2O
R'ONa R'O- R-O-R' Ether
NaI I- R-I Alkyl iodide
NH3 NH3 R-NH2 Primary amine
R'NH2 R'NH2 R-NH-R' Secondary amine
R'NHR'' R'NHR'' RNR'R'' Tertiary amine
KCN CN: R-CN Nitrile (cyanide)
AgCN AgCN: R-N=C Isonitrile (Isocyanide)
KNO2 O=N-O R-O-N=O Alkyl nitrite
AgNO2 Ag-O-N=O RNO2 Nitroalkane
R'COOAg R'COO- R'COOR Ester
LiAlH4 H- R-H Hydrocarbon
R'-M+ R'- R-R' Alkane
148
(i) Substitution of halogen by hydroxyl group (Formation of alcohols). Haloalkanes on treatment

with boiling aqueous alkalies or silver oxide in boiling water (AgOH) undergo hydrolysis to form alcohols.
R  X  K  OH  (aq) 
 R  OH  K  X 
Haloalkane Alcohol
(ii) Substitution of halogen by alkoxy group (Formation of ethers). Haloalkanes when treated with
sodium or potassium alkoxides form ethers or alkoxyalkanes.This reaction is called Williamson

R  X  R 'ONa 
synthesis. Alkyl  R  O  R ' Na  X 
halide Sodium alkoxide Ether
(iii) Substitution of halogen by cyano group (Formation of alkyl cyanides). Haloalkanes react with
alcoholic potassium cyanide to form alkyl cyanides or alkanenitriles along with small amount of alkyl
isocyanide.

 R  C  N K  X
R  X  KCN(alc.) 
Haloalkane Alkanenitrile
(iv) Substitution of halogen by isocyanide group (Formation of alkyl isocyanides). When aqueous
ethanolic solution of haloalkane (particularly iodoalkane) is heated with silver cyanide, alkyl isocyanide
or alkyl isonitrile or alkyl carbylamine is produced along with small amount of alkyl cyanide
 
C H OH/H O
R  X  Ag  CN 
2 5 2
 R  N C  AgX
Haloalkane  Alkylisocyanide
Cyanide ion is a resonance hybrid of the following two resonating structures :
Either the carbon or the nitrogen atom can act as the electron donor. Such a nucleophile which has
more than one site through which the reaction can occur is called ambident nucleophile.
Mechanism of Nucleophilic Substitution Reactions
There are two types of nucleophilic substitution reactions, SN2 and SN1.
1. Substitution nucleophilic bimolecular (SN2)
Edward Davies Hughes and Sir Christopher Ingold (1937) proposed a mechanism for SN2 reactions.
The reaction between methyl chloride (CH3Cl) and hydroxide ion (OH–) to yield methanol (CH3OH) and
chloride ion follows second order kinetics, i.e., the rate of the reaction depends on the concentration of
both the reactants.

H3C  Cl   H 3C  OH  Cl
OH 
; Rate = k [CH3Cl] [OH–]
Methyl chloride Methanol
The rate law implies that both the alkyl halide (CH3Cl) and the nucleophile (OH–) take part in the rate
determining step of the reaction. When the incoming nucleophile (OH–) starts interacting with the alkyl
halide (CH3Cl), the carbon-halogen bond starts breaking and a carbon –OH bond starts forming. These
two processes take place in a single step and no intermediate is formed. Thus, SN2 reactions are
concerted reactions. Such reactions occur through a transition state in which both reactants are
partially bonded to each other.
149
Figure - 01 Formation of transition state in a SN2 reaction

In the transition state, the carbon atom is bonded to five atoms and thus it is unstable and hence
cannot be isolated. Being unstable, it decomposes to give the product (CH3OH) and the leaving group
(Cl– ion).
In SN2 reaction, the attack of the nucleophile (OH–) occurs from the back side and the leaving group
(Cl–) leaves from the front side. As a result, SN2 reactions are always accompanied by inversion of
configuration (just as an umbrella turns inside out in a strong wind).
The reaction requires the approach of the nucleophile to the carbon bearing the leaving group, therefore,
the presence of bulky substituents on or near the carbon atom inhibits the reaction. Thus, methyl
halides are the most reactive while tertiary halides are the least reactive in SN2 reactions. The order of
reactivity is :
Methyl halides > Primary halide > Secondary halide > Tertiary halide.
2. Substitution nucleophilic unimolecular (SN1)
SN1 reactions are generally carried out in polar protic (hydroxylic) solvents such as water, alcohol,
acetic acid, etc. The reaction between tert-butyl bromide and OH– ion to yield tert-butyl alcohol follows
first order kinetics, i.e., the rate of reaction depends on the concentration of tert-butyl bromide only and
is independent of the concentration of OH– ions.

(CH3 )3 C  Br  OH 
 (CH3 )3 C  OH  Br  ; Rate = k [(CH3)3CBr]
2Bromo 2methylpropane 2Methylpropan  2ol
The rate law suggests that the reaction occurs in two steps. In the first step, tert-butyl bromide
undergoes ionisation to produce tert-butyl carbocation and a bromide ion. The energy needed for the
cleavage of the C – Br bond is obtained by the solvation of the bromide ion with proton from protic
solvents.
Step I. This step is slow and reversible, therefore, the rate-determining step of the reaction.
Step II. The carbocation is immediately attacked by the nucleophile (OH–) ion to give the substitution
product (tert-butyl alcohol). This step is fast and hence does not affect the rate of the reaction.
150
If the starting alkyl halide is optically active, the product formed is a racemic mixture. This is because
the carbocation formed in the first step is a planar species involving sp2 hybridisation. Therefore, the
attack of the nucleophile can occur from both sides giving an approximately 50:50 mixture of the two
enantiomers.
In SN1 reactions, carbocations are the intermediates. Greater the stability of the carbocation, easier its
formation and faster the rate of reaction. Since the stability of carbocations is in the order : 3° > 2° >
1° > CH 3 , the reactivity of alkyl halides towards SN1 reactions decrease in the same order : 3° alkyl
halides > 2° alkyl halides > 1° alkyl halides > methyl halides.
Relative Reactivity of Haloalkanes towards SN2 and SN1 reactions
The reactivity of alkyl halides towards SN2 and SN1 reactions follow opposite orders:
Whereas methyl and primary alkyl halides predominantly undergo substitution by SN2 mechanism,
tertiary alkyl halides undergo substitution by SN1 mechanism. Secondary, primary allylic and primary
benzylic halides react either by SN1 or SN2 mechanism or by both the mechanisms depending on the
nature of the nucleophile and the solvent.
Due to greater stabilisation of allyl and benzyl carbocation intermediates by resonance, even primary
allylic and primary benzylic halides show greater reactivity in SN1 reactions than other simple primary
halides.
STEREO CHEMICAL ASPECTS OF NUCLEOPHILIC SUBSTITUTION REACTION

i) Plane polarised light. Ordinary light consists of waves having oscillations in all the planes perpendicular
to the line of propagation. When a beam of light is passed through a Nicol prism (crystalline CaCO3, calcite)
the light that comes out has oscillations only in one plane. A beam of light that has vibrations only in one
plane is called plane-polarised light.
Optical activity. Certain substances rotate the plane of polarized light when it is passed through their
solutions. Such substances are called optically active substances and the property is called optical activity.
The angle through which the plane of polarized light is rotated is measured using a Polarimeter.
Figure - 01 Schematic representation of a polarimeter.
151
A substance which rotates the plane of polarised light towards right (clockwise direction) is said to be
dextrorotatory (Latin : dexter = right) and is represented by the sign (+) or (d). Any substance which
rotates the plane of polarised light towards left (anticlockwise direction) is said to be laevorotatory (Latin :
laevus = left) and is represented by (–) or (l) sign.
The (+) and (–) isomers of an optically active compound are called optical isomers and the phenomenon
is called optical isomerism.
An object which has no plane of symmetry is said to be dissymmetric or chiral. A symmetric object is
achiral. A dissymmetric object cannot be superimposed on its mirror image.
Molecular asymmetry, chirality and enantiomers
In 1848, Louis Pasteur observed that crystals of substances such as sodium ammonium tartrate exist in
two forms which have mirror-image relationship. He found that aqueous solutions of both types of crystals
rotate the plane of polarised light, equal in magnitude (for solution of equal concentration) but in opposite
directions.
He attributed this difference in optical activity to the three - dimensional arrangement of atoms (configurations)
in the two types of crystals.
Dutch scientist J. van’t Hoff and French scientist C. Le Bel (1874) pointed out that when all the four atoms/
groups attached to a carbon atom are different, such a carbon is called asymmetric carbon or chiral
carbon or stereocentre. A molecule which contains an asymmetric carbon has no elements of symmetry
and hence called an asymmetric molecule and asymmetry of the molecule is responsible for optical activity
in such organic compounds.
(a) (b)
Figure - 02 Examples of (a) chiral and (b) achiral objects.

A molecule which does not possess plane of symmetry and centre of symmetry is said to be dissymmetric.
A dissymmetric object cannot be superimposed on its mirror image.
Many objects are not superimposable on their mirror images, e. g., your hands look similar but if you put the
right hand over your left hand, they do not coincide (feet, gloves, shoes, etc.). Thus, objects which are non-
superimposable on their mirror images are called chiral and the property of non-superimposability is called
chirality. Objects which are superimposable on their mirror images (e.g. buttons, spheres, cubes, tumblers,
etc.) are called achiral.
A simple test of molecular chirality is the presence of an asymmetric carbon atom in the molecule. Consider
two simple molecules, propan-2-ol and butan-2-ol and their mirror images. Propan-2-ol does not contain an
asymmetric carbon atom, therefore, the molecule is achiral.
Figure - 03 Propan-2-ol is achiral because I and its mirror image II (or III) are superimposable.
152
The three-dimensional structure of propan-2-ol is I and that of its mirror image is II. To check the super-
imposability of II over I, rotate II horizontally through 180o such that the C–OH bond in the new structure (III)
projects in the same direction as that in structure I. On superimposing III over I, it can be seen that I and III are
superimposable (fig.03). Hence, propan-2-ol is an achiral molecule.
Figure - 04 Butan-2-ol is chiral because IV and its mirror image V (or VI) are non-
superimposable.
Butan-2-ol contains one asymmetric carbon atom. The three-dimensional structure of butan-2-ol is IV and
that of its mirror image is V. On rotating V horizontally through 180o, the C–OH bond in the new structure (VI)
projects in the same direction as that in structure IV. On superimposing VI over IV, they are found to be non-
superimposable (fig.04). Hence, butan-2-ol is a chiral molecule.
In chiral molecules, the asymmetric or chiral carbon is denoted by an asterisk (*).
Enantiomers. Optical isomers which are non-superimposable mirror images of each other are called
enantiomers and the phenomenon is called enantiomerism. Enantiomers have identical physical and
chemical properties, but rotate the plane of polarised light in opposite directions to the same extent.
Figure - 05 Enantiomers of bromochloroiodomethane.

Bromochrloroiodomethane contains one asymmetric (chiral) carbon atom and exists in two stereoisomeric
forms, I and II, which are non-superimposable mirror images of each other (Fig.05). Thus, I and II represent
enantiomers of bromochloroiodomethane. The enantiomer which rotates the plane of polarised light towards
right is called dextrorotatory and is represented as ‘d’ or (+) while the enantiomer which rotates the plane
of polarised light towards left is called laevorotatory and is represented as ‘l’ or (–).
Racemic mixture. A mixture of equal amounts of two enantiomers is called racemic mixture or racemic
modification. A racemic mixture is optically inactive because the rotation caused by the molecules of one
enantiomer is exactly cancelled by equal and opposite rotation caused by the same number of molecules of
the other enantiomer. It is represented by prefixing dl or (  ) before the name, e.g. (  ) butan-2-ol.
The process of conversion of one enantiomer (+ or –) into a racemic mixture is called racemisation.
153
Elimination Reactions (Dehydrohalogenation)

When haloalkane with b-hydrogen atom is heated with conc. alcoholic solution of KOH, hydrogen halide is
eliminated and an alkene is formed.
Since the hydrogen atom is eliminated from the b-carbon, this reaction is classified as β -elimination.
Orientation of dehydrohalogenation. If the halogen is present on the terminal carbon atom, dehydro-
halogenation occur only in one direction to give the terminal alkene, e.g., 1-chlorobutane gives but-1-ene.
If the halogen is present on a carbon atom within the chain, dehydrohalogenation can occur in two or more
directions depending on the number of different types of   hydrogens available. According to Alexander
Zaitsev (Russian chemist, 1875), the more highly substituted alkene will be the major product. In
dehydrohalogenation reactions, the preferred product is that alkene which has the greater number of alkyl
groups attached to the doubly bonded carbon atoms. This generalisation is known as Saytzeff’s rule and
this mode of elimination is called Saytzeff elimination.
Any alkyl halide that gives a more stable alkene undergoes dehydrohalogenation faster than one which gives
a less stable (i.e., less highly substituted) alkene. Among chloroethane (1o), 2-chloropropane (2o), and 2-
chloro-2-methyl propane (3o), the ease of dehydrohalogenation increases as the number of   hydrogens
increases, i.e., (CH3)3CCl > (CH3)2 CHCl > CH3CH2Cl.
In general, the ease of dehydrohalogenation of different alkyl halides containing the same alkyl group and
different halogens decreases in the order : R - I > R - Br > R - Cl > R - F.
Reaction with Metals
(i) Organometallic compounds. Compounds containing carbon -metal bond are called organometallic
compounds. Alkyl magnesium halides (RMgX) were discovered by Victor Grignard (Nobel Prize in
Chemistry, 1912), and are now called Grignard reagents.
Grignard reagents are prepared by the reaction of haloalkanes with magnesium in dry ether.
Dry ether
R  X  Mg    R  MgX Dry ether
Alkyl halide ; CH 3CH 2  Br  Mg    CH 3CH 2  MgBr
Grignard reagent
Ethyl bromide Ethylmagnesium bromide
154
The carbon-halogen covalent bond in Grignard reagents is highly polar due to large electronegativity
difference between carbon (2.5) and magnesium (1.2). Thus, the magnesium - halogen bond is ionic.
  
R  Mg X
Due to high polarity, Grignard reagents are a potential source of carbanions and hence are very reactive.
They react with any source of proton or acidic hydrogen to give hydrocarbons. Thus, water, alcohols,
H2S, thioalcohols, NH3, 1o and 2o amines and terminal alkynes convert them to hydrocarbons.
R  Mg  X  H 2 O 
 R  H  Mg(OH)X
Grignard reagents react with moisture, O2 and CO2, therefore, they should be prepared and used in
the absence of air. Grignard reagents are very useful for the preparation of different classes of organic
compounds like alcohols, aldehydes, ketones, carboxylic acids, etc.
(ii) Wurtz reaction. Alkyl halides react with metallic sodium in presence of dry ether to form symmetrical
alkanes containing double the number of carbon atoms.
Dry ether
R  X  2Na  X  R  R  R  2NaX
Dry ether
CH 3  X  2Na  X  CH 3  CH 3  CH 3  2NaX
The reaction generally fails with tertiary alkyl halides since under the basic conditions of the reaction,
they undergo dehydrohalogenation to form alkenes.
CHEMICAL REACTIONS OF HALOARENES

Haloarenes and vinyl halides are extremely less reactive than haloalkanes towards nucleophilic
substitution reactions due to the following reasons:
(i) Resonance effect. In haloarenes, a lone pair of electrons from the halogen atom can delocalize on
the benzene ring.
Figure - 05 Resonance structures of chlorobenzene

As a result, the C–Cl bond acquires some double bond character. Consequently, C–X bonds in aryl
halides are stronger than in alkyl halides, and hence cannot be easily broken.
(ii) Difference in hybridisation of carbon atom in C–X bond. In haloalkanes, the halogen is attached to
sp3-hybridized carbon while in haloarenes, the halogen is attached to sp2 -hybridized carbon. Since an
sp2-hybridised orbital is smaller than an sp3-orbital, the C–Cl bond in chlorobenzene is shorter and
hence stronger than in methyl chloride.
Thus, in chlorobenzene, C–Cl bond is stronger than in methyl chloride and hence difficult to break.
155
(iii) Polarity of the carbon-halogen bond. Another reason for the low reactivity of aryl halides over alkyl
halides is their lesser polar character.
Due to greater s-character, the sp2-hybrid carbon is more electronegative than sp3-hybrid carbon.
Therefore, the C-X bond in aryl halides has lesser tendency to release electrons to the halogen. As a
result, the C-X bond in aryl is less polar than in alkyl halide and the halogen atom cannot be easily
displaced by nucleophiles.
(iv) Instability of phenyl cation. In haloarenes, the phenyl cation formed by self-ionisation is not stabilized
by resonance because the sp2-hybridised orbital of carbon having +ve charge is perpendicular to the
p-orbitals of the phenyl ring. Therefore, these cations are not formed and hence aryl halides do not
undergo nucleophilic substitution reactions easily.
(v) Electronic repulsions. Since arenes are electron rich due to the presence of   bonds, they repel
the electron rich nucleophiles from attacking them.
Replacement by hydroxyl group
Due to low reactivity, aryl halides undergo nucleophilic substitution reactions only under drastic conditions.
E.g., chlorobenzene when heated with aqueous NaOH at 623 K and 300 atmospheres, gives sodium
phenoxide which on acidification gives phenol (Dow process for the manufacture of phenol).
Reactivity of haloarenes in nucleophilic substitution reactions. The displacement of the halogen

in haloarenes takes place only under drastic conditions. However, the presence of electron-withdrawing
groups such as –NO2, –CN, etc., at o- and p- positions (but not in m-positions) w.r.t. the halogen
greatly activates the halogen towards nucleophilic displacement. Greater the number of such groups
at o- and p- positions w.r.t. the halogen, the more reactive is the haloarene.
156
Mechanism. The presence of NO2 groups at o-and p-positions withdraws electrons from the benzene
ring and thus facilitates the attack of the nucleophile on haloarenes. The carbanion thus formed is
resonance stabilised.
(i) Attack at p-position
However, no effect is observed by the presence of electron withdrawing group at meta- position.
(ii) Attack at o-position
157
(iii) Attack at m-position
In case of o-and p-chloronitrobenzenes, one of the resonating structures (II in case of p- chloronitrobenzene
and IV in case of o-chloronitrobenzene) carries a negative charge on the carbon atom bearing the NO2
group. Therefore, these carbanions are stabilized by the NO2 group as well as by the p-electrons of the
benzene ring.
However, in case of m-chloronitrobenzene, there is no such structure in which the negative charge is
present on the carbon atom bearing the -NO2 group. Therefore, in case of m-chloronitrobenzene,
carbanion is not stabilized by the –NO2 group but is only stabilized by the p-electrons of the benzene
ring. In other words, carbanions resulting from o- chloronitrobenzene and p-chloronitrobenzene are
more stable than that resulting from m-chloronitrobenzene.
Electrophilic substitution reactions
Haloarenes undergo electrophilic substitution reactions of the benzene ring such as halogenation, nitration,
sulphonation, etc. Halogen atom is slightly deactivating and o-, p-directing, therefore, further substitution
occurs at o- and p-positions w.r.t.the halogen atom.
In the resonance structures II, III and IV of chlorobenzene (Fig. 05), there is a negative charge either at o- or
p-positions, i.e., the electron density increases at o- and p-positions. However, due to steric hindrance at the
o-position, the p-product usually predominates over the o-product. The halogen atom, because of its -I-
effect, has some tendency to withdraw electrons from the benzene ring. As a result, the ring becomes
some what deactivated and hence further electrophilic substitution occurs slowly and under more drastic
conditions as compared to benzene.
(i) Halogenation
(ii) Nitration
158
(iii) Sulphonation
(iv) Friedel-Crafts alkylation
(v) Friedel-Crafts acylation
3. Reactions with Metals

(a) Wurtz-Fitting reaction. Haloarenes when treated with ethereal solution of alkyl halide in presence
of sodium, form alkyl derivatives of benzene. This reaction is called Wurtz- Fittig reaction.
(b) Fittig reaction. When haloarenes are treated with sodium, diaryls are produced.
POLYHALOGEN COMPOUNDS
Carbon compounds containing more than one halogen atom are called polyhalogen compounds.
Many polyhalogen compounds are useful in industry and agriculture.
159
1. Dichloromethane (Methylene Chloride) - CH2Cl2

Uses. (i) It is widely used as solvent, paint remover, propellant in aerosols and as process solvent in
the manufacture of drugs. (ii) It is also used as metal cleaning and finishing solvent.
Physiological effects. Methylene chloride acts on the central nervous system (CNS). (i) Exposure to
small levels of methylene chloride in air causes slightly impaired hearing and vision. Higher levels of
methylene chloride in air causes dizziness, nausea, tingling and numbness in the fingers and toes. (ii)
Direct contact with skin causes intense burning and mild redness of skin. Direct contact with the eyes
can burn the cornea.
2. Trichloromethane (Chloroform), CHCl3 . It is a colourless, sweet-smelling, dense liquid (B.P. 61.15°C).
(i) It is slowly oxidised by air in presence of light to an extremely poisonous gas, carbonyl chloride
(phosgene).
Light
2CHCl3  O2  2COCl2  2HCl
Carbonyl chloride
It is, therefore, stored in dark coloured bottles completely filled to the brim and closed to exclude air.
0.6 - 1.0% alcohol is also added to destroy traces of phosgene that may be formed on storage. Any
Phosgene formed combines with ethyl alcohol to form non - toxic diethyl carbonate.
2C2 H5OH  COCl2 

 (C2 H5 )2 CO  2HCl
Phosgene Diethyl carbonate
Uses. (i) As a solvent for resins, rubbers, oils and fats, alkaloids, iodine, etc. In the production of freon
refrigerant, R-22 (chlorodifluoromethane).
Physiological effects. It was used as a general anaesthetic agent in surgery but has been replaced by
less toxic and safer anaesthetic agents such as ether. Inhaling chloroform vapours depresses the
central nervous system and causes dizziness, fatigue and headache. Chronic exposure may damage
the liver (where chloroform is metabolised to phosgene) and the kidneys. Some people develop sores
when skin is immersed in chloroform.
3. Triiodomethane (Iodoform), CHI3. Iodoform was earlier used as an antiseptic for dressing wounds.
Its antiseptic property is due to the liberation of iodine when it comes in contact with skin.
4. Tetrachloromethane (Carbon Tetrachloride), CCl4
Carbon tetrachloride is produced by the chlorination of methane in presence of light.
Uses. (i) In the manufacture of refrigerants and aerosol propellants. (ii) As a feedstock in the synthesis
of chlorofluorocarbons (freons ) and other chemicals. (iii) As a solvent in the manufacture of
pharmaceuticals.
(iv) Until the mid 1960s, it was widely used as a fire extinguisher under the name pyrene. (v) As
cleaning fluid in industry and as a degreasing agent and spot remover at home.
Physiological effects. (i) Exposure causes liver cancer. The most common effects are dizziness, light
headedness, nausea and vomiting, which can cause permanent damage to nerve cells. In severe
cases, these effects can lead to stupor (laziness), coma, unconsciousness and death. (ii) Exposure
to carbon tetrachloride vapours can make heart beat irregular or may even stop. It causes irritation to
the eyes.
160
Environmental effects. Carbon tetrachloride released into the air, goes to the upper atmosphere and
depletes the ozone layer. Depletion of ozone layer increases human exposure to ultraviolet radiations
which may lead to increased skin cancer, eye disease and disorders, and disruption of the immune
system.
5. Freons. Chlorofluoro compounds of methane and ethane in which all the H- atoms are replaced by
halogen atoms are collectively called freons. These are further classified on the basis of the number of
fluorine atoms present: CF4 (Freon - 14), CF3Cl (Freon - 13), CF2Cl2 (Freon - 12), CFCl3 (Freon - 11).
Preparation. Freon -12 is manufactured from carbon tetrachloride by Swarts reaction.
SbCl
3CCl4  2SbF3 
5
 3CCl2 F2  2SbCl3
Freon 12
Freon-12 is an odourless, noncorrosive, nontoxic gas which is stable even at high temperatures and
pressures. It has low b.p., and low specific heat and can be easily liquefied by applying pressure at
room temperature.
Uses. It is widely used as refrigerant in refrigerators and air conditioners. It is also used as propellant
in aerosols and foams (hair sprays, deodorants, shaving creams, cleansers, insecticides, etc).
Environmental effects. Freon diffuses unchanged into the stratosphere where it initiates radical chain
reactions which can disrupt the natural ozone balance.
6. p, p´-Dichlorodiphenyl Trichloroethane (DDT). The name p, p´-dichlorodiphenyltrichloroethane is
a misnomer. Its actual name is 2-2-bis(4-chlorophenyl)-1,1,1- trichloroethane.
Uses. DDT is a cheap but powerful insecticide. It is particularly effective against Anopheles mosquitoes
which spread malaria and lice that carry typhus. Through its use, malaria has virtually been eliminated
from India and large parts of the world.
Side effects. DDT is not completely biodegradable. Many species of insects developed resistance to
DDT. It has high toxicity towards fish.It gets deposited in fatty tissues of animals. This affects the
reproductive system of animals. Because of side effects, the use of DDT is banned.
161
QUESTIONS
LEVEL - I
1. Which of the following is a primary haloalkane?
1) Isopropyl iodide 2) Secondary butyl iodide
3) Tertiary butyl bromide 4) Neo hexyl chloride
2. Which one of the following is benzylic halide?
C Cl Cl
1) CH3 – CH2 – Cl 2) CH2 CH 3) 4)
H
Cl
3. Halogen atom bonded to sp2 hybridised carbon atom of carbon-carbon double bond is present in
1) Allylic halide 2) Alkyl halide 3) Vinylic halide 4) Benzylic halide
CH3
4. The IUPAC name of CH 3  CH 2  CH  C  CH 2  Br is :
1) 1-Bromo-2-methylpent-2-ene 2) 5-Bromo-4-methylpent-3-ene
3) 1-Bromo-4-methyl pent-2-ene 4) 2-methyl-1-Bromo pent-2-ene
5. What should be the correct IUPAC name for diethylbromomethane?
1) 1-bromo-1, 1-diethylmethane 2) 3-bromopentane
3) 1-bromo-1-ethylpropane 4) 1-bromopentane
6. Which of the following is an example of vic-dihalide?
1) Dichloromethane 2) 1, 2-dichloroethane
3) Ethylidene chloride 4) Allyl chloride
7. Which of the following compounds can yield only one monochlorinated product upon free radical
chlorination?
1) 2, 2-Dimethylpropane 2) 2-Methylpropane
3) 2-Methylbutane 4) n-Butane
8. The reaction of toluene with chlorine in the presence of iron and in the absence of light yields ....
CH2Cl CH3
Cl
1) 2)
3) H3C Cl 4) Mixture of 2 and 3
162
9. The reaction, C 6 H 5 N 2 Cl 

Cu 2 Cl 2
 C6H5Cl + N2 is an example of
1) Etard’s reaction 2) Stephen reaction
3) Sandmeyer’s reaction 4) Kolbe’s reaction
Br
10. The reaction, CH2 CH CH3 + HBr CH3 CH CH3 is an example of
1) Nucleophilic addition 2) Free radical addition

3) Electrophilic addition 4) Electrophilic substitution
11. What is the main product of the reaction between 2-methyl propene with HBr?
1) 1-bromo butane 2) 1-bromo-2 methyl propane
3) 2-bromo butane 4) 2-bromo-2 methyl propane
12. Finkelstein reaction is
1) CH 3  CH  CH 2  HI 
 CH 3  CH 2  CH 2 I  NaCl
2) CH 3  CH 2  CH 2  Cl  NaI 
dry acetone
 CH 3  CH 2  CH 2 I  NaCl
3) CH 2  CH 2  HCl 
 CH 3  CH 2  Cl
4) CH 3  CH 2  OH  HCl 
 CH 3  CH 2  Cl
13. Which among the following is Swarts reaction?
1) CH 3Cl  NaI 

acetone
 CH 3 I  NaCl 2) CH 3 Br  NaI 
acetone
 CH 3 I  NaBr

3) CH 3 Br  AgF   CH 3 F  AgBr 4) 2CH 3Cl  2Na 
Dry ether
 CH 3  CH 3  2NaCl
14. Treatment of ammonia with of ethyl chloride will yield
1) Dimethyl amine 2) Ethane 3) Ethyl amine 4) Methyl amine
15. The organic chloro compound, which shows complete stereochemical inversion during a SN 2 reac-
tion, is :
1) (CH3)3CCl 2) (CH3)2CHCl 3) CH3Cl 4) (C2H5)2CHCl
16. A primary alkyl halide would preferably undergo
1) SN1 reaction 2) SN2 reaction 3) -elimination 4) Racemisation
17. Consider the following bromides :
Me Me
Me
Me Br
Br Br
(A) (B) (C)
The correct order of SN1 reactivity is

1) A > B > C 2) B > C > A 3) B > A > C 4) C > B > A
163
18. SN1 reaction is fastest in
CH3 CH3 CH Cl
1) CH3CH2Br 2) CH3 CH CH3 3) CH3 C Cl 4) CH2
Cl CH3 CH3
19. Aryl halides are less reactive towards nucleophilic substitution reactions as compared to alkyl halides
due to
1) The formation of less stable carbanion 2) Longer carbon halogen bond
3) The inductive effect 4) sp2-hybridized carbon attached to the halogen
20. 2-chloro-2-methylpropane on reaction with alc.KOH gives X as the product. X is :
1) but-2-ene 2) 2-methylbut-1-ene 3) 2-methylprop-1-ene 4) 2-methylbutan-2-ol
21. When 2-bromohexane undergo dehydro halogenation the major product formed is :
1) CH3 – CH2 – CH = CH – CH2 – CH3 2) CH 3  CH  CH  CH  CH 3
CH3
3) CH3 – CH = CH – CH2 – CH2 – CH3 4) CH 3  C  CH  CH 2  CH 3
CH3
Cl
X
22.
1) Aq. NaOH 2) Alcoholic KOH 3) anhydrous AlCl3 4) Both 2 and 3

23. Chlorobenzene on heating with NaOH at 623 K and 300 atm pressure gives
1) Phenol 2) Benzaldehyde 3) Chlorophenol 4) Benzene
24. Which of the following can be used as the halide component for Friedel-Crafts reaction?
1) Isopropyl chloride 2) Chlorobenzene 3) Bromobenzene 4) Chloroethene
25. Bromobenzene treated with sodium in dry ether is Fittig reaction, the compound formed is :
CH3
1) 2) 3) 4)
26. Which of the following has highest chlorine content?

1) Chloral 2) Gammaxene 3) DDT 4) Chloroform
164
27. Chloroform is slowly oxidised by air in presence of light to form

1) Carbon dioxide 2) Carbon tetrachloride 3) Carbonyl chloride 4) Carbon monoxide
28. Which one of the following order is correct for dehydrohalogenation?
1) C2H5F > C2H5Cl > C2H5Br > C2H5I 2) C2H5Cl > C2H5F > C2H5Br > C2H5I
3) C2H5I > C2H5Br > C2H5Cl > C2H5F 4) C2H5F > C2H5Br > C2H5I > C2H5Cl
29. An organic halogen compound which was used as refrigerant in refrigerators and air conditioners is :
1) BHC 2) CCl4 3) Freon 4) CHCl3
30. The first prepared chlorinated organic insecticide is :
1) BHC 2) DDT 3) CHCl3 4) CCl4
LEVEL - II
Cl
1. The IUPAC name of the compound
CH3
a) o-chlorotoluene b) m-chlorotoluene
c) 1-chloro-2-methyl benzene d) 2-chlorotoluene
1) a only 2) a and c 3) c and d 4)d only
NO2
F
2. The IUPAC name of the compound is :
CH3
1) 1-fluoro-4-methyl-2-nitrobenzene 2) 4-fluoro-1-methyl-3-nitrobenzene
3) 4-methyl-1-fluoro-2-nitrobenzene 4) 2-fluoro-5-methyl-1-nitrobenzene
3. Which one of the following is a gem-dihalide?
1) CH3 CH2 CH CH2 2) CH3 CH CH2 CH CH3
Cl Cl Cl Cl
3) CH3 CH2 CH2 CH Cl 4) CH3 CH CH2 CH2 Cl
Cl Cl
4. The C – Cl bond in chlorobenzene as compared with C – Cl bond in methyl chloride is

1) Longer and stronger 2) Shorter and stronger
3) Shorter and weaker 4) Longer and weaker
165
5. The C – Cl bond length in haloalkane and haloarene respectively are
1) 177 pm and 169 pm 2) 169 pm and 177 pm
3) 206 pm and and 196 pm 4) 196 pm and 206 pm
6. Which of the following alcohols will yield the corresponding alkyl chloride on reaction with concen-
trated HCl at room temperature?
1) CH3CH2–CH2–OH 2) CH3CH2 CH OH
CH3
CH3
3) CH3CH2 CH CH2OH 4) CH3CH2 C OH
CH3 CH3
7. Preparation of alkyl halides in laboratory is least preferred by
1) Halide exchange
2) Treatment of alcohols
3) Direct halogenation of alkanes
4) Addition of hydrogen halides to alkenes
8. Chlorobenzene is formed by reaction of chlorine with benzene in the presence of AlCl3. Which of the
following species attacks the benzene ring in this reaction?
1) Cl– 2) Cl+ 3) AlCl3 4) [AlCl4]–
NH2
9. Consider the reaction NaNO 2  HCl

273 278K
  X  
CuCl 2
  Y  . The product (Y) is
1) C6H5 – NO2 2) C6H5Cl 3) C6H5 – C6H5 4) C6H6

10. Which of the following is a halogen exchange reaction?
1) RBr + NaI  RI + NaBr
2) C C + HX 
 C C
H X
3) R  OH  HX 
ZnCl2
 R  X  H 2O
CH3 CH3 CH3

4) + X2 
 Fe
dark + (where X = Cl, Br or I)
X X
166
11. Alkyl halides are immiscible in water though they are polar because
1) They react with water to give alcohols
2) They cannot form hydrogen bonds with water
3) C–X bond cannot be broken easily
4) They are stable compounds and are not reactive
12. The order of dipolemoment of CH3F, CH3Cl, CH3Br and CH3I is
1) CH3Cl > CH3F > CH3Br > CH3I 2) CH3F > CH3Cl > CH3Br > CH3I
3) CH3I > CH3Br > CH3Cl > CH3F 4) CH3I > CH3Cl > CH3F > CH3Br
13. Ortho and para isomers can easily separated due to large difference in their
1) Molecular mass 2) Boiling point 3) Melting point 4) No structure
14. Among the choices of alkyl bromide, the least reactive bromide in SN2 reaction is :
1)1-bromopentane 2) 2-bromo-2-methylbutane
3) 1-bromo-3-methylbutane 4) 1-bromo-2-methylbutane
15. Which of the following statements is not correct about SN2 reactions of alkyl halides?
1) Nucleophile attacks the carbon from the side opposite to where the leaving group is attached.
2) The bond formation and bond breaking take place in one step
3) The rate of reaction depends upon the concentration of nucleophile
4) SN2 mechanism is predominant in tertiary alkyl halides
16. Inversion of configuration generally takes place in
1) SN1 reaction 2) Elimination reaction
3) SN2 reaction 4) Substitution reaction
17. Reaction of C6H5CH2Br with aqueous sodium hydroxide follows ......
1) SN1 mechanism
2) SN2 mechanism
3) Any of the above two depending upon the temperature of reaction
4) Saytzeff rule
18. The order of reactivity of various alkyl halides towards nucleophilic substitution follows the order
1) R– I > R – Br > R – Cl > R – F 2) R – F > R– Cl > R – Br > R –I
3) R– Cl > R– Br > R– I > R – F 4) R – Br > R – I > R – Cl > R – F
19. A mixture of 1-chloropropane and 2-chloropropane when treated with alcoholic KOH gives
1) prop-1-ene 2) prop-2-ene
3) A mixture of prop-1-ene and prop-2-ene 4) propanol
167
Br
20. The major product of the following reaction is 
NaOMe
MeOH

OMe
1) 2)
OMe
3) 4)
21. The order of reactivities of methyl halides in the formation of Grignard reagent is :
1) CH3I > CH3Br > CH3Cl 2) CH3Cl > CH3Br > CH3I
3) CH3Br > CH3Cl > CH3I 4) CH3Br > CH3I > CH3Cl
Br + Mg   H2 O   
 A  
22.
dryether
 B . The product (B) is
MgBr OH
1) 2) 3) 4)
23. C6 H 5 Cl  2NaOH 

(i) 623K/300 atm
(ii) H 
  X  . The product (X) is
1) C6H5 – C6H5 2) C6H5 – OH 3) C6H5 – O – C6H5 4) C6H5 – COONa

24. Which of the following compound undergo nucleophilic substitution reaction most easily?
Cl Cl Cl
Cl
1) 2) 3) 4)
OCH3 CH3 NO2
25. Toluene reacts with a halogen in the presence of iron (III) chloride giving ortho and para halo com-
pounds. The reaction is :
1) Electrophilic elimination reaction
2) Electrophilic substitution reaction
3) Free radical addition reaction
4) Nucleophilic substitution reaction
168
26 The Wurtz-Fittig reaction involves condensation of:

1) two molecules of aryl halides
2) one molecule of each of aryl halide and alkyl-halide
3) one molecule of each aryl halide and phenol
4) two molecules of aralkyl halides
27. Which of the following reactions is not correctly matched?
1) 2C 2 H 5 Br  2Na  
dry ether
 C 4 H10  2NaBr; Wurtz reaction
2) CH 3 Br  AgF 
 CH 3 F  AgBr ; Etard reaction
3) C6 H 5 Br  2Na  BrC 2 H 5 

dry ether
C 6 H 5C 2 H 5  2NaBr ; Wurtz Fittig reaction
4) 2C 6 H 5 Br  2Na  
dry ether
 C 6 H 5  C 6 H 5  2NaBr ; Fittig reaction
28. Chloroform is kept in dark coloured bottles because
1) It reacts with clear glass
2) It undergoes chlorination in transparent glass bottles
3) It is oxidised to poisonous gas, phosgene in sunlight
4) It starts burning when exposed to sunlight
29. Which compound among the following is manufactured from tetrachloro methane by Swarts
reaction?
1) Gammaxene 2) Chloroform 3) DDT 4) Freon 12
30. How many  -electrons are present in DDT?
1) 10 2) 12 3) 14 4) 8
169
KEY WITH HINTS

LEVEL - I
CH3
1. 4 CH3 C CH2 CH2Cl
CH3
2. 3 Halogen atom is bonded to an sp3 hybridised carbon atom next to an aromatic ring.
3. 3 CH3 CH2CH = CH
Cl
1-chlorobut-1-ene
4. 1
1 2 3 4 5
5. 2 H3C CH2 CH CH2 CH3
Br
6. 2
7. 1 All the hydrogen atoms in 2, 2-dimethyl-propane are equivalent, hence it can form only one
monochlorinated product.
8. 4 The reaction of toluene with chlorine in the presence of iron and carried out in absence of light,
so the substitution occurs in the benzene ring. The –CH3 group of toluene is o and p-directing
then product is the mixture of (2) and (3) i.e., o-chlorotoluene and p-chlorotoluene.
CH3 CH3 CH3
Cl
+ Cl2 
Fe
+
o-chlorotoluene
Toluene
Cl
p-chlorotoluene
9. 3
10. 3 Alkenes undergo electrophililc addition with hdyrogen halide.
Br
CH2 +   CH3

HBr
11. 4 CH3 CH Markownikoffs
C CH3
addition
CH3 CH3
2-bromo-2-methyl propane
12. 2
170
13. 3 Swarts reaction, CH 3  Cl  AgF 

 CH 3 F  AgCl ; CH 3  Br  AgF 
 CH 3 F  AgBr
14. 3
15. 3 The reactivity order of alkyl halides for SN2 reaction is methyl > 1o > 2o > 3o halides. So complete
stereochemical inversion will take place in case of CH3Cl.
16. 2 Primary alkyl halides prefer to undergo SN2 reaction.
17. 2 SN1 reaction rate depends upon the stability of the carbocation.
Me Me Me Br
Me
Br > Br >
(C) (A)
(B)
18. 3
19. 4
Cl
20. 3 CH3 C CH3 

alc.KOH
 CH3 C CH2
CH3 CH3
2-Methylprop-1-ene
21. 1 The product is the alkene which has the greater number of alkyl groups attached to the doubly
bonded carbon atoms.
22. 2 In dehydro halogenation using alcoholic NaOH or KOH.
Cl OH
23. 1  NaOH 

300 C o
 + NaCl
CH3
CH
anhyd. CH3
24. 1 CH Cl 

AlCl3
+ CH3
Cumene
CH3
But in chlorobenzene, bromobenzene, chloroethene lone pair of halogen are delocalized with 
bonds. So attain double bond character.
25. 2 The compound is diphenyl.
26. 4
27. 3 Carbonyl chloride is also known as phosgene.
28. 3
29. 3
30. 2
171
LEVEL - II
1. 3
2. 1
3. 3 Halogen atoms are present on the same carbon atom.
4. 2 In chlorobenzene C – Cl bond acquires partial double bond character due to resonance.
5. 1
6. 4
7. 3 Direct halogenation is not preferred. A mixture of mono, di, tri and tetra halogen substituted
products are formed which are difficult to separate.
8. 2 In this reaction, AlCl3 is a catalyst which activate the chlorine molecule to show heterolytic cleav-
age. AlCl3 is electron deficient molecule and form AlCl 4 and Cl+ when reacts with Cl2. This Cl+
electrophile attacks on electron rich benzene ring.
Cl
 [AlCl 4 ]  Cl ;
AlCl3  Cl2  + Cl+ 

Chlorobenzene
9. 2 C6 H 5 NH 2 
NaNa 2 / HCl
 C6 H 5 N 2 Cl 
Cu 2 Cl 2
  X  C 6 H 5  Cl  Y 
10. 1 Halogen exchange reactions are those reactions in which one halide replaces another. In option
(1) halogen (–X) is replaced by iodine. This reaction is named as Finkelstein reaction.
11. 2 Though polar, alkyl halides cannot form hydrogen bonds with water hence they are insoluble in
water
12. 1 Dipole moment of CH3Cl is the largest.
13. 3
14. 2 The reactivity of different alkyl halides towards SN2 reaction decrease in the order : methyl
halides > 1o halides > 2o halides > 3o halides. Since, 2-bromo-2-methylbutane is a tertiary
bromide hence it is least reactive among the given.
15. 4
16. 3 The carbon atom is simultaneously bonded to incoming nucleophile and outgoing leaving group.
 
17. 1 In the given compound, C6H5CH2Br carbocation is C 6 H 5 C H 2 . This carbocation C 6 H 5 C H 2 is a
stable carbocation due to resonance therefore, it show SN1 mechanism.
18. 1 The alkyl halides are very reactive due to highly polarised C – X bond with a large difference in
electronegativities of carbon and halogen atoms. The order of reactivity is iodides > bromides >
chlorides > fluorides.
Cl
19. 1 CH3 CH2 CH2 Cl + CH3 CH CH3 

alc.KOH
 2CH 3  CH  CH 2
1-chloropropane prop 1 ene
172
Br
20. 4 
NaOMe
MeOH
 (E2)
(Major)
21. 1
Br MgBr
22. 3 
Mg
Ether
 
H 2O

(A) (B)
23. 2
Cl Cl Cl Cl
24. 4
NO2 CH3 OCH3
25. 2 Toluene reacts with a halogen in the presence of iron (III) chloride giving ortho and para halo
compounds. The reaction is electrophilic substitution reaction.
26. 2 Reaction between alkyl halide, aryl halide and sodium in presence of ether is known as Wurtz
fitting reaction.
27. 2
28. 3 Chloroform gets oxidised by air in sunlight to poisonous phosgene gas.
2CHCl3  O 2 
hv
 2COCl 2  2HCl
Phosgene
29. 4
Cl
Cl
30. 2 Cl Cl
Cl H
173
CHAPTER - 07
ALCOHOLS, PHENOLS AND ETHERS
INTRODUCTION
Alcohols and phenols are compounds containing one or more hydroxyl groups directly attached to carbon
atoms of aliphatic and aromatic hydrocarbons respectively. The subsitution of a hydrogen atom in a
hydrocarbon by an alkoxy or aryloxy group (R–O/Ar–O) yields another class of compounds called ethers.
Alcohols, phenols, and ethers find wide applications in industry as well as in day-to-day life. Starch, cellulose,
sugars, etc., are all made up of compounds containing hydroxyl groups. Ordinary spirit, used as antiseptic
for cleaning wounds, sterilising skin, as solvent in wood polish, and in alcoholic beverages is chiefly ethanol.
Glycerol is used as sweetner and in pharmaceutical and toilet preparations. Phenol, commonly called carbolic
acid is an antiseptic. Chloroxylenol is the active ingredent of dettol. Lysol, a saponified preparation of cresol
with vegetable oil is a disinfectant for domestic and hospital use. Diethyl ether was one of the first anaesthetics
used in surgery. Being an excellent solvent for nonpolar substances, it is used in industry and in the laboratory.
CLASSIFICATION
Aliphatic alcohols, Aromatic alcohols and Phenols. Aliphatic alcohols are those in which the hydroxyl
group is attached to an aliphatic carbon. Aromatic alcohols have the hydroxyl group attached to the side
chain of an aromatic hydrocarbon. Phenols are formed when one or more hydrogen atoms in benzene ring
are replaced by –OH groups.
Classification of Alcohols and Phenols
1. Classificationbased on number of hydroxyl groups. Based on the number of –OH groups
present in a molecule, alcohols and phenols are classified into monohydric, dihydric, trihydric, or
polyhydric.
2. Classification based on type of hybridisation. Monohydric alcohols can be further classified based
on the type of hybridisation of the carbon atom to which the hydroxyl group is attached.
174
a) Compounds with –OH bonded to sp3-hybridised carbon atom. The sp3-hybridised carbon atom
to which the -OH group is attached may be primary (1º), secondary (2º) or tertiary (3º).
i) Allylic alcohols. In these alcohols, the –OH group is attached to an sp3-hybridised carbon next to the
carbon-carbon double bond (allylic carbon). It may be 1o, 2o or 3o.
ii) Benzylic alcohols. In these compounds, the hydroxyl group is bonded to sp3 carbon next to an aromatic
ring system. Benzylic alcohols can also be primary, secondary or tertiary.
Classification of Ethers
Ethers have the general structural formula R-O-R´. They are isomeric with alcohols. Ethers are classified
as:
i) Simple or symmetrical ether. When the alkyl/aryl groups present in ether are the same, it is called a
simple ether or symmetrical ether.
CH3  O  CH3 CH3CH 2  O  CH 2CH3 C6 H 5  O  C 6 H 5
Methoxymethane (Dimethyl ether) Ethoxyethane (Diethyl ether) Diphenyl ether
ii) Mixed or unsymmetrical ether. When the alkyl/aryl groups are different, it called mixed ether or
unsymmetrical ether.
CH3  O  CH 2CH3 CH3  O  C6 H5 C6H5  O  CH 2  C6 H5
Methoxyethane (Ethylmethyl ether) Methyl phenyl ether Benzyl phenyl ether
NOMENCLATURE OF ALCOHOLS AND PHENOLS

Monohydric alcohols. The general formula of monohydric alcohols is CnH2n+1OH.
i) Common name. Monohydric alcohols are called alkyl alcohol, e.g., methyl alcohol, ethyl alcohol, etc.
175
ii) IUPAC name. IUPAC name of alcohol is obtained by the scheme, “Alkane – ‘e’ + ‘ol’ = Alkanol”, e.g.,
CH3OH (methanol), CH3CH2OH (ethanol), etc.
For naming alcohols containing substituents, the longest carbon chain is numbered from the end
nearest to the hydroxyl group. The positions of the –OH group and other substituents are indicated by
the numbers of carbon atoms to which these are attached.
Table - 01 Common name and IUPAC name of alcohols
Cyclic alcohols are named by adding the prefix ‘cyclo’ to the common or IUPAC name of the straight
chain alcohol. The positions of the substituents are indicated by Greek alphabets (in common system)
or arabic numerals (in IUPAC system) starting from the carbon atom bearing the -OH group.
Di and polyhydric alcohols. For naming polyhydric alcohols, the ‘e’ of alkane is retained and the ending ‘ol’
is added. The number of –OH groups is indicated by the prefix, di, tri, etc., before ‘ol’. Thus, dihydric alcohols
are called alkanediols, and trihydric alcohols are called alkanetriols, with the position of the -OH groups
indicated using numerals.
Nomenclature of Phenols. The simplest hydroxy derivative of benzene is called phenol in common as
well as IUPAC scheme. In substituted, the terms ortho (1, 2 disubstituted), meta (1, 3 disubstituted) and
para (1, 4 disubstituted) are used in common names. In IUPAC system, the positions of the substituents are
indicated by arabic numerals, with the numbering starting from the carbon bearing the –OH group.
176
Nomenclature of Ethers
The common names of ethers are derived from the names of alkyl/aryl groups written as separate words in
alphabetical order and adding the word ‘ether’ at the end. If both the alkyl groups are the same, the prefix ‘di’
is added before the name of the alkyl group.
In the IUPAC system, ethers are named as alkoxyalkanes. The ethereal oxygen along with the smaller alkyl
group forms the alkoxy group while the larger alkyl group is considered as a part of the alkane.
CH2 CH2
OCH3
O
2-Ethoxy propane (Ethyl isopropyl ether) Methoxy benezene (Anisole) Ethylene oxide (Oxirane)
Structure of Functional groups in Alcohols, Phenols and Ethers In alcohols, the oxygen of the –OH is
attached to carbon by a sigma bond formed by the overlap of sp3-hybridised orbitals of carbon and oxygen.
The bond angle is slightly less than the tetrahedral angle (109° 28') due to repulsion between the lone-pairs
on oxygen. In phenols, the –OH group is attached to sp2-hybridised carbon of an aromatic ring, therefore,
the carbon– oxygen bond length (136 pm) is slightly less than that in methanol. This is due to (i) partial
double bond character on account of conjugation of unshared electron pair of oxygen with the aromatic ring
and (ii) sp2-hybridised state of carbon to which oxygen is attached. In ethers, the two bond-pairs and two
lone-pairs of electrons on oxygen are approximately in a tetrahedral arrangement. The bond angle is slightly
greater than the tetrahedral angle due to repulsion between the two bulky (–R) groups. The C–O bond length
(141 pm) is nearly the same as in alcohols.
Figure - 01 Structures of alcohol, phenol and ether
177
METHODS OF PREPARATION OF ALCOHOLS

1. From alkenes
a) Acid catalysed hydration. Alkenes undergo acid catalysed hydration to form alcohols. In unsymmetrical
alkenes, addition take place according to Markovnikov’s rule.
H 
CH 2 = CH2  CH3CH2OH ; CH 3  CH  CH 2  H 2O 
H
 CH 3  CH  CH3
Ethene Ethanol
OH
Mechanism : (i) Protonation of alkene by electrophilic attack of H3O to form carbocation.
+
(ii) Nucleophilic attack of water on carbocation.
(iii) Deprotonation to form an alcohol.
b) Hydroboration-oxidation. Diborane (B2H6) adds to alkenes to form trialkyl boranes which on oxidation
using H2O2 and aqueous NaOH produce alcohols.
CH CH CH
CH 3CH  CH 2  (H  BH 2 ) 2 
 CH3CH 2CH 2 BH 2 
3 2
(CH3CH 2 CH 2 )2 BH
CH CH CH 3H O , OH 

3 2
(CH 3CH 2CH 2 )3 B 
2 2
 3CH3CH 2 CH 2  OH  Bi(OH)3
H 2O
Pr opan 1ol
The product of hydroboration-oxidation reaction is equivalent to addition of water to alkene against

Markovnikov’s rule.
2. From carbonyl compounds
i) By reduction of aldehydes, and ketones. Alcohols are produced by the reduction of aldehydes,
and ketones using H2 in presence of a catalyst (Pt, Pd, Ni, Ru, NaBH4, LiAlH4, or sodium and ethanol).
Aldehydes give 1o alcohols, whereas ketones give 2o alcohols.
NaBH H /Pd
CH 3CH 2CHO 
4
 CH3CH 2CH 2OH ; C6 H 5COCH 3 
2
C6 H5CHOHCH3
o
1 alcohol 2o alcohol
ii) By reduction of carboxylic acids, and esters. Carboxylic acids on reduction using LiAlH4 produce
1o alcohols.
(i)LiAlH
R  COOH 
(ii)H O
4
R  CH2OH
2
1o alcohol
Since LiAlH4 is expensive, acids are reduced to alcohols by converting them to the esters, followed by
reduction using hydrogen in presence of catalyst (commercial preparation).
178
R 'OH H
RCOOH 
H
RCOOR '  2
catalyst
 RCH 2OH  R 'OH
Acid Ester
Esters produce alcohols on reduction.

H
CH3CH 2COOC2 H5 
2
 CH3CH 2CH 2OH  C2 H5OH
catalyst
Ethylpropanoate Pr opanol Ethanol
3. From grignard reagents. Carbonyl compounds form addition product with RMgX, which on hydrolysis
produce alcohols. Formaldehyde produce 1o alcohols, aldehydes other than formaldehyde produce 2o
alcohols and ketones produce 3o alcohols.
HCHO  RMgX 
 R  CH 2  OMgX 
H 2O
 R  CH 2OH  Mg  OH  X
R R
R  CHO  RMgX 
 R  CH  OMgX 
H 2O
 R  CHOH  Mg  OH  X
R R
RCOR  RMgX 
 R  C  OMgX 
H2 O
 R  C  OH  Mg  OH  X
R R
The first step of the reaction is the nucleophilic addition of Grignard reagent to the carbonyl group to
form an adduct. Hydrolysis of the adduct gives alcohol.
METHODS OF PREPARATION OF PHENOLS

Phenol, also known as carbolic acid was earlier isolated from middle oil fraction of coal tar.
i. From Haloarenes (Dow’s process). It is prepared from chlorobenzene by fusion with NaOH at 623
K and 320 atm pressure followed by acidification.
ii. From Benzene. Benzene is sulphonated to benzenesulphonic acid using fuming H2SO4. The sulphonic
acid formed is heated with molten NaOH and the product is acidified to get phenol.
179
iii. From diazonium salts. Diazonium salt is obtained from aniline by reaction with NaNO2 and HCl
below 278K (diazotisation). Acidification of the sodium salt gives phenol.
iv. From cumene. Phenol is manufactured from the hydrocarbon, cumene (isopropylbenzene). Cumene
is oxidised with air to form cumene hydroperoxide. The hydroperoxide is converted to phenol and
acetone by treating it with dilute acid. Acetone is a valuable by-product of the reaction.
Physical Properties of Alcohols and Phenols

(i) The first eleven members of monohydric alcohols are colourless liquids. The higher members are
solids.
(ii) For monohydric alcohols, density is directly proportional to molar mass. Density of monohydric alcohols
are less than that of H2O.
(iii) Boiling points of alcohols are much higher than that of the corresponding aliphatic hydrocarbons and
haloalkanes due to hydrogen bonding : CH4 (90K) < CH3Cl (249K) < CH3Br (278K) < CH3OH (337.5K).
Among isomeric alcohols, b.p. decrease with branching due to decrease in surface area; 1° >2° >
3°>.
v) Solubility of alcohols and phenols in water is due to their ability to form hydrogen bonds with water
molecules. Solubility decreases with increase in size of alkyl/aryl (hydrophobic) groups (methyl alcohol,
ethyl alcohol, propyl alcohol and t-butyl alcohol are completely soluble in H2O).
CHEMICAL PROPERTIESOF ALCOHOLS AND PHENOLS
Alcohols are versatile compounds which can act as nucleophiles as well as electrophiles.
i) The bond between O–H is broken when alcohols react as nucleophiles.
ii) Protonated alcohols act as electrophiles. When they react as electrophiles, bond between C–O is
broken.
180
Based on the cleavage of O–H/C–O bond, reactions of alcohols and phenols may be divided into two
groups:
Reactions involving cleavage of O-H bond
1. Acidity of alcohols and phenols.
i) Reaction with metals. Alcohols and phenols are acidic. They react with metallic Na, K, Al, etc., to
form alkoxides or phenoxides liberating dihydrogen.
2ROH  2Na 
 2RONa  H 2 ; 2C 6 H 5OH  2Na 
 2C 6 H 5ONa  H 2
6(CH3 )3 C  OH  2Al 
 2[(CH3 )3 CO]3 Al  3H 2
tert Butyl alcohol Alu min ium tert  butoxide
Phenols are more acidic than alcohols. They react with aqueous NaOH to form sodium phenoxide.
The above reactions show that alcohols and phenols are acidic in nature. In fact, they are Bronsted
acids, i.e., they can donate a proton to a strong base.
ii) Acidity of alcohols. Acidity of alcohols is due to polar nature of O–H bond. An electron-releasing
group (–CH3, –C2H5) increases the electron density on the oxygen and decreases the polarity of the
O-H bond. This decreases the acid strength. Thus, the acidity of alcohols follows the order :
CH 3OH  1o  2o  3o .
However, alcohols are weaker acids than water. This is illustrated by the reaction of water with an
alkoxide.
Since alcohols are weaker acids than water, alkoxide is a stronger base compared to hydroxide. Due
to the presence of lone pairs of electrons, alcohols act as Bronsted bases. Basic strength decreases
as:
181
iii) Acidity of phenols. Phenols are acidic because the phenoxide ion is stable due to resonance. The
hydroxyl group in phenol is directly attached to sp2 hybridised carbon of benzene ring, which acts as
an electron withdrawing group. Due to this, the charge distribution in phenol makes the oxygen of –OH
group positive.
Figure - 02 Resonating structures of phenol

Eventhough both phenol and phenoxide ion exhibit resonance, the resonating structures of phenol are
less stable because of charge separation.
Figure - 03 Resonating structures of phenoxide ion

Effect of substituents on acidity of phenol. Acidity of phenol is influenced by substituents in the
aromatic ring system. Electron withdrawing groups like -NO2, -CN, -X (halogen), etc., enhances acidic
strength. The influence of the substituent is more pronounced at ortho and para positions. This is due
to delocalisation of the negative charge in the phenoxide ion. Due to -R (resonance effect) and -I
(inductive effect) effects, electron withdrawing group (EWG) withdraws electron concentration, disperses
the negative charge, stabilises the phenoxide ion w.r.t. phenol and thus increases acidic strength.
Electron releasing groups such as -R(alkyl), -NH2, -OH, OR(alkoxy), etc., do not favour the formation
of phenoxide ion and results in decrease of acid strength. E.g., cresols are less acidic than phenol.
Due to +I effect, electron donating group (EDG) donates electron concentration, enhances the negative
charge, destabilises the phenoxide ion w.r.t. phenol and thus decreases acidic strength.
2. Reaction with carboxylic acids (Esterification). The reaction is carried out in presence of a small
quantity of conc. H2SO4 or dry HCl gas as catalyst.


H
ROH  R 'COOH 
 ROCOR ' H 2O
Alcohol Acid Ester
H

C H3CH 2OH  CH3COOH  CH3COOCH 2CH3  H 2O
Ethanol Ethanoic acid Ethyl ethanoate ( Ethyl acetate )
3. Reaction with acid chlorides and acid anhydrides. Alcohols and phenols react with acid chlorides
and acid anhydrides to give esters.

Pyridine
Ar / ROH  R 'COCl  Ar / ROCOR ' HCl
Acid chloride Ester


H
Ar / ROH  (R 'CO)2 O 
 Ar / ROCOR ' R 'COOH
Acid anhydride Ester Acid
182
This reaction is called acylation. When the acid halide and the acid anhydride used are acetyl chloride
and acetic anhydride, the reaction is termed acetylation. Esterification of alcohols with acid chloride
is done in presence of bases like pyridine to remove HCl formed. The introduction of benzoyl group
(C6H5CO–) is called bezoylation. Benzoyl derivatives or esters of phenol can be made by reaction of
phenol with benzoyl chloride in presence of 10% NaOH solution. This is known as Schotten-Baumann
reaction.
Esterification of salicylic acid gives acetyl salicylic acid, commonly known as aspirin.
Reactions involving C–O bond cleavage. Reactions involving cleavage of C–O bond occur only in alcohols.
Phenols show this type of reaction only with zinc. The order of reactivity of alcohols is : 3o > 2o > 1o.
1. Reaction with hydrogen halides. Alcohols react with hydrogen halides to form alkyl halides. The
order of reactivity is : HI > HBr > HCl.
ROH + HX 
 RX  H 2 O
Lucas test. The difference in reactivity (tertiary > secondary > primary) of alcohols with HCl is used to
distinguish them from one another by Lucas test. Alcohols are soluble in Lucas reagent (conc. HCl
and ZnCl2) while their halides are insoluble and produce turbidity. In case of tertiary alcohols, turbidity
appears immediately. Primary alcohols do not produce turbidity at room temperature.
2. Dehydration. Dehydration is brought about by protic acids like conc. H2SO4 or H3PO4.
This elimination reaction is favoured by high temperature. The ease of dehydration among three types
of alcohols is 3o > 2o > 1o. Thus, the dehydrating conditions become milder as we proceed from 1o to
3o alcohols.
conc.H SO
CH3CH 2OH 2
443K
4
 H2C  CH 2  H 2O
Ethanol Ethene
85%H PO
CH 3CH(OH)CH 3 3
440K
4
 CH3CH  CH 2  H 2O
Pr opan  2ol Pr opene
20%H PO
(CH3 )3 C  OH 3
358K
4
 (CH3 )2 C  CH 2  H 2O
2Methylpropan 2ol 2Methylpropene
183
Mechanism. Mechanism of dehydration involves the following steps :
Step 1. Alcohol is protonated to form oxonium ion.
Step 2. H2O molecule is removed from oxonium ion and a carbocation is formed.
Step 3. Carbocation eliminates a proton to form ethene.
The forward rection is favoured by the removal of ethene from the system.
The dehydration of alcohols takes place in accordance with Saytzeff rule, i.e., the more highly
substituted alkene is always the major product.
conc. H SO
CH3CHOHCH 2CH3 
2 4
 CH3CH  CHCH3  CH3CH 2CH  CH 2
433 443K
2 Butanol 2 Butene (80%) 1Butene (20%)
If the major product is capable of exhibiting cis- trans isomerism, it is always the trans-isomer that
predominates. For example, in the above dehydration, about 70% of the product formed is trans-2-
butene.
i) Oxidation. Alcohols undergo oxidation resulting in the formation of a carbon-oxygen double bond.
These are also known as dehydrogenation reactions as these involve loss of dihydrogen from the
alcohol. Oxidation can be carried out using neutral, acidic or alkaline KMnO4, acidified K2Cr2O7 or dil.
HNO3.
a) Primary alcohol. Depending on the oxidising agent used, primary alcohol is oxidised to aldehyde
which in turn is oxidised to carboxylic acid. Strong oxidising agents such as acidified/neutral/alkaline
KMnO4, acidified K2Cr2O7, and dil. HNO3 oxidise primary alcohols to carboxylic acids.
184
K Cr O  dil.H SO [O]
CH 3CH 2  OH 
2 2 7
H O
2 4
 CH3CHO  CH3COOH
2
Aacetaldehyde Acetic acid
PCC
CH3  CH  CH  CH 2OH  CH3  CH  CH  CHO
b) Secondary alcohols. Secondary alcohols can be oxidised to ketones using acidified K2Cr2O7 or
Na2Cr2O7.
Chromic anhydride (CrO3) is used for getting ketones from secondary alcohols
c) Tertiary alcohols. Tertiary alcohols are oxidised by strong oxidising agent like KMnO4 at high
temperature to a mixture of carboxylic acids containing lesser number of carbon atoms.
ii) Catalytic dehydrogenation of alcohols. Alcohols undergo dehydrogenation when passed over copper
at 573 K (industrially silver is employed for oxidation).Primary alcohols are dehydrogenated to
aldehydes, secondary alcohols are dehydrogenated to ketones and tertiary alcohols are dehydrated
to alkenes:
Cu Cu
RCH 2OH 
573K
 RCHO  H 2 ; R 2CH  OH 
573K
 R 2C  O  H 2
Cu
R 3C  OH 
573K
 R 2C  CH 2  H 2
REACTIONS OF PHENOLS
Electrophilic aromatic substitution. The reactions that take place on the aromatic ring are electrophilic
substitution reactions. In phenols, the –OH group attached to the benzene ring activates it towards electrophilic
substitution. It also directs the incoming group to the ortho and para positions in the ring as these become
electron rich due to resonance effect.
i) Halogenation. On treating phenol with bromine, different products are formed under different conditions.
(a)When the reaction is carried out in solvents of low polarity such as CHCl3 or CS2 at low temperature,
monobromophenols are formed.
185
(b)When phenol is treated with bromine water, 2,4,6-tribromophenol is formed as white precipitate.
ii) Sulphonation. Phenol, on heating with conc. H2SO4 gives o-phenol sulphonic acid and p-phenol
sulphonic acid
i) Nitration. Nitration of phenol with dil. HNO3 at low temperature (298 K) produce a mixture of ortho-
and para- nitrophenols.
The products are separated by steam distillation. o-nitro phenol is steam volatile due to intramolecular
hydrogen bonding and p-nitro phenol is less volatile due to intermolecular hydrogen bonding.
ii) Nitration using concentrated nitric acid produce 2, 4, 6 tri nitrophenol (picric acid).
186
iii) Kolbe’s reaction. Sodium salt of phenol react with CO2 under pressure at 450K to form sodium salt
of salicylic acid. The free acid is formed by acidification.
iv) Reimer-Tiemann reaction. Phenol reacts with CHCl3 and alkali at 340K to form phenolic aldehyde.
This reaction is known as Reimer-Tiemann reaction. This is an example of a formylation reaction. A
benzal chloride derivative is initially formed, which is hydrolysed to the aldehyde in alkaline medium.
v) Friedel-Crafts Reaction. Phenols react with alkyl halides in presence of anhydrous AlCl3 to form
alkyl substituted phenols. Usually the p-isomer is the major product.
vi) Reaction with zinc dust. Phenol on distilling with zinc dust produces benzene.
vii) Oxidation. When phenol is oxidised with chromic acid benzoquinone is formed (in the presence of
air, phenols are slowly oxidised to dark coloured mixtures containing quinones).
187
COMMERCIALLY IMPORTANT ALCOHOLS
1. Methanol (Methyl alcohol, Wood spirit, Carbinol). It was called wood spirit because it was obtained
during distructive distillation of wood. Iit is prepared by catalytic hydrogenation of carbon monoxide.
ZnO Cr O
CO g   2H 2 g   2 3
573673K,200300bar
CH 3OH
It is a colourless poisonous liquid boiling at 337K. When consumed in small quantities, it causes
blindness and in larger quantities even death.
Uses. As solvent for paint, varnishes, etc. For the manufacture of HCHO. For denaturing ethyl alcohol.
As antifreeze in automobile radiators. As substitute for petrol. In the manufacture of perfumes.
The antidote for methanol poisoining is ethyl alcohol.
2. Ethanol (Ethyl alcohol, Grain alcohol). Prepared by fermentation of molasses, starch, grapes, etc.
a) From molasses. To molasses (mother liquor left after the crystallization of sugar from sugarcane
juice) or starch solution or grape juice, yeast is added and the temperature is maintained at about
305K. Yeast supplies the enzymes invertase and zymase which bring about fermentation.
Invertase
C12 H 22O11  H 2 O  C6 H12 O6  C6 H12O6
 Glu cos e   Fructose 
Zymase
C 6 H12 O 6  
 2C 2 H 5OH  2CO 2
Fermentation takes place in anaerobic conditions. The action of zymase is inhibited when the percentage
of alcohol formed exceed 14%. The dilute solution of alcohol obtained by fermentation is called ‘wash’.
Wash is fractionally distilled to get rectified spirit which is 95.6% alcohol. If air happens to enter to the
fermentation mixture, the wine formed becames sour due to oxidation of ethanol to ethanoic acid.
b) From starch. The enzyme diastase from germinated barley converts starch to maltose.
Diastase
2(C6 H12O5 )n  nH 2 O 
 n C12 H 22O11
Starch Maltose
Maltase from yeast, converts maltose to glucose and zymase converts glucose to alcohol.
Maltase
n C12 H 22O11  H 2O 
 2 C6 H12O6 ; C 6 H12 O 6 
Zymase
  2C 2 H 5OH  2CO 2
Maltose Glu cos e
c) Manufacture of Ethanol. Nowadays ethanol is manufactured by the hydration of ethene.

Catalyst
CH 2  CH 2  H 2O 
 CH3CH 2OH
573K, 200atm
Ethene Ethylalcohol
Propeties. Ethanol is a colourless liquid boiling at 351 K. It is used for the preparation of large number
of compounds and also as a solvent in paint industry.
Denatured spirit. Commercial alcohol made unfit for drinking purpose by adding copper sulphate,
methyl alcohol (methylated spirit), pyridine, etc., is known as denatured spirit.
188
Absolute alcohol. 100% pure alcohol is known as absolute alcohol. It is obtained from rectified spirit
by distilling with calculated quantity of benzene to remove remaining water by forming ternary mixture.
Power alcohol. A mixture of 80% petrol and 20% ethanol along with small amount of benzene is used
as petrol substitute. This mixture is called power alcohol.
Uses of alcohol. (i) As antiseptic in the form of rectified spirit. (ii) As solvent for paints varnishes,
lacquers, dyes, cosmetics, cough syrups etc. (iii) In the manufacture of ether, chloroform, iodoform,
acetic acid, acetaldehyde, etc. (iv) As a beverage. (v) In thermometers, sprit lamps and spirit levels.
(vi) As antifreeze in automobile radiators. (vii)As solvent in the extraction and purification (by
crystallisation) of substances.
Uses of Phenol. (i) As antiseptic and disinfectant in lotions and soaps. (ii) Hexachlorophene, a phenolic
compound is used in mouthwashes, deodorant soaps and medicinal skin cleaners. (iii) In the
manufacture of medicines like aspirin, salol, salicylic acid, phenacetin, methyl salicylate, etc. (iv) In
the manufacture of phenol-formaldehyde resins like Bakelite.
PREPARATION OF ETHERS
i) From alcohols. Alcohols undergo dehydration in presence of protic acids such as H2SO4 and H3PO4
to give either alkenes or ethers depending on the reaction conditions. E.g., when ethyl alcohol is
heated with H2SO4, ethene is the major product at 443 K and ethoxyethane is the major product at
413 K.
conc.H SO
2 CH3  CH 2OH 2
413K
4
 CH3CH 2  O  CH 2CH3  H 2O
Ethoxyethane
Mechanism. Dehydration of alcohol to ether in presence of protic acid is an SN2 reaction involving the
attack of alcohol molecule on a protonated alcohol molecule.
Step (i): Alcohol is protonated by H+ from protic acid to the oxonium salt (protonated alcohol).
This step is slow and and therefore, the rate-determining step.

Step (ii): Nucleophilic attack of an unprotonated alcohol on protonated alcohol produces protonated
ether.
Step (iii): De protonation of protonated ether forms ether as the product.
This step is fast and hence do not affect the rate of the reaction. Dehydration of alcohol is suitable for
the preparation of ethers having primary alkyl groups only. When the temperature is high and alcohol
is sterically hindered, alkene is obtained as the major product.
This method cannot be used for preparing unnsymmetrical ethers since complex mixtures are obtained.
conc. H SO
ROH  R 'OH 
2 4
 ROR  ROR ' R 'OR '
189
Dehydration of secondary and tertiary alcohols to corresponding ethers is unsuccessful as elimination

competes over substitution and as a consequence, alkenes are formed (the reaction follows SN1
pathway).
ii) Williamson’s Synthesis. This is a laboratory method for the preparation of symmetrical and
unsymmetrical ethers. In this method, an alkyl halide reacts with sodium alkoxide.
RONa  XR 
 R  O  R  NaX ; RONa  XR ' 
 R  O  R ' NaX
The reaction proceeds through SN2 mechanism and alkoxide is the nucleophile. It attacks the primary
halide to give ether.
Ethers containing secondary or tertiary alkyl goups may also be prepared by this method.
Primary halides react with alkoxides to form ethers, but tertiary halides with alkoxides produce alkenes.
This is because alkoxides are strong bases as well as nucleophiles. With tertiary halides, the strongly
basic alkoxide produces alkene by elimination reaction.
Secondary alkyl halides undergo elimination rather than substitution giving a mixture of products.
Williamson’s method is suitable for the preparation of alkyl aryl ethers (phenolic ethers). In this reaction,
phenoxides react with haloalkane.
Physical properties of ethers

Dimethyl ether and ethylmethyl ether are gases while other lower homologues are liquids with characteristic
smell. Due to higher electronegativity of oxygen, ethers are slightly polar. As the C – O – C angle is 110°, the
two C – O dipoles do not cancel each other. Therefore, ethers have dipole moment between 1.15 -1.3 D.
Eventhough polar, their solubilities are comparable to those of alkanes of comparable molecuar masses.
The solubility of isomeric alcohols are higher compared to ether since alcohols can form hydrogen bonds
with water.
Ethers containing up to three carbon atoms are soluble in water. Dimethyl ether is completely miscible with
water while diethyl ether is soluble up to 7.5 mL per 100 mL water. The solubility of lower ethers is due to the
formation of hydrogen bonds with water.
190
Chemical properties of ethers

1. Cleavage of C–O bond. The cleavage of C-O bond in ether takes place under drastic conditions with
excess of hydrogen halide (HBr or HI). The reaction of dialkyl ether gives two molecules of alkyl halide.
373K
R  O  R  HX  R  OH  R  X ; R  OH  HX 
 R  X  H 2O
373K
C2 H 5  O  C2 H5  2HI  2R  I  H 2O
Mechanism. Step - 1. Being Lewis bases, ethers undergo protonation to form oxonium ions.
The reaction takes place with HBr or HI because these reagents are sufficiently acidic and Br- and I-
are good nucleophiles.
Step - 2. Being a good nucleophile, I- attacks the least substituted carbon of the oxonium ion from step
1 and displaces a molecule of alcohol by SN2 mechanism.
Step - 3. With excess of HI at high temperature, ethanol reacts with another molecule of HI to form
ethyl iodide.
The order of reactivity of halogen acids follows the sequence :HI > HBr > HCl.
(i) In the cleavage of mixed ethers, the alcohol and alkyl iodide formed depend on the nature of alkyl
groups. When primary or secondary alkyl groups are present, the lower alkyl group forms the alkyl
iodide (SN2 reaction) because the halide ion attacks the smaller alkyl group due to steric hindrance.
For example, methyl isopropyl ether gives isopropyl alcohol and methyl iodide when treated with HI at
373K.
(ii) If one of the alkyl groups is tertiary, the alkyl halide is formed from the tertiary alkyl group.
This is because in step 2 of the reaction, the departure of the leaving group (HO–CH3) creates a more
stable carbocation (CH3)3C+, and the reaction follows SN1 mechanism.
191
2. Electrophilic Substitution Reactions. Aromatic ethers undergo electrophilic substitution reactions.

The alkoxy group is activating and ortho-, para- directing.
i. Halogenation. Halogenation of phenylethers produce a mixture o- and p-substituted products where

para- form is the major product.
ii. Nitration. Nitration of anisole using nitrating mixture produce p-nitroanisole as the major product.
iii. Friedel craft’s reaction. Aromatic ethers undergo Friedel craft’s alkylation and acylation.
a) Alkylation. Anisole reacts with CH3Cl and anhydrous AlCl3 to form 4-methoxy toluene as major
product.
b) Acylation. With acetylchloride in presence of anhydrous AlCl3 anisole produce 4-methoxy

acetophenone as the major product.
192
QUESTIONS
LEVEL - I
1. Organic compounds containing –OH group as functional group are called
1) Phenols 2) Alcohols 3) Ethers 4) Both 1 and 2
2. Which one of the following is a dihydric alcohol?
1) Ethanol 2) Cresol 3) Glycol 4) Glycerol
3. Which of the following is a secondary alcohol?
1) Butan - 2 - ol 2) Butan - 1 - ol
3) 2 Methyl propan - 2 - ol 4) Pentan - 1 - ol
4. Total number of isomeric alcohols with formula C4H10O is
1) 2 2) 3 3) 4 4) 5
5. Identify the unsymmetric ether from the following
1) CH3 – O – CH3 2) C2H5 – O – C2H5 3) C2H5 – O – C6H5 4) C3H7 – O – C3H7
CH3
6. The common name and IUPAC name of the given compound respectively are
OH
1) o- cresol, 2- methyl phenol 2) 2- methyl phenol, o- cresol

3) m- cresol, 3- methyl phenol 4) 3- methyl phenol, m- cresol
7. The correct IUPAC name of C6H5 – O – CH3 is
1) Anisole 2) Methoxy benzene
3) Methyl phenyl ether 4) Both 1 and 2
8. Phenol is also known as
1) Hexanoic acid 2) Carbolic acid 3) Carboxylic acid 4) Benzol
9. In hydroboration oxidation reaction the reagent used with alkene is
1) HCl 2) HBr 3) B2H6 4) H2O2
10. Reduction of aldehydes with LiAlH4 give
1) Secondary alcohol 2) Primary alcohol 3) Tertiary alcohol 4) Alkene
11. Ketones react with Grignard reagents to form
1) 1o alcohol 2) 2o alcohol 3) 3o alcohol 4) Alkene
12. In the following sequence of reactions 

Oleum
 X 
1) NaOH
2)H 
Y . The compound Y formed is
1) Benzene sulphonic acid 2) Benzaldehyde

3) Phenol 4) Acetophenone
193
13. Alcohols have higher boiling points than parent hydrocarbons because of
1) Higher molecular mass
2) Presence of intermolecular hydrogen bonding
3) Presence of carbon chain
4) van der Waal’s forces
14. Which of the following is the correct order of acidity of alcohols.
1) 1o < 2o < 3o 2) 3o < 2o < 1o 3) 2o < 1o < 3o 4) 1o < 3o < 2o
15. CH3 – CH2 – CH2 – COOH + CH3 – CH2 – OH 

 X + H2O. The product X is
1) CH3 – CH2 – COO – CH2 – CH2 – CH2 – CH3
2) CH3 – CH2 – COO – CH2 – CH2 – CH3
3) CH3 – CH2 – CH2 – COO – CH2 – CH3
4) CH3 – CH2 – COO – CH2 – CH3
16. Lucas test is used to identify
1) Aldehydes 2) Ketones 3) Amines 4) Alcohols
17. Which one of the following alcohols do not answer Lucas test at room temperature?
1) Secondary alcohol
2) Primary alcohol
3) Tertiary alcohol
4) All of these donot give turbidity at room temperature
18. The order of dehydration of alcohols is
1) 1o < 2o < 3o 2) 2o < 1o < 3o 3) 3o < 2o < 1o 4) 3o < 1o < 2o
CH3
19. CH3  C  OH 

Cu
573K
 X . The product X is
CH3
1) CH3 – CH = CH – CH3 2) CH3 – CH2 – CH = CH2
3) CH 3  C  CH 2 4) CH3 – CH2 – CH2 – CH3
CH3
20. Which one of the following is a better reagent for oxidation of primary alcohols?
1) KMnO4 2) K2Cr2O7 3) CrO3 4) PCC
21. Electrophilic substitution reaction in phenol takes place at
1) Ortho position 2) Meta position 3) Para position 4) Both 1 and 3
22. Phenol reacts with conc. HNO3 to form
1) M-nitrophenol 2) P-nitrophenol
3) 2, 4, 6-trinitrophenol 4) O-nitrophenol
23. The enzyme which can catalyse the conversion of glucose to ethanol is
1) Zymase 2) Invertase 3) Maltase 4) Diastase
194
24. Identify the incorrect statement

1) Phenols are more acidic than alcohols
2) Methanol is a poisonous substance
3) Reaction of Grignard reagent with formaldehyde give primary alcohol
4) Boiling points of alcohols are lower than corresponding alkanes
25. The commercial alcohol is made unfit for drinking by mixing in it with substances like
1) Pyridine 2) Sugar 3) Copper sulphate 4) Both 1 and 3
26. An ether is formed between the reaction of alkylhalide and sodium alkoxide. The reaction is called
1) Reimer-Tiemann reaction 2) Kolbe’s reaction
3) Williamson synthesis 4) Wurtz - fittig reaction
27. In Williamson synthesis ethoxy ethane is prepared by
1) Passing ethanol over alumina
2) Heating sodium ethoxide with ethyl bromide
3) Heating ethanal with dry Ag2O
4) Treating ethyl alcohol with excess H2SO4 at 443 K
28. Given below are two statements. One is labelled as Assertion (A) and the other is labelled as
Reason (R). In the light of the statements choose the most appropriate answer from the options given
below.
Assertion : Both symmetrical and unsymmetrical ethers can be prepared by Williamson’s synthesis.
Reason : Williamson’s synthesis is an example of nucleophilic substitution reaction.
1) Both (A) and (R) are correct and (R) is the correct explanation of (A)
2) Both (A) and (R) are correct and (R) is not the correct explanation of A
3) (A) is correct but (R) is not correct
4) Both (A) and (R) are not correct
29. An ether is more volatile than alcohol having the same molecular mass. This is due to:
1) Dipolar character of ethers 2) Resonance structure in alcohol
3) Intermolecular hydrogen bonding in alcohol 4) Intermolecular hydrogen bonding in ether
O CH3
30. Br2
 . The major product formed is
Ethanoic acid
O CH3 O
O CH3
C CH3
Br OH
1) 2) 3) 4)
Br
195
LEVEL - II
1. Which of the following is a trihydric alcohol?
1) Glycol 2) Glycerol 3) Phenol 4) Ethanol
2. How many isomers of C5H11O are primary?
1) 4 2) 3 3) 1 4) 2
3. CH 3  CH  CH 2  CH 2  CH  CH 3 . The IUPAC name of the compound given is
Cl OH
1) 5-chlorohexan-2-ol 2) 2-chlorohexan-5-ol
3) 2-chloro-5-hydroxyhexane 4) 5-chloro-2-hydroxyhexane
4. Acetone on treatment with CH3MgBr and further hydrolysis give
1) Iso propyl alcohol 2) n-Butanol 3) 2-methyl propan-2-ol 4) Acetic acid
5. Which reducing agent is used for the conversion of R – COOH to RCH2OH
1) K2Cr2O7 2) LiAlH4 3) KMnO4 4) H2SO4
6. Alcohols are prepared by the reaction of aldehydes and ketones with Grignard reagents by the following
reaction. CH 3  C  CH 3  CH 3 MgBr 
 X 
H 2O
 Y .The product Y is
O
CH3
1) CH 3  CH 2  CH  CH3 2) CH 3  C  CH 3
OH OH
3) CH 3  CH 2  CH 2  CH 2  OH 4) CH 3  CH  CH 2  OH
CH3
7. Which of the following are the starting materials for the synthesis of tert-butyl alcohol
1) CH 3 MgI  CH 3  CH 2  CHO 2) CH 3 MgI  CH 3  CH 2  C  CH 3
O
3) CH 3  CH 2 MgBr  CH 3  CHO 4) CH 3  MgI  CH 3  C  CH 3
O
8. Benzene is converted to phenol by the following reaction.
SO3H OH

X
 
1) NaOH
2)H 
What is X in the above reaction?

1) Sulphuric acid 2) Sulphur trioxide 3) Oleum 4) Sulphur dioxide
196
9. Benzene diazonium salt is treated with dil acid give
1) Toluene 2) Benzoic acid 3) Benzene 4) Phenol
10. Cumene is used for the manufacture of phenol cumene is
1) Propyl benzene 2) Ethyl benzene 3) Vinyl benzene 4) Iso propyl benzene
11. How many alcohols with molecular formula C4H10O are chiral in nature.
1) 4 2) 3 3) 1 4) 1
12. Identify the correct statement from the following
1) Alcohols react both as nucleophile and electrophile
2) Alcohols react as nucleophile when bond between O – H is broken
3) Alcohols react as electrophile when bond between C – O is broken
4) All the above statements are correct
13. Which one of the following statements is incorrect?
1) Phenol is an aromatic compound
2) Phenol is soluble in NaOH
3) Phenol is a weak acid
4) Phenol liberates CO2 from Na2CO3 solution
14. Phenol is more acidic than ethanol due to
1) Resonance effect 2) H-bonding 3) Inductive effect 4) Isomeric effect
15. Arrange the following compounds in the increasing order of their acidic strength.
i. m-nitrophenol ii. m-cresol iii. Phenol iv. m-chlorophenol
1) ii < iii < iv < i 2) ii < iv < iii < i 3) iii < ii < i < iv 4) ii < iii < i < iv
16. Lucas reagent is a mixture of
1) Anhydrous ZnCl2 and dil. HCl 2) Anhydrous MgCl2 and dil. HCl
3) Anhydrous ZnCl2 and conc.HCl 4) Anhydrous CaCl2 and conc. HCl
17. Which of the following substances are used to commercial alcohol made unfit for drinking?
1) Pyridine 2) Copper sulphate 3) Methanol 4) All of these
18. Dehydration of alcohol is an example of which type of reaction?
1) Substitution 2) Elimination 3) Rearrangement 4) Addition
197
19. The compound that undergoes dehydration very easily is
1) Butan-1-ol 2) Butan-2-ol 3) Propan-1-ol 4) 2-Methyl propan-2-ol
20. CH 3  CH 2  OH 
H 2SO4
413K
 X . Identify the product X.
1) CH3 – CH = CH – CH3 2) CH2 = CH2
3) C2H5 – O – C2H5 4) CH3 – CH = CH2
21. When vapours of primary and secondary alcohols passed over heated copper at 573 K the products
respectively are
1) Aldehydes, ketones 2) Ketones, aldehydes 3) Only aldehydes 4) Only ketones
22. When vapours of an alcohol is passed over heated copper, alcohol is converted to alkene. The alcohol
is
1) Primary alcohol 2) Tertiary alcohol 3) Secondary alcohol 4) All of these
23. Electrophilic substitution reaction in phenol takes place at
1) m-position 2) o-position 3) p-position 4) Both o-and p-position
24. Phenol is treated with bromine water 2, 4, 6-tribromophenol is formed. It is a

1) Red precipitate 2) White precipitate 3) Yellow precipitate 4) Green precipitate
OH ONa
25. 
NaOH
 
CO2
H
 X. Name the reaction and the product X.
1) Reimer - Tiemann reaction, salicylic acid

2) Kolbe’s reaction, salicylic acid
3) Reimer - Tiemann reaction, salicyl aldehyde
4) Kolbe’s reaction, salicyl aldehyde
26. Phenol is treated with chloroform in the presence of NaOH, followed by hydrolysis give
salicylaldehyde as final product. The reaction is
1) Cannizzaro reaction 2) Kolbe’s reaction
3) Reimer - Tiemann reaction 4) Wurtz reaction
27. The reaction between phenol and chloroform in the presence of aqueous NaOH is
1) Electrophilic addition 2) Electrophilic substitution
3) Nucleophilic addition 4) Nucleophilic substitution
198
28. The product formed by the oxidation of phenol by chromic acid is
CHO O
1) 2) 3) 4)
O O
29. The breaking of C – O bond in ether takes place under drastic conditions with excess of hydrogen
halides. The order of reactivity of hydrogen halides is
1) HI < HBr < HCl 2) HBr < HI < HCl 3) HCl < HI < HBr 4) HCl < HBr < HI
30. The major product formed when anisole reacts with a mixture of conc. H2SO4 and conc. nitric acid is
1) 2-nitroanisole 2) 3-nitroanisole 3) 4-nitroanisole 4) Trinitro anisole
199
KEY WITH HINTS

LEVEL - I
1. 4
2. 3 CH 2  CH 2
Glycol
OH OH
3. 1 CH 3  CH  CH 2  CH 3
OH
4. 3 1) CH 3  CH 2  CH 2  CH 2  OH  Butan  1  ol
2) CH 3  CH  CH 2  OH  2  Methyl propan  1  ol
CH3
3) CH 3  CH  CH 2  CH 3  Butan  2  ol
OH
CH3
4) CH 3  C  OH 2- Methyl propan-2-ol
CH3
5. 3 Alkyl groups attached to oxygen atoms are different.
6. 3
7. 4
8. 2
9. 3
10. 2 RCHO  H 2 
LiAlH 4
 RCH 2 OH
CH3 CH3
11. 3 CH 3  CO  CH 3  CH 3 MgBr 
 CH 3  C  OMgBr 
H 2O
 CH 3  C  OH  Mg  OH  Br
CH3 CH3
2-methyl propan-2-ol
SO3H OH
12. 3 
Oleum
 
NaOH
H

Benzene Phenol
sulphonic acid
200
13. 2 Inter molecular hydrogen bonding hold the molecules more firmly.
14. 2 Presence of electron releasing groups such as –CH3, –C2H5 etc increases the electron density
on oxygen atom tending to decreas the polarity of –OH group and decreases the acidic strength.
15. 3 Ethylbutanoate.
16. 4
17. 2
18. 1 The order of stability of carbocation 3o > 2o > 1o
19. 3
20. 4 PCC (Pyridinium chlorochromate).
21. 4 –OH group present on benzene due to +R effect, activate towards electrophilic substitution
reaction and are ortho and para directing.
OH OH
O2N NO2
22. 3

Conc.HNO3

NO2
2, 4, 6- trinitrophenol
(picric acid)
23. 1
24. 4 Boiling points of alcohols are higher than corresponding alkanes of comparable molecules
masses due to intermolecular hydrogen bonding.
25. 4 The process is called denaturation of alcohol.
26. 3 CH 3CH 2  Cl  CH 3CH 2 ONa 

 CH 3  CH 2  O  CH 2  CH 3  NaCl
27. 2 C 2 H 5 ONa  C 2 H 5 Br 
 C 2 H 5 O  C 2 H 5  NaBr
28. 2
29. 3
30. 2 Para-bromoanisole.
LEVEL - II
1. 2 CH 2  CH  CH 2
OH OH OH
Glycerol
201
2. 1 I. CH 3  CH 2  CH 2  CH 2  CH 2  OH
II. CH 3  CH 2  CH  CH 2  OH
CH3
III. CH 3  CH  CH 2  CH 2  OH
CH3
CH3
IV. CH 3  C  CH 2  OH
CH3
3. 1
O CH3 CH3
4. 3 CH 3  C  CH 3  CH 3 MgBr  CH 3  C  OMgBr 

H 2O
 CH 3  C  OH  Mg  OH  Br
CH3 CH3
5. 2
6. 2 Ketones with Grignard reagent give 3o alcohols.
CH3 CH3
 CH 3  C  CH 3  Mg  OH  I

7. 4 CH 3MgI  CH  C  CH 3  CH 3  C  CH 3 
H 3O
O O MgI OH
8. 3
N2Cl OH
9. 4 
dil H 2SO 4
 + N2 + HCl
10. 4 CH3 CH CH3
Cumene
202
11. 3 Four isomers of butanol are possible. Only Butan-2-ol have chiral carbon.
1) CH 3  CH 2  CH 2  CH 2  OH - Butan-1-ol
2) CH 3  CH 2  CH  CH 3 - Butan-2-ol
OH
CH3
3) CH 3  C  OH - 2-methyl propan-2-ol
CH3
4) CH 3  CH  CH 2  OH - 2-methyl propan-1-ol
CH3
12. 4
13. 4 Phenol is not sufficiently acidic to liberate CO2 from Na2CO3 solution.
14. 1 Phenoxide ion is resonance stabilised.
15. 1 Presence of electron attracting group (NO2) on the benzene ring increases acidity and electron
releasing group (–CH3) decreases acidity.
16. 3
17. 4
18. 2
19. 4 Tertiary alcohols undergo dehydration more easily than primary and secondary alcohols.
20. 3 At 413 K ethoxy ethane is the main product at 443 K the product is ethene.
21. 1 CH 3  CH 2  CH 2  OH 
Cu
573K
 CH 3  CH 2  CHO
CH 3  CH  CH3 
Cu
573K
 CH 3  C  CH 3
OH O
OH CH3
22. 2 CH3  C  CH3 

Cu
573K
 CH3  C  CH 2  H 2 O
CH3
23. 4 –OH group activates ortho and para positions.
203
OH OH
Br Br
24. 2 + 3 Br2
Br
2, 4, 6- tribromo phenol
(white precipitate)
OH
COOH
25. 2
Salicylic acid
OH ONa OH
CHO CHO

CHCl3


26. 3 aq.NaOH 
H

Salicylaldehyde
27. 2 The reaction is Reimer - Tiemann reaction and it is electrophilic substitution.
OH O
28. 2 
Na 2 Cr2 O7
H 2SO4

O
Benzoquinone
29. 4
O CH3 O CH3
30. 3 
conc.H 2SO 4
conc.HNO3
NO2
4-nitroanisole
204
CHAPTER - 08
ALDEHYDES AND KETONES
INTRODUCTION
Aldehydes and ketones are organic compounds containing carbonyl group (>C=O) as the functional group.
These are widely distributed both in the plant and animal kingdoms. Compounds such as cinnamaldehyde,
vanillin, citral, carvone (spearmint and caraway), camphor, salicylaldehyde, etc., are found in plants. Muscone,
testosterone, progesterone, cortisone, etc., have animal and human origin.
CLASSIFICATION
In aldehydes, the carbonyl group is attached to either two hydrogen atoms as in formaldehyde or one hydrogen
atom and one carbon containing group such as alkyl, aralkyl or aryl group. In ketones, the carbonyl group is
attached to two carbon containing groups which may be same or different. If R and R  groups are the
same, the ketone is called a simple ketone and if R and R  represent different groups, the ketone is
referred to as mixed ketone.
NOMENCLATURE
Aldehydes may be aliphatic or aromatic according as the –CHO group is attached to an alkyl group (or a
hydrogen atom as in HCHO) or an aryl group. Ketones may be aliphatic or aromatic according as the >C=O
group is attached to two alkyl groups, two aryl groups or one alkyl and one aryl group.
Most of the aldehydes and ketones are known by their common names rather than IUPAC names.
Aldehydes. The common names of aldehydes are derived by replacing the terminal, ic acid from the common
names of the corresponding carboxylic acids by the suffix aldehyde.
205
In substituted aliphatic aldehydes, the positions of the substituents are indicated by Greek letters, with the
carbon atom next to the –CHO group being designated as  .
The simplest aromatic aldehyde is benzaldehyde. The positions of substituents on the benzene ring w.r.t.
the –CHO group are indicated by prefixes; ortho-or o- (for 1, 2), meta-or m- (for 1, 3) and para -or
p-(for 1, 4). However, many aldehydes are known by their special names.
In IUPAC system, aliphatic aldehydes are called alkanals. The names of individual members are derived by
replacing the terminal ‘e’ of the name of the corresponding alkane by the suffix ‘al’. In substituted aldehydes,
the parent carbon chain containing the aldehydic group is selected and the positions of the substituents and
multiple bonds, if any, are indicated by arabic numerals. The numbering is done in such a way that the
aldehydic group (which is always present at the end of the chain) gets number 1.
When aldehyde group is directly attached to an alicyclic or aromatic ring, the suffix ‘carbaldehyde’ is added
to the full name of the hydrocarbon, e.g., benzaldehyde is called benzenecarbaldehyde.
The common names of some aldehydes are also adopted by the IUPAC system, e.g., benzaldehyde.
In case of alicyclic aldehydes, the positions of the substituents are indicated by Greek letters in the common
system and by arabic numerals in the IUPAC system. In aromatic aldehydes, the positions of the substituents
on the benzene ring are indicated by prefixes, ortho, meta and para in the common system and by arabic
numerals 1, 2 ; 1, 3 and 1, 4 respectively in the IUPAC system.
206
Table - 01 Common and IUPAC names of aliphatic and aromatic aldehydes.
207
The suffix carbaldehyde is also used when an unbranched carbon chain is linked to more than two aldehyde
groups. In such cases, the compound is named as a derivative of the parent alkane which does not include
the carbon atoms of the functional groups. In all other cases, the suffix ‘al’ is used and the carbon atoms of
the functional groups are included in the parent alkane.
Ketones. In the common system, the names of both aliphatic and aromatic ketones are obtained by naming
the two alkyl groups (in alphabetical order) and adding the suffix ‘ketone’. When the two alkyl groups are
same, the prefix ‘di’ is attached to the name of the alkyl or aryl group.
Some ketones have common names, e.g., simplest dimethyl ketone is called acetone. Aromatic ketones in
which the carbonyl group is directly attached to the benzene ring are called ‘phenones’.
In IUPAC system, ketones are named as alkanones. The names of the individual members are derived by
replacing the terminal ‘e’ of the name of the corresponding alkane by the suffix ‘one’.
If the carbonyl compound contains two or more keto groups, the terminal ‘e’ of the name of the
corresponding alkane is retained, the positions of the keto groups on the parent chain are indicated by
numbers and the numerical prefix di, tri, etc. is used before’one’. In the case of ketoaldehydes, the prefix
‘oxo’ is used for the keto group and its position on the chain is indicated by a suitable number.
The common names of some aromatic ketones have also been adopted by the IUPAC system, e.g.,
acetophenone and benzophenone. In these cases, the substituents on the benzene ring are indicated by
the prefixes o-, m- and p- in the common system and by arabic numerals in the IUPAC system.
208
Table - 02 The common and IUPAC names of aliphatic, alicyclic and aromatic ketones.
Structure and Nature of Carbonyl Group. The C=O bond is made up of one   bond and one   bond.
In the carbonyl group, carbon uses sp2-hybrid orbitals while oxygen uses its unhybridized atomic orbitals.
One of the sp2-orbitals of carbon overlaps with a p-orbital of oxygen forming a C–O, sp2–p,   bond. The
remaining two sp2-orbitals of the carbon atom form two   bonds either by overlapping with 1s orbitals of
two hydrogen atoms as in HCHO or with 1s -orbital of one hydrogen atom and one sp3-orbital of an alkyl
group in aldehydes or with two sp3-orbitals of two alkyl groups in ketones. All the three   bonds lie in the
same plane at an angle of 120o. The half-filled 2pz-orbitals on carbon and oxygen atoms overlap sideways to
form a   bond. The electron cloud of the   bond lies both above and below the C–O,   bond.
209
Oxygen, being more electronegative, attracts the electron cloud of the   bond towards itself, therefore,
the >C=O group is polar. Thus, aldehydes and ketones have large dipole moments (2.3–2.8 D). The high
polarity of the carbonyl group is due to resonance involving a netural (I) and a dipolar (II) structures.
METHODS OF PREPARATION
Preparation of both Aldehydes and Ketones
1. From alcohols : a) Oxidation
Alcohols on controlled oxidation using chromic anhydride or chromium trioxide (CrO3) give aldehydes
or ketones. Primary alcohols give aldehydes while secondary alcohols give ketones. Pyridinium
chlorochromate (PCC) is a better reagent for oxidation of alcohols to aldehydes.
To prevent oxidation of aldehydes to carboxylic acids, aldehydes are distilled off as soon as they are
formed.
b) Catalytic dehydrogenation of alcohols. Dehydrogenation is carried out by passing vapours of
alcohols over reduced copper at 573 K. Primary alcohols give aldehydes while secondary alcohols
give ketones.
2. From hydrocarbons: (a) Hydration of alkynes. In presence of hot dil. H2SO4 and HgSO4, alkynes
add a molecule of water to form aldehydes or ketones (formaldehyde cannot be prepared by this
method).
b) Reductive ozonolysis of alkenes. Alkenes react with ozone to form ozonides, which on reductive
cleavage with Zn dust and water give aldehydes and ketones. Ethylene gives formaldehyde.
210
Symmetrically disubstituted alkenes give other aldehydes while tetrasubstituted alkenes give ketones.
Preparation of Aldehydes only

1. From acyl chlorides (acid chlorides), Rosenmund reduction. Aldehydes are obtained on passing
H2 gas through boiling xylene solution of the acid chloride in presence of Pd catalyst supported over
BaSO4 and partially poisoned by sulphur or quinoline (formaldehyde cannot be prepared by this method).
Pd-BaSO , S
RCOCl  H 2  4
Boiling xylene
 RCHO  HCl
2. From nitriles and esters: (i) Stephen reduction. When ethereal solution of a nitrile is reduced using
SnCl2 and HCl gas at room temperature, imine hydrochloride is precipitated which on hydrolysis with
boiling water gives aldehyde.
H O
R  C  N  SnCl 2  HCl 
 RCH  NH 
3
 RCHO
i min e
(ii) Reduction using diisobutylaluminium hydride. Nitriles can be selectively reduced using
diisobutylaluminium hydride, [(CH3)2CH2CH]2AlH, abbreviated as AlH (iBu)2 or DIBAL-H, to imines which
on hydrolysis give aldehydes.
AlH iBu 2 H 2O
R  C  N   R  CH  NH   R  CHO  NH 3
Alkyl nitrile Dryether Hydrolysis Aldehyde
DIBAL-H reduces alkynes to alkenes but does not reduce ethylenic double bonds and hence it is used
to reduce unsaturated nitriles to the corresponding unsaturated aldehydes.
(i)DIBAL  H
CH3  CH  CH  CH 2  CH 2  CN 
(ii)H O
CH3  CH  CH  CH 2  CH 2  CHO
2
Hex-4-en-1-nitrile Hex-4-en-1-al
Esters are reduced to aldehydes at low temperature (195K).
211
3. From aromatic hydrocarbons: (i) By oxidation of methylbenzene. Strong oxidising agents like
acidified or alkaline KMnO4, acidified K2Cr2O7 or conc. HNO3 oxidise toluene and its derivatives to the
corresponding benzoic acids.
KMnO /KOH [O]
C6 H5  CH3 
4
 [C6 H5  CHO]  C6 H5  COOH

Toluene Benzaldehyde Benzoic acid
However it is possible to stop oxidation at the aldehyde stage using the following reagents.
a) With chromyl chloride (Etard reaction). Chromyl chloride (CrO2Cl2) in CS2or CCl4 oxidises toluene
to benzaldehyde.
b) With chromium trioxide (CrO3) in acetic anhydride. Aromatic aldehydes can be prepared by the
oxidation of toluene and its derivatives with chromium trioxide in acetic anhydride. The gem-diacetate
formed is hydrolysed with alkali or acid to yield the aldehyde.
p-nitrotoluene gives p-nitrobenzaldehyde.

ii) Manufacture of Benzaldehyde. Side chain chlorination of toluene gives benzal chloride which on
hydrolysis gives benzaldehyde (side chain chlorination followed by hydrolysis).
iii) Gattermann-Koch reaction. When a mixture of CO and HCl gas is passed through a solution of
benzene in nitrobenzene containing a catalyst consisting of anhydrous AlCl3 and a small amount of
CuCl at 323K, benzaldehyde is formed (toluene gives p-tolualdehyde).
CO  HCl 
  HCOCl ;
Formylchloride (unstable)
212
Preparation of Ketones only

1) From acyl chlorides. Ketones can be prepared by the action of dialkylcadmium (prepared by the
reaction of cadmium chloride with Grignard reagent) on an acid chloride.
2) From nitriles. Ketones can be prepared by the action of Grignard reagent on alkyl nitriles followed by
acid hydrolysis of the addition product.
3) From benzene or substituted benzenes (Friedel-Crafts acylation). It involves the treatment of an

aromatic hydrocarbon with an acid halide in presence of anhydrous aluminium chloride (Lewis acid).
PHYSICAL PROPERTIES
Physical state. At room temperature, methanal is a gas, ethanal is a volatile liquid, and other aldehydes
and ketones are liquids or solids.
Boiling points. The boiling points of aldehydes and ketones are higher than those of hydrocarbons
and ethers of comparable molecular masses. This is because they contain polar carbonyl groups and
hence undergo intermolecular association due to dipole-dipole interactions between the opposite ends
of the C O dipoles.
213
Among isomeric aldehydes and ketones, ketones have slightly higher boiling points due to the presence
of two electron-donating alkyl groups around the C=O group which makes them more polar.
CH 3CH 2CHO CH3COCH3
Propanal   2.52D, b.p.322 K  Propanone   2.88D,b.p.329 K 
Dipole-dipole interactions are weaker than intermolecular H-bonding, therefore, the boiling points of
carbonyl compounds are much lower than those of alcohols and carboxylic acids of comparable
masses.
Compound b.p. (K) Mol. mass Compound b.p. (K) Mol. mass
n -Butane 273 58 Acetone 329 58
Methoxyethane 281 60 Propan-1-ol 370 60
Propanal 322 58 Acetic acid 391 60
Solubility. Lower aldehydes and ketones containing upto four carbon atoms are soluble in water due
to H-bonding between the polar carbonyl group and water molecules.
Solubility decreases as the size of the alkyl group increases. Thus the higher members (C5-onwards)
are practically insoluble in water. Solubility of aromatic aldehydes and ketones are much lower than the
corresponding aliphatic analogues because of the larger hydrocarbon part (benzene ring) in their
molecules. However, all aldehydes and ketones are fairly soluble in organic solvents.
Smell. The lower aldehydes have sharp pungent (unpleasant) odour. As the size of the molecule
increases, the odour becomes less pungent and more pleasant. Lower ketones are generally pleasant
smelling liquids while the higher analogues are solids.
CHEMICAL PROPERTIES
Aldehydes and ketones show a number of common reactions since both have the same functional
group, i.e., polarized carbonyl group. Aldehydes are more reactive than ketones due to :
i. Inductive effect. Since an alkyl group has electron-donating inductive effect (+I-effect), greater number
of alkyl groups attached to the carbonyl group lowers its reactivity towards nucleophilic addition reactions.
Thus, formaldehyde is more reactive than other aldehydes and ketones.
ii. Steric effects. As the number and size of alkyl groups increases, attack of the nucleophile on the
carbonyl group becomes more and more difficult due to steric hindrance (crowding), and therefore,
reactivity decreases. Thus, reactivity decreases in the following order :
Aromatic aldehydes and ketones are less reactive than their aliphatic analogues. This is because the
+R-effect of the benzene ring increases the electron density on the carbonyl carbon, thereby repelling
nucleophiles.
214
Nucleophillic Addition Reactions

Mechanism. The carbonyl group is polar due to greater electronegativity of oxygen. The carbon atom
of the carbonyl group carries a small positive charge and hence behaves as an electrophile. A nucleophile
attacks the electrophilic carbon atom from a direction perpendicular to the plane of the sp2-hybridized
orbitals of the carbonyl carbon. The complete transfer of   electrons of the carbon-oxygen double
bond from carbon to oxygen takes place and the hybridisation of carbon changes from sp2 to sp3; a
tetrahedral alkoxide intermediate is formed. This intermediate then picks up a proton either from the
solvent (usually H2O) or from the reagent to give the electrically neutral addition product.
1. Addition of hydrogen cyanide (HCN). Both aldehydes and ketones add a molecule of hydrogen
cyanide to form cyanohydrins. The reaction is catalysed by base. The CN– ion, being a strong nucleophile,
readily adds to the carbonyl compound to yield the cyanohydrin.
Cyanohydrins are useful synthetic intermediates.

2. Addition of sodium bisulphite. Aldehydes and aliphatic methyl ketones add a molecule of sodium
bisulphite to form crystalline bisulphite addition compounds.
CH3CHO  NaHSO3 

 CH 3CH(OH)SO3 Na
Acetaldehyde Sodium bisulphite Acetaldehyde sodium bisulphite addition product
(CH 3 )2 CO  NaHSO 3   (CH3 )2 C(OH)SO3 Na

Acetone Sodium bisulphite Acetone sodium bisulphite addition product
The bisulphite adduct is water soluble and can be converted back to the original carbonyl compound
by treating with dilute mineral acid or alkali. Therefore, this reaction is used for the separation and
purification of aldehydes and ketones from non-carbonyl compounds. Amogst aromatic aldehydes
and ketones, benzaldehyde forms a sodium bisulphite adduct but acetophenone does not.
215
3. Addition of Grignard reagents. Aldehydes and ketones add on Grignard reagents to form addition
products which on hydrolysis with dil. mineral acids give alcohols.
Formaldehyde gives primary alcohol, other aldehydes give secondary alcohols and ketones yield tertiary
alcohols.
4. Addition of alcohols (Acetal and ketal formation). Aldehydes react with monohydric alcohols in
presence of dry hydrogen chloride gas to yield alkoxy alcohol intermediates called hemiacetals. These
then react with one more molecule of alcohol to give gem-dialkoxy compounds known as acetals.
Ketones do not react with monohydric alcohols but do so with dihydric alcohols to give cyclic ketals.
Acetals and ketals are hydrolysed by dilute acids to regenerate the original aldehydes and ketones.
5. Addition of ammonia and its derivatives. Aldehydes and ketones react with ammonia and its
derivatives, such as hydroxylamine (NH2OH), hydrazine (H2NNH2), phenyl hydrazine (C6H5NHNH2),
2, 4-dinitrophenylhydrazine (Brady’s reagent), and semicarbazide (NH2CONHNH2) to form compounds
containing C = N group. The reaction is reversible and catalysed by acid.
Z = Alkyl, aryl, OH, NH2, NHC6H5, NHCONH2, etc.
216
Table - 03 Some N-substituted derivatives of aldehydes and ketones
Reduction Reactions
1. Reduction to alcohols. Aldehydes and ketones on reduction give primary and secondary alcohols
respectively. Reduction is carried out either catalytically with H2 in presence of Ni, Pt or Pd or chemically
with lithium aluminium hydride (LiAlH4) or sodium borohydride (NaBH4) or simply diborane (B2H6).
2. Reduction to hydrocarbons: (i) Clemmensen reduction. Reduction of aldehyde or ketone with

zinc amalgam and conc. hydrochloric acid.
Zn  Hg,HCl Zn  Hg,HCl
RCHO  4[H]  R  CH3  H 2O ; R 2C  O 4[H]  R  CH 3  R  H 2O
Aldehyde Alkane Ketone Alkane
(ii) Wolff-Kisher reduction. Aldehyde or ketone heated with hydrazine and KOH or potassium tert-
butoxide in a high boiling solvent such as ethylene glycol gives alkane.
NH NH KOH,glycol
RCHO 
2 2
 R  CH  NNH 2 
 RCH3  N 2
Aldehyde  H 2O 453 473K
Hydrazone
NH NH KOH,glycol
R 2C  O 
2 2
 R 2C  NNH 2 
 R  CH 2  R  N 2
 H 2O 453473K
Ketone Hydrazone
Oxidation Reactions
(i) Aldehydes are readily oxidised to carboxylic acids containing the same number of carbon atoms by
strong (HNO3, KMnO4 and K2Cr2O7) as well as weak oxidising agents (bromine water, Ag+, Cu2+, etc.).
Thus, aldehydes are strong reducing agents.
[O]
RCHO  RCOOH
217
(ii) Ketones are oxidised under vigorous conditions (strong oxidising agents and elevated temperatures).
Oxidation involves carbon-carbon bond cleavage to give a mixture of carboxylic acids having lesser number
of carbon atoms than the parent ketone.
1 2 3
[O]
R  C H 2  C O  C H 2  R '  R  COOH  R ' CH 2 COOH  R  CH 2 COOH  R ' COOH
(cleavage of C1  C 2 bond) (cleavage of C 2  C 3 bond)
Mild oxidising agents are used to distinguish aldehydes from ketones:

i) Tollen’ test. Aldehydes reduce Tollens’ reagent (ammoniacal solution of silver nitrate) to metallic
silver which deposits on the walls of the test tube as bright silver mirror (silver mirror test).
RCHO  2[Ag  NH 3 2 ]  3OH  

 RCOO  
Heat
2 Ag  4 NH 3  2 H 2 O
Aldehyde Carboxylate ion Silver mirror
Both aliphatic and aromatic aldehydes reduce Tollen’s reagent.

ii) Fehling’s test. Fehling’s reagent is alkaline solution of CuSO4 containing Rochelle salt (sodium
potassium tartrate). It is prepared by adding alkaline solution of Rochelle salt (Fehling solution ‘B’) to an
aqueous solution of CuSO4 (Fehling solution ‘A’) until the blue precipitate of Cu(OH)2 first formed just
redissolves. Aliphatic aldehydes reduce Fehling’s solution to a red precipitate of cuprous oxide.
RCHO  2 Cu 2   5 OH    RCOO   Cu 2 O  3 H 2 O
Heat
Aldehyde   Carboxylate ion Cuprous oxide
Fehling 's solution
 Re d ppt.
Aromatic aldehydes, do not reduce Fehling’ solution.
iii. Oxidation of methyl ketones with sodium hypohalite -Haloform reaction. Aldehydes and ketones
containing CH3CO– group, on treatment with excess of halogen in presence of alkali (sodium hypohalite,
NaOX or X2+NaOH) produce a haloform (chloroform, bromoform, or iodoform).
O O
R  C  CH 3 
NaOX
 R  C  ONa  CHX 3  X  Cl, Br, I 
NaOH NaOH
CH3CHO  3I2  CI3CHO 
 CHI3  HCOONa
3HI Hydrolysis
Acetaldehyde Triiodoacetaldehyde Iodoform
NaOH NaOH
(CH3 ) 2 C  O  3I 2  CI3COCH3 
 CHI3  CH 3COONa
3HI Hydrolysis
Acetone  ,  , Triiodoacetone Iodoform
This is known as iodoform test and is used for characterising compounds containing CH3CO– group
or any group such as CH3CH(OH)– which can be easily oxidised to CH3CO– group by halogens.
Reactions due to α -hydrogen
Acidity of α -hydrogens
A characteristic of carbonyl compounds is the acidity of α -hydrogens. This is due to –I-effect of the carbonyl
group which weakens the C  H bond and the resonance stabilization of the resulting enolate anion.
218
i) Aldol condensation. Aldehydes and ketones having at least one α -hydrogen undergo reaction in
presence of dilute alkali to form β -hydroxy aldehyde (aldol) or β - hydroxyketone (ketol), respectively..
This reaction is called aldol reaction. The aldol and ketol readily loses water to form α , β -unsaturated
carbonyl compounds which are aldol condensation products and this reaction is called aldol
condensation. The general name aldol condensation is applied in case of ketones also due to their
similarity with aldehydes.
ii) Cross aldol condensation. Aldol condensation between two different aldehydes or two ketones or
between one aldehyde and one ketone is called mixed aldol condensation or cross aldol condensation.
If both reactants contain   hydrogens, it gives a mixture of four products, e.g., cross aldol
condensation between ethanal and propanal gives a mixture of the following four products:
Ketones can also be used as one component in cross aldol reactions.
Formaldehyde, benzaldehyde and benzophenone do not undergo aldol condensation since they do
not contain   hydrogen atoms.
219
2. Other Reactions
(i) Cannizzaro reaction. Aldehydes which do not contain an  -hydrogen, when treated with
concentrated alkali, undergo disproportionation (self oxidation-reduction). One molecule of the aldehydes
is reduced to alcohol at the cost of the other which is oxidised to carboxylic acid.
Electrophilic Substitution reactions. Aromatic aldehydes and ketones undergo electrophilic

substitution reactions of the benzene nucleus such as halogenation, nitration and sulphonation. Since
the aldehydic and ketonic groups are electron-withdrawing, they are deactivating and m-directing.
Nuclear halogenation is difficult in both aromatic aldehydes and ketones.
Nitration. Benzaldehyde gives m-nitrobenzaldehyde.
USES OF ALDEHYDES AND KETONES

Formaldehyde. (i) A 40% aqueous solution of formaldehyde, called formalin is used for the preservation of
biological or anatomical specimens. It is also used as a disinfectant and germicide. (ii) In the manufacture of
bakelite (a phenol-formaldehyde resin), urea-formaldehyde resins and other polymers. (iii) In leather industry
for tanning hides and as a reducing agent in silvering of mirrors and decolouring vat dyes.
Acetaldehyde. (i) In the manufacture of acetic acid, ethyl acetate, vinyl acetate, paraldehyde, metaldehyde,
polymers and drugs. (ii) In silvering of mirrors. (iii) Paraldehyde is used in medicine as a hypnotic.
Benzaldehyde. (i) For preparing a number of organic compounds such as benzoin, cinnamic acid, benzoyl
chloride, etc. (ii) As a flavouring agent in perfume industry. (iii) In the manufacture of dyes like malachite
green.
Ketones and other aldehydes. (i) Acetone and ethyl methyl ketone are used as solvents in industry.
(ii) Many aldehydes and ketones such as butyraldehyde, vanillin, acetophenone and benzophenone are
used for fragrance and as flavouring agents. (iii) Acetone is used to prepare chloroform, ketene, acetic
anhydride, etc.
220
QUESTIONS
LEVEL - I
CH = CHCHO
1. . The compound is :
1) Acetophenone 2) Vanillin 3) Cinnamaldehyde 4) Salicylaldehyde

2. Propiophenone is :
1) 1-phenyl ethanone 2) 1-phenyl propan-1-one
3) 4-methyl pent-3-en-2-one 4) propane-1, 2, 3-tricarbaldehyde
3. The carbonyl carbon atom is :
1) sp2 hybridised 2) sp hybridised 3) sp3 hybridised 4) sp3d hybridised
4. The reagent SnCl2/HCl is used in
1) Stephen’s reduction 2) Cannizzaro reaction
3) Clemmensen’s reduction 4) Rosenmund’s reduction

5. RCN  Y  HCl 
 RCH  NH 
H 3O
 RCHO . Identify Y and name the reaction.
1) NH3, Rosenmund reduction
2) SnCl2, Stephen reaction
3) NH2 – NH2, Wolff-kishner reduction
4) CO, Gatterman - Koch reaction
6. Which of the following is selectively reduced to aldehydes by DIBAL-H?
1) Halides 2) Nitrates 3) Nitriles 4) Amines
7. In Etard’s reaction, toluene is oxidised to benzaldehyde using:
1) H2O2 2) Cl2 3) KMnO4 4) Chromyl chloride
8. Which of the following on heating with aqueous KOH, produces acetaldehyde?
1) CH3COCl 2) CH3CH2Cl 3) CH2ClCH2Cl 4) CH3CHCl2
9. The reagent used in the conversion of benzene to benzaldehyde by Gatterman-Koch reaction is
1) CS2 2) CO + HCl 3) Pd/BaSO4 4) CrO3
10. Give the name of the reagent to bring about the transformation of allyl alcohol to propenal
1) PCC 2) CrO3 in presence of acetic anhydride
3) DIBAL-H 4) O3/H2O – Zn dust
11. Reaction of acyl chlorides with dialkylcadmium give
1) Aldehyde 2) Ketone 3) Alcohol 4) Carboxylic acid
12. Which of the following compounds gives a ketone with Grignard reagent?
1) Formaldehyde 2) Ethyl alcohol 3) Methyl cyanide 4) Methyl iodide
13. Acetophenone is prepared by the reaction of which of the following in the presence of AlCl3 catalyst?
1) Phenol and acetic acid 2) Benzene and acetone
3) Benzene and acetyl chloride 4) Phenol and acetone
221
14. The intermediate compound X in the following chemical reaction is :
CH3 C
 H
 CrO 2 Cl 2 
CS2
X 
H 3O

Cl
CH CH(OCrOHCl2)2
H
1) 2)
Cl
CH(OCOCH3)2 CH
Cl
3) 4)
15. Aldehydes are more reactive than ketones because

1) Molecular mass of ketones is higher than those of corresponding aldehyde
2) Two alkyl groups in ketone reduces the electrophilicity of carbonyl group more effectively than
aldehydes
3) The carbon oxygen bond length in ketones is smaller than aldehydes
4) Carbonyl carbon in ketones is sp2 hybridised while in aldehydes it is sp3 hybridised
16. Which one is most reactive towards nucleophilic addition reaction?
CHO CHO
CHO COCH3
1) 2) 3) 4)
CH3 NO2
17. Acetal is obtained by reacting alcohol with ...... in the presence of dry HCl
1) Aldehyde 2) Ketone 3) Ether 4) Carboxylic acid
18. Which among the following give tertiary butyl alcohol on reaction with methyl magnesium iodide fol-
lowed by hydrolysis?
1) HCHO 2) CH3CHO 3) CH3COCH3 4) CO2
19. The carbonyl compound producing an optically active product by reaction with LiAlH4 is :
1) propanone 2) butanone 3) 3-pentanone 4) benzophenone
20. Aldehydes react with NH2 – NH2 to form
1) Aniline 2) Nitrobenzene 3) Hydrazones 4) Ketones
222
21. In Clemmenson reduction, R  C  R 

x
HCl
R  CH 2  R  H 2 O , x is :
1) NH2 – NH2 2) Zinc amalgam 3) Na-K alloy 4) Sn
22. Tollens reagent used for the distinction of aldehydes with ketones is :
1) Cu(II)citrate  NH3  aq  2) Cu  NO3 2  NH3  aq 
3) Pb  NO3  2  NH3  aq  4) AgNO3  NH 3  aq 

23. When ethanal is treated with Fehling’s solution, it gives a precipitate of
1) Cu2O 2) Cu 3) Cu3O 4) CuO
24. Which reagent(s) can differentiate between benzaldehyde and acetophenone?
2)  Ag  NH 3 2 
2 
1) Cu  NH 3  4  3) NaOH / I2 4) Both (2) and (3)
25. An organic compound ‘X’ having molecular formula C5H10O yields phenylhydrazone and gives negative
response to the iodoform test and Tollens’ test. It produces n-pentane on reduction. ‘X’ could be:
1) 3-pentanone 2) n-amyl alcohol 3) pentanal 4) 2-pentanone
26. Ethanal in the presence of dil. alkali gives
1) 3-hydroxybutanal 2) Butanal 3) Butan-2-ol 4) Butane
27. Which of the following compounds is hydrogenated over catalyst palladium on barium sulphate in
Rosenmund reduction?
1) CH3 – CHO 2) CH3COOH 3) CH3COCl 4) CH3 – Cl
28. Cannizzaro reaction is not given by:
1) trimethylacetaldehyde 2) benzaldehyde
3) acetaldehyde 4) formaldehyde
29. Which of the following reactions will not result in the formation of carbon-carbon bonds?
1) Cannizzaro reaction 2) Wurtz reaction
3) Reimer-Tiemann reaction 4) Friedel-Crafts acylation
30. Formalin is 40% solution of
1) Acetaldehyde 2) Formaldehyde 3) Acetone 4) Formic acid
LEVEL - II
O
1. The IUPAC name of the compound CH 3  CH 2  CH 2  CH  CH  CH 2  C  H
Br CH3
1) 4-Bromo-5-methyl heptanal 2) 4-Bromo-3-methyl heptanal
3) 4- Bromo-5-methyl heptanone 4) 4-Bromo-3-methyl heptanone
2. IUPAC name of CCl3CHO is
1) Trichloro acetaldehyde 2) 2, 2, 2-trichloro ethanal
3) 1, 1, 1-trichloro ethanal 4) Trichloro ethanal
223
CHO
3. The IUPAC name of the compound is
CHO
1) Phthaldehyde 2) Benzene dialdehyde
3) Benzene - 1, 2-dicarbaldehyde 4) di Benzaldehyde
4. The structure of 3-methylcyclopentanone is :
O O
CH3 CHO
1) 2) 3) 4)
O CH3
CHO
5. . The compound is :
OH
OCH3
1) Vanillin 2) Salicylaldehyde 3) Acetal 4) Acetophenone
6. The most suitable reagent for the conversion of RCH2OH to R – CHO is
1) KMnO4 2) K2Cr2O7 3) PCC 4) CrO3

7. In the reaction, RCN  SnCl 2  HCl 
 X 
H 3O
 RCHO . X is
1) R – CH2 – NH2 2) R – CH = NH
3) CH3 NH CH3 4) CH3 – Cl
COOCH3
DIBAL  H
8. 
H O
 Product, Product is
2
CN
COOCH3 CHO CHO COOH
1) 2) 3) 4)
CHO CHO CN CHO
224
CH3
CHO
Cl2 / h
9. In the reaction,   R 
H2O
373K
 , R is :
1) Benzal chloride 2) Chlorobenzene 3) Benzene 4) Benzoic acid

10. Ethyl methyl ketone is prepared by the oxidation of
1) Propan-2-ol 2) Butan-1-ol 3) Butan-2-ol 4) Butane
11. Compound which gives acetone on reductive ozonolysis is
1) CH 3  CH  CH  CH 3 2)  CH 3 2 C  C  CH3 2
3) C6 H 5CH  CH 2 4) CH 3CH  CH 2
12. Ketones  R  C  R 1  where R, R1 = alkyl groups, can be obtained in one step by
1) Hydrolysis of esters 2) Oxidation of primary alcohol

3) Oxidation of secondary alcohol 4) Reaction of acid halide with alcohols
13. Select the reagent for the reaction :  OHC   CH 2  4  CHO
1) SeO2 2) O3, Zn/H2O

3) O3, H2O2– CH3COOH 4) PCC
14. Acetaldehyde reacts with
1) Free radicals only 2) Electrophiles only 3) Nucleophiles only 4) Both 2 and 3
15. Nucleophilic attack on carbon changes its hybridisation from
1) sp to sp2 2) sp2 to sp3 3) sp3 to sp2 4) sp to sp3
16. Nucleophilic addition reaction will be most favoured in:
1) (CH3)2C = O 2) CH3CH2CHO 3) CH3CHO 4) CH 3CH 2 CH 2 COCH3

17. The general order of carbonyl compounds for nucleophilic addition reactions is
1) H 2 C  O  RCHO  ArCHO  R 2 C  O  Ar2 C  O
2) ArCHO  Ar2 C  O  RCHO  R 2 C  O  H 2 C  O
3) Ar2 C  O  R 2 C  O  ArCHO  RCHO  H 2 C  O
4) H 2 C  O  R 2 C  O  Ar2 C  O  RCHO  ArCHO
225
18. Aldehydes and ketones react with which compound to form cyanohydrins.
1) NaNO2 2) CH3 - N2Cl 3) HCN 4) NH3
19. Grignard’s reagent reacts with ethanal (acetaldehyde) and propanone to give:
1) Higher aldehyde with ethanal and higher ketone with propanone
2) Primary alcohol with ethanal and secondary alcohol with propanone
3) Ether with ethanal and alcohols with propanone
4) Secondary alcohol with ethanal and tertiary alcohol with propanone
20. Cyclohexanone is subjected to reduction by NaBH4. The product formed is:
1) Cyclohexane 2) Cyclohexanal 3) Cyclohexadiene 4) Cyclohexanol
O
CH3   . The product of this reaction is :

N2H4
21. C KOH
CH3
CH3
1) C=N NH2 2) CH3
CH3 CH3
CH3 CH3
3) CH NH2 4) CH3
C2H5 OH
22. The reagent with which both acetaldehyde and acetone react easily is
1) Fehling’s reagent 2) Grignard reagent 3) Schiff’s reagent 4) Tollens reagent
23. The compound that will not give iodoform on treatment with alkali and iodine is:
1) acetone 2) ethanol 3) diethyl ketone 4) isopropyl alcohol
24. Assertion : Lower aldehydes and ketones are soluble in water, but the solubility decreases as
molecular mass increases.
Reason : Aldehydes and ketones can be distinguihed by Tollen’s reagent.
1) Both A and R are correct and R is the correct explanation of A
2) Both A and R are correct but R is not the correct explanation of A
3) A is correct but R is not correct
4) Both A and R are not correct
25. The aldol condensation product of ethanal is :
1) But-2-enal 2) But-1-enal 3) Butanal 4) 3-hydroxy butanal
26. Which of the following compounds will undergo self aldol condensation in the presence of cold dilute
alkali?
1) C6H5CHO 2) CH3CH2CHO 3) CH  C  CHO 4) CH2 = CH – CHO

226
27. Which of the following statements is/are correct regarding aldol reaction?
1) Aldehydes and ketones having at least one  -hydrogen
2) The reaction is carried out in the presence of concentrated alkali
3) The product formed is  -hydroxy aldehyde (aldol) or  -hydroxy ketone (ketol)
4) All of the above
28. The final product (z) in the following reaction is C6 H 5 CHO  CH 3CHO 
i) NaOH(aq)
ii) 
(Y) 
H 2 / Ni
(Z)
(X)
1) 3-phenyl propenal 2) 1-phenyl (propan-1-ol)

3) propylbenzene 4) 3-phenyl propan-1-ol
29. m-Chlorobenzaldehyde on reaction with concentrated KOH at room temperature gives:
1) potassium m-chlorobenzoate and m-hydroxy benzaldehyde
2) m-hydroxybenzaldehyde and m-chlorobenzyl alcohol
3) m-chlorobenzyl alcohol and m-hydroxybenzyl alcohol
4) potassium m-chlorobenzoate and m-chlorobenzyl alcohol
30. Which aldehyde is used for the preparation of bakelite?
1) Ethanal 2) Propanal 3) Methanal 4) Butanal
227
KEY WITH HINTS

LEVEL - I
1. 3
2. 2 Propiophenone is C6H5COCH2CH3
O
3. 1 C [Presence of double bond].

4. 1
5. 2
6. 3 Nitriles are selectively reduced by diisobutyl aluminium hydride.
7. 4
8. 4 Gem dihalides.
O
 H2O
CH 3  CH  Cl 
KOH (aq)
 CH 3  CH  OH   CH 3  C  H
Cl OH
(unstable) (acetaldehyde)
CHO
9. 2 
CO,HCl
Anhy.AlCl3 /CuCl
10. 1 CH 2  CH  CH 2 OH 
PCC
 CH 2  CH  CHO
11. 2 2R  C  Cl  R 2 Cd 
 2R  C  R  CdCl 2
O O
Ketone
12. 3 R  CN  R  MgX 

H2O
R CR
13. 3
O
CH3 CH(OCrOHCl2)2 C
 H
14. 2  CrO 2 Cl2 
CS2

H3O

(X) Benzaldehyde
228
15. 2
16. 4 Ketones are less reactive than aldehydes whereas electron-withdrawing groups (i.e., NO2)
increase the reactivity while electron donating groups (i.e., CH3) decrease the reactivity of aromatic
aldehydes towards nucleophilic addition reactions.
O OR'
17. 1 
R  C  H  2R   OH 
HCl
 R  C  H  H2O
OR'
(Acetal)
18. 3 CH 3COCH 3 

CH3 MgI
(CH3 )3 COH
Acetone tert  Butylalcohol
O OH
19. 2 a) CH 3C  CH 3 
LiAlH 4
 CH 3CHCH 3
O OH
b) CH 3C  CH 2 CH 3 
LiAlH 4
 CH 3 *C  CH 2 CH 3
H
(Optically active)
O OH
c) H 3C  CH 2  C  CH 2 CH 3 
LiAlH 4
 H 3C  CH 2  C  CH 2 CH 3
O OH
C 
LiAlH 4
 H C
d)
20. 3 R  C  H  NH 2  NH 2 
 R  CH  N  NH 2
Hydrazone
229
21. 2 Zinc Amalgam
22. 4 Tollens reagent is ammoniacal solution of silver nitrate in which silver remains as [Ag(NH 3 ) 2 ]
23. 1 CH 3CHO  2CuO  CH 3COOH  Cu 2O 

(Re d ppt.)
Thus, in this reaction, precipitate of copper oxide (Cu2O) is formed. Fehling solution is an alkaline
solution of cupric ions complexed with sodium potassium tartarate.
24. 4 Benzaldehyde gives Tollens test, but acetophenone does not. On the other hand, acetophenone
(Ph – COCH3) gives iodoform test but benzaldehyde does not.
25. 1 Since X (C5H10O) forms a phenylhydrazone but does not give Tollens’ test, it cannot be an
aldehyde but must be a ketone. Since (X) does not give, iodoform test, it can not be a methyl
ketone.
26. 1 CH3  CH  CH 2  CHO

Aldol
OH
[3-hydroxy butanal]
27. 3 Acid chlorides are reactants.

28. 3
H
H H
O  O
29. 1 C O+ C Conc KOH

 H C OH + H C
H H OK
H
30. 2
LEVEL - II
O
7 6 5 4 3 2 1
1. 2 CH 3  CH 2  CH 2  CH  CH  CH 2  C  H
Br CH3
2. 2 2, 2, 2- trichloroethanal.
3. 3
4. 3
5. 1
6. 3 PCC is pyridinium chlorochromate is an oxidising agent.
7. 2 R  CH  NH
 i min e 
230
8. 2 DIBAL-H reduces –COOR as well as C  N groups to –CHO group.
CHCl2
9. 1
10. 3 CH 3  CH  CH 2  CH 3 
KMnO4
CH 3  C  CH 2  CH 3
OH
Butan-2-ol
O
H3C CH3
11. 2 C C 
O3 , Zn
 Ozonolysis  2CH 3  C  CH 3  ZnO
H3C CH3 Acetone
OH O
12. 3 CH 3  CH  CH 3  PCC
 CH 3  C  CH 3
mild oxidation
Secondary alcohol Ketone
13. 2
14. 3 Carbonyl groups are strongly polarized. Partially positive at the carbon end. It is able to attack
nucleophiles.
3
sp

     
15. 2 C  O  
Nu
 C  O  
H
 C  OH
2
sp
Nu Nu
16. 3
17. 1 The size of the alkyl group causes hindrance the to attacking group. As the number and size of
the alkyl groups increase, hindrance to attack of nucleophile also increases. Thus, the reactivity
follows the order H 2 C  O  RCHO  ArCHO  R 2 C  O  Ar2 C  O
CH3 CN
18. 3 
CH 3  C  CH 3   

CN 
H C
O CH3 OH
Cyanohydrin
19. 4
231
20. 4 NaBH4 reduces (C = O) to CH2OH.

21. 2 This is an example of Wolff-Kishner reduction.
22. 2 Fehling solution, Schiff’s reagent and Tollens reagent react only with aldehydes but Grignard
reagent reacts with both aldehyde and ketones.
23. 3 Diethyl ketone (C2H5COC2H5) will not show iodoform test.
24. 2
25. 1 
dil NaOH
2CH 3CHO  
 CH 3  CH  CH 2  CHO 

 H2O
 CH 3  CH  CH  CHO
But  2  enal
OH
26. 2 CH3CH2CHO has two   hydrogen atoms so it can undergo self aldol condensation in presence
of cold dilute alkali.
OH
CH3  CH 2CHO  CH3  CH 2 CHO dil

alkali
 CH3  CH  CH  CH 2  CH 3
CHO
27. 3 Aldehydes and ketones having at least one  -hydrogen, in the presence of dilute alkali as
catalyst, form  -hydroxy aldehdes (aldol) or  -hydroxy ketones (ketol) respectively. This is
known as aldol reaction.
28. 4 C6 H 5CHO CH 3CHO 

NaOH

 C6 H 5CH  CH  CHO 
H 2 / Ni
 C6 H 5CH 2 CH 2 CH 2 OH
(X) (Y)
29. 4 m-Chlorobenzaldehyde in the presence of concentrated alkali will undergo Cannizzaro reaction.
The products will be potassium m-chlorobenzoate and m-chlorobenzyl alcohol.
30. 3 Methanal
232
CHAPTER - 09
CARBOXYLIC ACIDS
INTRODUCTION
Organic compounds containing carboxyl (–COOH) functional group are called carboxylic acids. Carboxylic
acids occur widely in nature and are among the earliest compounds to be isolated from natural sources;
formic acid from red ants, acetic acid from vinegar, citric acid, tartaric acid, ascorbic acid, and oxalic acid
from fruits and vegetables, tannic acid, and salicylic acid from the bark of trees, etc.
Carboxylic acids serve as starting material for the preparation of acid chlorides, acid anhydrides, esters,
amides, etc. The food industry uses many organic acids for the production of soft drinks and food products.
Organic acids also find use in making dyestuffs, perfumes, etc.
Fatty acids are carboxylic acids with long aliphatic chains which are either saturated or unsaturated. They
occur in natural fats as triesters of glycerol. These are important dietary sources of fuel and important
structural components of cells. Soaps are sodium or potassium salts of higher fatty acids.
CLASSIFICATION
Carboxylic acids may be classified into aliphatic or aromatic depending on the group, alkyl or aryl, attached
to the carboxyl carbon.
where R = H or any alkyl group for aliphatic acid and aryl group for aromatic acid.
Aliphatic and aromatic carboxylic acids are classified as mono-, di-, tri-, and poly-carboxylic acids depending
on the number of carboxyl groups in their molecules.
NOMENCLATURE
Nomenclature of Aliphatic Carboxylic Acids
a) Monocarboxylic acids. Monocarboxylic acids have the general formula, RCOOH, where R = H or
any alkyl group. They may be represented as CnH2n+1 COOH or CnH2nO2 where n = 1, 2, 3....etc.
The common names of aliphatic monocarboxylic acids are derived from the Greek or Latin names of
their natural sources. Formic acid (Latin : formica means ant) was first prepared by distillation of red
ants, acetic acid from vinegar (Latin : acetum means vinegar), and butyric acid from rancid butter
(Latin : butyrum means butter), caprylic, caproic and capric acids (Latin: Caper means goat), and so
on.
In IUPAC system, aliphatic carboxylic acids are named by replacing the terminal ‘e’ of the name of the
corresponding straight chain alkane by the suffix ‘oic acid’.
233
Table - 01 The common and IUPAC names of some monocarboxylic acids
Substituted and branched-chain compounds are named as derivatives of the acid having the longest
chain. In the common system, the positions of the substituents are indicated by Greek letters, a, b, g,
etc. with the carbon adjacent to the carboxyl group being designated as  .
In the IUPAC system, the positions of the substitutents are indicated by arabic numerals with the
carbon atom of the carboxyl group being numbered 1.
    5 4 3 2 1
 C C C  C  COOH  C C C C C OOH
Common system IUPAC system
(b) Dicarboxylic acids. Most aliphatic dicarboxylic acids are known by their common names, e.g., oxalic
acid, malonic acid, etc. In IUPAC system, names of dicarboxylic acids are obtained by adding the
suffix ‘dioic acid’ to the name of the parent alkane, the positions of the carboxyl groups being indicated
by arabic numerals.
234
c) Tricarboxylic acids. If three carboxyl groups are directly attached to an unbranched carbon chain,
the acid is named as a derivative of the parent alkane which does not include the carbon atoms of the
carboxyl groups. However, if all the three carboxyl groups are not directly linked to the unbranched
carbon chain, the two like carboxyl groups are included in the parent chain while the third is considered
as a substituent group.
Structure of the Carboxyl Group

In carboxylic acids, the carbon atom is sp2 hybridised. The bonds to the carboxyl carbon are in one plane at
an angle 120°. The carboxylic carbon is less electrophilic than carbonyl carbon due to resonance.
Thus, RCOOH may be represented as a resonance hybrid of two canonical structures.
Due to resonance, the C–O single bond length in carboxylic acids (136 pm) is shorter than the normal C–O
single bond (142 pm) and C = O double bond length (123 pm) is slightly longer than normal C = O double
bond length (120 pm).
METHODS OF PREPARATION
1. From primary alcohols and aldehydes. Primary alcohols and aldehydes are oxidised to
carboxylic acids by oxidising agents such as KMnO4 in neutral, acidic or alkaline media or by K2Cr2O7–
H2SO4 or CrO3– H2SO4 (Jone’s reagent). Potassium salts of the acids formed on treatment with dil.
H2SO4 gives carboxylic acids.
H O
RCOOK 
KMnO /KOH
RCH 2OH 
4

 
3
 RCOOH
1 Alcohol Potassium carboxylate Carboxylic acid
(i) KMnO /KOH,

CH3CH 2OH 
4
 CH3COOH
(ii) Dil.H 2SO4
Ethanol Ethanoicacid
235
(i)KMnO /KOH,
C6H5CH2OH  4
(ii)Dil.H SO
 C6H5COOH
2 4
Benzylalcohol Benzoicacid
CrO  H SO
CH 3 (CH 2 )8 OH 
3 2 4
(Jone 's reagent)
 CH 3 (CH 2 )8 COOH
1 Decanol Decanoic acid
Tollens’ reagent. Aldehydes are oxidised to the corresponding carboxylic acids by mild oxidising
agents such as Tollens’ reagent (ammoniacal silver nitrate).
CH3CHO   O 
Tollens '
 CH3COOH
reagent
Acetaldehyde Aceticacid
2. From alkylbenzenes and alkenes. Aromatic acids are obtained by oxidation of alkylbenzenes with
acidic or alkaline KMnO4, acidified K2Cr2O7 or dil. HNO3. The aromatic nucleus remains intact while
the entire side chain is oxidised to a –COOH group except 3° alkyl group.
3. From nitriles and amides. Acid or alkaline hydrolysis of nitriles give carboxylic acids (mild conditions
are used to stop the reaction at the amide stage).
H  or OH  H  or OH 
RCN  H 2O 
 RCONH 2 
 RCOOH  NH 3
Alkanenitrile   Carboxylic acid
Acid amide
H O
CH3CONH 2 
3

 CH3COOH  NH3
Ethanamide Ethanoic acid
C6 H5CONH 2  HCl  H 2O 
 C6 H5COOH  NH 4Cl
Benzamide Benzoic acid
4. From Grignard reagents. Grignard reagents react with carbon dioxide (dry ice) to form salts of carboxylic
acids which give carboxylic acids on acidification with mineral acid.
236
This method is useful for converting alkyl halides into a carboxylic acids having one carbon atom more
than the alkyl halide.
5. From acyl or acid halides and anhydrides. Acyl or acid chlorides are hydrolysed by water to carboxylic
acids or more readily by aqueous base to carboxylate ions which on acidification give the corresponding
acids.
RCOCl  H 2 O 
 RCOOH  HCl
(i) Aq.NaOH, 
RCOCl 
 RCOOH
(ii) Dil.HCl
Anhydrides are slowly hydrolysed by cold water and rapidly by hot water to the corresponding acids.
 C6H5CO 2 O  H 2O 
 2 C6 H 5COOH
Benzoic anhydride Benzoicacid
C6 H5COOCOCH3  H 2O 
 C6 H5COOH  CH3COOH
Benzoic ethanoic anhydride Benzoic acid Ethanoic acid
6. From esters. Hydrolysis of esters with mineral acids gives carboxylic acids. Hydrolysis with alkalies
gives carboxylates, which on acidification forms the corresponding carboxylic acids.
PHYSICAL PROPERTIES
The first three aliphatic acids are colourless pungent smelling liquids. The next six acids, (C4– C9) are
colourless oily liquids with unpleasant smell (butyric acid has smell of rancid butter). Acids with ten or more
carbon atoms are colourless waxy solids with no distinct smell. Most of the aromatic acids are colourless
solids with no distinct smell.
Solubility. Simple aliphatic carboxylic acids having up to four carbon atoms are miscible with water due to
the formation of hydrogen bonds with water. The solubility decreases as the number of carbon atoms
increases. Pentanoic acid (n-valeric acid) and hexanoic acid (caproic acid) are only slightly soluble in water.
Higher carboxylic acids are insoluble due to increased hydrophobic interactions of the hydrocarbon part.
Benzoic acid is almost insoluble in cold water but soluble in hot water. However, all carboxylic acids are
soluble in less polar solvents such as benzene, ether and alcohol.
(a) (b)
Figure - 01 Carboxylic acid (a) H-bonding with water (b) Dimerisation in aprotic solvents.
237
Boiling points. The boiling points of both aliphatic and aromatic carboxylic acids increase with molecular
size due to increase in van der Waals force of attraction. The boiling points are much higher than hydrocarbons
and somewhat higher than aldehydes, ketones and alcohols of comparable molecular masses because of
stronger intermolecular H-bonds.
In the vapour phase and in aprotic solvents, most carboxylic acids exist as cyclic dimers in which two
molecules of the acid are held together by two hydrogen bonds. The existence of cyclic dimers is supported
by the fact that the molecular mass of acetic acid in solvents like benzene is 120 instead of 60.
ACIDITY OF CARBOXYLIC ACIDS
Carboxylic acids are weaker acids than mineral acids. In aqueous soution, carboxylic acid ionizes and
exists in dynamic equilibrium with the carboxylate ion and the hydronium ion.
 RCOO   H3O 
RCOOH  H 2 O 
RCOO  H3O  RCOO  H3O 
Keq  or K a  Keq [H2O] 
 RCOOH H2O  RCOOH
Keq is the equilibrium constant and Ka is called dissociation constant of the acid.
Greater the value of Ka greater the tendency of the acid to ionize and hence stronger the acid.
pKa values. Acid strength can be expressed in terms of its pKa value which is the negative logarithum of the
equilibrium constant Ka.
pKa = –log Ka
(i) The smaller the numerical value of pKa, stronger is the carboxylic acid. Strong acids have pKa values
< 1 (HCl = –7, H2SO4 = –9, (CF3COOH = 0.23).
(ii) Acids with pKa values between l and 5 are moderately strong (CH3COOH = 4.76, C6H5COOH = 4.19).
(iii) Weak acids have pKa values between 5 and 15 and extremely weak acids have pKa values greater
than 15. Thus, carboxylic acids are stronger than alcohols (pKa ~ 16) and phenols (pKa = 10).
Cause of acidic nature of carboxylic acids. Carboxylic acid may be regarded as a resonance hybrid of
structures, I and II.
Due to the presence of positive charge, oxygen atom attracts the electrons of the O–H bond towards itself
and facilitates the release of a proton. The resulting carboxylate ion is resonance stabilised.
The carboxylic acid and the carboxylate ion are resonance stabilised, but the stabilisation is greater in the
latter. This is because canonical structures III and IV for the carboxylate ion are equivalent and do not
involve separation of positive and negative charges. Thus the greater stability of the carboxylate anion is the
reason for the acidic character of carboxylic acids.
238
Comparison of acidic character of alcohols phenols and carboxylic acids

The relative strength of alcohols, phenols, and carboxylic acids depends on the relative stability of alkoxide
ions and carboxylate ions formed by the removal of a proton.
(i) Carboxylic acids are much stronger acids than alcohols. This is because the carboxylate ion
(RCOO–) is resonance stabilised while the alkoxide ion (RO–) is not.
(ii) Carboxylic acids are more acidic than phenols. Resonance stabilisation in phenoxide ion is much
less than in carboxylate anion because in the phenoxide ion, structures carry a negative charge on the
less electronegative carbon atom.
Since the delocalisation of electrons in benzene contributes little towards the stability of the phenoxide ion,
carboxylate anion is much more resonance stabilised than phenoxide ion.
Effect of substituents on the acid strength of aliphatic acids. Electron withdrawing groups (EWG)
increase the stability of the carboxylate anion by dispersing the negative charge and hence increase the
acidity of the substituted acid. Electron donating groups (EDG) decrease the stability of the carboxylate ion
by enhancing the negative charge and decreases the acidity of the substituted carboxylic acid.
a) Electron withdrawing groups (EWG). The effect of some substituents in increasing the acidity of
carboxylic acids is : Ph < I < Br < Cl < F < CN < NO2 < CF3.
(i) Since –I -effect of halogens decreases in the order F > Cl > Br > I, the acidic strength of  -haloacids
decreases in the same order. (ii) Greater the number of electron withdrawing substituents, greater the
dispersal of the negative charge and stronger the acid. (iii) Inductive effect decreases rapidly with
distance, therefore, acidic strength decreases with distance between the electronegative atom and
the COOH group. (iv) Acid strength varies with the type of hybridisation of carbon atom carrying the
COOH group: sp > sp2 > sp3.
Contarary to an expected decrease in acid strength, direct attachment of groups like acetylenic, phenyl,
vinyl, etc., to the –COOH group increases the acidity of the carboxylic acid.
This is due to greater electronegativity of sp2 hybridised carbon attached to the carboxyl carbon.
239
b) Electron donating groups (EWG). Methyl group in acetic acid has electron-donating inductive effect
(+ I effect) which increases the electron density of the O–H bond. As a result, release of H+ ions from
acetic acid is more difficult compared to formic acid. The +I effect of CH3 group intensifies the negative
charge on the carboxylate ion thereby making acetate ion less stable than formate ion.
Since +I effect increases in the order, CH3– < CH3CH2– < (CH3)2CH– < (CH3)3C–, the relative acid
strength decreases in the same order.
c) Effect of substituents on the acid strength of aromatic acids. Presence of EWGs on the phenyl
ring of aromatic carboxylic acid increases its acidity while EDGs decreases acidity:
The acid-weakening effect of electron-donating substituents and the acid-strengthening effect of

electron-withdrawing substituents are more pronounced at the para- and meta- positions.
Thus, the increasing order of acidity of acids is : CF3COOH > CCl3COOH > CHCl2COOH >
NO 2CH2COOH > NC-CH 2COOH > FCH 2COOH > ClCH 2COOH > BrCH2COOH > HCOOH >
ClCH2CH2COOH > C6H5COOH > C6H5CH2COOH > CH3COOH > CH3CH2COOH.
CHEMICAL REACTIONS
Reactions involving Cleavage of O–H Bond
(i) Reaction with metals. Carboxylic acids, like alcohols and phenols, react with electropositive metals
evolving hydrogen.
2 RCOOH  2 Na 
 2RCOONa  H 2
Sodiumcarboxylate
(ii) Reaction with alkalies. Carboxylic acids neutralize alkalies forming salts.
RCOOH  NaOH 
 RCOONa  H 2 O
Sodium carboxylate
CH 3COOH  NaOH 
 CH3COONa  H 2 O
Acetic acid Sodium acetate
(iii) Reaction with metal carbonates and bicarbonates. Carboxylic acids react with weak bases such
as carbonates and hydrogen carbonates evolving carbon dioxide.
2 RCOOH  Na 2 CO 3 
 2RCOONa  CO 2  H 2 O
RCOOH  NaHCO3 
 RCOONa  CO 2  H 2 O
C6 H5COOH  NaHCO3 
 C6 H5COONa  CO2  H 2O
Benzoic acid Sodium benzoate
The reaction of carboxylic acids with NaHCO3 is used to detect the presence of carboxyl group in an
organic compound. Since most phenols do not produce effervescence with aqueous solution of NaHCO3,
this reaction can be used to distinguish phenols from carboxylic acids.
240
Reactions involving Cleavage of C–OH Bond

(i) Formation of anhydrides. Carboxylic acids, when heated in presence of a strong dehydrating agent
such as phosphorus pentoxide or conc. H2SO4, form anhydrides.
Acid anhydrides can also be obtained by treating acid chlorides with carboxylic acids in presence of
pyridine or by treating acid chlorides with sodium salts of carboxylic acids.
CH3COOH  CH3COCl 

Pyridine
 CH3CO 2 O  HCl
  CH3CO 2 O  NaCl
CH3COONa  CH3COCl 
(ii) Esterification. When carboxylic acids are heated with alcohols or phenols is presence of conc. H2SO4
or dry HCl gas, esters are formed (Fischer-Speier esterification).


H
RCO OH  R OH 
 RCOOR   H 2 O
Acid Alcohol Ester


H
CH3COOH  C 2 H5OH 
 CH 3COOC2 H5  H 2 O
Aceticacid Ethylalcohol Ethylacetate
Mechanism. Esterification is a nucleophilic acyl substitition reaction involving three steps:

Step 1. Protonation of the carbonyl group. In presence of mineral acid (H2SO4 or HCl), the carbonyl
group of the carboxylic acid accepts a proton to form protonated carboxylic acid.
Step 2. Nucleophilic attack by alcohol molecule. Protonation of the carbonyl oxygen activates the
carbonyl group towards nucleophilic addition of alcohol to form tetrahedral intermediate.
Step 3. Loss of a molecule of water and a proton. Proton transfer in the tetrahedral intermediate
converts -OH group into OH 2 , which being a good leaving group is eliminated as a water molecule to
form the protonated ester which finally loses a proton to give the ester.
(iii) Formation of acid chlorides. Carboxylic acids react with thionyl chloride (SOCl2), phosphorus
pentachloride, and phosphorus trichloride to form acid chlorides.
241
RCOOH  SOCl2 
 RCOCl  SO2  HCl
Acid chloride
3RCOOH  PCl3 
 3RCOCl  H3PO3
Phosphorus acid
RCOOH  PCl5 
 RCOCl  POCl3  HCl
Phosphours oxychloride
Thionyl chloride is preferred because the other two products (SO2 and HCl) are gases and escape
from the reaction mixture, making the purification of product easier.
(iv) Reaction with ammonia. With ammonia, carboxylic acids form ammonium salts which on heating
lose a molecule of water to form amides.

 RCOO  NH 4 
RCOOH  NH3 

Heat
 RCONH 2  H 2O
Ammoniumsalt Acid amide
 CH3COO  NH 4 
Heat
CH3COOH  NH3   CH3CONH 2  H 2O
Acetic acid Ammonium acetate Acetamide
Reactions involving Carboxyl Group
a) Reduction to alcohols. The reduction of carboxylic acids with lithium aluminium hydride (LiAlH4) or
diborane (B2H6) gives primary alcohols. The CO group of the carboxyl group is reduced to CH2.
(i) LiAlH /ether or B H /ether

RCOOH 
4
(ii) H O 
2 6
 RCH 2OH
Carboxylic acid 3
1o Alcohol
Sodium borohydride does not reduce carboxyl group. Diborane does not easily reduce functional groups
like halo, nitro, ester etc.
b) Decarboxylation. (i) Using soda-lime. Sodium salt of carboxylic acid when heated with sodalime
(NaOH + CaO in the ratio 3 : 1) undergos decarboxylation to yield alkane.
CaO/630K
RCOONa  NaOH 
 RH  Na 2 CO3
Alkane
242
Substitution reactions in the hydrocarbon part

Halogenation. Carboxylic acids having hydrogen (except formic acid which does not contain an alkyl group)
react with chlorine or bromine in presence of red phosphorus to give a-chloro or a-bromo acids. This is
known as Hell-volhard-Zelinsky (H.V.Z.) reaction.
R  CH 2  COOH 
2 (i) X ,red P
 R  CHX  COOH
(ii) H 2O
 X  Cl or Br 
Carboxylic acid Halocarboxylicacid
With more of chlorine or bromine, the second and third a-hydrogen atoms can be successively replaced.
Reactions of the Aryl group
Ring Substitution in Aromatic Acids : Aromatic carboxylic acids undergo electrophilic substitution reactions
of the ring. Since –COOH group is electron-withdrawing (deactivating) and meta-directing, reactions occur
only under drastic conditions.
Carboxylic acids do not undergo Friedel-Crafts reaction because the carboxyl group is strongly deactivating
and the catalyst, AlCl3 (Lewis acid) gets strongly bonded to the carboxyl group.
USES OF CARBOXYLIC ACIDS

Methanoic (formic) acid is used (i) as a coagulating agent for latex in rubber industry, (ii) for dehydration of
hides in leather industry, (iii) as an acid bath in textile dyeing and electroplating industries and (iv) as a
medicine for gout and neuritis. Ethanoic acid is used (i) as a solvent, (ii) as vinegar in food industry, (iii) in the
manufacture of plastic (polyvinyl acetate), rayon (cellulose acetate), and silk. Hexane-1, 6-dioic acid (adipic
acid) is used in the manufacture of nylon-6,6. Sodium benzoate is used as a preservative in food industry.
Esters of benzoic acid are used in perfumery. Higher fatty acids are used for the manufacture of soaps and
detergents.
243
QUESTIONS
LEVEL - I
1. The general formula for aliphatic saturated monocarboxylic acids is :
1) C n H 2n 1O 2 2) C n H 2n O 2 3) C n H 2n 1O 2 4) Cn H 2n  2 O 2
2. In carboxylic acids, a carbonyl group is attached to a/an

1) Aldehydic group 2) Oxygen 3) Hydroxyl group 4) Hydrogen
CH2 CH2 COOH

3. . IUPAC name of this compound is :
1) 3-phenyl propanoic acid 2) 1-phenyl propanoic acid

3) Benzene propanoic acid 4) Benzopropanoic acid
4. The IUPAC name of OH is :

1) but-3-enoic acid 2) but-1-enoic acid 3) pent-4-enoic acid 4) prop-2-enoic acid

5. CH 3  CH 2  CH 2  COONa 
H2 O
 X. The product X is
1) CH3 – CH2 – COOH 2) CH3 – CH2 – CH2 – COOH
3) CH3 – COOH 4) CH 3  CH  COOH
CH3
6. CH 3  CH 2  CH 2  CH 2 OH 
X,Y
 Z . X, Y and Z respectively are :
1) CrO3, H2SO4, CH3 – CH2 – CH2 – COOH 2) CO2, HCl, CH3 – CH2 – CH2 – COOH
3) CrO2Cl2, CS2, CH3 – CH2 – COOH 4) AgNO3, Mg, CH3 – CH2 – COOH
7. The final product formed when Grignard reagent reacts with dry ice
1) Aldehydes 2) Ketones 3) Alcohols 4) Carboxylic acids
8. The acid formed when propyl magnesium bromide is treated with CO2 is :
1) C2H5COOH 2) C3H7COOH 3) CH3COOH 4) Both 1 and 2
2
9. C2 H 2 
Hg 1%
H2SO 4
 A 
[O]
 B . B is :
1) Ethanoic acid 2) Ethanal 3) Propanone 4) Ethanol

10. An acyl halide is formed when PCl5 reacts with
1) Carboxylic Acid 2) Alcohol 3) Amide 4) Aldehyde
244
11. The reagent which does not give acid chloride on treating with a carboxylic acid is :
1) PCl5 2) Cl2 in presence of traces of red P
3) SOCl2 4) PCl3
12. Formic acid can reduce
1) Tollen’s reagent 2) Mercuric chloride 3) Fehling’s solution 4) All of these
13. Carboxylic acids have higher boiling points than aldehydes, ketones and even alcohols of comparable
molecular mass. It is due to
1) formation of intramolecular H-bonding
2) formation of carboxylate ion
3) extensive association of carboxylic acid via van der Waals’ forces of attraction
4) formation of intermolecular H-bonding
14. Identify the correct order of boiling points of the following compounds
CH 3CH 2 CH 2 CH 2 OH , CH 3CH 2 CH 2CHO , CH 3CH 2 CH 2 COOH

(1) (2) (3)
1) 1 > 2 > 3 2) 3 > 1 > 2 3) 1 > 3 > 2 4) 3 > 2 > 1

15. The correct order of acidic strength of carboxylic acids is:
1) formic acid < benzoic acid < acetic acid 2) formic acid < acetic acid < benzoic acid
3) acetic acid < formic acid < benzoic acid 4) acetic acid < benzoic acid < formic acid
16. Identify the incorrect statement from the following
1) Carboxylic acids are weaker than mineral acids
2) Carboxylic acids are less acidic than phenols
3) Electron withdrawing groups increase the acidity of carboxylic acids
4) Electron donating groups decrease the acidity of carboxylic acids
17. Carboxylic acids are reduced to primary alcohols better with
1) KMnO4 2) H2O2 3) B2H6 4) NaOH
18. Which of the following compounds will react with NaHCO3 solution to give sodium salt and carbon
dioxide?
1) Phenol 2) n-hexanol 3) Acetic acid 4) Both 1 and 2
19. The ester formed by the reaction of propanoic acid and propanol is :
1) Ethyl butanoate 2) Propyl propanoate 3) Butyl ethanoate 4) Methyl pentanoate

20. CH 3COOH 
P2 O5
 X. Identify X
1) CH3COCH3 2) CH3COCl 3) (CH3CO)2O 4) ClCH2COOH

NaOH  CaO
21. CH 3  CH 2  COONa 
X  Na 2 CO3 . X is :
1) Propane 2) Ethane 3) Methane 4) Ethene
245

22. Name the end product in the following series of reactions, CH 3COOH 
NH3

 A 
PO
B 2 5
1) Methane 2) Methanol 3) Ethanenitrile 4) Ammonium acetate

23. In the preparation of an ester, the commonly used catalyst is :
1) Phosphorus pentoxide 2) Anhydrous calcium carbide
3) Anhydrous aluminium chloride 4) Concentrated sulphuric acid
24. A liquid was mixed with ethanol and a drop of concentrated H2SO4 was added. A compound with a
fruity smell was formed. The liquid most probably is :
1) CH3OH 2) HCHO 3) CH3COCH3 4) CH3COOH
25. Which among the following statements is incorrect?
1) Carboxylic acids are reduced to primary alcohols by LiAlH4
2) Diaborane easily reduce functional groups such as ester, nitro, halo etc.
3) Sodium borohydride does not reduce carboxyl group
4) Soda lime is a mixture of NaOH and CaO in the ratio 3 : 1
COOH
26. 
Conc.HNO3
Conc.H 2SO 4
. The product formed is :
NO2 COOH
NO2 NO2 NO2
NO2
1) 2) 3) 4)
NO2
NO2
27. Vinegar is 6 - 10% aqueous solution of
1) Ethanoic acid 2) Methanoic acid 3) Citric acid 4) Tartaric acid
COOH
28. 

H 3 O
A   C2 H 5OH . A is :
COOC2H5 CH2 – CH2 – OH

1) 2)
OH O
CHO C– CH3
3) 4)
246
29. In the presence of a small amount of red phosphorous, aliphatic carboxylic acids react with chlorine
or bromine to yield a compound in which  -hydrogen has been replaced by halogen. This reaction is
known as
1) Wolff-Kishner reaction 2) Etard reaction
3) Hell-Volhard-Zelinsky reaction 4) Rosenmund reaction
30. Why the aromatic carboxylic acids do not undergo Friedel-Crafts reaction?
1) Carboxyl group acts as an activating and meta-directing group
2) Carboxyl group is deactivating and act as Lewis base
3) Carboxyl group acts as an activating and ortho-directing group
4) Carboxyl group acts as deactivating group and the catalyst
LEVEL - II
1. Which among the following is a tribasic acid?
1) Oxalic acid 2) Tartaric acid 3) Lactic acid 4) Carballylic acid
2. The IUPAC name of the compound HOOC  CH 2  CH  CH 2  COOH is
COOH
1) Hexane tricarboxylic acid 2) Hexane trioic acid
3) Propane -1, 2, 3-tricarboxylic acid 4) 1, 2, 3- propane trioic acid
3. Which of the following acids is isomeric with phthalic acid?
1) Succinic acid 2) Salicylic acid
3) 1,4-Benzenedicarboxylic acid 4) Methyl benzoate
COOH
COOH
4. . IUPAC name of the compound is :
1) Phthalic acid 2) Benzene-1,2-dicarboxylic acid

3) Phenyl acetic acid 4) Phenyl-1,2-dioic acid
5. Conversion of butan-2-one to propanoic acid requires
1) Tollen’s reagent 2) NaOH/NaI/H+ 3) Fehling’s solution 4) NaOH/I2/H+
6. Acetic acid reacts with sodium metal at room temperature to produce
1) CO2 2) H2 3) H2O 4) CO
7. Which one of the following orders of acid strength is correct?
1) RCOOH > HC  CH > HOH > ROH 2) RCOOH > ROH > HOH > HC  CH
3) RCOOH > HOH > ROH > HC  CH 4) RCOOH > HOH > HC  CH > ROH
8. Carboxylic carbon is less electrophilic than carbonyl carbon because of
1) Inductive effect 2) Less polarity 3) Resonance effect 4) Electromeric effect
247
9. The compound formed as a result of oxidation of ethylbenzene by KMnO4 followed by acidification is

1) benzyl alcohol 2) benzophenone 3) acetophenone 4) benzoic acid
10. When CH2 = CH – COOH is reduced with LiAlH4, the compound obtained will be:
1) CH 3  CH 2  CHO 2) CH 3  CH 2  COOH
3) CH 2  CH  CH 2OH 4) CH 3  CH 2  COOH
11. Treatment of benzoic acid with Cl2/FeCl3 will give :

1) p-chlorobenzoic acid 2) o-chlorobenzoic acid
3) 2,4-dichlorobenzoic acid 4) m-chlorobenzoic acid
12. CH3CH = CHCHO is oxidised to CH3CH = CHCOOH using:
1) Alkaline KMnO4 2) Selenium dioxide 3) Ammoniacal AgNO3 4) All of these
13. Reaction of 2-butene with acidic KMnO4 gives
1) CH3CHO 2) HCOOH 3) CH3CH2OH 4) CH3COOH
14. Which of the following acids is most reactive towards esterification with cyclohexanol?
1) CH3COOH 2) CH3CH2COOH 3) HCOOH 4) (CH3)2CHCOOH
15. The groups CF3, Ph, CN, NO2 increases the acidity of carboxylic acids. Arrange the correct increasing
order.
1) –Ph < –CN < –NO2 < –CF3 2) –CF3 < –NO2 < –CN < –Ph
3) –NO2 < –CF3 < –CN < –Ph 4) –CN < –Ph < –NO2 < –CF3
16. The molecular weight of acetic acid in vapour phase is :
1) 60 2) 30 3) 120 4) 240
MgBr
17. 
(i) CO2
(ii) H 2 O P. In the reaction, product P is :
CHO COOH OH
O
1) 2) 3) 4) C6H5 C C6H5
18. The pKa of trifluoroacetic acid, benzoic acid, acetic acid and hydrochloric acid are respectively
1) 4.76, 4.19, 0.23 and –7.0 2) 0.23, 4.19, 4.76 and –7.0
3) 4.19, 4.76, –7.0 and 0.23 4) –7.0, 4.19, 4.76 and 0.23
19. Which of the following tests would help in the distinction of HCOOH and CH3COOH?
1) Treatment with Tollens reagent 2) Treatment with NaOH
3) Treatment with Na 4) Formation of their respective amides
248
20. p-Nitrobenzoic acid is a stronger acid than benzoic acid. This is due to :
1) direct resonance interaction between –NO2 and –COOH groups.
2) –NO2 group generates a strong-electron withdrawing inductive effect due to positive charge on
carbon bearing –COOH group.
3) –NO2 group generates a strong-electron withdrawing inductive effect due to positive charge on
meta position to –COOH group.
4) strong inductive effect of –NO2 group.
21. In the presence of KMnO4 and H2SO4 cyclohexene is converted to
1) Oxalic acid 2) Adipic acid 3) Benzoic acid 4) Phenyl ethanoic acid
22. What happens when 2-hydroxy benzoic acid is distilled with zinc dust, it gives
1) Phenol 2) Benzoic acid
3) Benzaldehyde 4) A polymeric compound
23. The final product formed when acetic acid is treated with NH3 followed by heating is :
1) Ammonium acetate 2) Methyl amine
3) Ethylamine 4) Ethanamide
24. Which reagent will bring about the conversion of caboxylic acids into esters?
1) C2H5OH 2) Dry HCl + C2H5OH 3) LiAlH4 4) Al(OC2H5)3
25. Hydrolysis reaction of fats with caustic soda is known as :
1) Esterification 2) Saponification 3) Acetylation 4) Carboxylation
26. The final product (R) in the following reaction sequence is
  P     Q   R 


C6 H 5CH 2OH  
HBr KCN H 3O

1) Benzoic acid 2) 3-Bromobenzoic acid

3) Benzyl cyanide 4) Phenyl ethanoic acid
27. A halogen compound on hydrolysis with dilute alkali followed by acidification gives acetic acid. The
compound is:
1) CH3CHCl2 2) CH3CCl3 3) ClCH2CH2Cl 4) ClCH2CHCl2
28. The acid used for the preparation of nylon-6,6 is :
1) Benzoic acid 2) Hexane-1, 6-dioic acid
3) Propanedioic acid 4) Glutaric acid
29. The carboxylic acid which does not undergo Hell Vohlard Zelinsky reaction is:
1) HCOOH 2) (CH3)2CHCOOH
3) CH3CH2CH2CH2COOH 4) CH3 – CH – CH2 – CH3
COOH
30. HVZ reaction is used for the formation of
1)  -halocarboxylic acid 2)  -halocarboxylic acid
3) Aromatic acids 4) Dicarboxylic acids
249
KEY WITH HINTS

LEVEL - I
1. 2
2. 3 Carbonyl group is attached to hydroxyl group.
3. 1
O
4 3 2 1
4. 1 CH 2  CH  CH 2  C  OH
But-3-enoic acid
5. 2
6. 1 CH 3  CH 2  CH 2  CH 2 OH 
CrO 3 /H 2SO 4
 CH 3  CH 2  CH 2  COOH
O

7. 4 RMgX  CO 2 
 R  C  OMgX 
H 3O
 RCOOH
8. 2 C3 H 7 MgBr  CO 2 
 C3 H 7 COOH  Mg(OH)Br
2
9. 1 CH  CH 
1%Hg
H2SO4
CH3CHO  CH3COOH [O]
acetic acid
10. 1 CH3COOH  PCl5  CH3COCl POCl3  HCl

Acid Acid chloride
11. 2 (1) CH 3COOH  PCl5 

 CH3 CO Cl + POCl3 + HCl
(Acid chloride)
(2) CH 3COOH  Cl 2 
 Cl  CH 2  COOH  HCl
(Chloroacetic acid)
(3) CH 3COOH  SOCl 2 

 CH 3  COCl  SO 2  HCl
(Acid chloride)
(4) 3CH 3COOH  PCl3 

 3CH 3COCl  H 3 PO3
(Acid chloride)
12. 4 Tollen’s reagent - HCOOH  Ag 2 O  CO 2  H 2 O  2Ag

(silver mirror)
Fehling’s solution - HCOOH  2CuO  CO 2  H 2O  Cu 2 O

(red ppt )
Mercuric chloride - 2HCOOH  2HgCl 2  2CO 2  4HCl  2Hg

(black )
250
13. 4 Due to the formation of intermolecular H-bonding, association occurs in carboxylic acids.
O H O
R C C R
O H O
So, they have higher boiling points than aldehydes, ketones and alcohols of comparable mo-
lecular mass.
14. 2 –COOH and –OH group from the hydrogen bond by which they have high boiling point –COOH
group show strong hydrogen bonding so it form dimer and have more boiling point than –OH
group. While –CHO group do not form hydrogen bond. Thus the BP order are as 3 > 1 > 2.
15. 4 Acetic acid < benzoic acid < formic acid.
16. 2 Carboxylic acids are more acidic than phenols.
17. 3 RCOOH 

B2 H 6
H O
 RCH 2  OH
3
18. 3 CH 3COOH  NaHCO3  CH 3COONa  H 2O  CO 2
19. 2 CH 3  CH 2  COO H  HO  CH 2  CH 2  CH 3 
 CH 3  CH 2  COO  CH 2  CH 2  CH 3  H 2 O
Propylpropanoate
O O O O
P2 O5 / 
20. 3 CH 3  C  OH  HO  C  CH 3   CH 3  C  O  C  CH 3
(Acetic anhydride)
NaOH  CaO
21. 2 CH 3CH 2 COONa 
CH 3  CH 3  Na 2 CO3
[decarboxylation ]

22. 3 CH 3COOH 
NH3
 CH 3CONH 2 
P2 O5
 CH3  C  N
23. 4
24. 4 CH 3COOH  C2 H 5OH 

H 2SO 4
 CH 3COOC2 H5  H 2 O
Ester(Fruity smell)
25. 2 Diborane does not easily reduce functional groups such as ester, nitro, halo etc.
26. 4 Carboxyl group acts as a deactivating and meta directing.
27. 1 Vinegar is 6-10% aqueous solution of acetic acid.
28. 1 Ethyl benzoate.
29. 3 Hell-Volhard-Zelinsky reaction
30. 2 Aromatic carboxylic acids do not undergo Friedel-Craft’s reaction because the carboxyl group
is deactivating and the catalyst aluminium chloride (Lewis acid) gets bonded to the carboxyl
group, which facilitate the reaction at ortho and para-position.
251
LEVEL - II
1. 4 HOOC CH2 C CH2 COOH is carballylic acid.
COOH
2. 3
3. 3 Phthalic acid is the isomer of 1, 4-benzenedicarboxylic acid.
4. 2
5. 4 C 2 H 5  C  CH 3  NaOH  I 2 
 C 2 H 5 COONa  CHI3
O

C2 H 5COONa 
H
 C2 H 5COOH  Na 
O O
6. 2 2CH 3C  OH  2Na  2CH 3C  ONa  H 2 

Acetic acid Sodium Sodium salt Hydrogen
metal of acetic
acid
7. 3
8. 3
9. 4 Alkyl chains on aromatic ring can be oxidized to – COOH by oxidizing agent KMnO4.
10. 3 LiAlH4 reduces only the –COOH without reducing the double bond.
COOH COOH
11. 4 
FeCl3
Cl2

Cl
12. 3 Tollens reagent oxidises CHO to COOH without affecting the (C = C) bond.

13. 4 CH 3  CH  CH  CH 3 
KMnO4 / H
 2CH 3COOH
14. 3
15. 1 Electron withdrawing groups increases the acidity.
16. 3 In vapour phase and aqueous solution acetic acid exists as dimer so molecular weight is 120.
17. 2 C6 H 5 MgBr 

(i) CO 2
(ii) H  O
 C6 H5 COOH
3
(P)
18. 2 pKa of CF3COOH = 0.23 ; C6H5COOH = 4.19 ; Acetic acid = 4.76 ; HCl = –7.0
252
19. 1 HCOOH gives positive Tollens test (silver mirror).

20. 2 The nitro group interacts with the phenyl ring and thereby induces some positive charge on the
ring bearing the COO– causing a strong electron-withdrawing inductive effect on COO– group.
This effect is base-stabilizing and thus acid strengthening.
COOH
21. 2 
KMnO4 / H 2SO 4
Heat

COOH
Cyclohexene Hexane-1,6-dioic acid
[Adipic acid]
22. 2 The –OH group will reduce to H by zinc dust and benzoic acid will form.
23. 4  CH 3COONH 4 

CH 3COOH  NH3  
 H 2O
 CH 3CONH 2
[Ethanamide]
24. 2 RCOOH  C2 H5OH 

dry
HCl
RCOOC2 H5  H 2O
25. 2

26. 4 C6 H 5CH 2OH  
HBr
 C6 H 5CH 2 Br 
KCN
 C6 H 5CH 2CN 
H 3O

 C6 H 5CH 2 COOH
 
(i) NaOH aq
27. 2 CH3CCl3 
(ii)H 
 CH 3COOH
28. 2 Hexane-1, 6- dioic acid is adipic acid. Hexamethylene diamine and adipic acid are used for the
preparation of Nylon-6,6.
29. 1 The acid which does not contain   hydrogen atom.
30. 2 RCH 2  COOH 

X 2 /Red P
H2 O
 R CH COOH
X
-halocarboxylic acid
253
CHAPTER 10
ORGANIC COMPOUNDS CONTAINING NITROGEN
INTRODUCTION
Nitrogen containing functional groups such as amino, cyano, diazo, isocyano, nitro, nitrite, amino, etc. are
present in many natural and synthetic organic compounds. Amines are compounds containing amino
functional group. In nature, amines are present in proteins, vitamins, alkaloids and hormones. Synthetic
amines include polymers, dyestuffs and drugs. Biologically active compounds such as adrenaline and
ephedrine, containing secondary amino group are used for increasing blood pressure. Aniline, ethanolamines,
and several other amines are major industrial commodities used in making rubber, dyes, pharmaceuticals
(Novocain, Benadryl, etc), synthetic resins, fibres, etc. Diazonium salts are intermediates in the preparation
of aromatic compounds including dyes.
CLASSIFICATION
Amines are a class of compounds derived by replacing one or more hydrogen atoms of ammonia molecule
by alkyl/aryl groups. Amines are classified as primary (1o), secondary (2o), and tertiary (3o) depending on
the number of hydrogen atoms in ammonia molecule that are replaced by alkyl or aryl groups.
Amines are further divided into aliphatic amines and aromatic amines.
1. Aliphatic amines. Amines in which the nitrogen atom is directly linked to one, two or three (same or
different) alkyl groups.
2. Aromatic amines
(i) Aryl amines or nucleus substituted amines. These are amines in which the nitrogen atom is directly
linked to one, two or three (same or different) aromatic rings.
254
Structure of Amine
The nitrogen atom in amines, like ammonia, is sp3 hybridised. Three sp3 hybridised orbitals of nitrogen
overlap with carbon and hydrogen atoms depending on the composition of the amine. The fourth sp3
hybridised orbital contains a lone-pair of electrons. Due to the presence of the lone pair, amines have
trigonal pyramidal geometry. The C–N–E (where E is C or H) bond angles are less than the tetrahedral
angle (109° 28´) due to lone pair - bond pair repulsion. Thus, the C-N-C bond angle in trimethylamine is
108° which is greater than ammonia (107° ) due to repulsion between bulky alkyl groups.
Figure - 01 Trigonal pyramidal shape of trimethylamine.
Table - 01 Common and IUPAC names of some amines.
In case of unsaturated amines, the amino group is given preference, e.g., CH2=CH-CH2-NH2 is called
prop-2-en-1-amine or prop-2-enamine (Allylamine).
The simplest arylamine, C6H5NH2, is known as aniline in the common system. It is also an accepted
IUPAC name. While naming arylamines according to IUPAC system, suffix ‘e’ of arene is replaced by
‘amine’. Thus, C6H5–NH2 is named as benzenamine.
255
PREPARATION OF AMINES
1. Reduction of nitro compounds
i) Catalytic reduction. Nitro compounds are reduced to amines on passing hydrogen gas in presence
of finely divided nickel, palladium or platinum at room temperature.
Ni or Pt
CH3CH 2  NO2  3H 2 
 CH3CH 2  NH 2  2 H 2O
Ethanol
Nitroethane Ethyla min e
ii) Reduction with active metals. Active metaals such as Fe, Sn, Zn, etc. and conc.HCl are used.
Fe/HCl
C6 H 5  NO 2  6[H] 
or Sn/HCl
 C6 H5  NH 2  2 H 2O
Nitrobenzene Aniline
2. Ammonolysis of alkyl halides (Hofmann’s ammonolysis method). Cleavage of the C–X bond by
ammonia is known as ammonolysis. An alkyl or benzyl halide on reaction with an ethanolic solution of
ammonia undergoes nucleophilic substitution reaction in which the halogen atom is replaced by an
amino (–NH2) group.
The primary amine behaves as a nucleophile and react further with alkyl halide to form secondary and
tertiary amines, and finally quaternary ammonium salt.
 
RX RX RX
RNH 2 
 HX
 R 2 NH 
 HX
 R3N 
 R 4 NX
1 a mine 2 amin e 3 a min e Quaternaryammoniumsalt(4)
The free amine can be obtained from the ammonium salt by treatment with a strong base:
   
R NH3X +NaOH 
 RNH 2  H 2O  NaX
Substituted ammonium salt
The order of reactivity of halides with amines is RI > RBr > RCl.
3. Reduction of nitriles. Nitriles on reduction with lithium aluminium hydride (LiAlH4) or catalytic
hydrogenation produce primary amines. Reduction with sodium and alcohol is called Mendius
reduction.
256
H /Raney Ni
CH3  C  N 
2
 CH3CH 2  NH 2
or Na  Hg/C2 H5OH
Acetonitrile Ethyla min e
H /Raney Ni
C6 H5  C  N 
2
C6 H5  CH 2 NH 2
or LiAlH 4
Benzonitrile Benzyla min e
This reaction is used for ascent of amine series (preparation of amines containing one carbon atom
more than the starting amine).
4. Reduction of amides. 1°, 2°, and 3° amines, containing the same number of carbon atoms as the
starting amide, can be prepared by the reduction of amides with lithium aluminium hydride.
(i)LiAlH
R  CO  NH 2 
(ii)H 2O
4
R  CH 2 NH 2 ; (i)LiAlH
R  CO  NHR '  4
R  CH 2 NHR '
Amide 1 a min e Amide (ii)H O2
2 a min e
5. Gabriel phthalimide synthesis - Preparation of primary amines. Phthalimide on treatment with

ethanolic KOH forms potassium salt of phthalimide which on heating with alkyl halide followed by
alkaline hydrolysis gives primary amine.
Aromatic primary amines cannot be prepared by this method since aryl halides do not undergo
nucleophilic substitution with the anion formed by phthalimide.
6. Hofmann bromamide degradation reaction. Preparation of primary amines by treating amide with
bromine in aqueous or ethanolic KOH. The amine has one carbon less than the amide.
CH 3CH 2  CONH 2  Br2  4KOH 

 CH 3CH 2  NH 2  K 2 CO 3  2KBr  2 H 2 O
Pr opionamide Ethyla min e
In this degradation reaction, migration of an alkyl or aryl group takes place from carbonyl carbon of the
amide to the nitrogen atom.
PHYSICAL PROPERTIES
The lower aliphatic amines are gases with fishy smell. Primary amines with three or more carbon atoms are
liquids and higher ones are solids. Aniline and other arylamines are colourless but becomes coloured due to
atmospheric oxidation.
Amines are less polar than alcohols. Lower aliphatic amines are soluble in water due to the formation of
hydrogen bonds with water molecules. Solubility decreases with increase in molar mass due to increase in
size of the hydrophobic alkyl/aryl part. Higher amines are insoluble in water. Amines are soluble in organic
solvents like alcohol, ether, benzene, etc.
257
Primary and secondary amines exhibit intermolecular association due to hydrogen bonding. Intermolecular
association is more in primary amines than in secondary amines as there are two hydrogen atoms available
for hydrogen bond formation. Tertiary amines do not show intermolecular association due to the absence of
hydrogen atom. The order of boiling points of isomeric amines is : Primary > Secondary > Tertiary.
CHEMICAL REACTIONS
1. Basic character of amines. Amines are basic (act as nucleophiles) due to the presence of the lone
pair of electrons on the nitrogen atom. In the vapour phase and in organic solvents such as benzene,
chlorobenzene, etc., they act as Lewis bases but in aqueous solution, they act as Bronsted bases
(accept a proton from H2O libereting OH- ions).
Due to the formation of OH- ions, aqueous solutions of amines are basic. When AlCl3 or FeCl3 is added
to aqueous solutions of amines, metal hydroxides are precipitated.
AlCl3  3OH  
 Al(OH)3  3Cl
White gelatinous ppt.
(a) Reaction with acids. Amines react with mineral acids such as HCl, HNO3, H2SO4, etc. to form salts.

RNH 2  HX 
 R N H3X 
1 A min e Alkylammonium halide

 (R 2 N H 2 ) 2 SO 42
2R 2 NH  H 2SO 4 
2A min e Dialkylammoniumsulphate
 C6 H5 NH3 Cl
C6 H 5 NH 2  HCl 
Aniline Anilinium chloride
Amine salts are crystalline solids, soluble in water but insoluble in organic solvents. Amine salts
regenerate the parent amine when treated with a base.
This difference in solubilities of amines and their salts is the basis for their separation from non basic
organic compounds insoluble in water.
(b) Measurement of basic strength. In aqueous solution, the basic strength of amines is measured
either in terms of its basicity constant, Kb or the pKb value.

 R N H 3  OH 
RNH 2  H 2 O 
 
[R N H3 ][OH  ] [R N H3 ][OH  ]
K or K b  K[H 2O] 
[RNH 2 ][H 2O] [RNH 2 ]
Kb, is called the dissociation constant of the base or basicity constant.
pKb=-log Kb
Larger the value of Kb or smaller the value of pKb, stronger is the base.
258
Table - 02 pKb values of amines in aqueous phase.

Name of Amine pKb Name of Amine pKb
Methanamine 3.38 N, N - Diethyl methanamine 3.25
N-Methyl methanamine 3.27 Benzenamine 9.38
N, N - Dimethyl methanamine 4.22 Phenylmethanamine 4.70
Ethanamine 3.29 N-Methylaniline 9.30
N-Ethylethanamine 3.00 N, N-Dimethylaniline 8.92
pKb value of ammonia is 4.75. Aliphatic amines are stronger bases than ammonia due to +I effect of
alkyl groups leading to high electron density on the nitrogen atom. Their pKb values lie in the range of 3
to 4.22. Aromatic amines are weaker bases than ammonia due to electron withdrawing nature of the
aryl group.
(c) Basicity of aliphatic amines. Aliphatic amines are stronger bases than ammonia due to +I effect of
the alkyl group.
The order of basic strength of 1°, 2°, and 3° amines in aqueous solution depends on three factors:
(i)+I -effect of alkyl groups. On the basis of +I effect alone, the basicity of amines should be in the
order: R3N > R2NH > RNH2.
(ii) Stability of the conjugate acids or ammonium cations in aqueous solution due to hydrogen bonding
(with water molecules) should be 1° amine > 2° amine > 3° amine
> >
(iii) Steric effect (hindrance) of the alkyl groups. Order of steric hindrance : R3N > R2NH > RNH2.
These three factors are favourable for 2° amines, therefore, they are the strongest bases.
If the alkyl group is small, i.e., CH3, there is no steric hindrance to H-bonding. Stability due to H-bonding
predominates over stability due to +I-effect of the CH3 group, therefore, 1° amine is a stronger base
than 3° amine. The overall decreasing strength of methylamines is : (CH3)2NH > CH3NH2 > (CH3)3N or
2° > 1° > 3°.
If the alkyl group is larger than CH3, there will be steric hindrance to H-bonding. Stability due to +I-effect
predominates over stability due to H-bonding and hence 3° amines are more basic than 1° amines.
The order of strength of ethylamines is : (CH3CH2)2NH > (CH3CH2)3N > CH3CH2NH2, i.e.,,2° > 3° > 1°.
In the gaseous phase or in non-aqueous solvents, solvation effects (stabilisation of the conjugate
acid due to H-bonding) are absent and hence basicity of amines depends only on the +I-effect of the
alkyl groups. Thus, basicity follows the order : 3° amine > 2° amine > 1° amine >NH3.
(d) Basicity of aromatic amines. Aromatic amines are weaker bases than aliphatic amines and ammo-
nia due to delocalisation of the lone pair of electrons on the nitrogen atom over the benzene ring.
259
Aniline has five resonating structures while anilinium ion, obtained by accepting a proton has only
two resonating structures. Thus, aniline is more stable (less basic) than anilinium ion.
(e) Effect of substituents on the basicity of aromatic amines. (i) Electron-donating groups such as -
CH3, –OCH3, –NH2, etc., increase the basicity while electron- withdrawing groups like –NO2, –CN,
–SO3H, –COOH, –X, etc., decrease the basicity of amines.
(f) Basicity of N-substituted anilines. Due to +R effect of alkyl groups, basicity increases as : C6H5N(CH3)2 >
C6H5NHCH3 > C6H5NH2. Basicity decreases when the substituent is electron-withdrawing (e.g.,
phenyl) : C6H5NH2 > (C6H5)2NH > (C6H5)3N.
(g) Basicity of aralkylamines. Aralkyamines are stronger bases than arylamines (C6H5CH2NH2 >
(C6H5)NH2) and weaker bases than alkylamines but stronger bases than ammonia (CH3NH2 >
C6H5CH2NH2 > NH3).
2. Acylation. Aliphatic and aromatic primary and secondary amines react with acid chlorides, acid anhy-
drides and esters to form amides. This nucleophilic substitution occurs by the replacement of the
hydrogen atom of –NH2 or >NH group by acyl group. The reaction is carried out in presence of a
stronger base like pyridine which removes HCl and shifts the equilibrium to the right hand side.
3. Carbylamine reaction. Both aliphatic and aromatic primary amines when warmed with chloroform
and alcoholic potash (KOH) gives isocyanides or carbylamines having foul smell.
 
RNH 2  CHCl3  3KOH  alc.   R  N  C 3KCl  3H 2O
1o Amine Chloroform Alkylcarbyla min e
260
 
C6 H5 NH 2  CHCl3  3KOH  alc.   C6 H5  N  C 3KCl  3H 2O
Aniline Chloroform Phenylcarbyla min e
2o and 3o amines do not undergo this reaction, therefore, this is used as a test to distinguish 1o
amines from 2o and 3o amines (Isocyanide test).
4. Reaction with nitrous acid. (i) Aliphatic primary amines react with nitrous acid in the cold to form
aliphatic diazonium salts which being unstable decomposes to give alcohols with quantitative evolu-
tion of N2 gas which is employed for the estimation of amino acids and proteins..
 
NaNO  HCl HO
RNH 2  HNO 2 
2
[R N 2 Cl] 
2
 ROH  N 2  H 2O
Nitrous acid is prepared in situ from a mineral acid and sodium nitrite.
(ii) Aromatic primary amines react with nitrous acid at 273-278 K to form diazonium salts. This reac-
tion is called diazotisation.

NaNO  2HCl
 C6 H5  N  NCl   2H 2O
C6 H5 NH 2  HONO  HCl 
2
273298K
Aniline Benzenediazonium chloride
If the temperature exceeds 278 K, diazonium salts decompose giving phenols.


C6 H 5 N 2 Cl   H 2O 
 278K
 C 6 H 5 OH  N 2  HCl
Diazonium salts are used for the synthesis of a variety of aromatic compounds.
5. Reaction with benzene sulphonyl chloride (Hinsberg’s reagent). Primary and secondary amines
react with Hinsberg’s reagent (C6H5SO2Cl) to form sulphonamides.
a) With primary amine N-ethylbezenesulphonyl amide which is soluble in alkali is formed.
The hydrogen attached to nitrogen in sulphonamide is strongly acidic due to the presence of strongly
electron withdrawing sulphonyl group.
b) With secondary amine, N, N-diethylbenzenesulphonamide is formed.
N, N-Diethylsulphonamide is not acidic since it does not contain any hydrogen atom attached to the
nitrogen and hence insoluble in alkali.
c) Tertiary amines do not react with Hinsberg’s reagent due to the absence of replaceable hydrogen. p-
toluenesulphonyl chloride (tosyl chloride) is a better reagent than benzenesulphonyl chloride. The re-
action of amines with benzenesulphonyl chloride can be used for the distinction of 1o, 2o, and 3o amines
and also for the separation of mixtures of amines.
6. Electrophilic substitution reactions. Aromatic amines readily undergo electrophilic substitution re-
actions. The -NH2 group is activating and o-, p-directing.
261
(i) Halogenation. Halogenation of amines occurs very fast and the halogen enters the o- and p-
positions even in the absence of a catalyst.
In order to prepare monosubstitution product, the activating effect of the –NH2 group is reduced by
acetylation prior to halogenation. The acetyl group is finally removed by hydrolysis to give
monohalogenated amine.
The lone pair of electrons on nitrogen of acetanilide interacts with oxygen due to resonance.
As a result, availability of the lone pair of electrons on nitrogen is reduced and hence the deactivating
effect.
ii) Nitration. Direct nitration of aromatic amines gives tarry oxidation products along with some nitra-
tion products, but nitration under controlled conditions gives a mixture of p-nitroaniline and m-nitroaniline.
The reason for the unexpected formation of a large amount of m-nitroaniline is the protonation of
aniline to anilinium ion which is m-directing. The most convenient method is nitration after protecting
the amino group by acetylation. The acetyl group is finally removed by hydrolysis to give a mixture of o-
and p-nitroanilines.
262
iii) Sulphonation. Aniline on sulphonation with conc. H 2SO 4 at 455-475 K gives

p-aminobenzenesulphonic acid (sulphanilic acid).
Sulphanilic acid exists as a zwitter ion and is amphoteric in nature.

USES
Low molecular aliphatic amines (diethyl amine, triethyl amine etc.) are used as solvents in the laboratary
and industry, as reagents in organic synthesis, and in the manufacture of drugs. Quaternary ammonium
salts are used as detergents, e.g., n-Hexadecyltrimethylammonium chloride or Cetyltrimethyl ammonium

chloride, CH 3 (CH 2 )15 N(CH 3 )3 Cl .
Aromatic amines like aniline are used in the manufacture of dyes, drugs and plastics (polyurethane). For the
preparation of arene diazonium salts. As antioxidants and vulcanisation accelerators in rubber industry.
DIAZONIUM SALTS
Diazonium salts are a class of compounds (discovered by John Peter Greiss in 1858) having general
   
formula R N 2 X , where R is an aryl group and X may be Cl–, Br–, BF–4, etc. N 2 is called diazonium group.
Diazonium salts are named by adding the suffix diazonium to the name of the parent hydrocarbon from
which they are derived, followed by the name of the anion.
Diazonium salts formed by aliphatic primary amines are highly unstable due to the tendency to eliminate a
molecule of N2 (which is exceptionally stable). Arenediazonium salts in solution are more stable due to
resonance (or alternatively, phenyl carbocation is less stable than alkyl carbocation).
Methods of Preparation
Diazotisation. Arenediazonium salts are prepared by adding a cold aqueous solution of sodium nitrite to a
solution of an aromatic primary amine in an acid at 273–278 K.

273 278K
 C6 H5  N  NCl  NaCl  2H 2 O
C6 H5 NH 2  NaNO 2  2HCl 
Aniline Benzenediazonium chloride
263
Since diazonium salts slowly decompose even at low temperature (273 – 278 K), they are used immedi-
ately after preparation. Aromatic 1o amines containing electron donating groups at o- and p-positions (e.g.,
o- toluidine, p-anisidine, etc.) undergo diazotisation much more readily than aniline while those containing
electron-withdrawing groups such as –NO2, –CN, COOR, etc. are difficult to diazotise.
Physical Properties
Arene diazonium chlorides are colourless crystalline solids, highly soluble in water. Their aqueous solutions
are stable in the cold, but reacts with water on warming. They decompose easily in the dry state, therefore,
they are prepared in situ and used immediately after preparation.
Benzene diazoniumfluoroborate is insoluble in water and stable at room temperature.
Chemical Reactions
A. Reactions involving displacement of diazo group as nitrogen. Being a very good leaving group,
diazo group can be easily substituted by monovalent atoms or groups.
1. Replacement by halide or cyanide ion. (i) Sandmeyer Reaction. Nucleophiles such as halide and
cyanide ions can be introduced into the benzene ring in presence of Cu(I) ion.
   
CuCl/HCl CuBr/HBr
C6 H 5 N 2 Cl 
N
C6 H5Cl ; C6 H 5 N 2 Cl 
 N2
 C6 H 5Br
2
Chlorobenzene Bromobenzene
 
CuCN/KCN
C6 H5 N 2 Cl 
N
 C6 H5CN
2
Benzonitrile
ii) Gatterman reaction.Alternatively, nucleophiles can be introduced into the benzene ring using
halogen in presence of copper powder.
   
Cu /HCl
C 6 H 5 N 2 Cl  N
 C 6 H 5 Cl ; C 6 H 5 N 2 Cl  
Cu /HBr
 C 6 H 5 Br
2
Chlorobenzene N2
Bromobenzene
 
Cu /KCN
C 6 H 5 N 2 Cl 
N
 C 6 H 5 CN
2
Benzonitrile
The yield is better in Sandmeyer reaction (80%) than in Gattermann reaction (40%).
2. Replacement by iodide ion. Direct introduction of iodine to benzene ring is difficult, but, it can be
easily achieved by treating the diazonium salt with potassium iodide.

Ar N 2 Cl   KI 
 ArI  KCl  N 2
3. Replacement by fluoride ion (Balz-Schiemann reaction). When aqueous solution of arenediazonium

chloride is treated with fluoroboric acid, arene diazonium fluoroborate is precipitated. The precipitate
on heating gives aryl fluoride.
 

Ar N 2 Cl  HBF4  Ar N 2 BF4 
 ArF  BF3  N 2
 HCl
Aryldiazonium fluoroborate
264
4. Replacement by hydrogen (Deamination). Diazonium salts can be reduced to arenes using mild
reducing agents like (i) ethanol and (ii) hypophosphorous acid (phosphinic acid) in presence of Cu (1)
ions as catalyst at room temperature.

Ar N 2 X   CH 3CH 2 OH 

 Ar  H  N 2  HX  CH 3CHO

Cu  I 
Ar N 2 X   H3PO 2  H 2O  Ar  H  H3PO3  HX  N 2
Hypophosphorous acid Phosphorous acid
5. Replacement by hydroxyl group. When the temperature of diazonium salt solution increases be-
yond 278 K, the salt is hydrolysed to phenol.
ArN 2Cl  HOH 

 ArOH  N 2  HCl
Phenol
6. Replacement by nitro group. The diazonium group is replaced by nitro group on heating diazonium
fluoroborate with aqueous sodium nitrite solution in presence of copper powder.
Coupling reactions. Arenediazonium salts react with highly reactive (electron-rich) amines to form
highly coloured azo compounds, Ar–N = N – Ar. Coupling with phenols occurs in basic medium (pH 9-
10) and of amines occurs in faintly acidic medium (pH 4-5) at 273-278 K. Coupling reaction is an
electrophilic substitution reaction in which the diazonium cation with positive charge on the nitrogen
acts as electrophile and the electron rich compounds act as nucleophiles.
Coupling usually occurs at p-position w.r.t. to OH or NH2 group. However, if the p-position is blocked,
coupling occurs at the o-position.
This reaction, known as coupling reaction is extensively used in azo dye industry.
Importance of Diazonium Salts in Synthesis of Aromatic Compounds
Diazonium salts are very good intermediates for the introduction of –F, –Cl, –Br, –I, –CN, –OH, –NO2
groups into the aromatic ring. Aryl fluorides and iodides cannot be prepared by direct halogenation. The
cyano group cannot be introduced by nucleophilic substitution of chlorine in chlorobenzene, but
cyanobenzene can be easily obtained from diazonium salt. Thus, the replacement of diazo group by
other groups is helpful in preparing substituted aromatic compounds.
265
QUESTIONS
LEVEL - I
1. Amines are
1) Lewis acids 2) Arrhenius acids 3) Lewis bases 4) Arrhenius bases
2. The hybridisation of nitrogen in amines is
1) sp 2) sp2 3) sp3 4) sp3d
NH2
3. . IUPAC name of the given compound is
1) Aniline 2) Benzenamine 3) Amino benzene 4) Both 1 and 2

4. The correct IUPAC name of the compound CH2 = CH – CH2 – NH2 is
1) Allyl methyl amine 2) 2-amino-4-pentene
3) 4-amino-pent-1-ene 4) Prop-2-en-1-amine
5. Aniline is prepared in the presence of Fe/HCl from which compound.
1) Benzene 2) Chlorobenzene 3) Nitrobenzene 4) Toluene
NO2
6. 
H2 / Pd
Ethanol
 X . The compound X is
NO2 OH
NH2
OH
1) 2) 3) 4)
7. CH 3  C  N  H 2 / Ni
Na  Hg  /C 2 H5 OH
 X . The product X is
1) CH3 –NH2 2) CH3 – CH2 – NH2

3) CH3 – CH2 – CH2 – NH2 4) CH3 – CH3
8. Amine that cannot be prepared by Gabriel phthalimide synthesis is
1) Aniline 2) Methanamine 3) Ethanamine 4) Iso-butylamine
9. Which of the following reactions is appropriate to converting propanamide to ethanamine?
1) Stephen reaction 2) Gabriel phthalimide reaction
3) Hoffmann bromamide reaction 4) Carbylamine reaction
10. The compound CH 3  CH 2  C  NH 2 treating with bromine in aqueous NaOH solution. The product
O
amine is
1) CH3 – CH2 – CH2 – NH2 2) CH3 – CH2 – NH2
3) CH3 – NH2 4) CH3 – CH2 – CH2 – CH2 – NH2
266
11. Which of the following statements is/are correct?

1) Lower aliphatic amines are soluble in water
2) Inter molecular hydrogen bonding is more in primary amine than in secondary amine
3) Tertiary amines do not form intermolecular H-bond
4) All of these
12. The order of boiling points of isomeric amines is
1) IIIo < IIo < Io 2) Io < IIo < IIIo 3) IIo < IIIo < Io 4) IIo < Io < IIIo
13. The order of basicity of amines in the gaseous phase follows the order
1) NH3 > Io > IIIo > IIo 2) NH3 > IIIo > Io > IIo 3) IIIo > IIo > Io > NH3 4) NH3 > IIo > Io > IIIo
14. Considering the basic strength of amines in aqueous solution. Which one has smallest pKb value?
1) (CH3)2NH 2) CH3NH2 3) (CH3)3N 4) C6H5NH2
15. Which one of the following increases the basic strength of substituted aniline?
1) –NO2 2) –COOH 3) –OCH3 4) –SO3H
16. Carbylamine test is used for the detection of
1) Aliphatic 2o amine 2) Aliphatic 1o amine
3) Aromatic 1o amine 4) Both aliphatic and aromatic primary amine
17. Methyl amine is heated with CHCl3 and alcoholic KOH, the foul smelling substance formed is
1) Butane 2) Methyl Isocyanide 3) Nitromethane 4) Ethanol
18. Methyl isocyanide is prepared by
1) Carbyl amine reaction 2) Wurtz reaction
3) Hoffmann reaction 4) HVZ reaction
19. Aliphatic amines react with nitrous acid to form aliphatic diazonium salt. Which is being unstable the
gas liberated is
1) Oxygen 2) Hydrogen 3) Chlorine 4) Nitrogen
20. C6 H 5 NH 2 
NaNO 2 / 2HCl
273 278K
 X  NaCl  2H 2 O . The product X is
NO2 N 2Cl NH2

NO2
1) 2) 3) 4)
21. Hinsberg’s reagent is

1) C6H5SO2Cl 2) C6H5N2Cl 3) C6H5COCl 4) SOCl2
22. The amine which can react with C6H5SO2Cl to form a product that is insoluble in alkali is
1) Primary amine 2) Secondary amine
3) Tertiary amine 4) Both primary and secondary
267
23. Which of the following does not react with Hinsberg reagent ?
NH2
1) CH3NH2 2) 3) (CH3)3N 4) C2H5– NH – CH3
24. Reaction of aniline with Bromine water at room temperature give
NH2
Br Br
Br Br
1) 2) 3) 4)
Br
Br
25. The product formed on heating anilinium hydrogen sulphate with sulphuric acid at 473 K is
NH2 NO2 NH2 NH2

NO2
1) 2) 3) 4)
SO3H
26. Which of the following is a zwitter ion?
NH3+ NO2 SO3H

SO3H
OH
1) 2) 3) 4)
SO3– CH3
27. The conversion of primary aromatic amines into diazonium salt is known as
1) Aromatisation 2) Diazotisation
3) Ammonolysis 4) Nitration
N2Cl Cl
28. 
Cu
HCl
+ N2 + CuCl. The reaction is named as
1) Sandmeyer reaction 2) Gatterman reaction

3) Cannizzaro reaction 4) Kolbe’s reaction
268
29. At 283 K benzenediazonium chloride is hydrolysed to

1) Benzene 2) Nitrobenzene 3) Chlorobenzene 4) Phenol
30. Benzene diazonium chloride coupled with phenol to form p-hydroxyazobenzene. Which is a/an
1) yellow dye 2) Red dye 3) Orange dye 4) Blue dye
LEVEL - II
1. Hybridization of nitrogen atom in amines is sp3. Its geometry is
1) Pyramidal 2) Tetrahedral 3) Trigonal 4) Square pyramidal
2. Which of the following is not a primary amine?
1) Tert-butyl amine 2) Ethyl amine 3) Sec.butyl amine 4) Trimethyl amine
3. C3H9N cannot represent a
1) 1o amine 2) 2o amine 3) 3o amine 4) Quaternary ammonium salt

4. IUPAC name of the compound (CH3)2 – N – CH3 is
1) 2, 2-dimethyl methanamine 2) N-ethyl-methanamine
3) N, N-dimethyl methanamine 4) n-methyl propanamine
NH2
CH3
5. IUPAC name of the given compound is
1) o-Toluidine 2) 1-methyl aniline 3) 1-amino toluene 4) 2-methyl aniline

6. How many different isomeric amines corresponding to the molecular formula C4H11N.
1) 2 2) 3 3) 6 4) 7
7. The free amine can be obtained from the ammonium salt, RNH 3 X  by treatment with
1) Strong acid 2) Haloalkane (RX) 3) Strong base 4) Water

8. Which of the following reagents can be used to convert primary amides into primary amines containing
the same number of carbon atoms?
1) Br2 + NaOH 2) LiAlH4 3) Sn + HCl 4) CHCl3 + KOH
9. Which of the following methods of preparation of amines will not give same number of carbon atom
in the chain of amines as in the reactant?
1) Reaction of alkyl nitrile with LiAlH4
2) Reaction of amide with LiAlH4 followed by treatment with water
3) Heating alkyl halide with potassium salt of phthalimide followed by hydrolysis
4) Treatment of amide with Br2 in aqueous solution of sodium hydroxide
10. Acetamide is treated with the following reagents separately. Which one of these would yield methyl
amine?
1) NaOH + Br2 2) Hot conc. H2SO4 3) PCl5 4) NaOH + CaO
269
11. Which of the following is used for the preparation of a primary amine having one C-atom more than
the starting haloalkane?
1) Reaction with aqueous KCN followed by reduction
2) Reaction with AgCN followed by reduction
3) Reaction with aqueous NH3
4) All of these
12. Method by which aniline cannot be prepared is
1) Hydrolysis of phenyl isocyanide with acidic solution
2) Degradation of benzamide with bromine in alkaline solution
3) Reduction of nitrobenzene with H2/Pd in ethanol
4) Potassium salt of phthalimide treated with chlorobenzene followed by hydrolysis with aq.NaOH
solution.
13. An organic compound A on reduction gives a compound B which on reaction with trichloromethane
and caustic potash forms C. The compound C on catalytic reduction give N-methylbenzenamine.
The compound A is
1) nitro benzene 2) nitro methane 3) benzenamine 4) methanamine

14. Which of the following reagents can be used for the given conversion
NO2 NH2
1) Sn – HCl 2) Fe – HCl 3) H2/Pd 4) All of these

15. Which of the following statements about primary amines is ‘False’?
1) Alkyl amines are stronger bases than aryl amines
2) Aryl amines react with nitrous acid to produce phenols
3) Alkyl amines react with nitrous acid to produce alcohols
4) Alkyl amines are stronger bases than ammonia
16. pKb value of methanamine is
1) 9.38 2) 8.92 3) 3.38 4) 3.25
17. The correct order of basic strength of ethyl substituted amines in aqueous solution is
1) 2o > 3 o > 1o > NH3 2) NH3 > 1o > 3o > 2o 3) 3o > 2o > 1o > NH3 4) NH3 > 1o > 2o > 3 o
18. Aniline is more stable than anilinium ion because
1) Aniline has more resonating structures than anilinium ion
2) Aniline has less resonating structures than anilinium ion
3) Aniline has more π -bonds than anilinium ion
4) Aniline has less π -bonds than anilinium ion
270
19. The correct increasing order of basic strength for the following compounds is :
NH2 NH2 NH2
NO2 CH3
(I) (II) (III)
1) II < III < I 2) III < I < II 3) III < II < I 4) II < I < III
20. Consider the following reaction, CH 3 NO 2 

Sn / HCl
 X 
C6 H 5 COCl
 Y  HCl . What is Y?
1) Acetanilide 2) N-Methylbenzamide
3) Azobenzene 4) Hydrazobenzene
21. Chloroform when treated with aniline and alcoholic KOH give
1) Phenol 2) Chlorobenzene 3) Phenyl cyanide 4) Phenyl isocyanide
22. The reagent that is used to distinguish between secondary amine and tertiary amine is
1) Lucas reagent 2) Benzene sulphonyl chloride
3) Chloroform and alcoholic KOH 4) Tollen’s reagent
23. Which of the following compounds will dissolve in an alkali solution after it undergoes reaction with
Hinsberg’s reagent?
1) CH3NH2 2) (CH3)3N 3) (C2H5)2NH 4) C6 H 5  N  C6  H 5
H
24. When secondary amine react with Hinsberg’s reagent, the product formed is
1) N, N-diethyl benzene sulphonamide
2) N-ethyl benzene sulphonamide
3) Benzene diazonium chloride
4) P-hydroxyazobenzene
25. Which among the following is used these days in place of benzene sulphonyl chloride for the
distinction of primary, secondary and tertiary amines
1) Benzene diazonium chloride 2) Sulphanilic acid
3) p-toluene sulphonyl chloride 4) Nitrobenzene

26. Which one of the following statements is not a property of diazonium salt?
1) Diazonium salts are colourless crystalline solids
2) Being ionic in nature they are soluble in water
3) Most of these salts explode when dried
4) The aqueous solutions of these are poor conductors of electricity
271
27. Benzene diazonium salt solution treated with potassium iodide the product formed is
1) Benzene 2) Phenol 3) Nitrobenzene 4) Iodobenzene
CH3
Br
28. 
H2 O
H3 PO 2
 X 
KMnO4
OH 
Y . The final product Y is
N2Cl
OH COOH Br COOH
Br Br Br
1) 2) 3) 4)
N2Cl N2BF4 NO2
29.  A 
 
B/Cu
  N 2  NaBF4 . A and B respectively are

1) HBF4, NaNO2 2) NaNO2, HBF4 3) LiAlH4, KMnO4 4) LiAlH4, HClO3

30. Reaction of diazonium salt with aniline yields an yellow dye p-aminoazobenzene. This reaction is an
example of
1) Nucleophilic substitution reaction 2) Coupling reaction
3) Electrophilic substitution reaction 4) Both 2 and 3
272
KEY WITH HINTS

LEVEL - I
1. 3 Amines have an unshared pair of electrons in its nitrogen atom.
2. 3 Nitrogen orbitals in amine is sp3 hybridised.
3. 4
4. 4
NO2 NH2
5. 3 
Fe/ HCl

6. 1
7. 2 This reaction is used to ascent the amine series.
8. 1 Aromatic primary amines can’t be prepared by Gabriel phthalimide synthesis.
9. 3 CH 3  CH 2  CO  NH 2  Br2  4NaOH 
 CH 3  CH 2  NH 2  2NaBr  Na 2CO 3  2H 2 O
10. 2 The amine formed has one carbon atom less than the amide.
11. 4
12. 1 Intermolecular H-bonding is present in Io amine and abscent in IIIo amine.
13. 3
14. 1 The order of basic strength is (CH3)2NH > CH3NH2 > (CH3)3N > NH3.
15. 3 Electron releasing groups increase the basic strength.
16. 4
17. 2
18. 1 CH 3  NH 2 CHCl3  3 KOH 

Heat
 CH 3 NC  3 KCl  3H 2 O
NaNO 2  HCl
19. 4 R  NH 2  HNO 2   R  N 2 Cl 
H2O
 R  OH  N 2  HCl
20. 3
21. 1
22. 2 C6H5SO2Cl react with secondary amine to form a product which is insoluble in alkalies.
23. 3 tert. amines donot react with Hinsberg reagent (C6H5SO2Cl) due to absence of acidic hydrogen.
NH2 NH2
Br Br
24. 1  3Br2 
Br2 /H 2 O
 + 3 HBr
Br
2, 4, 6 - tribromoaniline
273
25. 4 Sulphanilic acid is the product.

26. 1
27. 2
28. 2
N2Cl OH
29. 4 
H 2O
 + N2 + HCl
30. 3 N N Cl + H OH 
OH


N N OH + [Cl] + H2O. P-hydroxyazobenzene (Orange dye).
LEVEL - II
1. 1
2. 4
3. 4 Quarternary ammonium salt is (CH3)4N+Cl–
4. 3 CH 3  N  CH 3
CH3
(Tertiary amine)
5. 4
6. 4 1) CH 3  CH 2  CH 2  CH 2  NH 2 2) CH 3  CH 2  CH  CH 3
NH2
CH3 H
3) CH 3  C  NH 2 4) CH 3  CH 2  CH 2  N  CH 3
CH3
CH3
5) CH 3  CH 2  N  CH 2  CH 3 6) CH 3  CH  N  CH 3 7) CH 3  N  CH 2  CH 3
H CH3 H
274
7. 3 RNH 3 X   NaOH 
 R  NH 2  H 2 O  Na  X 
8. 2 R  CO  NH 2 
LiAlH 4
 R  CH 2  NH 2
9. 4
10. 1 CH 3  CONH 2 

NaOH
Br2
 CH 3 NH 2
11. 1 RX 
KCN
 R  CN  KX 
1) LiAlH 4
2) H 2 O
 R CH 2  NH 2
12. 4 Aryl halides do not undergo nucleophilic substitution reaction with potassium phthalimide easily.
13. 1 C6 H 5 NO 2 
Reduction
 C6 H 5 NH 2 
CHCl3
 C6 H 5 N  C 
H 2 / Ni
 C6 H 5 NHCH 3
N-methyl benzenamine
14. 4
15. 2 Aryl amines react with nitrous acid to form diazonium salt.
16. 3
17. 1
18. 1 Greater the number of resonating structures greater is the stability.

19. 4 EDG increases the basic strength and EWG decreases the basic strength.
20. 2 CH3 NO2 

Sn/HCl
 CH 3 NH 2 
 HCl  CH 3 NHCOC 6 H 5
C6H5COCl
Methanamine N  Methylbenzamide
X Y
NH2 N C
21. 4  CHCl3  Alk.KOH 

  3KCl  3H 2 O
Phenylisocyanide
22. 2
23. 1 1o amines form benzenesulphonamide which are soluble in alkali.
O H O
24. 1 S Cl + N C2H5 S N C2H5 + HCl
O C2H5 O
25. 3
275
26. 4 The aqueous solutions of diazonium salts are good conductors of electricity.
N2Cl I
27. 4  KI 
  KCl  N 2
CH3 CH3 COOH

Br Br Br
28. 2 
H2 O
H3 PO 2
 
KMnO4
OH 
o-bromobenzoic acid
X
N2Cl
29. 1
30. 4
276
CHAPTER - 11
BIOMOLECULES
INTRODUCTION
Complex organic molecules that are required for the occurance and sustenance of life processes are
called biomolecules. They include macromolecules such as proteins, carbohydrates, lipids, and nucleic
acids, as well as small molecules such as primary metabolites, secondary metabolites, and natural products.
Proteins and carbohydrates are essential constituents of our food. Simple molecules like vitamins and
minerals play an important role in the functions of an organism. DNA, a double-helix polymer codes genetic
information for the transmission of inherited traits.Within the cell, DNA is organized into dense protein-DNA
complexes called chromosomes. RNA functions in cellular protein synthesis and as a carrier of genetic
codes in some viruses.
CARBOHYDRATES
Carbohydrates are compounds of carbon, hydrogen and oxygen. They are primarily produced by plants.
Usually they have general formula Cx(H2O)y, eg. glucose (C6H12O6), sucrose (C12H22O11) etc. There are
some carbohydrates do not have a formula agreeing with Cx(H2O)y eg. deoxy ribose (C5H10O4).
Now a days carbohydrates are defined as optically active poly hydroxy aldehydes or ketones or compounds
producing them on hydrolysis. A large number of carbohydrates are found in nature.
CLASSIFICATION
1. Sugars and non sugars. Based on their physical properties, carbohydrates are classified into sugars
and non sugars. Sugars. These are sweet crystalline water soluble carbohydrates such as glucose,
sucrose etc. Non-sugars. These are polysaccharides; water insoluble carbohydrates that are neither
crystalline nor sweet in nature, e. g., starch, cellulose, etc.
2. Monosaccharides, oligo saccharides and polysaccharides. Carbohydrates are calssified into
monosaccharides, oligo saccharides and polysaccharides based on hydrolysability.
i. Monosaccharides. These are carbohydrates that cannot be hydrolysed into simpler carbohydrates,
e.g., glucose, fructose, etc.
ii. Oligo-saccharides. These are carbohydrates that can be hydrolysed to a limited number (2-9) of
monosaccharide units. They are further classified into disaccharides, trisaccharides, etc., depending
on the number of monosaccharide units they produce on hydrolysis. Disaccharides give two molecules
of the same or different monosaccharide units, e. g., sucrose, maltose, lactose, etc.
iii. Polysaccharides. These are carbohydrates which produce a large number of monosaccharide
units on hydrolysis, e.g., starch and cellulose, etc.
3. Reducing sugars and non reducing sugars. Carbohydrates are also classified into reducing sugars
and non reducing sugars. Carbohydrates that reduce Fehlings solution to red cuprous oxide and
Tollens reagent to metallic silver are called reducing sugars. All monosaccharides and disaccharides
such as maltose and lactose are reducing sugars. Sucrose which do not reduce Fehlings solution
and Tollens reagent is a non reducing carbohydate.
277
4. Aldoses and ketoses. Monosaccharides are further classified into aldoses and ketoses.
i. Aldoses are monosaccharides containing aldehydic (–CHO) group. Glucose, galactose etc. are
aldoses.
ii. Ketoses are monosaccharides containing keto (–CO–) functional group. Fructose is a ketose.
Aldoses and ketose are further classified into trioses, tetroses etc. based on number of carbon
atoms present in a molecule, e. g., glucose is an aldohexose while frucose is a ketohexose.
The simplest carbohydrate is the aldotriose, glyceraldehyde. The ketose corresponding to this aldose
is dihydroxy acetone, CH2OH-CO-CH2OH which cannot considered as a carbohydrate since it is
optically inactive.
MONOSACCHARIDES
1. Glucose or Grape sugar (dextrose), C6H12O6. Glucose is the monomer of a number of larger
carbohydrates like starchand cellulose. It is present in ripe grapes, fruits, honey etc.
i. Preparation. It is prepared from cane sugar (sucrose) by hydrolysis using mineral acids like HCl or
H2SO4 in alcoholic solution. An equimolar mixture of gluose and fructose are formed.
H
C12 H 22O11  H 2O  C6 H12O 6  C6 H12O6
glu cos e fru c t os e
Glucose is produced commercially by the hydrolysis of starch by boiling it with dil. H2SO4 at 393 K.
H ,393K
 C6H10O5 n  nH2O nC6H12O6
23atm
Starch or Cellulose Glucose
ii. Physical Properties. Glucose is a white crystalline solid, m.p. 419K. When crystallised from cold
water, it forms glucose monohydrate (C6H12O6.H2O), m.p. 359K. It is extremely soluble in water, only
sparingly soluble in ethanol and insoluble in ether. It is about 3 times as sweet as cane sugar (sucrose).
It is optically active and the ordinary naturally occuring form is (+)-glucose.
iii. Structure of glucose. It is an aldohexose.
1. Molecular formula of glucose is C6H12O6.
2. On prolonged heating with HI, glucose gives n-hexane indicating the presence of a six carbon straight
chain.
3. Glucose reacts with HCN to form cyanohydrin and with hydroxyl amine to form oxime.
278
(3) ;
These reactions indicate the presence of carbonyl group (>C=O) in glucose.

4. Bromine water oxidises glucose to gluconic acid. Gluconic acid is a carboxylic acid with the same
number of carbon atoms as glucose. This shows that the carbonyl group is present as an aldehydic
group.
(4) (5)
5. With acetic anhydride, glucose forms a penta acetate indicating the presence of five -OH groups.
Since it is a stable compound, the five -OH groups should be attached to different carbon atoms.
6. Oxidation of glucose with HNO3 produces saccharic acid, a dicarboxylic acid containing six carbon
atoms. The same acid is obtained on oxidising gluconic acid with HNO3. This shows the presence of
a primary alcoholic group (-OH) in glucose.
The exact spatial arrangement of -OH groups was given by Fischer; glucose is assigned structure I
gluconic acid II and saccharic acid III.
iii. D and L configurations of glucose. The correct name of glucose is D(+) glucose; configuration
is represented by ‘D’ and optical rotation by (+). Configuration of carbohydrates can be ascertained on
the basis of their relationship with the stereoisomers of glyceraldehyde.
Glyceraldehyde has one chiral carbon atom. The two stereoisomers are (+) -glyceraldehyde and
(–) -glyceraldehyde. The fischer projection formulae for these stereoisomers are
Compounds that are correlated to D(+) -glyceraldehyde are said to have ‘D’ configuration whereas
those that are correlated to L (–) -glyceraldehyde have ‘L’ configuration.
279
iv. Assigning configuration to monosaccharides. (i) The Fisher projection formula of the sugar is
drawn. (ii) The asymmetric carbon farthest from the CHO group is considered. (iii) If the –OH is on
right side the monosaccharide is ‘D’ and if it is on left side it is ‘L’. (iv) Optical rotation is mentioned
separately as (+) or (–). D or L is not related to optical rotation.
v. Cyclic structure of glucose (Limitations of open chain structure of glucose). The open chain
structureof glucose cannot explain the following observations:
(i)Glucose does not form addition compound with NaHSO3 and do not answer schiff’s reagent test.
(ii) Glucose pentaacetate does not react with NH2OH.
(iii)The existance of two different forms of glucose,  -glucose and  -glucose.  -D-(+)-glucose with
(m. p. 419K) is obtained by crystallising it from a concentrated solution at 303K (specific rotation
+111°) and  -D-(+) glucose (m. p. 423K) by crystallising from a hot saturated aqueous solution at
371K (specific rotation +19.2°) in freshly prepared aqueous solution.
In order to account for the two different forms of glucose, it is assigned a cyclic structure.
Glucose forms a cyclic hemiacetal with its CHO group and OH group on C5. The cyclic hemiacetal
formation produces a stereocentre at CHO carbon. Stereoiosmers formed due to ring formation are
called anomers. Thus,  -glucose and  -glucose are anomers.
Ring formation results in the absence of free CHO group in glucose. The CHO carbon in glucose,
involved in ring formation is the C1 carbon. It is called anomeric carbon.  and  forms of glucose
differ only in the configuration of –OH group at C1.
vi. Haworth structure. The Haworth structure better represents the ring structure of carbohydrates.
The cyclic structure of glucose is related to pyran, a six membered oxide ring compound.
280
In the  -form, the –OH on C1 is below the plane of the ring while in the  -form, it is above the ring.
2. Fructose. Fructose or fruit sugar is a ketohexose with formula C6H12O6. It is a laevo rotatory
monosaccharide found in ripe fruits. It is obtained along with glucose by the hydrolysis of disaccharide,
sucrose. It is also called laevulose. It is assigned an open chain structure with the keto group at C2
(a). Like glucose, it also exists in two anomeric forms  and  . The Haworth structures of the two
anomers of fructose are (b).
(a) (b)
The ring structure contain a cyclic hemiacetal linkage between C = Ogroup at C2 carbon and OH on
C5. It forms a five membered oxide ring structure similar to furan. The ring structures of the anomers
of fructose are:
In the  -form, the CH2OH attached to C2 is above the plane of the ring while in the  -form, it is below
the plane of the ring.
DISACCHARIDES
Disaccharides are carbohydrates that produce two monosaccharides on hydrolysis. These
monosaccharides can be the same or different. Disaccharides are formed by joining two monosaccharides
through a glycosidic linkage. Glycosidic linkage is the oxide linkage formed by the removal of a molecule
of H2O between two monosaccharide units in oligosaccharides and polysaccharides. Reducing sugars
contain free –OH groups on anomeric carbon. In monosaccharides, the –OH on anomeric carbon are free
(not involved in ring formation), therefore, they are reducing sugars.
1. Sucrose (cane sugar). In sucrose, the glycosidic linkage involves -OH on C1 of  -glucose and -OH
on C2 of  -fructose. These carbon atoms are the anomeric carbons of glucose and fructose
respectively. The resulting disaccharide does not have free –OH group on any of the anomeric carbon
atoms and hence it is a non-reducing sugar.
281
Sucrose is dextrorotatory. Hydrolysis of sucrose brings about a change in optical rotation. The
hydrolysed mixture consists of equimolar amounts of glucose (+52.5º) and fructose (-92.4º) which is
laevorotatory. Hence, hydrolysis of cane sugar using enzyme or dilute mineral acid is called inversion
of cane sugar. The hydrolysed equimolar mixture of glucose and fructose is called invert sugar.
Sucrose does not exhibit mutarotation.
2. Maltose. It is a reducing disaccharide, formed from two  -D glucose units through glycosidic linkage.
The -OH groups on C1 of one glucose and C4 of the other glucose molecule are involved in glycosidic
linkage. The OH on anomeric carbon on second glucose is free. Hence it is a reducing sugar.
3. Lactose or milk sugar. It is a disaccharide formed between  -D- galactose and  -D-glucose. The
glycosidic linkage is between C1 on galactose and C4 carbon of glucose. Since the –OH group on
anomeric carbon of glucose is free, it is a reducing sugar.
IMPORTANCE OF CARBOHYDRATES
Carbohydrates are essential for plant and animal life. They form the major portion of human and animal
food. Honey is an instant source of energy in ayurvedic medicine. Carbohydrates are used as storage
molecules both in plants (starch) and in animals (glycogen). Cell walls of plants and bacteria are made up
of cellulose. Wood, cotton, jute, etc., are different forms of cellulose. They are the raw materials for many
important industries like textiles, paper, lacquers and breweries.
Aldopentoses such as D-ribose and 2-deoxy-D-ribose are present in nucleic acids.
Carbohydrates in combination with proteins and lipids are present in many biosystems.
282
PROTEINS
Proteins are the most abundant biomolecules in the living system. They occur in every part of the body and
are the basis of structure and functions of life. They are essential for growth and maintenance of the body.
The word protein is derived from the Greek word, “proteios” meaning primary or of prime importance. The
chief sources of proteins are milk, cheese, pulses, peanuts, fish, meat, etc. Proteins are polymers of
 -amino acids.
Amino Acids
Proteins are condensation polymers of  -amino acids.  -amino acids contain both -COOH and -NH2
groups on the same carbon atom.
Essential amino acids and non-essential amino acids. Only twenty amino acids are involved in protein
formation; ten of them, synthesised in the human body are called non-essential amino acids. The other ten
which are obtained through food are called essential amino acids.
Naming of amino acids. Most  -amino acids have trivial names which indicate its property or source, e.g.,
glycine is so named since it has sweet taste (Greek glykos means sweet) and tyrosine was first found in
cheese (Greek, tyros means cheese). Amino acids are generally represented by a three letter symbol,
e. g., Gly for glycine, Ala for alanine, etc. Sometimes one letter symbol is used.
Classification of amino acids
Amino acids are classified on the basis of relative number of amino and carboxylic acid groups in one
molecule.
(i) If equal number number of -NH2 and -COOH groups are present, they are called neutral amino acids.
(ii) If more carboxyl groups are present, they are called acidic amino acids and if more -NH2 groups are
present, they are called basic amino acids.
Except glycine, all other naturally occurring  -amino acids are optically active, since the  -carbon atom is
asymmetric. These exist both in ‘D’ and ‘L’ forms. Most naturally occurring amino acids have L-configuration.
L-Aminoacids are represented by writing the –NH2 group on the left hand side.
(iii) Due to the presence of both acidic and basic groups in the same molecule, amino acids exist as dipolar
ions or Zwitter ions. This ion is neutral, but contains both positive and negative charges.
In zwitter ionic form, amino acids exhibit amphoteric behaviour.
283
Table - 01 Natural amino acids.
ii. The Peptide bond. The amide linkage between amino acid residues in a protein or polypeptide is called
peptide bond. It is formed by the elimination of a molecule of H2O between -COOH, and -NH2 groups of
neighbouring amino acids. One peptide bond is formed when two amino acids join to form a dipeptide, e.g.,
glycylalanine
284
A tripeptide is formed when a third amino acid combines with a dipeptide and so on. Thus, a tripeptide
contains three amino acids linked by two peptide linkages.
Polypeptides. When four, five or six amino acids are linked, the respective products are known as
tetrapeptide, pentapeptide or hexapeptide. When the number of amino acids is more than ten, the
product is called polypeptide.
Proteins. Polypeptides containing more than 100 amino acids bonded through peptide linkage and have
molecular mass more than 10,000u are called proteins.
Polypeptides with fewer amino acids may be called proteins if they have well defined conformation of
protein, e.g., insulin which contains 51 amino acids.
Classification of Proteins
Based on molecular shape proteins are classified into fibrous proteins and globular proteins.
i. Fibrous proteins. When parallel polypeptide chains are held together by hydrogen bonds or polysulphide
bonds, fibre-like structure is formed. Fibrous proteins posses fibre like structure and are generally insoluble
in water, e. g., keratin (hair, wool, silk), myosin (in muscles), etc.
ii. Globular proteins. These are proteins in which the polypeptide chains coil and attain spherical shape.
These are soluble in water, e. g., insulin, albumins, etc.
Structure of a Proteins
The actual structure of protein is sum total of its primary (1°) , secondary (2°), tertiary (3°) and quarternary
(4°) structures.
1. Primary structure. It is the sequence of amino acids linked through peptide bonds to form a polypeptide
chain.
2. Secondary structure. It is the shape in which a long polypeptide chain exists. They are found to exist
in two different structures viz., α -helix or β -pleated sheet. These structures arise due to the
regular folding of the polypeptide chain due to hydrogen bonding between >C=O and –NH– groups of
the peptide bond.
(i) α -helix. In a-helix, the polypeptide chain forms all possible hydrogen bonds by twisting into a right
handed screw (helix) with the –NH group of each amino acid residue hydrogen bonded to the >C =O of an
adjacent turn of the helix.
(ii) β -pleated sheet. In a β -pleated sheet, parallel polypeptide chains, laid side by side, are held together
by intermolecular hydrogen bonding. This resembles the pleated folds of drapery, and therefore, known as
b-pleated sheet.
3. Tertiary structure. It is the overall folding of the secondary structures. It gives rise to fibrous and
globular molecular shapes. Hydrogen bonds, disulphide linkages, van der Waals and electrostatic
forces of attraction stabilise the 2° and 3° structures of proteins.
4. Quarternary structure. The spatial arrangement of subunits in different polypeptide chains with respect
to each other in a protein is called quarternary structure.
285
5. Denaturation. It is the phenomenon of loss of biological activity and unique three dimensional structure
of proteins due to change in temperature, pH, etc. Denaturation is due to destruction of 2o and 3o
structure. Coagulation of egg white on boiling and curding of milk are examples of denaturation.
ENZYMES
Enzymes are globular proteins that function as catalyst in biological process occuring in living organisms.
Enzymes are specific for a particular reaction and for a particular substrate.
Maltase
C12 H 22O11 
 2C6 H12O6
Maltose glu cos e
Their names are derived from the names of the compounds which they act upon, e. g., maltase, sucrase,
etc.
Sometimes they are named after the type of reaction which they catalyse, e.g., oxidoreductase, etc.
The ending of the name of an enzyme is -ase.
Mechanism of enzyme action. Enzymes catalyse biological process by decreasing the activation energy.
E.g., activation energy for acid hydrolysis of sucrose which is 6.22 kJ mol–1 is lowered to only
2.15 kJ mol–1 when hydrolysed using sucrase.
VITAMINS
These are organic compounds that are required in the diet in small quantities. They perform specific biological
functions for normal maintanance of optimum growth and health of the organism. Their deficiency causes
specific diseases, so they are considered as essential food factors.
Vitamins are classified into two types: fat soluble vitamins and water soluble vitamins.
i. Fat soluble vitamins: Vitamin A, D, E and K are soluble in fat.
ii. Water soluble vitamins: Vitamin B group and C are soluble in water.
Table - 02 Important Vitamins, Sources and Deficiency Diseases.
Vitamin Deficiency symptom Source
1.Vitamin (Retinol) Xerophthalmia (hardening of Fish oil, rice-bran, liver, kidney
cornea), Night blindness, dry skin
2.Thiamine (Vitamin B1 ) Fatigue, depression, beri-beri Yeast, milk, green vegetables
3.Riboflavin (Vitamin B2 ) Cracked lips, scaly skin Yeast, milk, vegetables, egg-
white, liver, kidney
4.Pyridoxine (Vitamin B6 ) Anaemia, irritability Cereal, grams, molasses, yeast,
egg-yolk and meat
5.Niacin Dermatitis, dementia
6.Folic acid (Vitamin M) Megaloblastic anaemia
7.Vitamin B12 Megaloblastic anaemia, Liver of ox, sheep, pig, milk
(Cyanocobalmine) neurodegeneration
8.Pantothenic acid Weight loss, irritability
9.Biotin (Vitamin H) Dermatitis, anorexia, depression Yeast, liver, kidney, milk
10.Ascorbic acid (Vitamin C) Bleeding gums (Scurvy) Citrus fruits, green vegetables
11.Vitamin D (Calciferol) Rickets, osteomalacia
12.Vitamin E (Sterility Hemolysis of red blood cells Wheat germ oil, cotton seed oil
vitamin) and soyabeen oil
13.Vitamin K Hemorrhage, delayed blood clotting Cereals, leafy-vegetables
286
NUCLEIC ACIDS
Nucleic acids are biomolecules responsible for storage and transfer of genetic information. They are of two
types, viz. deoxyribonucleic acid (DNA) and ribonucleic acid (RNA). Nucleic acids are long chain
polymers of nucleotides, so they are also called polynucleotides.
Chemical Composition of Nucleic Acids. Complete hydrolysis of DNA and RNA yields a pentose sugar,
phosphoric acid (H3PO4) and nitrogen base (nitrogen containing heterocyclic compound).
Pentose sugar. In DNA, the sugar moiety is  -D-2-deoxyribose and in RNA, it is  -D-ribose.
Nitrogen bases. DNA contains four bases viz. adenine (A), guanine (G), cytosine (C) and thymine (T).
RNA contains uracil (U) instead of thymine. Adenine and guanine are purines, whereas cytosine, thymine
and uracil are pyrimidines.
Structure of Nucleic Acids

Nucleoside. It is formed by the attachment of a base to 1' position of sugar. In nucleosides, the carbon
atoms in the sugar moiety are numbered as 1', 2', 3', etc., in order to distinguish these from the bases.
Nucleotides. A nucleoside linked to phosphoric acid at 5'-position of sugar moiety is called nucleotide.
One molecule of water is eliminated in this esterification.
Formation of dinucleotide. Nucleotides are joined together by phosphodiester linkage between 5' and 3'
carbon atoms of the pentose sugar. The formation of a typical dinucleotide may be depicted as:
(a) (b)
(a) Formation of dinucleotide (b) Double strand helix structure of DNA.
287
Formation of Polynucleotide.The polynucleotide chain can be represented as :
Nucleic acids have primary and secondary structures.

Primary structure. Information regarding the sequence of nucleotides in the polynucleotide chain is called
its primary structure.
Secondary structure of DNA. James Watson and Francis Crick (Nobel Prize, 1962) proposed a double
stranded helix structure for DNA. Two nucleic acid chains are wound about each other and held together by
hydrogen bonds between pairs of bases. The two strands are complementary to each other in terms of
base pairing since hydrogen bonds are formed between specific pairs of bases- adenine with thymine (AT)
and guanine with cytosine (GC).
Secondary structure of RNA. In RNA, the helics are single stranded. The single strand can fold back on
itself and acquire double stranded characteristics with AU, GC base-pairing. Three types of RNA which
performs different functions are messenger RNA (m-RNA), ribosomal RNA (r-RNA) and transfer RNA
(t-RNA).
BIOLOGICAL FUNCTIONS OF NUCLEIC ACIDS
Nucleic acids are responsible for preserving genetic information. and for maintaining the identity of different
species of organisms.DNA molecule is capable of self-replication during cell division. It is therefore, a
reproducing molecule. This unique property is the basis of reproduction.
Another important function of nucleic acids is protein synthesis in the cell. Based on coded information
from DNA, RNA synthesises specific proteins. Under certain conditions, DNA may undergo mutation. This
is equivalent to evolution.
DNA Fingerprinting. Every individual has unique fingerprints. These have been used for identification, but
can be altered by surgery. DNA fingerprinting is an unalterable technique for identification.
The sequence of bases in DNA is also unique for a person and information regarding this is called DNA
fingerprinting. It is same for every cell and cannot be altered by any known technique. DNA fingerprinting is
used in forensic laboratories for identification of criminals, to determine paternity of an individual, to identify
dead bodies by comparing the DNA’s of parents or children, and to identify racial groups to rewrite biological
evolution.
HORMONES
Hormones are biomolecules which are produced in the ductless glands and are carried to different parts of
the body through the blood stream where they control various metabolic process or show physiological
activity. These are mainly of three types
i) Steroid hormones eg : cortisone, aldosterone, estradiol etc.
ii) Peptide hormones eg : oxytosin, insulin, glucagon etc.
iii) Amine hormones eg : adrenaline, thyroxine, epinephrine etc.
288
QUESTIONS
LEVEL-I
1. Select the biomolecule(s) that help during the formation of the living system.
1) Carbohydrates 2) Nucleic acids 3) Lipids 4) All of these
2. How many natural monosaccharides are known to occur in nature?
1) 5 2) 10 3) 15 4) 20
3. Which of the following is the sweetest sugar?
1) Glucose 2) Fructose 3) Lactose 4) Sucrose
4. Which one of the following is not sweet in taste?
1) Glucose 2) Fructose 3) Sucrose 4) Glycogen
5. Which one of the following is a non-reducing sugar?
1) Maltose 2) Lactose 3) Ribose 4) Sucrose
6. Glucose reacts with hydroxylamine to form
1) Oxime 2) Gluconic acid 3) Glyceraldehyde 4) Glucopyranose
7. The correct name of the compound
COOH
 CHOH 4
is
CH2OH
1) Saccharic acid 2) Gluconic acid 3) Sucrose 4) Lactose
8.  -D-glucose and  -D-glucose are :
1) epimers 2) anomers
3) enantiomers 4) conformational diastereomers
9. Two monosaccharides of D(+) glucose and D(–) fructose are held together by a glycosidic linkage
between
1) C2 of  -glucose and C1 of  -fructose 2) C2 of  -glucose and C2 of  -fructose
3) C1 of  -glucose and C1 of  -fructose 4) C1 of  -glucose and C2 of  -fructose

10. What will be produced if a molecule of sucrose is hydrolysed?
1) One molecule of glucose
2) Two molecules of glucose
3) One molecule of glucose and one molecule fructose
4) One molecule of glucose and one molecule of maltose
11. Which one of the following amino acid has phenyl (–OH) group?
1) Lysine 2) Arginine 3) Proline 4) Tyrosine
289
12. Which of the following amino acids is not optically active?

1) Lysine 2) Glycine 3) Leucine 4) Glutamine
13. Which of the following is a basic amino acid?
1) Alanine 2) Tyrosine 3) Lysine 4) Serine
14. Which one of the following is an essential amino acid?
1) Glycine 2) Glutamine 3) Tryptophan 4) Proline
15. Amino acids have a peptide linkage which has the structure
S O
1) C O 2) C NH 3) S NH 4) C NH
O
O
16. Which one of the following is an example of a globular protein?
1) Keratin 2) Myosin 3) Collagen 4) Albumin
17. Secondary structure of proteins refers to
1) Mainly denatured proteins and structure of prosthetic group
2) Three dimensional structure, especially the bond between amino acid residue that are distant from
each other in the polypeptide chain
3) Linear sequence of amino acid residues in the polypeptide chain.
4) Regular folding patterns of continuous portions of the polypeptide chain
18. Denaturation of protein leads to loss of its biological activity by:
1) formation of amino acids
2) loss of primary structure
3) loss of both primary and secondary structure
4) loss of both secondary and tertiary structures
19. Which of the following statements are correct about enzymes?
1) Accelerate biochemical reactions 2) Most of them are globular proteins
3) They are very specific 4) All are correct
20. The human body does not produce most of the
1) Hormones 2) Enzymes
3) DNA 4) Vitamins
21. Which of the following B group vitamins can be stored in our body?
1) Vitamin B1 2) Vitamin B2 3) Vitamin B6 4) Vitamin B12
22. Which of the following is a water soluble vitamin?
1) Vitamin A 2) Vitamin K 3) Vitamin D 4) Vitamin B
290
23. The RBC deficiency is deficiency disease of :

1) Vitamin B2 2) Vitamin B12 3) Vitamin B6 4) Vitamin B1
24. The deficiency of which vitamin causes night blindness?
1) Vitamin B 2) Vitamin C 3) Vitamin A 4) Vitamin B12
O
H C
N H
C
25. C C
O The compound is
H N
H
1) Cytosine 2) Guanine 3) Adenine 4) Uracil
26. Which of the following is correct about H-bonding in DNA?
1) A-T, G-C 2) A-G, T-G 3) G-T, A-C 4) A-A, T-T
27. Which one of the following is not present in the three types of RNA?
m-RNA 2) nc-RNA 3) r-RNA 4) t-RNA
28. Which of the following is not a constituent of RNA?
1) Ribose 2) Phosphate 3) Adenine 4) Pyridine
29. Which of the following is/are the application(s) of the DNA fingerprinting?
1) in forensic laboratories for the identification of criminals
2) to identify racial groups to rewrite biological evolution
3) to determine paternity of an individual
4) All of the above
30. Which one of the following is a peptide hormone?
1) Testosterone 2) Thyroxine 3) Adrenaline 4) Glucagon
LEVEL-II
1. Which one of the following pairs is the essential constituent of our food?
1) Nucleic acids and lipids 2) Proteins and carbohydrates
3) Proteins and nucleic acids 4) Proteins and lipids
2. Name the reagent and condition required for carrying out of the following reaction.
CHO
 CHOH 4 
 CH 3  CH 2 4 CH 3
n  hexane
CH2OH
1) HF,  2) HCl,  3) HBr,  4) HI, 
291
3. When glucose reacts with bromine water, the main product is

1) Acetic acid 2) Saccharic acid 3) Glyceraldehyde 4) Gluconic acid
4. Glucose reacts with acetic anhydride to form
1) Mono-acetate 2) Tetra-acetate
3) Penta-acetate 4) Hexa-acetate
5. Glucose as well as gluconic acid both get oxidised with HNO3, to give dicarboxylic acid. This indicates
the presence of which group in glucose?
1) Aldehydic group 2) Primary alcoholic group
3) Ketonic group 4) Carboxylic acid group
6. Assign the configuration to glyceraldehyde (I) and glucose (II)
CHO
H OH
CHO
HO H
H OH
H OH
CH2OH
H OH
Glyceraldehyde
I CH2OH
Glucose
II
Choose the correct option.
1) I  D; II  D 2) I  L; II  L 3) I  L; II  D 4) I  D; II  L
7. Which of the following reactions of glucose can be explained only by its cyclic structure?
1) Glucose forms pentaacetate
2) Glucose reacts with hydroxylamine to form an oxime
3) Pentaacetate of glucose does not react with hydroxylamine
4) Glucose is oxidised by bromine water to gluconic acid
8. Consider the following reagents,
I. Br2 water II. Tollen’s reagent III. Fehling’s solution
Which can be used to make distinction between an aldose and a ketose?
1) I, II and III 2) II and III 3) Only I 4) Only II
9. Which of the following statements is not true about glucose?
1) It is an aldohexose 2) On heating with HI it forms n-hexane
3) It is a ketohexose 4) It does not give 2, 4-DNP test
292
10. Hydrolysis of maltose gives

1) One molecule of fructose and one molecule of glucose
2) Two molecules of fructose
3) Two molecules of glucose
4) Do not hydrolyse
11. Which one of the following statement is correct?
1) Maltose is a non-reducing sugar 2) Lactose is a non-reducing sugar
3) Sucrose is called invert sugar 4) Sucrose is a non reducing sugar
12. Which of the following statement is correct about fructose?
1) It is dextrorotatory compound
2) It exists in the two cyclic forms which is obtained by the addition of OH at C – 5 to the > C = O group
3) It exists as a six membered ring
4) It is named as furanose as it contains one oxygen and six carbon atoms
HOH2C O OH
OH CH2OH
H H
13. . The compound is
OH H
1)   D     Fructo furanose 2)   D     Fructo furanose
3)   D      Glucopyranose 4)   D      Glucopyranose
14. The non-essential amino acid among the following is :

1) valine 2) leucine 3) alanine 4) lysine
15. Amino acids are classified as acidic, basic or neutral depending upon the relative number of amino
and carboxyl groups in their molecule. Which of the following are acidic amino acids?
i) (CH3)2CH CH COOH ii) HOOC CH2 CH2 CH COOH
NH2 NH2
iii) H2N CH2 CH2 CH2 COOH iv) HOOC CH2 CH COOH
NH2
1) (ii) and (iv) 2) (iii) and (iv) 3) (i) and (ii) 4) (ii) and (iii)
16. Which of the following statements is not correct about a Zwitter ion?
1) It is neutral and does not contain any charges
2) It consists of carboxyl and amino groups
3) It is dipolar
4) Many amino acids exist as Zwitter ions
293
17. Peptide linkage is an amide linkage formed between - NH2 group and group Y of aminoacids forming
protein. The group ‘Y’ is
O O O
1) C H 2) C OH 3) C 4) OH
 H 2O
18. In the given reaction, H 2 NCH 2 COOH  H 2 N  CH  COOH   H 2 NCH 2 CONH  CH  COOH
CH3 CH3
Name the dipeptide which is formed in the above reaction.
1) Alanglycine 2) Glycylalanine 3) Alaninglycine 4) Glycinalanine
19. Name the molecule which is eliminated during the formation of peptide bond.
1) Hydrogen 2) Oxygen 3) Water 4) Alcohol
20. Which of the following statements is incorrect about the secondary structure of protein?
1) It refers to the shape in which long polypeptide chain can exist
2) It exists in two different type of structures, i.e. α -helix and β -pleated sheet structure
3) Its structure arises due to regular folding of the backbone of the polypeptide chain
4) There is the covalent bonding between > C = O and –NH groups of the peptide bond
21. The spatial arrangement of the two or more polypeptide chains with respect to each other is known
as
1) Primary structure 2) Secondary structure
3) Tertiary structure 4) Quaternary structure
22. On boiling, what structural changes take place in the egg white?
1) Globular protein becomes fibrous protein
2) 2o and 3o structures are destroyed but 1o structure remains intact
3) 1o, 2o and 3o structures are destroyed
4) A reversible change takes place which can be reversed by cooling
23. Consider the following statements concerning proteins:
I. All natural amino acids which are constituents of proteins, are  -amino acids.
II.  - Amino acids are all optically active and have L-configuration.
III.  - Amino acids are connected by ester linkages.
IV. Favourable conformation for the peptide linkages in protein is the  - helix arrangement.
Of these statements:
1) I and II are correct 2) II and III are correct
3) I and IV are correct 4) I, II, III and IV are correct
24. Vitamin B1 is
1) Riboflavin 2) Cobalamin 3) Thiamine 4) Pyridoxine
294
25. Match the vitamins given in Column I with their deficiency disease given in Column II and select the
correct option from the codes given below.
Column I (Vitamins) Column II (Diseases)

A Vitamin B12 1 Increased blood clotting time
B Vitamin C 2 Pernicious anaemia
C Vitamin D 3 Scurvy
D Vitamin K 4 Rickets
Codes
A B C D
1) 1 2 3 4
2) 2 3 4 1
3) 2 4 3 1
4) 1 2 3 4
26. The presence or absence of hydroxyl group on which carbon atom of sugar differentiates RNA and
DNA?
1) 1st 2) 2nd 3) 3rd 4) 5th
27. DNA and RNA are chiral molecules due to the presence of:
1) chiral bases 2) phosphate ester unit
3) D-sugar component 4) L-sugar component
28. The reason for double helical structure of DNA is the operation of:
1) electrostatic attractions 2) van der Waals forces
3) dipole-dipole interactions 4) hydrogen bonding
29. Which of the following statements about RNA is not correct?
1) It has a single strand 2) It does not undergo replication
3) It does not contain any pyrimidine base 4) It controls the synthesis of proteins
30. Which one of the following hormones modulate inflammatory reactions and are involved in the
reactions to stress ?
1) Thyroxine 2) Insulin 3) Glucocorticoids 4) Estradiol
295
KEY WITH HINTS

LEVEL-I
1. 4
2. 4
3. 2
4. 4 Glycogen is a polysaccharide, they are not sweet in taste.
5. 4
6. 1 CHO CH  N  OH
 CHOH 4 
NH 2 OH
 CHOH 4
CH2OH CH2 OH
Oxime
7. 2
8. 2  -D-glucose and  -D-glucose are anomers.
9. 4
10. 3
11. 4
12. 2 Except glycine (Gly), all the other naturally occuring α -amino acids are optically active.
13. 3 H 2 N   CH 2 4  CH  COO
+
NH3
Lysine
14. 3
15. 4 Two or more than two amino acids unite through a bond - CO-NH. It is known as peptide bond
or peptide linkage.
16. 4 Globular proteins have compact, spherical shape because sections of the polypeptide chain
fold over on top of each other due to the various interactions between R groups.
17. 4 Secondary structure of proteins refers to shape of polypeptide chain and regular folding patterns
of continuous portion of the polypeptide chain.
18. 4 Denaturation results in loss of both secondary and tertiary structures.
19. 4
20. 4
296
21. 4 The human body needs a constant supply of vitamin. They cannot be stored in large amounts.
But the liver can store vitamin B12 for a long time.
22. 4 Vitamin B and Vitamin C are water soluble.
23. 2
24. 3
25. 4
26. 1 In DNA, adenine (A) forms two hydrogen bonds with thymine (T) and guanine (G) forms three
hydrogen bodns with cytosine (C).
27. 2
28. 4
29. 4
30. 4
LEVEL-II
1. 2
2. 4 On prolonged heating with HI, glucose forms hexane, suggesting that all 6 C-atoms are linked in
a straight chain.
3. 4 Glucose on reaction with bromine water followed by oxidation gives gluconic acid
C6 H12 O6   O 
Br2 /H 2 O
 CH 2OH  CHOH 4 COOH
Glu cos e Gluconicacid
4. 3 Glucose has 5-OH groups, which are replaced by acetate groups.

5. 2
6. 1
7. 3 Due to absence of free OH group at C1, cyclic structure of glucose pentacetate cannot revert to
open chain aldehydic form and hence cannot form an oxime.
8. 3
9. 3 Glucose is an aldohexose.
10. 3
11. 4 Maltose and Lactose are reducing sugars. Sucrose is a non-reducing sugar.
12. 2
13. 2
14. 3
15. 1 Amino acids which contain one –NH2 group and two –COOH groups are acidic in nature.
16. 1 It contains both positive and negative charges, but due to cancellation of charge it appears
neutral.
297
17. 2
18. 2
19. 3 There is the elimination of a water molecules and formation of a peptide bond (–CONH–).
20. 4 α -helix and β -pleated sheet structure arise due to the regular folding of the backbone of the
O
polypeptide chain due to hydrogen bonding between C and –NH -group of the peptide
bond.
21. 4
22. 2 During denaturation of proteins, 2o and 3o structures are destroyed but primary structure remains
intact.
23. 3
24. 3 Vitamin B1 is thiamine. Its main source is cereals.
25. 2
26. 2
27. 3 DNA has D(-)-2-deoxyribose and RNA has (3)-ribose, both are chiral.
28. 4 Double helical structure of DNA is due to the presence of hydrogen bonding. Hydrogen bonding
leads to base pairing in a specific way that makes two chains of DNA complementary.
29. 3 The pyrimidine bases in RNA are cytosine and uracil.
30. 3
298
CHAPTER - 12
THE p-BLOCK ELEMENTS
GROUP - 15 ELEMENTS : THE NITROGEN FAMILY
INTRODUCTION
The elements of group 15 of the periodic table are nitrogen, phoshorus, arsenic, antimony, and bismuth.
These are called pnicogens and their compounds as pniconides, the names derived from the Greek
word pnicomigs meaning suffocation. Nitrogen and phosphorus are non-metals, arsenic and antimony are
metalloids and bismuth and moscovium are typical metals.
OCCURRENCE
Nitrogen occurs as a diatomic gas, N2. It constitutes about 78% by volume of the atmosphere. Despite this,
nitrogen is not very abundant on the earth’s crust. It is only the thirty-third most abundant element by mass
in the earth’s crust (~9 ppm). Nitrogen mainly occurs as nitrates, e.g., NaNO3 (Chile saltpetre) and KNO3
(Indian saltpetre). It is an essential constituent of proteins, amino acids and nucleic acids.
Phosphorus is the eleventh most abundant element by mass (~1120 ppm) in the earth’s crust. It occurs in
apatite minerals, Ca9(PO4)6.CaX2 (X = F, Cl or OH). Fluoroapatite, 3Ca3(PO4)2.CaF2, chloroapatite, 3Ca3
(PO4)2.CaCl2, and hydroxyapatite, 3Ca3(PO 4)2.Ca(OH)2 are the major contents of phosphate rocks.
Phosphorus is an essential constituent of animal (bones and cells) and plant matter. Phosphoproteins are
present in milk and eggs.
Arsenic, antimony and bismuth are not very abundant. They mainly occur as sulphide minerals such as
mispickel (arsenopyrites), FeAsS, stibnite, Sb2S3 and bismuth glance, (Bi2S3).
Moscovium (Mc, atomic number 115) is a synthetic element and its electronic configuration is [Rn] 5f14 6d10
7s2 7p3.
ATOMIC AND PHYSICAL PROPERTIES
1. Electronic Configuration. The general valence shell electronic configuration of group15 elements
is ns2 np3. The three electrons in the p-orbitals are distributed as px1, py1, pz1 in accordance with
Hund’s rule. The fully filled ns orbital and exactly half-filled np-orbitals provide extra stability to their
configuration.
299
Table - 01 Atomic and physical properties of Group 15 elements
Property Nitrogen Phosphorus Arsenic Antimony Bismuth

Atomic number 7 15 33 51 83
2 3 2 3 10 2 3 10 2 3 1 10 2 3
Electronic configuration [He]2s 2p [Ne]3s 3p [Ar]3d 4s 4p [Kr]4d 5s 5p [Xe]4f 5d 6s 6p
–1)
Atomic mass (g mol 14.01 30.97 74.92 121.76 208.98
Ionisation enthalpy ∆i H1 1402 1012 947 834 703
-1
(kJ mol ) ∆i H2 2856 1903 1798 1595 1610
∆i H3 4577 2910 2736 2443 2466
Electronegativity 3 2.1 2 1.9 1.9
Covalent radius (pm) 70 110 121 141 148
3- 3- 3- 3+ 3+
Ionic radius (pm) 171(N ) 212(P ) 222(As ) 76(Sb ) 103(Bi )
Melting point (K) 63 317.1 1089 904 544
(grey a -form at
(white P)
38.6 atm)
Boiling point (K) 77.2 554 888 1860 1837
(sublimation
(white P)
temperature)
–3
Density (g cm at 298 K) 0.879 1.823 5.778 6.697 9.808
at 63K (grey a -form)
2. Atomic and ionic radii. The covalent and ionic radii of group 15 elements are lower than those of the
corresponding elements of group 14. Down the group, covalent and ionic radii increase with increase
in atomic number. There is considerable increase in covalent radius from N to P, but only very small
increase from As to Bi due to the presence of completely filled d-and/or f- orbitals in their inner shells.
3. Ionization enthalpy. The ionization enthalpies of group 15 elements are much higher than those of
the corresponding elements of group 14. This is due to increased nuclear charge, reduced atomic
radius and stable half-filled (p-orbital) electronic configuration. The decrease in ionization enthalpy
down the group is due to increase in atomic size. Ionization enthalpies increase in the order:
 i H1   i H 2   i H 3 .
4. Electronegativity. These elements are more electronegative than group 14 elements. This is due to
smaller atomic size and lesser number of electrons needed to attain noble gas configuration.
Electronegativity decreases down the group due to increase in atomic radii, but the difference is very
small among heavier members.
5. Metallic character. Due to increased nuclear charge and higher electronegativity, elements of group
15 are less metallic than the corresponding elements of group 14. Down the group, metallic character
increases. Thus, N and P are non-metals, As and Sb are metalloids, and Bi is a typical metal.
6. Melting and boiling points. The melting points of group 15 elements increase from N to As and then
decrease to Sb and Bi. The decrease in melting points of Sb and Bi may be due to inert pair effect.
The boiling points increase down the group from N to Bi due to increase in atomic size.
7. Allotropy. Elements of this group exhibit allotropy. Phosphours exists in three allotropic forms (white,
red and black), As and Sb exist in two allotropic forms (yellow and grey).
300
CHEMICAL PROPERTIES
i. Oxidation states. The common oxidation states are -3, +3 and +5. Nitrogen forms N3– (nitride) ion in
nitrides of highly electropositive metals (Mg3N2, Ca3N2, etc.). Other elements form covalent compounds
even with metals and exhibit a formal oxidation state of -3, e.g., calcium phosphide (Ca3P2), sodium arsenide
(Na3As), zinc antimonide (Zn3Sb2) and magnesium bismuthide (Mg3Bi2). However, the tendency to show -3
oxidation state decreases down the group due to gradual decrease in electronegativity and ionisation enthalpy.
Besides -3, N and P also exhibit -2 oxidation state in hydrazine (NH2NH2) and diphosphine (P2H4). Nitrogen
also shows an oxidation state of -1 in hydroxylamine (NH2OH).
Down the group, stability of +5 oxidation state decreases while that of +3 oxidation state increases due to
inert pair effect; the only stable compound of bismuth having +5 state is BiF5.
Due to large amount of energy needed to lose all five valence electrons, M+5 ions are not formed. Thus,
compounds having +5 oxidation state such as PF5, PCl5, SbF5, and BiF5 are covalent. However, these
elements form both ionic (BiF3, SbF3) and covalent compounds (NCl3, PCl3, AsCl3, SbCl3) in +3 oxidation
state. Thus, covalent character decreases in the order: N > P > As > Sb > Bi.
Nitrogen, because of small size, high electronegativity and strong tendency to form p  p multiple bonds,
shows oxidation states from -3 to +5.
Compound : NH3 NH2NH2 NH2OH N2 N 2O NO N 2O 3 NO2 or N2O4 N 2O 5
Oxidation state : –3 –2 –1 0 +1 +2 +3 +4 +5
ii. Maximum covalency. Since nitrogen does not possess d-orbitals, its maximum covalency is 4 when it
donates its lone pair of electrons (NH4+, R4N+). That is why nitrogen does not form NF5 or NCl5. All other
elements of the group have empty d-orbitals, and therefore, they exhibit covalency of 5 or 6, e.g., PCl5,
AsF5, [PF6]–, [SbF6]–, etc.
iii. Disproportionation. All oxidation states of N from +1 to +4 exhibit disproportionation in acidic medium.
3 5 2
3HNO 2 
 HNO3  2NO  H 2 O
Nitrous acid Nitric acid Nitricoxide
Phosphorus, in all oxidation states from –3 to +5 shows disproportionation both in acid and base. However,
due to inert pair effect, the stability of +3 oxidation state increases from As to Bi and the tendency to
undergo disproportionation decreases.
iv. Anomalous Properties of Nitrogen. Nitrogen differs from the other elements of group 15 due to
exceptionally small atomic size, high electronegativity, high ionisation enthalpy and absence of d-orbitals.
Nitrogen forms pπ - pπ multiple bonds with itself and with other elements having small size and high
electronegativity like carbon and oxygen. The other elements of this group do not form p  p multiple
bonds because their atomic orbitals, being very large and diffused, cannot overlap effectively. Thus, N2 is a
diatomic molecule with a triple bond having very high bond enthalpy (941.4 kJ mol-1).
Phosphorus, arsenic and antimony form single bonds, P–P, As–As and Sb–Sb, while bismuth forms metallic
bonds. They exist as discrete tetraatomic tetrahedral molecules, P4, As4 and Sb4, containing E–E single
bonds. Due to larger size, forces of attraction holding the tetraatomic molecules of P4, As4and Sb4 are quite
strong, therefore, these are solids at room temperature. Nitrogen has little tendency for catenation since N–
N single bond is very weak due to repulsion between lone pairs (N–N bond having small bond length).
Nitrogen forms chains containing up to three N-atoms, e.g., hydrazoic acid , N3H or azide ion, N3 .
The heavier elements can form dπ - pπ multiple bonds as in R3P = O or R3P = CH2 (R = alkyl group).
Phosphorus and arsenic form dπ - pπ bond with transition metals when their compounds like P(C2H5)3 and
As(C6H5)3 act as ligands.
301
v. Reactivity towards hydrogen. All elements of group 15 form volatile hydrides of the formula EH3;
Ammonia (NH3), Phosphine (PH3), Arsine (AsH3), Stibine (SbH3), and Bismuthine (BiH3). The lighter elements
also form hydrides of the formula E2H4, viz. N2H4 (hydrazine), P2H4 and As2H4. Nitrogen forms a hydride of
the formula HN3, called hydrazoic acid.
Properties of hydrides. Due to intermolecular H- bonding, NH3 has high melting and boiling points. It is
highly soluble in water due to its ability to form H-bonds with water molecules.
Thermal stability decreases from NH3 to BiH3 due to decrease in M–H bond strength with increase in size
of the atom. This is evident from their bond dissociation enthalpies.
The reducing character of group 15 hydrides increases with increase in atomic number. Thus, NH3 is a mild
reducing agent while BiH3 is a strong reducing agent.
The hydrides have a lone pair of electrons on the central atom, therefore, they are Lewis bases. The basic
character decreases down the group from NH3 to BiH3.
Table - 02 Properties of hydrides of Group 15 elements
Proprty NH3 PH3 AsH3 SbH3 BiH3

Melting point/K 195.2 139.5 156.7 185 -
Boiling point/K 238.5 185.5 210.6 254.6 290
E-H distance (pm) 101.7 141.9 151.9 170.7 -
HEH angle (°) 107.8 93.6 91.8 91.3
∆fH° (kJ/mol) -46.1 13.4 66.4 145.1 278
-1
∆dissH° (E-H)/kJ mol 389 322 297 255
vi.Reactivity towards oxygen. All these elements form two types of oxides; E2O3 and E2O5. Nitrogen has
a strong tendency to form p  p multiple bonds with oxygen. Thus, it forms five oxides with oxidation
states ranging from +1 to +5 while other elements form oxides with only +3 and +5 oxidation states.
Among the oxides of the same element, higher the oxidation state of the element, greater is its acidic
strength.
i) Acidic strength of oxides of nitrogen increases in the order : N2O < NO < N2O3 < N2O4 < N2O5. However,
N2O and NO are neutral.
ii) In the group, acidic strength of trioxides follows the order : N2O3 > P4O6 > As4O6 > Sb4O6. As4O6 and
Sb4O6 are amphoteric while Bi2O3 is basic.
iii) Within the group, acidic strength of pentoxides follows the order : N2O5 > P4O10 > As4O10 > Sb4O10
vii. Reactivity towards Halogens. The elements of group 15 form trihalides (EX3) and pentahalides (EX5).
Nitrogen does not form pentahalides due to the absence of d-orbitals in its valence shell. In case of nitrogen,
only NF3 is known to be stable. Pentahalides are less stable than trihalides due to inert pair effect and steric
hindrance. Thus, bismuth forms only BF5. Trihalides except BiF3 are predominantly covalent in nature.
Pentahalides are more covalent than trihalides.
viii. Reactivity towards Metals. All elements of group 15 form binary compounds with metals in the +3
oxidation state,e.g., Ca3N2 (calcium nitride), Ca3P2 (calcium phosphide), Na3As2 (sodium arsenide), Zn3Sb2
(zinc antimonide) and Mg3Bi2 (magnesium bismuthide).
302
GROUP 16 ELEMENTS : THE OXYGEN FAMILY

INTRODUCTION
Group 16 consists of five elements viz., oxygen, sulphur , selenium, tellurium, polonium and livermorium.
These are called chalcogens (meaning ore forming) because many metals occur as oxides and sulphides.
Oxygen and sulphur are non-metals, selenium and tellurium, are metalloids, and polonium and livermorium
are metallic. Polonium is radioactive with very short half-life. Livermorium is a synthetic radio active element.
OCCURRENCE
Oxygen is the most abundant element. It occurs in the free state as dioxygen (O2) and constitutes up
20.946% by volume and 23% by mass of the atmosphere. It also occurs as ozone (O3). Oxygen makes up
46.6% by weight of the earth’s crust where it mainly occurs as silicate minerals. It also makes up 89% by
weight of water in the oceans.
Sulphur constitutes 0.03 to 0.1% by mass of the earth’s crust. It occurs as sulphates such as gypsm,
CaSO4.2H2O; epsom salt, MgSO4.7H2O; baryte, BaSO4 and as sulphides such as galena, PbS, zinc blende,
ZnS and copper pyrites, CuFeS2. Sulphur also exists as H2S in volcanoes. It is present in living matter and
is a constituent of many organic materials.
Selenium and tellurium are less abundant (0.05 ppm and 0.002 ppm respectively in earth’s crust) and occur
as selenides and tellurides in sulphide ores. The principal source of Se and Te is the anode mud deposited
during electrolytic refining of Cu. Polonium is even less abundant (0.001 ppm). It occurs as decay
product of thorium and uranium minerals.
i. Electronic Configuration. The general outer electronic configuration of group 16 elements is ns2np4.
ii. Atomic and ionic radii. The atomic radii of group 16 elements are smaller than those of the
corresponding elements of group 15. This is due to increased nuclear charge which results in greater
attraction of the electrons by the nucleus. The increase in the atomic radii down the group is due to
increase in the number of shells.
Table - 03 Atomic and physical properties of Group 16 elements.
Property Oxygen Sulphur Se lenium Tellurium Polonium
2 4 2 4 10 2 4 10 2 4 1 10 2 4
Electronic configuration [He]2s 2p [Ne]3s 3p [Ar]3d 4s 4p [Kr]4d 5s 5p [Xe]4f 5d 6s 6p
-1 16 32.06 78.96 127.6 210
Atomic mass (g mol )
Covalent radius (pm) 66 104 117 137 146
2- 140 184 198 221 230
Ionic radius (E )/ (pm)
Ionisation enthalpy (∆i H1) 1314 1000 941 869 813
-1
(kJ mol ) (∆i H2) 3388 2251 2045 1790 _
Electronegativity 3.5 2.44 2.48 2.01 1.76
Electron gain enthalpy
-1 -141 -200 -195 -190 -174
(egH)/kJ mol
-3 1.32 (at m.p) 2.06 (a -S) 4.19 (grey) 6.25 9.4
Density/g cm at 293K
Melting point/K 55 393 490 725 520
(monoclinic
form, 673K)
Boiling point/K 90 718 958 1260 1235
Oxidation state -2,-1,+1,+2 -2,+2,+4,+6 -2,+2,+4,+6 -2,+2,+4,+6 +2, +4
303
iii. Ionization enthalpy. The first ionization enthalpies of group 16 elements are low while their second
ionization enthalpies are higher than those of the corresponding elements of group 15. This is due to
the relatively symmetrical and more stable electronic configuration. Ionization enthalpies decrease
down the group due to increasing atomic size and increasing shielding effect of the inner electrons.
iv. Electron gain enthalpy. Elements of group 16 are only two electrons short of noble gas configuration,
therefore, they have large negative electron gain enthalpies, next only to the halogens. The electron
gain enthalpy of oxygen is the least negative. This is because the electron-electron repulsions in the
relatively small 2p-subshell are comparatively high.
v. Electronegativity. Elements of group 16 have higher electronegativities than the corresponding

elements of group 15. Oxygen is the second most electronegative element (EN = 3.5). This is due to
smaller atomic size and lesser number of electrons required to attain noble gas configuration. The
electronegativity of sulphur is much smaller than oxygen. Electronegativity decreases regularly from
selenium to polonium.
vi. Metallic character. Because of high ionization enthalpy, elements of group 16 are less metallic.
However, down the group, metallic character increases due to decrease in ionisation enthalpy.
vii. Elemental state. Oxygen exists as a diatomic gas at room temperature; other elements exist as
octaatomic solids. Oxygen forms p  p double bond in oxygen molecule. Other elements do not
form p  p multiple bonds. S, Se and Te exist as octa-atomic molecules (S8, Se8, Te
e8) having
puckered crown shaped rings.
viii. Multiple bonding. Oxygen forms p  p double bonds, but other elements do not. However, other
elements of this group posses d-orbitals and hence form p  d multiple bonds.
ix. Melting and boiling points. In the group, m.p and b.p. increase regularly. However, m.p. and b.p. of
polonium are lower than those of tellurium. The large difference in the melting and boiling points of
oxygen and sulphur may be because oxygen is diatomic (O2) while sulphur is polyatomic (S8).
x. Catenation. Because of stronger S–S bonds as compared to O–O bonds, sulphur has greater
tendency for catenation than oxygen. Thus, chains of sulphur atoms are present in polysulphides,
polysulphanes, H–Sn–H and polysulphuric acids, HO3S–Sn–SO3H. Oxygen forms polyoxides such as
H2O2.
xi. Allotropy. All the elements of this group show allotropy. Oxygen exists in two forms, viz., dioxygen
(O2) and ozone or trioxygen (O3). Sulphur has several allotropic forms (rhombic, prismatic, plastic).
Selenium has eight allotropic forms.
CHEMICAL PROPERTIES
Oxidation states. Oxygen is highly electronegative, therefore, all metal oxides are ionic and contain O2–
ions in which oxygen shows an oxidation of –2. In addition, oxygen shows –1 in peroxides such as H2O2, –
1/2 in superoxides such as KO2, zero in O2 and O3, +1 in O2F2 and +2 in OF2. Since electronegativity
decreases down the group, the tendency to show–2 oxidation state decreases from sulphur to polonium.
Oxygen shows positive oxidation states only in O2F2 and OF2. The other elements show +2, +4, and +6 due
to promotion of electrons to vacant d-orbitals. Due to inert pair effect, the stability of +6 oxidation state
decreases down the group. Thus, +6 oxidation state is most stable in case of S and least stable in case of
Po.
304
In general, compounds of S, Se, Te and Po with oxygen are tetracovalent. These +4 compounds show both
oxidising and reducing properties. Compounds of S, Se, Te and Po with fluorine show an oxidation state of
+6. Compounds in +6 oxidation state show only oxidising properties.In higher oxidation states, particularly in
+4 and +6, bonding is primarily covalent.
Anomalous Behaviour of Oxygen. Oxygen, differs considerably from the rest of the Group 16 elements
due to small size, higher electronegativity and non-availability of d-orbitals. At room temperature, oxygen is
a gas while all other members of group 16 are solids. Oxygen is a typical non-metal and shows an oxidation
state of –2 in most of its compounds. Other elements of the group do not show negative oxidation states.
Due to the absence of d-orbitals, oxygen cannot expand its octet and hence cannot show positive oxidation
states. Compounds of oxygen are ionic as well as covalent while those of other members are mostly
covalent. Oxygen forms p  -p  multiple bonds with elements having similar size. Oxygen forms
intermolecular H-bonds in H2O, therefore, H2O is a liquid while hydrides of other elements are gases at
room temperature. Dioxygen (O2) is paramagnetic while oxides of the other elements of this group are
diamagnetic.
Reactivity. The reactivity of oxygen is only slightly less than the most reactive halogens. Sulphur is also
very reactive, particularly at high temperatures. Down the group, reactivity decreases.
1. Reactivity towards Hydrogen
All the elements of group 16 form hydrides of the general formula, H2E , i.e., H2O, H2S, H2Se, H2Te
and H2Po. Oxygen forms another hydride, H2O2.
i. Preparation of Hydrides. Hydrides are prepared by the action of acids with metal sulphides, selinides,
etc.
FeS(s)  2H3O (aq) 

 Fe 2 (aq)  H 2S(g)  2H 2 O(l )
ii. Structure of Hydrides. The hydrides have angular shape involving sp3-hybridization of the central
atom. The bond angles decrease from H2O to H2Te : H2O (104.5o), H2S (92.1o), H2Se (91o) and H2Te
(90o).
Table - 04 Properties of hydrides of Group 16 elements.
Property H 2O H 2S H 2Se H2Te

Melting point (K) 273 188 208 222
Boiling point (K) 373 213 232 269
H-E distance (pm) 96 134 146 169
HEH angle (°) 104.5 92.1 91 90
-1
∆fH° (kJ mol ) -286 -20 73 100
-1
∆dissH (H-E)/kJ mol 463 347 276 238
Dissociation constant (aqueous -16 -7 -4 -3
1.8×10 1.3×10 1.3×10 2.3×10
solution, 298 K)
iii. Physical state. The hydride of O, H2O, is a colourless, odourless liquid while the hydrides of the
other elements are foul smelling, poisonous gases.
iv. Melting and boiling points. The high boiling point of H2O is due to strong intermolecular H-
bonding. Other elements of the group do not form H-bonds. As the size of the atom increases, van der
Waals forces of attraction increases, therefore, the boiling points increase from H2S to H2Se.
305
v. Acidic character. The hydrides of group 16 elements act as weak, diprotic or dibasic acids. Acid
strength, increases down the group, from H2O to H2Te : H2O < H2S < H2Se < H2Te. The increase in
acid strength is due to decrease in bond dissociation energy.
vi. Thermal stability. Thermal stability decreases from H2O to H2Te. Thus, water dissociates at
about 2073–2273 K, H2S at 673–873 K, H2Se at about 423 K and H2Te. This is due to increase in size
of the atom.
vii. Reducing character. Hydrides of group 16 elements except oxygen (water) are reducing agents.
Their reducing character increases from H2S to H2 Te.
2. Reactivity towards oxygen
All the elements of this group form two types of oxides, EO2 and EO3.
a. Dioxides. S, Se and Te, when burnt in air form dioxides of the formula EO2.
S8 ( s   8O 2 ( g  
 8SO 2 ( g 
Ozone (O3) and SO2 are gases at room temperature. SeO2, TeO2 and PoO2 are crystalline ionic
solids.
i) Acid-base character of oxides. Acidic character of dioxides decreases down the group. Dioxides
differ in their reaction with water. SO2 dissolves giving sulphurous acid (H2SO3) which exists only in
solution. SeO2 dissolves in water forming selenious acid, H2SeO3, which can be isolated. TeO2 and.
PoO2 are amphoteric.
ii) Reducing-oxidising properties of oxides. Since +6 oxidation state of S is more stable than +4,
SO2 acts as a reducing agent. The stability of +6 state decreases from S to Te, therefore, the reducing
character of dioxides decreases while their oxidising character increases. Thus, TeO2 acts as an
oxidising agent.
b. Trioxides. Elements of 16 group form trioxides of the formula EO3. O3 and SO3 are gases. All
trioxides are acidic in nature.
3. Reactivity towards Halogens
The elements of group 16 form halides with oxidation states +1, +2, +4 and +6. The stability of the
halides in any particular oxidation state decreases in the order : F > Cl > Br > I. The highest oxidation
state is realised only in the case of fluorides, e.g., SF6.
i. Monohalides. Most monohalides are dimeric in nature, e.g., S2F2, S2Cl2, S2Br2, Se2Cl2 and Se2Br2.
These dimeric halides undergo disproportionation.
1 4 0
2Se2Cl2 
SeCl4  3Se
ii. Dihalides. All group 16 elements except oxygen form dichlorides and dibromides. The dihalides
have sp3-hybridisation and tetrahedral structures.
iii. Tetrahalides. Among tetrahalides, tetrafluorides are the most stable. SF4 is a gas, SeF4 is a liquid
and TeF4 is a solid. These fluorides have sp3d hybridisation and thus, have trigonal bipyramidal
structures in which one of the equatorial positions is occupied by a lone pair of electrons. Thus, these
molecule have see-saw geometry.
iv. Hexahalides. Only fluorine forms hexa halide. All hexafluorides are gases. The stability of
hexafluorides decreases in the order : SF6 > SeF6 > TeF6. SF6 has sp3d2 hybridisation and octahedral
geometry.
306
GROUP 17 ELEMENTS : THE HALOGEN FAMILY

INTRODUCTION
Group 17 of the periodic table (halogens) consists of fluorine, chlorine, bromine, iodine, astatine and tennessine
(Ts). These are collectively named as halogens. Among the halogens, fluorine is the most reactive and
hence is also called super halogen. Astatine and tennessine are radioactive.
OCCURRENCE
Halogens are highly reactive and hence do not occur in the free or native state. They mainly occur in the
combined state in the form of their halide (X-) salts.
Fluorine occurs as insoluble fluorides to the extent of 0.07% in earth’s crust. Small amounts of fluorides are
present in soil, river water, plants, bones and teeth of animals. The chief minerals are: i) Fluorspar, CaF2,
ii) Cryolite, Na3AlF6 and iii) Fluoroapatite, CaF2.3Ca3(PO4)2.
Chlorine is the most abundant halogen and occurs as chlorides to the extent of 0.14% in earth’s crust. The
chief sources of chlorine are sea water (2.5% by mass), salt wells and salt beds. In salt beds, it mainly
occurs as Sodium chloride (Rock salt), NaCl, Carnallite KCl. MgCl2.6H2O, and Calcium chloride, CaCl2.
Bromine occurs as bromides to the extent of 2.5×10–4 % in earth’s crust. It mainly occurs in sea water and
salt lakes as bromides of alkali and alkaline earth metals, i.e., NaBr, KBr and MgBr2.
Iodine occurs to the extent of 8×10–5% in earth’s crust. It mainly occurs in sea weeds (0.5% by mass) as
alkali metal iodides and in chile saltpetre which is mainly sodium nitrate containing 0.2% by mass of iodine
as sodium iodate (NaIO3).
1. Electronic Configuration. The elements of group 17 have seven electrons in the valence shell.
Their general outer electronic configuration (ns2np5) is one electron short of the nearest inert gas.
2. Atomic and ionic radii. Halogens have the smallest atomic radii in the respective periods due to
maximum effective nuclear charge. The atomic and ionic radii increase from fluorine to iodine.
3. Ionization enthalpy. Halogens have very little tendency to lose electrons. Therefore, ionization
enthalpies of halogens are very high. On moving down the group, ionization enthalpies decrease with
increase in size.
4. Electron gain enthalpy. Halogens have one electron less than the nearest noble gas, therefore, they
have strong tendency to accept an electron and hence large negative electron gain enthalpies. In the
group, electron gain enthalpies become less negative as the size of the halogen increases. Due to
small size, strong electron-electron respulsions are present in the relatively compact 2p-orbitals of
fluorine, therefore electron gain enthalpy of fluorine is less negative than chlorine. The order of electron
gain enthalpies are : Cl > F> Br > I.
5. Electronegativity. Halogens are highly electronegative. Due to small size and high nuclear charge,
halogen has the highest electronegativity in its period. Fluorine has the highest electronegativity value
of 4.0. Down the group, electronegativity decreases due to increase in the size of the atom.
307
Property/Element Fluorine Chlorine Bromine Iodine Astatine

Electronic configuration 2
[He]2s 2p
5 2
[Ne]3s 3p
5 10
[Ar]3d 4s 4p
2 5
[Kr]4d
10
[Xe]4f 5d
1 10
2 5 2 5
5s 5p 6s 6p
-1
Atomic mass/g mol 19.00 35.45 79.90 126.90 210
Covalent radius/pm 64 99 114 133 150
-
Ionic radius (X )/pm 133 184 196 220 202
-1
Ionisation enthalpy/kJ mol 1680 1256 1142 1008 899
Electronegativity 4.0 3.2 3.0 2.7 2.2
Electron gain enthalpy
-1
(kJ mol ) -333 -349 -325 -296 -
- -1
Hyd.H(X )/kJ mol 515 381 347 305 -
Oxidation states -1 -1,+1,+3,+5,+7 -1,+1,+3,+5,+7 -1,+1,+3,+5,+7
Melting point/K 54.4 172 265.8 386.6 575
Boiling point/K 84.9 239 332.5 458.2 610
-3
Density/g cm (liquid) 1.51 (85K) 1.66 (203K) 3.19 (293K) 4.94 (273K) 6.35
Distance X-X/pm 143 199 228 266 -
-1
X2(g)  2X (g)/kg mol 158.8 242.6 192.8 151.1 -
o
E /V 2.87 1.36 1.09 0.54 -
6. Melting and boiling points. Fluorine and chlorine are gases, bromine is a liquid and iodine is a solid.
Due to increase in van der Waals forces of attraction, the melting and boiling points increases down
the group.
7. Non-metallic character. Due to high ionization enthalpies and electronegativities, halogens are non-
metallic in nature. Non-metallic character decreases from fluorine to iodine. Iodine is a solid having
metallic lustre.
8. Colour. Halogens are coloured due to absorbtion of light in the visible region for excitation of electrons
to higher energy levels. The colour of halogens is the colour of the trasmitted light; fluorine (pale
yellow), chlorine (greenish yellow), bromine (reddish brown) and iodine ( deep violet). In the group,
energy required for electron excitation decreases, therefore, energy of transmitted light increases and
hence the deepening of colour.
9. Solubility. F2 and Cl2 react with water. Br2 and I2 are sparingly soluble in water, but soluble in organic
solvents such as CHCl3, CCl4, CS2, and hydrocarbons such as hexane, benzene, etc., to give coloured
solutions.
10. Nature of bonds. Halogens form ionic as well as covalent compounds. The halides of highly
electropositive metals are ionic while those of weakly electropositive metals and non-metals are
covalent.
As the electronegativity decreases from fluorine to iodine, their tendency to form ionic bond decreases
while the tendency to form covalent bond increases.
CHEMICAL PROPERTIES
1. Oxidation States. All halogens exhibit -1 oxidation state. Chlorine, bromine and iodine exhibit +1, +3,
+5, and +7 oxidation states. Halogens except fluorine have vacant d-orbitals. As a result, one, two or
three electrons can be excited from np and ns orbitals to nd-orbitals, thereby making 3, 5 or 7 half-
filled orbitals available for bond formation.
308
Thus, besides –1 and +1 oxidation states, Cl, Br, and I exhibit +3, +5 and +7 states in their oxides,
oxoacids and interhalogen compounds. Chlorine also shows +4 oxidation state in ClO2 and +6 state
in Cl2O6 and ClO3. Br shows +4 oxidation state in BrO2. Chlorine, bromine and iodine show +1 oxidation
state by sharing its unpaired electron with more electronegative elements such as fluorine in interhalogen
compounds (ClF, BrF and IF) or with compounds of oxygen in oxoacids (HOCl, HOBr and HOI). Being
the most electronegative element, fluorine should not exhibit positive oxidation state, but it exhibits +1
state in highly unstable HOF.
2. Oxidising Power. Halogens have strong tendency to accept an electron, therefore, they act as strong
oxidising agents. Oxidising power decreases from F2 to I2. Fluorine oxidises all other halide ions to the
corresponding halogen.
 2F  X 2 ( X   C , Br  , I  
F2  2X  
Similarly, chlorine oxidises Br– and I– ions while bromine oxidises only I– ions from their solutions.
 2Cl   X 2 ( X   Br  , I   ; Br2  2I  
Cl2  2X    2Br   I 2
In general, a halogen of lower atomic number oxidises halide ions of higher atomic number.
The relative oxidising power of halogens can be seen by their reaction with water. Fluorine oxidises
water to O2 and O3, whereas Cl2 and Br2 react with water to form the corresponding hydrohalic and
hypohalous acids. The reaction of I2 with water is non-spontaneous. I– ions can be oxidised by O2 in
acidic medium which is the reverse of the reaction observed in case of fluorine.
2F2 ( g   2H 2 O ( l  
 4H  ( aq   4F ( aq   O 2 ( g 
X 2 ( g   H 2O ( l  
 HX ( aq   HOX ( aq  (where X=Cl or Br)
4I ( aq   O 2 ( g   4H ( aq  
 
 2I 2 ( s   2H 2 O ( l 
3. Anomalous Behaviour of Fluorine. Fluorine shows remarkable difference in behaviour from other
halogens. Ionisation enthalpy, electronegativity, and electrode potential of fluorine are higher than those
of other halogens. Ionic and covalent radii, melting and boiling points, bond dissociation enthalpy and
electron gain enthalpy are lower than expected. The reasons for the anomalous behaviour are small
size, high electronegativity, low bond dissociation enthalpy of F2 molecule, and absence of d-orbitals
in its valence shell.
Fluorine is the most reactive halogen; most of the reactions are exothermic. Being the most
electronegative element, it always shows -1 oxidation state except in HOF. Hydrogen fluoride is a
liquid (b.p. 293 K) due to strong hydrogen bonding. Other hydrogen halides are gases.
4. Reactivity towards hydrogen. All halogens combine with hydrogen to form hydrogen halides, but
reactivity decreases from fluorine to iodine. Fluorine combines violently even in the dark, chlorine
reacts even in diffused sunlight, bromine reacts only on heating and iodine reacts on heating in presence
of platinum catalyst.
309
Whereas, HBr, HCl and HI are gases, HF is a low boiling liquid (b.p. 293 K). This is due to intermolecular
hydrogen bonding in HF. Melting and boiling points increase from HCl to HI.
They dissolve in water to form hydrohalic acids. The acidic strength of these acids varies in the order:
HF < HCl < HBr < HI. The stability of these halides decreases down the group due to decrease in bond
dissociation enthalpy in the order: H–F > H–Cl > H–Br > H–I.
Table - 06 Physical properties of hydrogen halides
Property HF HCl HBr HI

Melting point (K) 190 159 185 222
Boiling point (K) 293 189 206 238
Bond length, (H-X)/pm 91.7 127.4 141.4 160.9
o -1 574 432 363 295
diss H /kJ mol
Dipole moment m/D 1.86 1.11 0.79 0.38
Acid dissociation constant/pKa 3.2 -7.0 -9.5 -10.0
5. Reactivity towards Oxygen. Halogens form binary compounds with oxygen, but most of them are
unstable. Fluorine forms OF2 (oxygen difluoride) and O2F2 (dioxygen difluoride) with oxygen. OF2 is
thermally stable at 298 K while O2F2 is highly unstable and decomposes even at 178K. O2F2 is used
for removing Pu from spent nuclear fuel as PuF6.
Chlorine, bromine and iodine form oxides in which the oxidation states of halogens range from +1 to
+7. Chlorine forms the largest number of oxides while iodine forms the least. In these compounds, the
bonds are covalent due to small difference in electronegativity between the halogens and oxygen. The
bond polarity increases from Cl to I.
The stability of oxides of iodine is greater than those of chlorine while bromine oxides are the least
stable. Iodine-oxygen bond is stable due to greater polarity of the bond while the stability of the chlorine-
oxygen bond is due to multiple bond formation involving d-orbitals of the chlorine atom. Bromine, being
in between, lacks both these characteristics. Thus, the stability of oxides of halogens decreases in
the order : I > Cl > Br. The higher oxides of halogens are more stable than the lower ones.
The bromine oxides, Br2O, BrO2, BrO3 are the least stable halogen oxides (middle row anomally) and
exist only at low temperatures. They are very powerful oxidising agents. Their structures are similar to
those of chlorine oxides having similar molecular formulae.
Iodine forms three oxides, I2O4, I2O5 and I4O9 of which I2O5 is the most stable. It is the only true oxide
of idoine while others are regarded as iodates of tripositive iodine. I2O5 is a very good oxidising
agent and is used in the estimation of carbon monoxide.
6. Reactivity towards Metals. Halogens combine directly with most metals to form the corresponding
halides.
M ( s   X 2 ( l  
 MX 2 ( s 
Due to decrease in electronegativity of the halogens, ionic character of the M–X bond (monovalent
metal, decreases in the order : M–F > M–Cl > M–Br > M–I
However, when the metal exhibits more than one oxidation state, the halide in the higher oxidation
state will be more covalent, e.g., SnCl4, PbCl4, SbCl5, UF6 are more covalent than SnCl2, PbCl2, SbCl3
and UF4.
7. Reactivity of Halogens towards other Halogens. Halogens react among themselves to form
compounds called interhalogens of the type XX, XX3 , XX5 and XX7 where X is the halogen with
larger size.
310
GROUP 18 ELEMENTS : THE NOBLE GASES

INTRODUCTION
The group 18 of the perodic table consists of monoatomic gaseous elements : helium (He), neon (Ne),
argon (Ar), krypton (Kr), xenon (Xe), radon (Rn) and oganesson (Og). All these gases except radon and
oganesson are present in the atmosphere in very small quantities and hence they are known as rare
gases. These are also referred to as aerogens (present in air), inert gases or noble gases.
OCCURRENCE AND ISOLATION
Noble gases occur in elemental state in the atmosphere. Their total percentage in dry air is about 1% by
volume of which argon is the major component. Helium is present in natural gas (2–7%). Helium and
sometimes neon are present in small quantities in radioactive minerals such as clevite, monazite, pitchblende,
etc.Lord Rayleigh and William Ramsay made the first discovery of argon in 1894.
Helium was discovered in 1895 by William Ramsay. The main source of helium is natural gas. Natural gas
is compressed to about 100 atm and cooled to 73 K when all gases except helium are liquefied. About 99%
pure helium is obtained by this method.
Neon, argon, krypton and xenon are obtained by fractionation of liquid air. Fractional distillation of liquid air
gives O2, N2 and a mixture of noble gases. The individual noble gases are then separated by adsorption over
coconut charcoal which adsorbs different gases at different temperatures.
Radon is the decay product of radium. It has a halt-life of only 3.82 days.
222
226
88 Ra 
 86 Rn  24 He
249 48
Oganesson is synthetically produced by collision of 98 C f and 20 C a atoms.
Cf 48
20 Ca 
118 Cg  3n . Half life of ognesson is 0.7 milliseconds.
249 294
98
Atomic Properties
1. Electronic Configuration. The general outer electronic configuration of noble gases is ns2np6 except
helium, which has 1s2 configuration. In these gases, all the orbitals are completely filled (closed-shell
structure). This imparts stability to the atoms which make them almost chemically inert and
monoatomic.
2. Atomic radii. The atomic radii of noble gases are the largest in their respective periods. This is
because they have only van der Waals radii while others have covalent radii (van der Waals radii are
larger than covalent radii). Down the group, atomic radius increases due to increase in the number of
shells.
Property Heilum Neon Argon Krypton Xenon Radon
Atomic number 2 10 18 36 54 86
-1 4 20.18 39.95 83.8 131.3
Atomic mass (g mol ) 222
Atomic radius (pm) 120 160 190 200 220 -
-1 2372 2080 1520 1351 1170 1037
Ionisation enthalpy(kJ mol )
-1 48 116 96 96 77 68
Electron gain enthalpy(kJ mol )
-3 -4 -4 -3 -3 -3 -3
Density/g cm at 293K 1.8×10 9.0×10 1.8×10 3.7×10 5.9×10 9.7×10
Melting point/K 0.9 24.6 83.8 115.9 161.3 202
Boiling point/K 4.2 27.1 87.2 119.7 165 211
Atmospheric content(vol %) -4 - -3 0.934 -4 -6
5.24×10 1.82×10 1.14×10 8.7×10
311
3. Ionisation enthalpy. Due to stable electronic configurations, ionization enthalpies of noble gases are
the highest in their respective periods. Down the group, ionization enthalpies decrease due to increase
in atomic radii and shielding effect of the inner electrons.
4. Electron gain enthalpy. Noble gases have completely filled subshells, therefore, the additional electron
has to be placed in the next higher shell. Thus, energy has to be supplied to add an electron and
hence, electron gain enthalpy of noble gases is positive. Down the group, size of the atom increases
and hence electron gain enthalpies become less positive.
Physical Properties
Noble gases are monoaomic, colourless, odourless and tasteless gases.
i. Melting and boiling points. The melting and boiling points of noble gases are very low. Helium has the
lowest boiling point (4.2 K) of all the known substances. This is because the atoms are held together by
weak van der Waals forces both in the liquid as well as soild states. Down the group, melting and boiling
points increase due to increase in van der Waals forces of attraction.
ii. Ease of liquefaction. Since the atoms are held together by weak van der Waals forces, these gases
cannot be easily liquefied. However, as the atomic size increases, the magnitude of van der Waals forces
increases and hence ease of liquefaction increases He to Xe.
iii. Solubility in water. Noble gases are slightly soluble in water. The solubility increases from He to Rn.
This is due to dipole-induced dipole interaction.
iv. Adsorption over charcoal. Except He, all other noble gases are adsorbed by coconut charcoal at low
temperatures. The extent of adsorption increases as the atomic size of the noble gas increases.
v. Diffusion. Helium has an unusual property of diffusing through materials such as glass, rubber and
plastics.
Chemical Properties
The noble gases are chemically inert due to the following reasons:
(i) Noble gases have completely filled, ns2 np6, electronic configuration. (ii) They have high ionization
enthalpies. (iii) Their electron gain enthalpies are positive. Thus, noble gases have no tendency to lose or
gain electrons and hence do not enter into chemical combination.
However, in 1962, Neil Bartlett observed that platinum hexafluoride (PtF6), a powerful oxidising agent, reacts
with Xe to give a red solid with formula Xe [Pt F6].
Xe  PtF6 
278K
 Xe  [PtF6 ]
Compounds of krypton are fewer; only krypton difluoride (KrF2) has been studied in detail. The compounds
of radon (e.g., RnF2) has not been isolated. No true compounds of Ar, Ne or He are known.
312
QUESTIONS
LEVEL - I
1. The element with the electronic configuration [Ar]183d104s24p3 represents a

1) Metal 2) non-metal 3) Metalloid 4) Transition element
2. Nitrogen molecule is chemically less active because of
1) Small dissociation energy 2) High dissociation energy
3) High electronegativity 4) Stable electronic configuration
3. The element that has the least tendency to show inert-pair effect is:
1) Bi 2) P 3) As 4) N
4. Fluorapatite which in the main component of phosphate rocks has the composition
1) Ca3(PO4)2.CaF2 2) Ca9(PO4)6.CaF2
3) Ca3SiO5.CaF2 4) Ca9(PO4)6.Ca(OH)2
5. N2 forms NCl3, whereas P can form both PCl3 and PCl5. Why?
1) P has d orbitals which can be used for bonding but N does not have d orbitals
2) N atom is larger than P in size
3) P is more reactive towards Cl than N
4) The size of N is comparable to Cl while P size is greater than that of Cl
6. The trend in the hydrides from Bi to N is
1) Bond length increases 2) Bond length decreases
3) Acidic nature increases 4) Bond energy decreases
7. Which of the following oxide is most acidic?
1) As2O3 2) P2O5 3) Sb2O3 4) Bi2O3
8. The most stable allotropic form of sulphur is
1) Rhombic 2) Monoclinic 3) Plastic 4) Colloidal
9. Which of the following is most electronegative?
1) O 2) S 3) Te 4) Se
10. At room temperature, H2O is liquid while H2S is a gas. The reason is:
1) electronegativity of O is greater than S
2) difference in the bond angles of both the molecules
3) association takes place in H2O due to H-bonding while no H-bonding in H2S
4) O and S belong to different periods
313
11. Which is the correct thermal stability order for H2E (E = O, S, Se, Te and Po)?
1) H2Se < H2Te < H2Po < H2O < H2S 2) H2S < H2O < H2Se < H2Te < H2Po
3) H2O < H2S < H2Se < H2Te < H2Po 4) H2Po < H2Te < H2Se < H2S < H2O
12. Element ‘x’ is radioactive 16th group element with half life ‘y’. Then x and y are
1) Fr, 13.8 days 2) Po, 13.8 years
3) Te, 13.8 days 4) Po, 13.8 days
13. SF6 is exceptionally stable due to
1) S - F Bond is strong 2) Steric reasons
3) Symmetrical geometry 4) Exothermic compound
14. Which of the following halogen does not exhibit positive oxidation state in its compounds?
1) Cl 2) Br 3) I 4) F
15. Which of the following halogens is a solid at room temperature?
1) Chlorine 2) Iodine 3) Bromine 4) Fluorine
16. Which of the following elements does not form stable diatomic molecules?
1) Fluorine 2) Phosphorus 3) Nitrogen 4) Oxygen
17. The shape of SCl2 molecule is
1) Linear 2) Triangular 3) Angular 4) Pyramidal
18. Fluorine reacts with water to give
1) HF and O2 2) HF and OF2 3) HF and HOF 4) HF and O2F2
19. The most powerful oxidising agent is :
1) Fluorine 2) Chlorine 3) Bromine 4) Iodine
20. Which of the following orders is correct for the bond dissociation enthalpy of halogen molecules?
1) Br2 > I2 > F2 > Cl2 2) F2 > Cl2 > Br2 > I2
3) I2 > Br2 > Cl2 > F2 4) Cl2 > Br2 > F2 > I2
21. Which of the following is used to remove plutonium from spent nuclear fuel?
1) OF2 2) O2F2 3) OF3 4) O2F3
22. When Br2 is treated with aqueous solutions of NaF, NaCl, NaI separately
1) F2, Cl2 and I2 are liberated 2) Only F2 and Cl2 are liberated
3) Only I2 is liberated 4) Only Cl2 is liberated
23. The weakest acid HX (X = F, Cl, Br, I) is
1) HF 2) HCl 3) HBr 4) HI
24. Which one of the following reactions does not occur?
1) F2  2Cl   2F  Cl2 2) Cl2  2F  2Cl   F2
3) Br2  2I   2Br   I 2 4) Cl2  2Br   2Cl  Br2

314
25. The correct order of electron affinity of halogens is

1) F > Cl > Br > I 2) Cl > F > Br > I 3) I > Br > Cl > F 4) F > Br > I > Cl
26. Which type of bond is present between Xe molecules?
1) Covalent 2) Ion-dipole 3) Van der Waals 4) Dipole-dipole
27. Which of the following gases exist more abundantly in nature than the others?
1) Helium 2) Neon 3) Argon 4) Krypton
28. The formation of O 2 [PtF6 ] is the basis for the formation of xenon fluorides. This is because :
1) O2 and Xe have comparable sizes

2) Both O2 and Xe are gases
3) O2 and Xe have comparable ionisation energies
4) O2 and Xe have comparable electronegativities
29. Assertion: Helium has lowest boiling point (4.2 K)
Reason: The forces that exist between Helium atoms are weak dispersion forces
1) Both Assertion and Reason are correct and Reason is the correct explanation of Assertion
2) Both Assertion and Reason are correct and Reason is not the correct explanation of Assertion
3) Assertion is correct but Reason is not correct
4) Assertion is not correct but Reason is correct
30. The noble gas having highest value of electron gain enthalpy is is
1) He 2) Ne 3) Kr 4) Xe
LEVEL - II
1. Which of the following tendencies remains unchanged on going down in the nitrogen family
(Group-15)?
1) Highest oxidation state 2) Non-metallic character
3) Stability of hydrides 4) Physical state
2. Which of the following has highest boiling point?
1) NH3 2) PH3 3) AsH3 4) SbH3
3. Which one of the following halide does not hydrolyse?
1) SbCl3 2) AsCl3 3) PCl3 4)NF3
4. The correct sequence of decrease in the bond angle of the following hydrides is :
1) NH3 > PH3 > AsH3 > SbH3 2) NH3 > AsH3 > PH3 > SbH3
3) SbH3 > AsH3 > PH3 > NH3 4) PH3 > NH3 > AsH3 > SbH3
5. Which of the following elements can be involved in d  p bonding?
1) Carbon 2) Nitrogen 3) Phosphorus 4) Boron
315
6. Which of the following fluorides does not exist?

1) NF5 2) PF5 3) AsF5 4) SbF5
7. The following are some statements related to group 15 hydrides,
I. Reducing property increases from NH3 to BiH3
II. Basicity decreases from NH3 to BiH3
III. Thermal stability of hydrides decreases form NH3 to BiH3
IV. Bond angle of hydrides decreases from NH3 to BiH3
The correct statements are
1) I, II, III and IV 2) I, III and IV 3) I, II and IV 4) I and IV
8. The correct order of increasing bond angles is :
1) PF3 < PCl3 < PBr3 < PI3 2) PF3 < PBr3 < PCl3< PI3
3) PI3 < PBr3 < PCl3 < PF3 4) PF3 > PCl3 < PBr3 <PI3
9. Which among the following elements do not form dichlorides and dibromides?
1) Tellurium 2) Selenium 3) Sulphur 4) Oxygen
10. The pair of exothermic hydrides of 16 group are
1) H2O, H2S 2) H2O, H2Se 3) H2Se, H2Te 4) H2S, H2Te
11. The acidity of diprotic acids in aqueous solutions increases in the order:
1) H2S < H2Se < H2Te 2) H2Se < H2S < H2Te
3) H2Te < H2S < H2Se 4) H2Se < H2Te < H2S
12. Which one of the following is wrong?
1) Oxygen and sulphur belong to the same group of periodic table
2) Oxygen is a gas while sulphur is a solid
3) Both oxygen and sulphur show +2, +4 and +6 oxidation states
4) H2S has no hydrogen bonding
13. Which one of the following group 16 elements does not exist in –2 oxidation state?
1) S 2) Se 3) O 4) Po
14. Which is the correct thermal stability order for H2E (E = O, S, Se, Te and Po)?
1) H2Se < H2Te < H2Po < H2O < H2S 2) H2S < H2O < H2Se < H2Te < H2Po
3) H2O < H2S < H2Se < H2Te < H2Po 4) H2Po < H2Te < H2Se < H2S < H2O
15. Which of the following hydrides of the oxygen family shows the lowest boiling point?
1) H2O 2) H2S 3) H2Se 4) H2Te
16. For which one of the following properties of halogens the sequence F > Cl > Br > I holds good
1) Electron affinity 2) Electronegativity 3) Atomic radius 4) Boiling point
316
17. Sea weed is employed as a source for manufacture of

1) F 2) I 3) Br 4) Cl
18. Which of the following halogen does not exhibit positive oxidation state in its compounds?
1) Cl 2) Br 3) I 4) F
19. HF has the highest boiling point among hydrogen halides, because it has :
1) lowest dissociation enthalpy
2) strongest van der Waal’s interactions
3) strongest hydrogen bonding
4) lowest ionic character
20. Which of the following properties does not correspond to the order HI < HBr < HCl < HF?
1) Thermal stability 2) Reducing power 3) Ionic character 4) Dipole moment
21. As the atomic number of halogens increases, the halogens
1) Lose the outermost electrons less readily 2) Become lighter in colour
3) Become less denser 4) Gain electrons less readily
22. Halogen that absorbs visible radiation of least wavelength is
1) Chlorine 2) Fluorine 3) Bromine 4) Iodine
23. Which of the following is a false statement?
1) Halogens are strong oxidising agents
2) Halogens show only-1 oxidation state
3) HF molecules from intermolecular hydrogen bonding
4) Fluorine is highly reactive
24. Strongest reducing agent is
1) F– 2) Cl– 3) Br– 4) I–
25. The decreasing order of stability of oxides formed by halogens is
1) F > Cl > Br 2) Cl > Br > I 3) I > Cl > Br 4) Br > Cl > I
26. Which of the following is not the reason for the higher EA1 of halogens?
I) High nuclear charge
II) Larger atomic size
III) Easy to get octet configuration, ns np6
IV) Half filled p-orbitals. The correct answer is
1) I and IV 2) I, II and III 3) II and IV 4) II and III
317
27. Which one of the following noble gases is the least polarizable?
1) Xe 2) Ar 3) Ne 4) He
28. The oxidation state of oxygen in O2[PtF6] is
1) zero 2) –1/2 3) +1 4) +1/2
29. Radon is obtained from Radius due to
1)  -decay 2) a -decay 3) neutron decay 4) position decay
30. The solubility of noble gases in water shows the order?

1) He > Ar > Kr > Ne > Xe 2) He > Ne > Ar > Kr > Xe
3) Xe > Kr > Ar > Ne > He 4) He > Kr > Ar > Ne > Xe
318
KEY WITH HINTS

LEVEL - I
1. 3 With its incomplete p subshell, the element must be in p block. Also Z = 33, which suggests
arsenic a metalloid.
2. 2
3. 4
4. 2 Fluorapatite is Ca9(PO4)6.CaF2.
5. 1 P has empty d orbitals which can be used for bonding, whereas N2 does not have d orbitals.
6. 2 Atomic sizes decrease as we move up along group V from bismuth to nitrogen. As atomic size
decreases, the bonding in hydrides improves with better overlap between atomic orbitals. Hence
bond lengths decrease from BiH3 to NH3.
7. 2 From top to bottom acidic nature of oxides decreases.
8. 1 Rhombic sulphur is most stable.
9. 1 Oxygen is the most electronegative.
10. 3 H2O contains hydrogen bond while no hydrogen bonding is present in H2S.
11. 4 The correct order of thermal stability is H2Po < H2Te < H2Se < H2S < H2O.
12. 4 Half life period of polonium is 13.8 days.
13. 1 ‘F’ is more electronegative and hence strong bond formed with other elements.
14. 4 Fluorine does not exhibit positive oxidation state, it always show –1 oxidation state.
F2 
15. 2  gases
Cl2 
Br2  liquid
I 2  solid
As we go down the group vander Waals forces increase in strength. Hence, physical state
changes to a more condensed form.
16. 2 Fluorine, nitrogen and oxygen atoms are quite small, small atoms can approach each other
closely with strong interaction between atomic orbitals. Hence they can form diatomic molecules.
Phosphorous is a large atom and does not form diatomic molecules.
17. 3
18. 1 2F2  2H 2 O  4HF  O 2
319
19. 1
20. 4
21. 2 Dioxygen difluoride (O2F2) is used to remove plutonium from spent nuclear fuel.
22. 3 A halogen of lower atomic number oxidises halide ions of higher atomic number.
Br2  2NaI  2NaBr  I 2

23. 1 HI > HBr > HCl > HF
Acidic character decreasing order.
24. 2 F2 acts only as strong oxidising agent. Oxidising property F > Cl > Br > I.
25. 2 Chlorine has suitable size and it can gain electrons more readily, so it has higher electron
affinity. Fluorine has small size and there exist repulsion between incoming electrons and
electrons already present on small sized fluorine electron, so it has a lower electron affinity.
26. 3 Xenon is a monoatomic gas having Xe atoms which are nonpolar. At sufficiently low temperature,
Xenon can be liquidfied under pressure. Therefore some forces must exist become atoms.
These forces are very weak van der waals forces of attraction.
27. 3 Gas (Abundance in air by volume (ppm))
Helium 5.2
Neon 18.2
Argon 93.4
Krypton 1.1
Xenon 0.09
28. 3 Ionisation enthalpy of O2 is almost similar to that of Xe.
29. 1 Due to weak dispersion forces between He atoms, Helium has abnormally low boiling point
4.2 K)
30. 2 Electron gain enthalpy of Neon is higher than that of other group 18 elements.
LEVEL - II
1. 1 Highest oxidation state is +5 remains unchanged.
2. 4 B.P of SbH3 is the highest.
3. 4 Neither nitrogen nor fluorine has vacant orbitals.
4. 1 This is due to decrease in electronegativity difference from N to Sb.
5. 3 For the formation of PCl5 p  d bonding involved.
6. 1 P, As and Sb form pentahalides of the general formula EX5 (where, E = P, As and Sb) due to the
presence of vacant d-orbitals in their respective valence shell. N does not form pentahalides
due to the absence of d-orbitals in its valence shell.
7. 1 Atomic sizes increase from N to Bi. Hence atomic orbitals overlaps and bond strength decrease
from NH3 to BiH3. Hydrogen loss or reducing nature increase from NH3 to BiH3. N is a small
atom and the lone pair is more focussed and directed better. Hence electron pair donation or
basic nature is highest for NH3 for other hydrides the lone pair is more diffuse. All these hydrides
have a lone pair and three bond pairs. Nitrogen is most electronegative. The electron pairs
seek maximum separation and spread out so that NH3 has the highest bond angle. As
electronegativities decrease bond angle also decreases.
320
8. 1 The phosphorous tri halide shows bond angles as PF3  PCl3  PBr3  PI3 . The trend is
96.3o 100.3o 101.0o 102.0o
generally attributed to change in the electron negativity of halogen.
9. 4 All group 16 elements except oxygen form dichlorides and dibromides.
10. 1 H (formation) < 0 for H2O and H2S but positive for H2Se and H2Te.
11. 1 As the atomic size increases down the group, the bond length increases and the bond strength
decreases and the cleavage of E - H bond becomes easier thus, more will be the acidity. Thus,
the correct order is H2S < H2Se < H2Te.
12. 3 Oxygen do not exhibit +4, +6 oxidation states.
13. 4 Since the electronegativity decreases down the group ; the tendency for –2 oxidation state also
decreases. So Po does not exist in –2 oxidation state.
14. 4 On going down the group, thermal stability order of H2E decreases.
15. 2 H2S has lowest boiling point amongst the hydrides of oxygen family.
16. 2 F > Cl > Br > I. As the size increases electronegativity decreases.
17. 2 Sea weeds accumulate iodine from seawater and these are good source of iodine.
18. 4 Fluorine does not give positive oxidation state; it always shows –1 oxidation state.
19. 3 There is strong intermolecular hydrogen bonding is HF.
20. 2 Reducing power increases in the order. HF < HCl < HBr < HI
21. 4 As the atomic number increases, tendency to gain electron decreases.
22. 2 F2 is a small molecule, in which valence electrons are strongly held by the nuclei in the molecule.
Hence its absorbs least wavelength.
23. 2 Halogens Cl, Br and I shows –1, +1, +3, +5, +7 oxidation states.
24. 4 Iodide easily undergoes oxidation 2I   I 2  2e 

25. 3 Bromine oxides are the least stable. Stability of halogen oxides follows the order I > Cl > Br.
26. 3 Small size - more E. N & E. A, Half filled - Stable.
27. 4 He is least polarizable because of small atomic size.
O 2  Pt F6   O 2  Pt F6 

28. 4
1
So, oxidation state of oxygen is  
2
29. 2 88 Ra 226 86 Rn 222  2 He 4

30. 3 Solubility of noble gases in water increases from ‘He’ to ‘Xe’
321
CHAPTER - 13
PRINCIPLES RELATED TO PRACTICAL CHEMISTRY
PRACTICAL ORGANIC CHEMISTRY

I. QUALITATIVE ANALYSIS OF ORGANIC COMPOUNDS
DETECTION OF EXTRA ELEMENTS (N, S, HALOGENS) IN ORGANIC COMPOUNDS
Lassaigne’s test : Organic compound fused with metallic sodium and dissolved in water is called
Lassaigne’s extract or sodium fusion extract.
1. Detection of Nitrogen
During fusion, nitrogen of organic compound reacts with sodium to form sodium cyanide.
Na  C  N 
 NaCN
From organic compound
Lassaigne’s extract, treated with ferric chloride is acidified with dil.HCl.

Appearance of bluish green or blue (Prussian blue) colouration.
 Fe  CN 2  Na 2SO 4
FeSO 4  2NaCN 
Fe  CN 2  4 NaCN  
 Na 4 [Fe  CN 6 ]
Sodium ferrocyanide
3Na 4 [Fe  CN 6 ]  4FeCl 3  Fe 4 [Fe  CN 6 ]3 2NaCl


formed by oxidation of Fe 2  Ferric ferrocyanide Blue colour 
2. Detection of Sulphur
During fusion, sulphur reacts with sodium to form sodium sulphide (Na2S).
(a) Sodium nitroprusside test: Lassaigne’s extract is treated with sodium nitroprusside solution.
Appearance of violet coloration.
Na 2S + Na 2 [Fe(CN)5 NO] 
 Na 4 [Fe(CN)5 NOS]
Sodium nitroprusside Violet colouration
(b) Lead acetate test : Lassaigne’s extract is acidified with acetic acid and lead acetate is added.
Formation of black precipitate.
Na 2S  Pb(CH 3COO)2  PbS  2CH3COONa

Black ppt.
322
DETECTION OF HALOGENS
(a) Lassaigne’s test: During fusion, sodium combines with halogen of organic compound to form
sodium halide.
Na  X 
Fusion
 NaX  X  Cl, Br, I 
Lassaigne’s extract is acidified with dil.HNO3, boiled well, cooled and silver nitrate solution is added.
(i) White precipitate soluble in NH4OH solution indicates the presence of chloride.
NaCl + AgNO3 
 AgCl + NaNO3
White ppt.
(ii) Pale yellow precipitate partially soluble in NH4OH solution indicates the presence of bromide.
NaBr + AgNO 3 
 AgBr + NaNO 3
Dull yellow ppt.
(iii) Bright yellow precipitate, completely insoluble in NH4OH solution, indicates the presence of iodide.
NaI + AgNO3 
 AgI + NaNO3
Bright yellow ppt
(b) Layer test : Orange/violet colour in organic layer when Lassaigne’s extract, acidified with dil.
HNO3 is shaken with chlorine water and CHCl3.
(i) 2NaBr + Cl 2 
 2NaCl + Br2 (Turns organic layer orange)
(ii) 2NaI + Cl 2 
 2NaCl + I2 (Turns organic layer violet)
Bromine and iodine are much more soluble in organic solvents than in water.
Chlorine is used as oxidant in the redox reaction.
DETECTION OF FUNCTIONAL GROUPS
1. Tests for Alcoholic Group
Alcohols may be considered as neutral compounds. They are soluble in water or dioxane.
(a) Ester test : Alcohol is warmed with acetic acid in presence of drops of conc. H2SO4.
A fragrant smell indicates the formation of ester.
ROH + CH3COOH 

H 2SO 4
 RCOOCH3 + H 2O
(b) Ceric ammonium nitrate test : Alcohol is treated with ceric ammonium nitrate solution.
A red color is produced (phenols give a green or brown color) due to the formation of a complex.
3ROH + (NH 4 ) 2 [Ce(NO3 )6 ] 

 [Ce(NO3 ) 4 (ROH)3 ] + 2NH 4 NO3
(Re d complex )
Distinction between primary, secondary and tertiary alcohols

(a) Lucas test : Alcohol is mixed with Lucas reagent (anhydrous ZnCl2 + conc.HCI) and allowed to
stand at room temperature.
323
(i) A cloudy precipitate obtained immediately indicates tertiary alcohol
R 3C  OH  HCl 
ZnCl2
 R 3CCl  H 2 O
(ii) A cloudy precipitate obtained in about 5 minutes indicates secondary alcohol
R 2 CH  OH  HCl 
ZnCl2
 R 2CHCl  H 2O
(iii) No cloudy precipitate even after long standing indicates primary alcohol
RCH 2  OH  HCl 

ZnCl2
 No reaction / Slow reaction
Alcohols are soluble in Lucas reagent, but the formed alkyl halides are not soluble, therefore, formation
of two layers in the reaction medium indicate the occurrence of the reaction.
Primary alcohols – Layers do not separate
Secondary alcohols – Layers separate within 1-5 minutes
Tertiary alcohols – Layers separate immediately
(b) Iodoform test : Potassium iodide(KI) and sodium hypochlorite(NaClO) solution are added to the
compound in presence of NaOH solution.
Yellow precipitate with characteristic(antiseptic) smell.
CH3CH 2 OH 
KIO
 CH3CHO 
KIO
 CI3CHO 
NaOH
 CHI3  HCOONa
Iodoform
Ethanol and secondary alcohols which contain CH3-CH(OH)R group give positive iodoform test.
NaClO first oxidses KI to KIO, which oxidises CH3-CH(OH)R group to CH3COR group and then iodinates
it in alkaline medium by replacing the   hydrogens attached to the carbon atom adjacent to carbonyl
group by iodine. Iodoform is formed after cleavage of C-C bond.
2. Tests for Phenolic Group
Phenols are weakly acidic. They are soluble in NaOH solution, but not sufficiently acidic to be
soluble in sodium bicarbonate solution.
(a) Neutral FeCl3 test : Phenols give coloured complex with neutral ferric chloride solution.
 [Fe(C6 H 5O)6 ]3  3HCl  3H 

6C6 H 5 OH  FeCl3 
(Violet complex)
The color of the complex may be violet, red, blue or green.

Resorcinol, o–, m– and p–cresol give violet or blue colouration, catechol gives green colour, which
rapidly darkens. 1 and 2–Naphthol do not give characteristic colours.
This is a characteristic reaction of compounds having enolic group (–C–OH).
(b) Phthalein dye test. Phenols condense with phthalic anhydride in the presence of concentrated
H2SO4, to give phenolphthalein which gives dark pink colour with NaOH solution.
324
Colours given by some other phenolic compounds phthalein dye test are : Resorcinol (Green
fluorescent colour of fluorescein), o–cresol (red), m–cresol(bluish-purple), p–cresol(No colour),
Catechol (blue colour -takes longer time to appear).
Tests for Aldehyde and Ketonic Groups (-CHO and >C=O)
Identification of aldehydes and ketones is done by (i) addition reactions on double bond of >C = O
group and (ii) oxidation of carbonyl group.
OH
 H 2O
 C  O  RNH 2 
 C     C  NR [R = alkyl, aryl or C6H5NH etc.]
NHR
Addition reactions of derivatives of ammonia are important in the identification of carbonyl compounds.
Addition is generally followed by elimination resulting in the formation of unsaturated compound. These
reactions are catalysed by acid or base and do not occur under strongly acidic or basic conditions
(each reaction requires an optimum pH).
Aldehydes are easily oxidised to carboxylic acids while ketones require relatively stronger oxidising
agents.
Tests given by both aldehydes and ketones
(a) 2,4-Dinitrophenylhydrazine test (2,4-DNP test) : On reaction with 2,4-dinitrophenylhydrazine

(2,4-DNP), aldehydes and ketones form the respective 2,4–dinitrophenyl hydrazones.
325
2,4-DNP moistened with conc.HCl and dissolved in CH3OH is called Borsche’s reagent.
Aldehydes and ketones are distinguished by tests using mild oxidising reagents, like Tollen’s reagent
and Fehling’s reagent or Benedict’s reagent.
2. Tests given by aldehydes only
(a) Schiff test: Organic compound is treated with Schiff’s reagent.
Pink color appears within 2 minutes.
Schiff’s reagent is prepared by decolourising aqueous solution of p–rosaniline hydrochloride dye by

adding sodium sulphite or by passing SO2 gas.
(b) Fehling’s test : Aldehyde is boiled for some time with a mixture of equal volumes of Fehling’s (A)
and Fehling’s (B) solutions.
Red precipitate of Cu2O is obtained.
RCHO + 2Cu 2+ (complexed) + 2OH  

 RCOO  + Cu 2 O  3H 2 O
Red
Aromatic aldehydes do not give positive Fehling’s test.
Fehling’s solution A is aqueous copper sulphate and Fehling’s solution B is alkaline sodium potassium
tartarate (Rochelle’s salt, KNaC4H4O6·4H2O). The reagent contains Cu2+ ion complexed with tartarate
ions.
326
Fehling’s reagent is freshly prepared by mixing equal amounts of Fehling’s solution A and Fehling’s
solution B. Fehlings reagent deteriorates on keeping while Fehling’s solutions A and B are quite stable.
(c) Tollen’s test : Aldehyde is heated with Tollen’s reagent on a water bath.
A shining silver mirror is formed on the inner walls of the test tube.
RCHO  2[Ag(NH3 )2 OH 
 RCOONH 4 + 3NH3  2Ag + H 2O
Tollen 's reagent Silver mirror
Tollen’s reagent is alkaline solution of silver cation complexed with ammonia.
(d) Benedict’s test: Aldehyde is heated to boiling with Benedict’s reagent. Red precipitate of Cu2O.
 Cu 2 O + RCOO  Na + + 3H 2O
RCHO + 2Cu(OH) 2 + NaOH 
Re d ppt.
Benedict’s solution is an alkaline solution of copper sulphate and sodium citrate (2Na3C6H5O7.11H2O).
It is more stable than Fehling’s reagent and can be stored.
4. Tests for Ketonic Group
Ketones, unlike aldehydes, neither restore the pink color of Schiffs reagent nor do they reduce Fehling’s
solution or ammoniacal silver nitrate solution. However, they form crystalline precipitates with 2, 4-
dinitro phenylhydrazine and also with sodium bisulphite reagent.
(a) Sodium nitroprusside test: Organic compound is treated with freshly prepared solution of sodium
nitroprusside and excess of NaOH solution is added.
A wine-red color is obtained due to the formation of a complex.
CH 3COCH3  OH  
 CH3COCH 2  H 2O
[Fe(CN)5 NO]2   CH 3COCH 2 

 [Fe(CN)5 NO.CH 3COCH 2 ]3
Nitroprusside ion wine  red complex
5. Tests for Carboxyl Group (-COOH)

(a) Litmus test : The compound/aqueous solution is brought into contact with moist blue litmus paper.
Blue litmus paper turns red.
(b)Sodium bicarbonate test : Organic compound is treated with sodium bicarbonate solution.
327
Compound dissolves with brisk effervescence.
RCOOH + NaHCO3 
 RCOONa + H 2O + CO 2
This test distinguishes carboxylic acids from phenols.
(c) Ester test : Organic compound is warmed on a water bath with alcohol and a few drops of conc.
sulphuric acid.
Pleasant fruity smell of ester.
RCOOH + R OH 

Conc.H 2SO4 , 
 RCOOR  + H 2 O
Ester
Carboxylic acids react with alcohols in acidic medium to produce esters.

6. Tests for Amino Group
Tests for Primary Amines (–NH2)
(a) Solubility test : Dil. HCl is addded to the organic compound and shaken well.
Organic compound dissolves.

C6 H 5 NH 2  HCl 
 C6 H5 N H3Cl
Anilinium chloride(so luble in water )
Organic compounds containing amino group are basic; they react with acids to form salts, which
are soluble in water.
(b) Carbylamine test : Organic compound is heated with chloroform and alcoholic KOH.
Highly offensive smell due to formation of isocyanides (carbylamine is highly toxic).
RNH 2 + CHCl3 + 3KOH 

 RNC + 3KCl + 3H 2 O
Carbyla min e
This test is applicable to aliphatic and aromatic primary amines.

(c) Azo dye test : A cold mixture of the organic compound in dil. HCI and sodium nitrite is mixed with
  naphthol in NaOH solution.
An orange-red dye is obtained.
NaNO 2 + HCI 
 HNO 2 + NaCl
328
Primary amine reacts with nitrous acid generated in situ by the reaction of sodium nitrite with HCl at
0 –5°C to produce diazonium salt which couples with   naphthol to give a scarlet dye.
This test is applicable only for aromatic primary amines.
II. PREPARATION OF ORGANIC COMPOUNDS
1. Preparation of Acetanilide
Acetanilide is obtained by the replacement of a hydrogen atom of the -NH2 group of aniline by
CH3 CO  group in presence of glacial acetic acid. Acetylation is usually carried out with acetic
anhydride. Acetyl chloride may also be used. Acetylation with CH3COCl is usually carried out in
presence of pyridine.
Acetanilide is prepared by heating (refluxing) aniline with acetic anhydride in an R.B. flask.
Pure crystals are plate shaped and colourless to white.

Melting point of acetanilide = 114oC.
2. Preparation of p-Nitroacetanilide
p-Nitroacetanilide (C6H5NHCOCH3) is prepared by the nitration of acetanilide using a mixture of conc.HNO3
and conc. H2SO4 as nitrating reagent. The mixture of the acids releases nitronium ion( NO2 ), which acts
as electrophile in the reaction.
 NO2  H3 O   2HSO4
HNO3 + 2H2SO4 
Nitronium ion attacks the benzene ring containing anilide group, mainly at the para position to give
p-nitroacetanilide as major product. It is an aromatic electrophilic substitution reaction.
Temperature is kept below 20oC throughout.

Colourless to white crystalline solid
Melting point of p-nitroacetanilide = 214oC.
3. Preparation of Aniline Yellow
Aniline yellow (p-aminoazobenzene) is a yellow azo dye and an aromatic amine; it is a derivative of
azobenzene. It has the appearance of an orange powder. Aniline yellow was the first azo dye.
It is prepared by coupling reaction between benzenediazonium chloride and aniline in acidic medium.
329
Step I : ArNH 2  NaNO 2  HCl  ArN 2 Cl
Step II :
Orange coloured powder.

Melting point of p-aminoazobenzene= 126oC.
4. Preparation of Iodoform
lodoform or Triiodomethane is prepared out by warming (to 333 K), RCH(OH)CH3, CH3CHO or RCOCH3
with aqueous solution of sodium hydroxide or sodium carbonate (mild alkali) and iodine.
RCOCH3  3I 2  4NaOH 
 CHI3  RCOONa  3NaI  3H 2O
Iodoform
Yellow crystalline precipitate of iodoform, with characteristic odour, is obtained.

Melting point of iodoform = 119oC.
PRACTICAL INORGANIC CHEMISTRY
(a) Quantitative analysis (Volumetric/Titrimetric analysis)
(b) Qualitative analysis
III. QUANTITATIVE ANALYSIS (VOLUMETRIC ANALYSIS)
It involves the measurement of the volume of a solution of known concentration required to bring about
the completion of reaction with a measured volume of a solution of unknown concentration.
The reagent of known concentration is called titrant and the substance being titrated is called titrand.
The process of adding the standard solution to the solution of unknown concentration until the reaction
is just complete is called titration.
The point at which reaction is completed is called equivalence point or the theoretical or stoichiometric
end point.
DETECTION OF END-POINT
The end point is detected either by some physical change by the addition of an auxiliary reagent,
known as indicator or by some other physical measurement.
In an ideal titration, the visible end point coincides with the stoichiometric or theoretical end point, but
in practice some small difference may occur which is the titration error.
REQUIREMENT FOR A REACTION IN TITRIMETRIC ANALYSIS
(i) The substance to be estimated must react rapidly and completely with the other reagent in
stoichiometric proportion.
330
(ii) There must be alteration in physical or chemical property of the solution at the equivalence point,
which can be detected using an indicator or by measuring the potential difference, current etc.
1. ACIDIMETRY AND ALKALIMETRY
In these titrations, standard solutions of acids (acidimetry) and bases (alkalimetry) are used. In
titrimetric analysis, concentration of solution is expressed in terms of molarity, which is number of
moles of solute dissolved in 1 litre of solution.

Molarity, M =
Volume of solution in litres
STANDARD SOLUTION
A solution of exactly known concentration is called standard solution. Any substance, which is
stable at room temperature and does not react with solvent in which it is dissolved, can be directly
weighed to prepare its standard solution.
PRIMARY AND SECONDARY STANDARDS

Primary standard : A compound of high purity in which the impurities does not exceed 0.01-0.02%.
The standard solution can be prepared by direct weighing of a sample of primary standard followed
by its dissolution in water (or solvent) to obtain a definite volume of solution.
A primary standard should also satisfy the following requirements:

i. It must be easily available in pure and dry form.
ii. It should not undergo change in air
iii. It should be easy to detect the impurities present in it.
iv. It should have high relative molecular mass so that weighing errors are neglible.
v. Its reaction with another substance should be instantaneous and stoichiometric.
vi. The substance should be readily soluble in water.
vii. Its solution should not deteriorate on keeping.
Unstable hydrated salts should not to be used as primary standards, however, sodium carbonate,
sodium tetraborate, potassium hydrogen phthalate, oxalic acid, ferrous ammonium sulphate etc.
are used as primary standards due to their sufficient stabilities.
Secondary Standard : Substance having characteristics nearer to the primary standards, e.g.,NaOH
and KMnO4.
A secondary standard cannot be used for preparing standard solution by direct weighing. A solution
of secondary standard may be used for standardization only after determining its exact
concentration by titration against a standard solution of primary standard.
INDICATORS IN ACID BASE TITRATION
Acid base indicators are sensitive to pH change. These exhibit colour change at pH close to the
equivalence point.
331
Indicator pH range Colour in acid Colour in alkali

Methyl orange (weak base) 3.1 - 4.4 Red Yellow
Methyl red (weak acid) 4.2 - 6.3 Red Yellow
Phenolphthalein (weak acid) 8.3 - 10 Colourless Pink
(1) Phenolpthalein
Being a weak acid, phenolpthalein does not dissociate in acidic medium and remains in the
unionised form, which is colourless.
HPh  H   Ph 

Unionised (Colourless) Ionised (Pink )
In acidic medium, equilibrium lies to the left. In alkaline medium, the ionisation of phenolphthalein
increases considerably due to removal of H+ ions from HPh by the OH– ions from the alkali. So the
concentration of Ph– ion increases in solution, which imparts pink colour to the solution.
For a weak acid vs strong alkali titration, phenolphthalein is the most suitable indicator because the
last drop of added alkali brings the pH of the solution in the range in which phenolphthalein shows
sharp colour change.
(2) Methyl orange
Methyl orange is a weak base, which is yellow in the unionised form.
The anion formed from the indicator is an active species, which on accepting a proton changes
from the benzenoid form to the quinonoid form.
The quinonoid form, which is deeper in colour is responsible for the colour change at the end point.
332
(a) Choice of Indicator
Indicator Suitable Indicator Colour in acid Colour in alkali

a. Strong acid vs Strong base Methyl orange/ Phenolphthalein Red/Colourless Yellow/Pink
b. Strong acid vs weak base Methyl orange Red Yellow
c. Weak acid vs Strong base Phenolphthalein Colourless Pink
d. Weak acid vs Weak base None avilable
Titration curve is a graphical representation the variation of pH of a solution during a tiration.
Figure. 01 Acidimetry and Alkalimetry - Titration Curves

(i) Titration of Oxalic acid vs Sodium hydroxide
In the titration between oxalic acid (weak acid) and sodium hydroxide (strong base), following reaction
takes place:
H 2C2O4 + 2NaOH 
 Na 2C2O4 + 2H 2O
End point is the point of completion of the reaction indicated by the indicator. Hence, it has an additional
drop of titrating reagent, but molarity is calculated using the formula
a1M1V1 = a 2M2 V2
where a1, M1, V1 are respectively basicity, molarity and volume of acid used and a2, M2 and V2 are
acidity, molarity and volume respectively of base used in the titration.
333
a1 and a2 are respectively the basicity of oxalic acid (=2) and acidity of sodium hydroxide(=1).
Molar mass of oxalic acid, (COOH) 2.2H2O = 126 g mol–1 and molar mass of (NaOH) = 40 g mol –1.
Concentration (strength) in g/L = Molarity×Molar mass.
(ii) Titration of Hydrochloric acid vs Sodium Carbonate
In this titration between hydrochloric acid (strong acid) and sodium hydroxide (weak base), the following
reaction takes place:
(i) Na 2 CO3 + HCl 

 2NaHCO3  NaCl
(ii) NaHCO3 + HCl 
 NaCl  H 2 O  CO2
Na 2 CO 3 + 2HCl 
 2NaCl  H 2 O  CO 2
In this titration, methyl orange, a weak base is used as indicator. At the end point, the solution changes
from golden yellow to pale red orange.
In this titration, phenolphthalein could not be used as indicator because only 50% of the reaction, i.e., up
to NaHCO3 will be indicated (pH of solution becomes < 8.0).
The concentration (strength) of the unknown solution is calculated in g/L.
a1M1V1 = a 2 M 2 V2
where, a1 (=2) and a2 (=1) are the acidity and basicity of the alkali and the acid respectively. M1 and M2 are
the molarities, V1 and V2 are the volumes of the base and acid respectively.
Potassium hydrogenphthalate (C6H5O4K) as primary standard
Potassium hydrogenphthalate is used as primary standard for standardisation of NaOH solution. It
behaves as a monobasic acid and reacts with sodium hydroxide.
Phenolphthalein can be used as indicator in this titration.

Titration of Bases with Two Indicators (Phenolphthalein and Methyl orange)
Methyl orange with lower pH range can indicate complete neutralization of all types of bases. Extent of
reaction of different bases with acid (HCI) using these two indicators is summarised below:
Base Phenolphthalein Methyl orange

100% reaction is indicated 100% reaction is indicated
NaOH
NaOH  HCl 
 NaCl  H2O NaOH  HCl 
 NaCl  H2 O
50% reaction up to NaHCO3 is indicated 100% reaction is indicated
Na2CO3
Na2CO3  HCl 
 NaHCO3  NaCl Na2CO3  2HCl 
 2NaCl  H2O  CO2
100% reaction is indicated
NaHCO3 No reaction indicated
NaHCO3  HCl  NaCl  H2O  CO2
334
For complete reaction, we may adopt two methods :

Method I : Conduct two titrations separately with two different indicators.
Method II : Conduct single titration, but add second indicator after first end point is reached.
CONCENTRATION (STRENGTH) IN TERMS OF NORMALITY
In volumetric titration, equivalent of acid = equivalent of base.
At neutralization point, N1V1 = N2V2
1 equivalent of H2C2O4 = 0.5 mol of H2C2O4= 1 equivalent of NaOH =1 mol of NaOH
Relationship between Normality and Molarity
w
N=
Equivalent mass × V
w
M=
Mol. mass × V
where w = mass of substance in grams, N = Normality, M = Molarity and V = Volume of solution in litre.
If acidity or basicity of substance is ‘a’, then
Molar mass
Equivalent mass =
a
w
N=
 Molar mass  a w
  × V or N = Molar mass  V
 a 
i.e., N = a M
Precautions to be Taken During Volumetric Titrations
(a) Always rinse the burette and the pipette with the respective solutions, which are to be taken in
them.
(b) Always read the lower meniscus for transparent solutions and upper meniscus for coloured
solutions.
(c) To note the burette reading, place the eye exactly at the level of the meniscus.
(d) Never hold the pipette at the bulb.
(e) Never suck strong acid or alkali with the pipette.
(f) Do not blow out the last drop of the solution from the jet end of the pipette into the flask.
(g) The concentration (strength) of the solution must be calculated up to the fourth place of decimal.
2. REDOX TITRATION
Ttitrations involving redox reaction are called redox titrations.Redox titrations can be used to determine
the exact amount of an oxidizing/reducing agent in a given solution by titrating it against the standard
solution of a suitable reducing/oxidising agent.
335
Choice of Indicators
Indicators used in redox reactions are sensitive to change in oxidation potential. The ideal oxidation-
reduction indicators have oxidation potential intermediate between the values for the solution being
titrated and the titrant and these show sharp readily detectable colour change.
The oxidising action of KMnO4 in the acidic medium can be represented as
MnO -4 + 8H + + 5e - 
 Mn 2+ + 4H 2 O
The acid used in this titration is dilute sulphuric acid. Nitric acid is not used as it is itself an oxidising
agent. Hydrochloric acid is avoided because it reacts with KMnO4 producing chlorine, which is also an
oxidising agent in aqueous solution.
2KMnO 4 + 16HCl 
 2KCl + 5Cl 2 + 8H 2 O
(i) Titration of KMnO4 vs. Oxalic acid
Potassium permanganate oxidizes oxalic acid, in an acidic medium, at around 60oC itself getting
reduced to a colourless ion.
 K 2SO 4  2MnSO 4  3H 2 O  5  O 
Reduction half reaction: 2KMnO 4  3H 2SO 4 
Oxidation half reaction: H 2 C2 O 4   O  

o
60 C
 2CO 2  H 2 O]  5
2KMnO 4  3H 2SO 4  5H 2 C 2O 4 
 K 2SO 4  2MnSO 4  10CO 2  8H 2O
Ionic equations :
Reduction half reaction: 2MnO 4  16H   5C2 O 42 

 2Mn 2  10CO3  8H 2O
Oxidation half reaction: C2 O 4 

 2CO2  2e  ]  5
2MnO 4  5C 2O 42  16H  

 2Mn 2  10CO 2  8H 2 O
During the reaction, MnO4 is reduced to Mn2  and C2 O42 is oxidised to CO2. The oxidation number of
carbon in C2 O42 changes from +3 to +4.
For the titration of H2C2O4 against KMnO4, the mixture of oxalic acid and dil. H2SO4 is warmed to 50°–60°C
because the reaction takes place at higher temperature.
During the titration, manganous sulphate is formed, which acts as a catalyst for the reduction of KMnO4
by oxalic acid. Therefore, in the beginning the reaction rate is slow and as the reaction proceeds, the
rate of the reaction increases.
Indicator : KMnO4 as self indicator.
End point : Colorless to pink. (KMnO4 solution in burette)
Calculations :
a1 M1 V1 = a2 M2 V2
a1 = Number of electrons lost per formula unit of H2C2O4.
a2 = Number of electrons gained per formula mass of KMnO4.
336
M1, V1 are respectively, molarity and volume of oxalic acid and M2 and V2 are molarity and volume
respectively of potassium permanganate used in the titration.
2M1V1 = 5M 2 V2
M1V1
Molarity of KMnO4, M2 =
5V2
Strength of KMnO 4 = Molarity  Molar mass
(ii) Titration of KMnO4 vs. Mohr’s salt

Ferrous ammonium sulphate acts as a reducing agent in the titration against potassium permanganate.
 K 2SO 4  2MnSO 4  3H 2 O  5  O 
Reduction half reaction: 2KMnO 4  3H 2SO 4 
Oxidation half reaction: 2FeSO 4 .  NH 4  2 SO 4 .6H 2 O  H 2SO 4   O  


Fe 2  SO 4 3  2  NH 4 2 SO 4  13H 2 O]  5
2KMnO 4  8H 2SO 4  10FeSO 4 .  NH 4 2 SO 4 .6H 2 O 

 K 2SO 4  2MnSO 4  5Fe 2  SO 4 3
 10  NH 4 2 SO 4  68H 2 O
Ionic equations :
Reduction half reaction: MnO 4  8H   5e  

 Mn 2  4H 2O
Oxidation half reaction: [Fe 2 

 Fe3  e ]  5
MnO 4  8H   5Fe 2 
 5Fe3  Mn 2  4H 2O
During the reaction, oxidation number of iron changes from +2 to +3.
In this titration, heating of Mohr’s salt solution is not needed because reaction rate is very high even at
room temperature. Also, at high temperatures, ferrous ions may be oxidised to ferric ions by oxygen of
air causing error in the experiment.
Indicator : KMnO4 as self-indicator.
End point : Colorless to permanent pink color (KMnO4 solution in burette)
Calculations : a1 M1 V1 = a2 M2 V2
IV. INORGANIC PREPARATIONS
1. Preparation of ferrous ammonium sulphate or Ammonium iron(II)sulphate
FeSO4(NH4)2SO4.6H2O) or Mohr’s Salt
Theory : A double salt is made up to different single salts that crystallize as a single substance, but
ionize as two distinct salts when dissolved in water.
Mohr’s salt is a double salt having a formula of FeSO4.(NH4)2SO4.6H2O. It produces Fe2+, NH+4 , SO24
ions on dissolving in water, and hence, can be considered to be consisting of two single salts, i.e.,
FeSO4 and (NH4)2SO4.
337
A hot mixture containing equimolar proportions of hydrated ferrous sulphate and ammonium sulphate
is prepared (small amount of dilute sulphuric acid is added while preparing ferrous sulphate solution to
prevent hydrolysis. The solution is cooled to room temperature. Light green crystals of Ferrous
ammonium sulphate separate out.
FeSO 4 + (NH 4 ) 2 SO 4 + 6H 2 O 
 FeSO 4 .(NH 4 ) 2 SO 4 .6H 2 O
2.Preparation of potash alum or Potassium aluminium sulphate (K2SO4.Al2(SO4)3.24H2O)
Theory : Potash alum (fitkari) is a double salt of potassium sulphate and aluminium sulphate having
composition K2SO4.Al2(SO4)3.24H2O.
Equimolar amounts of Aluminium sulphate and potassium sulphate are separately taken. Aluminium
sulphate is dissolved in water containing sulphuric acid (sulphuric acid prevent the hydrolysis of the
salt) potassium sulphate is added to the solution and heated with constant stirring to dissolve it. The
hot mixture containing equimolar amounts of Aluminium sulphate and potassium sulphate is slowly
cooled to room temperature while crystals of potash Alum separate out.
K 2SO 4  Al2  SO 4 3  24H 2 O 

 K 2SO 4 .Al 2  SO 4 3 .24H 2 O or 2KAl(SO 4 )2 .12H 2O
1mol 1mol 1mol
V. QUALITATIVE ANALYSIS
The basic principles involved in qualitative analysis are: (i) Solubility product and (ii) Common ion
effect.
When ionic product of a salt exceeds its solubility product, precipitation occurs. Ionic product of
salt is controlled by making use of common ion effect.
SYSTEMATIC ANALYSIS OF ANIONS
Step - I : Preliminary Test with Dilute Sulphuric Acid or Dilute Hydrochloric acid
Salt is treated with, dil. H2SO4 and reaction observed in the cold and when warmed.
Anions that emanate gases on reaction with Dil. H2SO4/dil. HCl
1. Carbonate  CO 32- 
(a) Dil. H2SO4 : Effervescence due to the evolution of carbon dioxide
CO32  2H  
 CO 2  H 2O
White turbidity when the gas is passed into lime water due to the formation of calcium carbonate.
CO 2 + Ca 2+ + 2OH  
 CaCO3 + H 2 O
On prolonged passage of carbon dioxide into lime water, turbidity slowly disappears due to the formation
of soluble hydrogen carbonate.
CaCO3 + CO 2 + H 2 O 
 Ca(HCO3 ) 2
2.Sulfide ( S 2- )
(a) Dil. H2SO4 : Evolution of colourless gas with the smell of rotten eggs. H2S is evolved.
338
S2 + 2H + 
 H 2S
The evolved gas turns lead acetate paper black due to the formation of lead sulphide
(CH 3COO) 2 Pb + H 2S 
 PbS+ 2CH 3COOH
Black
(b) Sodium nitroprusside solution : Purple colour is produced. Formation of sodium pentacyano-
thionitroferrate(II), Na4[Fe(CN)5NOS] complex.
Na 2S + Na 2 [Fe(CN)5 NO] 
 Na 4 [Fe(CN)5 NOS]
Sodium nitroprusside Sodium thionitroprusside
Purple complex
3. Nitrites ( NO-2 )
(a) Dil. H2SO4: Solid nitrite is treated with dil H2SO4 and warmed. Brown fumes of nitrogen dioxide
evolved by combination of nitric oxide with oxygen of the air.
2NaNO 2  H 2SO 4 
 Na 2SO 4 + 2HNO 2
3HNO 2 
 HNO 3 + 2NO + H 2 O
2NO + O 2 
 2NO2
Brown gas
(b) Potassium iodide : Salt solution is treated with potassium iodide solution. Appearance of blue
colour on addition of starch solution followed by acidification with acetic acid.
NO -2 + CH 3COOH  HNO 2 + CH 3 COO -
2HNO2 + 2KI + 2CH3COOH 

 2CH3COOK + 2H 2 O + 2NO + I 2
I 2 + Starch  Blue complex

(c) Sulphanilic acid - 1- naphthylamine reagent test (Griess-Ilosvay test) : Formation of red azo-
dye.
Sulphanilic acid is diazotised in the reaction by nitrous acid. Diazotised acid couples with 1-naphthylamine
to form red azo-dye.
NO2 + CH3COOH  HNO2 + CH 3 COO 
339
Step - II : Preliminary Test with Concentrated Sulphuric Acid

When no positive result is obtained in dil. H2SO4 test, salt is treated with conc. H2SO4 and the changes in
the reaction mixture in the cold and after warming are observed.
4. Chloride (Cl–)
(a) Conc. H2SO4 : Decomposes with the evolution of HCI.
Cl + H 2SO 4 
 HCl + HSO 4
The above gas turns blue litmus paper red and gives white fumes of NH4CI, when a glass rod moistened
with ammonia solution is brought to the mouth of test tube.
NH 4 OH + HCl 
 NH 4Cl  H 2 O
(White fumes)
(b) Manganese dioxide and conc. sulphuric acid : Effervescence on heating. Light greenish yellow
pungent gas is evolved.
MnO 2 + 2H 2SO 4 + 2Cl  

 Mn 2+ + Cl2 + 2SO 24 + 2H 2O
(c) Silver nitrate solution : Silver nitrate solution added to salt solution acidified with dil.HNO3 gives
curdy white precipitate soluble in ammonium hydroxide.
Cl  + Ag + 
 AgCl
AgCl + 2NH 4 OH 
 [Ag(NH 3 ) 2 ]Cl +2H 2 O
Diamine silver(i)chloride
(d) Chromyl chloride test : Chloride, when heated with K2Cr2O7 and conc. H2SO4 forms orange red
fumes of chromyl chloride (CrO2Cl2).
K 2 Cr2 O7 + 4NaCI + 6H 2SO 4 

 2KHSO 4 +4NaHSO 4 + 2CrO 2 Cl 2 + 3H 2O
Orange-redfumes
(i) When chromyl chloride vapours are passed into NaOH, yellow solution of sodium chromate is
formed, which when treated with lead acetate, gives yellow ppt. of lead chromate.
CrO 2Cl2 + 4NaOH 

 Na 2 CrO 4 + 2NaCl + 2H 2 O
Yellow solution
Na 2CrO 4 + (CH 3COO) 2 Pb 

 PbCrO 4  2CH 3COONa
Lead chromate (yellow ppt.)
(ii) Sodium chromate is acidified with dil. H2SO4 and mixed with amyl alcohol and 10% H2O2. Organic
layer turns blue.
CrO 24 +2H   2H 2 O 2 

 CrO 5  3H 2O
Chromium pentoxide
340
CrO24 ion, formed in the reaction of chromyl chloride with NaOH, reacts with H2O2 to form CrO5, which
dissolves in amyl alcohol to give blue colour.
5. Bromide (Br–)
(a) Conc. H2SO4 : Gives reddish brown vapors of bromine and hydrogen bromide
2KBr + H 2SO 4 
 K 2SO 4 + 2HBr
2HBr + H 2SO 4 
 2H 2O + SO 2 + Br 2
(Reddish brown)
(b) Manganese dioxide and conc. H2SO4 : A mixture of solid bromide, MnO2, and conc. H2SO4 is
heated. Reddish brown vapours of bromine emanate.
2KBr + MnO2 + 2H 2SO 4 

 Br2 + K 2SO 4 + MnSO 4 + 2H 2 O
(c) Silver nitrate solution: Curdy pale yellow ppt. of silver bromide is obtained.
This ppt. is sparingly soluble in dil. ammonia solution, but readily soluble in conc. ammonia solution
and insoluble in dil. HNO3.
Ag + +Br  
 AgBr
(d) Chlorine water: Bromide is treared with chlorine water and CHCl3. The CHCl3 layer turns orange-
red. Bromine dissolves in organic layer.
2KBr + Cl2 (water) 

 2KCl + Br2
Br2 + Chloroform 
 Orange red color
(e) Potassium dichromate and conc. H2SO4: A mixture of solid bromide, K2Cr2O7, and conc. H2SO
4
is heated and the evolved vapours are passed over water. A yellowish brown solution is obtained.
2KBr + K 2Cr2O 7 + 7H 2SO 4 

 3Br2 + Cr2 (SO 4 )3 + 4K 2SO 4 + 7H 2 O
6. Iodide (I–)
(a) Conc. H2SO4: Violet vapors of iodine, which turns starch paper blue.
2I  + 2H 2SO 4 
 I2 + SO 24 + 2H 2 O + SO 2
Violet vapors
(b) Silver nitrate solution: Yellow, curdy ppt. of silver iodide, Agl, which is very slightly soluble in
conc. ammonia solution and insoluble in dil. nitric acid.
I  +Ag + 
 Agl
(c) Potassium dichromate and conc. H2SO4 : Iodine is liberated
6I  Cr2 O72  7H 2SO 4 

 3I 2  2Cr 3  7SO24  7H 2 O
341
(d) Chlorine water : On addition of chlorine water followed by CHCl3 to iodide, CHCl3 layer turns violet.
2I + Cl2 
 I 2 + 2Cl 
I2 + Chloroform 
 Violet colour
7. Nitrate ( NO3- )
(a) Conc. H2SO4: Salt is heated with conc.H2SO4.

Evolution of reddish brown fumes of nitrogen dioxide.
NaNO3  H 2SO 4 
 NaHSO 4  HNO3
4HNO3 
 4NO 2  O 2  2H 2 O
To the above solution, copper turnings are added.
Excess brown fumes of NO2 and solution turns blue due to the formation of copper sulphate.
2NaNO3  4H 2SO 4  3Cu 

 3CuSO 4  Na 2SO4  4H 2 O  2NO
(Blue)
2NO  O2 
 2NO2
Brown fumes
(b) Brown ring test: Freshly prepared saturated solution of iron (II) sulphate is mixed with nitrate
solution and conc. H2SO is added slowly down the sides of the test tube. Brown ring at the junction of
4
the two solutions due to the formation of nitroso ferrous sulphate.
NaNO3 + H 2SO 4 
 NaHSO 4 +HNO3
6FeSO4 + 3H 2SO4 + 2HNO3 

 3Fe 2 (SO 4 )3  4H 2 O  2NO
FeSO 4  NO 
 [Fe(NO)]SO 4
Nitroso ferrous sulphate(Brown )
On shaking and warming the mix, the brown color disappears, nitric oxide is evolved and a yellow
solution of iron (Ill) ions remains.
8. Sulphate (SO 42 - )
(a) Barium chloride solution : Aqueous solution of sodium carbonate extract of the salt acidified with
acetic acid on addition of barium chloride gives a white precipitate of barium sulphate insoluble in
conc. HCl or conc. HNO3.
Na 2SO 4  BaCl2 
 BaSO 4  2NaCl
Barium sulphate(white ppt.)
(b) Lead acetate solution : Sulphate ions give white precipitate of lead sulphate when aqueous
solution or sodium carbonate extract neutralised with acetic acid is trated with lead acetate solution.
Na 2SO 4   CH3COO 2 Pb 
 PbSO 4  2CH 3COONa
Lead sulphate White ppt.
342
SYSTEMATIC ANALYSIS OF CATIONS

Step - I : Preliminary Examination of the Salt for Identification of Cation
1. Colour Test : Observing the colour of the salt may provide useful information about the cations.
Fe2+, Fe3+ (Light green, Yellow, Brown); Cu2+ (Blue); Ni2+ (Bright green).
2. Dry Heating Test : Heat the dry salt for about one minute and observe the colour of the residue
when hot and also when it becomes cold.
Colour when Cold Colour when Hot Inference

2+
Blue White Cu
2+
Green Dirty white or Yellow Fe
2+
White Yellow Zn
3. Flame test : Some volatile salts impart characteristic color to the non-luminous flame because they
absorb energy from the flame and transmit the same as the characteristic colour.
The chlorides of metals are more volatile in comparison to other salts; metal chloride volatilises and
thermal ionisation takes place.
The various zones of flame an shown below :
Fig. 2 Bunsen flame

The blue flame comprises two parts i.e. a smaller and brighter section at the bottom (region of complete
combustion) and a larger and less bright section (region of incomplete combustion). In a flame, the
hottest portion is the tip of the middle zone, where the temperature can reach about 1500°C, and the
coolest part is the whole of the middle zone except the tip. Blue flame is hotter than yellow flame as it
transfers more energy due to complete combustion. Incomplete combustion forms yellow flame.
Colour of the flame Colour of the flame observed

Inference (Metal ion)
observed by naked eye through blue glass
Green flame with blue centre Same colour as observed
without glass Cu2+
2+
Apple reen Bluish green Ba
Brick red Green Ca2+
343
4. Borax bead test

On heating borax, the colorless glassy bead formed consists of sodium metaborate and boric anhydride.

Na 2 B4 O 7 .10H 2 O   2NaBO 2  B2O 3

Glassy bead
On heating with a colored salt, the glassy bead forms a colored metaborate in oxidizing flame.
CuO + B2O3 
 Cu(BO ) 2 2
Copper metaborate Blue 
The metaborates possess different characteristic colors. The shade of the color gives a clue regarding
the presence of the radical. However, in reducing flame, the colors may be different because of different
reactions. E.g., copper metaborate may be reduced to a colourless cuprous metaborate or to metallic
copper, which appears red and opaque.
2Cu(BO2 )2 + C 
 2CuBO 2 + B2 O3 + CO
2Cu(BO 2 )2 + 2C 
 2Cu + 2B2O3 + 2CO
Heating in oxidising (non-luminous) flame Heating in reducing(luminous) flame

Metal Colour of the salt bead Colour of the salt bead
In cold In hot In cold In hot
Copper (Cu2+) Blue Green Red opaque Colourless
3+
Iron (Fe ) Yellow Yellowish brown Green Green
2+
Nickel (Ni ) Reddish brown Violet Gray Gray
5. Charcoal cavity test

When a metallic salt is heated with Na2CO3 on a charcoal block, the metal carbonate is formed, which
decomposes into the oxide. The carbon of the block reduces the oxide to metal.

(i) CuSO 4 + Na 2 CO3   CuCO3 + Na 2SO4

CuCO3   CuO + CO2

CuO + C   Cu + CO

(ii) ZnSO 4 + Na 2 CO3   ZnCO3 + Na 2SO4

ZnCO3   ZnO + CO 2
Observation
When hot When cold Inference(Metal ion)
2+
Yellow Grey metal Pb
Red metal White Cu2+
2+
Yellow White Zn
344
6. Cobalt Nitrate Test

When the residue in the charcoal cavity is white, it is heated strongly with cobalt nitrate in a non-
luminous flame. Cobalt nitrate decomposes into cobalt(II)oxide, which gives characteristic colour with
metal oxide.
Co(NO 3 ) 2 
Heat
 CoO  4NO 2  O 2
CoO  ZnO 
 CoO.ZnO
Green
CoO  MgO 
 CoO.MgO
Pink
CoO  Al2 O3 
 CoO.Al2O3
Blue
Step-II : Wet Tests for Identification of Cations

Preparation of Original Solution (O.S.)
The following solvents are tried : (i) water, (ii) dil.HCl, (iii) conc.HCl, (iv) dil.HNO3, (v) conc.HNO3, (vi)
Aqua-regia (conc.HCl + conc.HNO3 in the ratio 3:1).
In case the salt does not dissolve in a particular solvent even on heating, the next solvent is tried.
GROUP ANALYSIS
I. Chemistry of Confirmatory Tests for NH+4 ion

(a) NaOH solution: Ammonium salts on heating with alkali gives smell of ammonia. The gas evolved
reacts with HCl to give ammonium chloride, which is visible as dense white fumes.

(NH 4 ) 2 SO 4  2NaOH   Na 2SO 4  2NH 3  2H 2 O
NH 3  HCl 
 NH 4 Cl
(b) Nessler’s reagent: On passing the gas (ammonia) through Nessler’s reagent, a brown colouration
or precipitate of basic mercury (II) amido-iodine (Million’s base) is formed.
2K 2 HgI 4  NH 3  3KOH 
 HgO.Hg(NH 2 )I  7KI  2H 2 O
Basic mercury(II)amido iodine
(Brown precipitate)
Group Cations Group Reagent Composition and Colour of Precipitate

+
0 NH4 None
2+
I Pb Dil. HCl PbCl2 - White
2+ 2+
II Pb , Cu Dil. HCl + H2 S PbS - Black, CuS - Black
3+ 3+
III Al , Fe NH4 Cl + NH4 OH Al(OH)3 - White, Fe(OH)3 - Reddish brown
2+ 2+
IV Ni , Zn NH4 OH + H2 S NiS - Black, ZnS - White
2+ 2+
V Ba , Ca NH4 OH + (NH4 )2 CO 3 BaCO 3 - White, CaCO 3 - White
2+
VI Mg None
345
Points to remember:
(i) Group I radicals are precipitated as chlorides because the solubility product of these chlorides is
less than the solubility product of all other chlorides that remain in solution.
(ii) Group II radicals are precipitated as sulfides because sulfides of other metals remain in solution
due to their low solubility products. HCI acts as a source of H+ which decreases the concentration of
S2– due to common ion effect. Low concentration of S2– is sufficient to precipitate the Group II metal.
(iii) Group Ill A radicals are precipitated as hydroxides and the NH4CI suppresses the ionization of
NH4OH so that only the group Ill A metals are precipitated because of their low solubility product.
(iv) In group IV, NH4OH increases the ionization of H2S by removing H+ from H2S as unionised water
so that excess of S2– ions are available. Thus, the ionic product of Group IV exceeds their solubility
product and ppt. will be obtained.
(v) Ammonium hydroxide is added before adding ammonium carbonate to precipitate Group V cations
because NH4OH reacts with ammonium bicarbonate present as impurity in ammonium carbonate.
NH 4 HCO3  NH 4OH 
(NH 4 )2 CO3  H 2O
The presence of bicarbonate is undesirable as the bicarbonates of group V ions are soluble in water.
Confirmatory test for Group-I Cation
2. Chemistry of Confirmatory Tests for Pb2+ ions
Lead chloride (Group-I) precipitate is soluble in hot water.
(a). Potassium iodide (KI) : Lead chloride gives yellow precipitate of lead iodide.
PbCl + 2KI 
2  PbI 2 + 2KCl
(Hot solution) Yellow precipitate
PbI2 is soluble in boiling water and reappears on cooling as shining crystals (golden spangles).
(b) Potassium chromate (K2CrO4): Yellow precipitate of lead chromate.
PbCl +K 2 CrO 4 
2  PbCrO 4 + 2KCl
(Hot solution) Lead chromate (Yellow ppt.)
Lead chromate is soluble in hot NaOH solution.

PbCrO 4 + 4NaOH  Na [Pb(OH) ]
2 4 + Na 2 CrO 4
Sodium tetrahydroxoplumbate (II)
(c) Alcohol and dil.H2SO4 : White precipitate of lead sulphate is formed
PbCl 2 + H 2SO4 
 PbSO 4 + 2HCl
Lead sulphate (white ppt.)
PbSO4 is soluble in ammonium acetate solution due to the formation of tetra aceto plumbate(II) ions.
PbSO 4 + 4 CH3COONH 4 
 (NH 4 ) 2 [Pb(CH 3COO)4 ] + (NH 4 ) 2SO 4
Ammonium tetraacetoplumbate(II)
346
Confirmatory test for Group-II Cations

3. Confirmatory Tests for Copper ion (Cu2+)
(a) Copper sulphide dissolves in nitric acid to form copper nitrate.
3CuS + 8HNO3 
 3Cu(NO 3 )2 + 2NO + 3S + 4H 2 O
On prolonged heating, sulphur is oxidised to sulphate; copper sulphate is formed and the solution
turns blue. NH4OH precipitates basic copper sulphate which is soluble in excess of ammonium
hydroxide due to the formation of tetraaminecopper(II).
S + 2HNO3 
 H 2SO 4 + 2NO
2Cu 2+ +SO 42  +2NH 3 +2H 2 O 

 2Cu(OH) 2 .CuSO 4 +2NH 4
Cu(OH) 2 .CuSO 4 + 8NH 3 

 2 [Cu(NH3 )4 ]SO 4 + 2OH  +SO 24
Tetraamminecopper (II)sulphate(Deep blue)
(b) The blue solution on acidification with acetic acid followed by addition of potassium ferrocyanide,
[K4Fe(CN)6] solution gives chocolate colouration due to the formation of copper ferrocyanide,
Cu2[Fe(CN)6].
[Cu(NH 3 ) 4 ] SO 4 + 4CH 3COOH 

 CuSO 4 + 4CH 3COONH 4
2CuSO 4 + K [Fe(CN) ]
4 6 
 Cu [Fe(CN) ] + 2K 2SO 4
2 6
Potassium hexacyanoferrate (II) Copperhexacyanoferrate (II)
(Chocolate brown precipitate)
Confirmatory Tests for Group-III cations

When the original solution is heated with conc. HNO3, ferrous (Fe2+) ions are oxidised to ferric (Fe3+)
ions.
2FeCl 2 + 2HCl + [O] 

 2FeCl3 + H 2 O
Group-III cations are precipitated as their hydroxides, which dissolve in dil. HCl due to the formation of
corresponding chlorides.
4.Chemistry of Confirmatory Tests for Aluminium ions (Al3+)
(a) NaOH solution: Aluminium chloride gives white gelatinous precipitate of aluminium hydroxide,
which is soluble in excess of NaOH due to the formation of sodium metaaluminate.
AlCl3 + 3NaOH 
 Al(OH)3 + 3NaCl
Al(OH) 3 + NaOH 
 NaAlO 2 + 2H 2 O
White gelatinous precipitate Sodium meta aluminate
(b) Lake test: When blue litmus is added to AlCl3 solution, a red colouration is obtained due to the
acidic nature of the solution. On addition of NH4OH, the solution becomes alkaline and aluminium
hydroxide is precipitated. Aluminium hydroxide adsorbs blue colour from the solution and forms insoluble
adsorption complex named ‘lake’ (a blue mass floating in the colourless solution).
347
5. Chemistry of Confirmatory Tests for ferric ions (Fe3+)

Reddish brown precipitate of ferric hydroxide dissolves in hydrochloric acid to give ferric chloride.
Fe(OH)3 + 3HCl 
 FeCl3 + 3H 2 O
(a) Potassium ferrocyanide: Ferric chloride is treated with potassium ferrocyanide solution. Blue
precipitate/colouration (Prussian blue) due to the formation of ferric ferro-cyanide.
4FeCl3 + 3K 4 [Fe(CN)6 ] 
 Fe 4 [Fe(CN)6 ]3 + 12KCl
Potassium ferrocyanide Prussian blue precipitate
when potassium hexacyanoferrate (II) (i.e. potassium ferrocyanide) is added in excess, KFe[Fe(CN)6]
is formed, which forms a colloidal ‘soluble Prussian blue’.
FeCl3 + K 4 [Fe(CN)6 ] 
 KFe[Fe(CN)6 ] + 3KCl
(Soluble prussian blue)
(b) Potassium thiocyanate: Ferric chloride solution is treated with potassium thiocyanate (potassium
sulphocyanide) solution. Appearance of blood red colouration.
Fe3  SCN  
 [Fe(SCN)]2 
Blood red colour
Confirmatory tests for Group–IV cations

Fourth group cations are precipitated as sulphides. White colour of the precipitate indicates the
presence of zinc ions and black colour indicates the presence of Ni2+ ions.
6. Chemistry of Confirmatory Tests for Zinc ion (Zn2+)
Zinc sulphide dissolves in hydrochloric acid to form zinc chloride.
ZnS + 2HCl 
 ZnCl2 + H 2S
(a) NaOH solution: White precipitate of zinc hydroxide, which is soluble in excess of NaOH solution
on heating.
ZnCl2 + 2NaOH 
 Zn(OH) 2 + 2NaCl
Zn(OH) 2 + 2NaOH 
 Na 2 ZnO2 + 2H 2O
Sodium zincate
(b) Potassium ferrocyanide : K4Fe(CN)6 solution is added to the solution after neutralisation by
NH4OH solution. White or a bluish white precipitate of zinc ferrocyanide.
2 ZnCl2 + K 4 [Fe(CN)6 ] 
 Zn 2 [Fe(CN)6 ] + 4KCl
Zinc ferrocyanide
7. Chemistry of Confirmatory Tests for Nickel ion (Ni2+)

The black precipitate of nickel sulphide dissolves in aqua regia
3NiS + 2HNO3 + 6HCI 

 3NiCl 2 + 2NO + 3S + 4H 2 O
(a) Dimethyl glyoxime : Nickel-chloride is treated with dimethyl glyoxime and made alkaline by adding
NH4OH solution gives brilliant red precipitate of nickel dimethylglyoxime.
348
Ni 2+ + 2C 4 H8 N 2 O 2  Ni  C 4 H 7 N 2 O 2 2 + 2H +
Dimethyl glyoxime Nickel dimethylglyoxime  red precipitate 
Confirmatory Tests for Group–V cations

Group–V cations, precipitated as carbonates, dissolve in acetic acid forming the corresponding
acetates.
8. Chemistry of Confirmatory Tests for Barium ion (Ba2+)
(a) Potassium chromate : Yellow precipitate of barium chromate when the solution of fifth group
precipitate dissolved in acetic acid is treated with potassium chromate.
BaCO3 + 2CH 3COOH 

 (CH 3COO) 2 Ba + H 2 O + CO 2
(CH3COO)2 Ba + K 2 CrO 4 
 BaCrO 4 + 2CH3COOK
Barium chromate(yellow ppt. )
(b) Dil. H2SO4 : Barium acetate gives heavy white ppt. of barium sulphate.
(CH 3COO) 2 Ba + H 2SO 4 

 BaSO 4 + 2CH 3COOH
(c) Ammonium oxalate : Barium acetate gives white ppt of barium oxalate.
(CH 3COO) 2 Ba + (NH 4 ) 2 C 2 O 4 

 BaC 2 O 4 + 2CH 3COONH 4
(b) Flame test : Grassy green colour of the flame confirms the presence of Ba2+ ions
9. Chemistry of Confirmatory Tests for Calcium ion (Ca2+)
(a) Ammonium oxalate : Solution of the fifth group precipitate in acetic acid gives white precipitate
with ammonium oxalate solution.
CaCO3 + 2CH 3COOH 

 (CH 3COO) 2 Ca + H 2 O + CO 2
(CH3COO) 2Ca + (NH 4 ) 2 C 2 O 4 

 (COO) Ca 2 + 2CH 3COONH 4
Ammonium oxalate Calcium oxalate (white ppt.)
(b) Flame test: Calcium imparts brick red colour to the flame which looks greenish-yellow through
blue glass.
Confirmatory Tests for Group–VI cation
10. Chemistry of Confirmatory Tests for Magnesium ion (Mg2+)
When group-V is absent, the solution may contain magnesium carbonate, which is soluble in water in
the presence of ammonium salts because the equilibrium is shifted towards the right hand side.
349
 NH 3 + HCO3
NH 4 + CO32  
The concentration of carbonate ions required to produce a precipitate is not attained.
(a) Disodium hydrogenphosphate: White crystalline precipitate of magnesium ammonium phosphate
is formed (when the walls of the test tube is scratched with glass rod).
Mg 2+ + Na 2 HPO 4 
 Mg (NH 4 )PO 4 + NH 4OH + 2Na + + H 2 O
Magnesium ammonium
phosphate (White ppt.)
(b) Magneson Test: A blue precipitate is obtained when the test solution is treated with a few drops
of magneson reagent (p-nitrobenzeneazoresorcinol) and excess of NaOH solution.
Mg(OH)2 formed adsorbs magneson reagent and the resulting mass appears blue in colour.
PRACTICAL PHYSICAL CHEMISTRY

VI THERMOCHEMICAL MEASUREMENTS
Enthalpy changes are directly related to the temperature changes by the relation:
H  q P  mC p T  VdC p T
where V = Volume of the solution, d = Density of the solution, Cp = Heat capacity, and ΔT = Change in
temperature
In thermochemical measurements, generally aqueous solutions are mixed, therefore, water in the
reaction medium and the temperature changes due to the chemical reactions taking place. According
to law of conservation of energy, the sum of enthalpy changes taking place in the calorimeter must be
zero.
H1  H 2  H 3  H 4  0
where ΔH1 = Heat gained by calorimeter, stirrer and thermometer, ΔH2 = Enthalpy change of solution/
water in calorimeter, ΔH3 = Enthalpy change of added solution/water in calorimeter and ΔH4 = Enthalpy
change of reaction.
In these reactions, the product of density and heat capacity of solutions, dCp, is taken as 4.184 J mL–
1
K–1, nearly the same as that of pure water.
1. Enthalpy of Dissolution of Copper Sulphate
Enthalpy of solution is the amount of heat liberated or absorbed when one mole of solute is dissolved
in such a large quantity of solvent that further dilution does not make any heat changes.It is also
known as heat of solution or enthalpy of solution.
Procedure: A known mass of finely powdered CuSO4.5H2O is quickly dissolved (by stirring) in a
known quantity (100 mL) of water contained in a calorimeter of known water equivalent (calorimeter
constant) and the fall in temperature is accurately measured using a sensitive thermometer. From the
data, the quantity of heat absorbed when one gram molecular mass of CuSO4.5H2O in a particular
volume of water is calculated.
350
Calculation
Total mass of the solution = Mass of solvent + Mass of solute = (100 + W 1) g
(Assuming density of water to be equal to 1 g L–1 at the experimental temperature)
Change in temperature = (t'2 - t'1) °C
Enthalpy change of the Calorimeter = W (t'2 - t'1)
where, W = Calorimeter constant.
Enthalpy change of solution = [(100 + W 1) (t'2 - t'1)] 4.184 J
Total enthalpy change of the Calorimeter and solution
= W (t'2 - t'1 )+ [(100 + W1 ) (t'2 - t'1 )] 4.184 J
[W (t'2 - t'1 )+ [(100 + W1 ) (t'2 - t'1 )] 4.184 J

Heat liberated on dissolution of 1 g copper sulphate 
W1
Since 1 mol of copper sulphate weighs 249.5 g,  sol H of CuSO4 .5H2O
[W (t'2 - t'1 )+ [(100 + W1 ) (t'2 - t'1 )] 4.184

 249.5  J mol 1
W1
Precautions
(a) In the determination of calorimeter constant, record the temperature of hot water just before mixing.
(b) Avoid using very large amounts of copper sulphate/potassium nitrate.
(c) Avoid too much stirring, it may produce heat due to friction.
(e) Weigh copper sulphate carefully as it is hygroscopic in nature.
(f) Use cotton wool to create insulation between the two beakers.
2. Enthalpy of Neutralisation of a Strong Acid and Strong Base
Neutralisation reaction is the combination of H+ (aq) ions furnished by an acid and OH– (aq) ions
furnished by a base, leading to the formation of H2O(l). Since the reaction involves bond formation, it
is always exothermic.
Enthalpy of neutralisation is defined as the amount of heat liberated when 1mol of H+ ions furnished by
acid combine with 1 mole of OH– ions furnished by base to form water. The relevant equatios are:
HCl(aq) + NaOH(aq) 
 NaCl(aq) + H 2 O(l); H  57.3 kJ
H + (aq) + Cl  (aq) + Na + (aq)  OH  (aq) 

 Cl (aq) + Na + (aq)  H 2 O(l)
H + (aq) + OH  (aq) 
 H 2 O(l); H neut is negative
(Acid) (Base)
where ΔHneut is the enthalpy of neutralisation.
351
If both the acid and the base are strong, then for the formation of 1 mol H2O (l), always a fixed amount
of heat, viz, 57 kJ mol–1 is liberated. If any one of the acid or base or both are weak, some of the heat
liberated is used for the ionisation of the acid, base or both and the amount of heat liberated will be
less than 57 kJ mol–1.
Procedure: Known volumes of the standard alkali and acid are neutralised and the heat evolved is
determined by calorimetric method. From this, the quantity of heat evolved by 1000 mL of 1N alkali by
acid is calculated.
Calculation of enthalpy of neutralisation
Rise in temperature of the mixture = (t2-t1) °C.
Calorimeter constant = W
Heat evolved = (100 + 100 + W) (t2 - t1) × 4.18 J .....(i)
Heat evolved when 1000 mL of 1M HCl neutralises 1000 mL of 1M NaOH would be ten times the
quantity obtained in (i).
Precautions
(a) Proper insulation should be made between the two beakers.
(b) Avoid unnecessary and excessive stirring to prevent heating due to friction.
II. COLLOIDS
A colloidal solution is a heterogeneous system in which very fine particles of one substance disperse
(dispersed phase) in another substance called dispersion medium. Colloidal particles are larger
than simple molecules, but small enough to remain suspended in the dispersion medium (10–9 –10–6
m).
A sol is a heterogeneous system of a solid as dispersed phase and a liquid as dispersion medium.
Colloidal sols are divided into two categories, namely, lyophilic (solvent attracting) and lyophobic
(solvent repelling). Egg albumin, starch and gum are lyophilic sols. Freshly prepared ferric hydroxide,
aluminium hydroxide and arsenic sulphide sols are examples of lyophobic sols.
Lyophilic sols are formed by mixing and shaking the substance with a suitable liquid. Lyophobic sols
cannot be prepared by direct mixing and shaking; special methods are employed for their preparation.
A. Preparation of Lyophilic Sol
1. Egg Albumin Sol : Break one egg into a porcelain dish and pipette out the albumin into 100 mL of 5%
(w/v) aqueous solution of NaCl in a 250 mL beaker and stir well.
2. Starch/gum Sol : Make a paste of 500 mg of starch/gum in hot water and transfer it to 100 mL
boiling water with constant stirring. Keep water boiling and stir for 10 minutes.
B. Preparation of Lyophobic Sol
I. Ferric hydroxide/Aluminium hydroxide: Add 2g of ferric chloride/aluminium chloride powder to 100
mL boiling water and stir it well. Pour 10 mL of ferric chloride/aluminium chloride solution drop by drop
into 100 mL boiling water in another beaker with constant stirring. Keep the water boiling till brown/
white sol is obtained.
II. Arsenious Sulphide Sol: Add 0.2 g of arsenious oxide to 100 mL distilled water in a 250 mL beaker;
boil, cool and filter. Pass H2S gas through the filtered solution till it smells of H2S. Expel H2S from the
sol by slow heating and filter.
352
Precautions
(a) While preparing colloidal solutions of starch, gum, ferric chloride, aluminium chloride etc., pour the
paste/solution gradually into boiling water with constant stirring. Addition of these substances in excess
may cause precipitation.
(b) Arsenious oxide is highly poisonous.
III. CHEMICAL KINETICS

Effect of Variation in Concentration of Iodide ions on the Rate of Reaction of Iodide ions with
Hydrogen peroxide at Room Temperature.
Rate of reaction can be measured either in terms of decrease in concentration of any one of the
reactants or increase in concentration of any one of the products with time.
For a hypothetical reaction, A 

 B,
[A] [B]
Rate of reaction   
T T
Factors such as concentration, temperature and catalyst affect the rate of a reaction.
The reaction between iodide ions and hydrogen peroxide in acidic medium can be represented as:
2I (aq)  H 2 O2 (l)  2H  (aq) 

 I 2 (g)  2H 2 O(l)
In this reaction, hydrogen peroxide oxidises iodide ions to molecular iodine. If calculated amount of
sodium thiosulphate is added in the presence of starch solution as indicator to the above reaction
mixture, the liberated iodine reacts with thiosulphate ions as soon as it is formed and is reduced back
to iodide ions till all the thiosulphate ions are oxidised to tetrathionate ions.
I 2 (g)  2S2 O 32 (aq) 

 S4 O 62 (aq)  2I  (aq)
After the complete consumption of thiosulphate ions, the concentration of iodine liberated in the reaction
of H2O2 with I– increases rapidly to a point where iodine forms intense blue complex with starch.
I 2 (g)  Starch 
 Starch  I2 complex
Colourless Blue colour
This is a clock reaction because the reaction rate can be easily timed by the sudden appearance of
blue colour. The thiosulphate ion acts as the reaction detector and does not participate in the main
reaction. They are not involved in the reaction rate expression because its reaction with iodine is very
fast. The larger the concentration of thiosulphate ions in the reaction mixture, the more gradual the
appearance of blue colour.
Time of appearance of blue colour depends on: (i) the rate of formation of iodine depending on the
concentration of H2O2 and I– ions and (ii) the amount of thiosulphate present.
Since concentration of thiosulphate is kept constant, the different times of appearance of blue colour
with change in concentration of either of the reactants indicates the relative rate of reaction.
From the above observations, it is clear that the time of appearance of blue colour goes on decreasing
as the amount of iodide ions increases, i.e., the rate of reaction between iodide ions and hydrogen
peroxide increases with increase in concentration of iodide ions.
353
Precautions
(a) Keep the concentration of sodium thiosulphate solution less than that of potassium iodide solution.
(b) Always use freshly prepared starch solution.
(c) Use fresh samples of hydrogen peroxide and potassium iodide.
(d) Record the time immediately after the appearance of blue colour.
354
QUESTIONS
LEVEL - I
1. Phenolic group is identified by a positive
1) Phthalein dye test 2) Lucas test 3) Tollen’s test 4) Carbylamine test
2. The appearence of blood red colour on treatment of sodium fusion extract of an organic compound
with FeSO4 in presence of conc. H2SO4 indicate the presence of element(s)
1) Br 2) N 3) N and S 4) S
3. The Lassaigne’s extract is boiled with dil. HNO3 before testing for halogens because
1) AgCN is soluble in HNO3 2) Silver halides are soluble in HNO3
3) Ag2S is soluble in HNO3 4) Na2S and NaCN are decomposed by HNO3
4. Match List I with List II
Choose the correct Answer from the options given below.

1) A - II, B - IV, C - I, D - III 2) A - IV, B - II, C - I, D - III
3) A - II, B - I, C - IV, D - III 4) A - III, B - I, C - IV, D - II

1) A - II, B - IV, C - III, D - I 2) A - IV, B - I, C - II, D - III
3) A - III, B - IV, C - I, D - II 4) A - III, B - IV, C - II, D - I
355
6. During halogen test, sodium fusion extract is boiled with concentrated nitric acid to
1) remove unreacted sodium
2) decompose cyanide or sulphide of sodium
3) extract halogen from organic compound
4) maintain the pH of extract
Reason (R)
Assertion (A) : An aqueous solution of KOH when used for volumetric analysis, its concentration
should be checked before the use.
Reason (R) : On ageing, KOH solution absorbs atmospheric CO2.
1) (A) is not correct but (R) is correct
2) Both (A) and (R) are correct but (R) is not the correct explanation of (A)
3) Both (A) and (R) are correct and (R) is the correct explanation of (A)
4) (A) is correct but (R) is not correct
8. NaCl react with conc.H2SO4 and K2Cr2O7 to give reddish fumes (B) which react with NaOH to give
yellow solution (C). (B) and (C) respectively are
1) CrO2Cl2, Na2CrO4 2) Na2CrO4, CrO2Cl2
3) CrO2Cl2, KHSO4 4) CrO2Cl2, Na2Cr2O7
9. In chromyl chloride test for confirmation of Cl– ions a yellow solution is obtained. Acidification of the
solution and addition of amyl alcohol and 10% H2O2 turns organic layer blue indicating the formation of
chromium pentoxide. The oxidation state of chromium in it is
1) +6 2) +5 3) +10 4) +3
10. Statement - I : The gas liberated on warming a salt with dilute H2SO4 turns a piece of paper dipped in
lead acetate into black, it is a confirmatory test for sulphide ion.
Statement - II : In statement - I the colour of paper turns black because of formation of lead sulphite.
In the light of the above statements choose the most appropriate answer from the options given
below.
1) Both statement - I and statement - II are false
2) Statement - I is false but statement - II is true
3) Statement - I is true but statement - II is false
4) Both statement - I and statement - II are true
11. A reagent which give brilliant red precipitate with Nickel ion in basic medium is
1) sodium nitro prusside
2) neutral FeCl3
3) m-dinitrobenzene
4) dimethyl glyoxime
356
12. On passing a gas X through Nessler’s reagent, a brown precipitate is obtained. The gas X is
1) H2S 2) CO2
3) NH3 4) Cl2
13. Given below are two statements
Statement - I : Potassium hydrogen phthalate is a primary standard for standardisation of sodium
hydroxide.
Statement - II : In this titration phenolphthalein can be used as indicator.
below.
1) Both statement - I and statement - II are correct
2) Statement - I is correct but statement - II is incorrect
3) Statement - I is incorrect but statement - II is correct
4) Both statement - I and statement - II are incorrect
14. The compound that is insoluble in water and that is white in colour is
1) Ammonium sulphate 2) Lead sulphate
3) Lead iodide 4) Ammonium arsenomolybdate
15. Ammoniacal metal salt solution gives a brilliant red precipitate on addition of dimethyl glyoxime. The
metal ion is
1) Cu+ 2) CO2+ 3) Fe2+ 4) Ni2+
Reason (R)
Assertion (A) : 3.1500 g of hydrated oxalic acid dissolved in water make 250.0 mL. Solution will result
in 0.1 M oxalic acid solution.
Reason (R) : Molar mass of hydrated oxalic acid is 126 g mol–1.
1) Both (A) and (R) are true but (R) is not the correct explanation of (A)
2) (A) is false but (R) is true
3) (A) is true but (R) is false
4) Both (A) and (R) are true and (R) is the correct explanation of (A)
17. K2Cr2O7 paper acidicfied with dil. H2SO4 turns green when exposed to
1) Carbon dioxide 2) Sulphur trioxide
3) Hydrogen sulphide 4) Sulphur dioxide
357
1) P - (i), Q - (ii), R - (ii), S - (iv) 2) P - (iv), Q - (ii), R - (iii), S - (i)

3) P - (iii), Q - (i), R - (iv), S - (ii) 4) P - (i), Q - (iii), R - (iv), S - (ii)
19. During qualitative analysis of SO32 using dilute H2SO4, SO2 gas is evolved which turns K2Cr2O7
solution (acidified with dilute H2SO4)
1) Black 2) Red 3) Green 4) Blue
Statement - I : Dimethyl glyoxime forms a six membered covalent chelate when treated with NiCl2
solution in presence of NH4OH.
Statement - II : Prussian blue precipitate contains iron both in (+2) and (+3) oxidation states.
below.
4) Statement - I is true but statement - II is false
21. Formula of Nessler’s reagent is
1) K2Hg2I2 2) KHgI3 3) K2HgI4 4) HgI2
22. In Lucas test, an alcohol reacts immediately and gives insoluble chloride. The alcohol is
1) CH3OH 2) CH3CH2OH 3) (CH3)2CHOH 4) (CH3)3COH
Statement - I : Upon heating a borax bead dipped in cupric sulphate in a luminous flame, the colour of
the bead becomes green.
Statement - II : The green colour observed is due to the formation of copper (I) metaborate.
below.
2) Statement - I is true but statement - II are false
358
1) A - (II), B - (III), C - (I), D - (IV) 2) A - (III), B - (IV), C - (II), D - (I)

3) A - (II), B - (IV), C - (I), D - (III) 4) A - (II), B - (III), C - (IV), D - (I)
25. During qualitative analysis of salt with cation (y2+) addition of reagent (X) to an alkaline solution of the
salt gives a bright red precipitate. The reagent (X) and cation (y2+) present respectively are
1) Dimethyl glyoxime and Ni2+ 2) Dimethyl glyoxime and Co2+
3) Nessler’s reagent and Hg2+ 4) Nessler’s reagent and Ni2+
26. Given below are two statements.
Statement I : Sulphanilic acid gives esterification test for carboxyl group.
Statement II : Sulphanilic acid gives red colour in Lassaigne’s test for extra element detection.
below.
1) Statement I is correct but statement II is incorrect
2) Both statement I and statement II are incorrect
3) Both statement I and statement II are correct
4) Statement I is incorrect but statement II is correct
27. In the flame test of a mixture of salts a green flame with blue centre was observed. Which one of the
following cations may be present?
1) Cu2+ 2) Ca2+ 3) Ba2+ 4) Sr2+
28. The white precipitate of AgCl dissolve in aqueous ammonia due to formation of
1) [Ag(NH3)4]Cl2 2) [Ag(Cl)2(NH3)2] 3) [Ag(NH3)2]Cl 4) [Ag(NH3)Cl]Cl
29. Which statement is not true with respect to nitrate ion test?
1) A dark brown ring is formed at the junction of two solutions
2) Ring is formed due to nitroferrous sulphate complex
3) The brown complex is [Fe(H2O)5NO]SO4
4) Heating the nitrate salt with conc. H2SO4 light brown fumes are evolved
359
30. For the kinetic study of the reaction of iodide ion with H2O2 at room temperature
A) Always use freshly prepared starch solution
B) Always keep the concentration of sodium thiosulphate solution less than that of KI solution
C) Record the time immediately after the appearence of blue colour
D) Record the time immediately before the appearence of blue colour
E) Always keep the concentration of sodium thiosulphate solution more than that of KI solution
Choose the correct answer from the options given below.
1) A, B, C only 2) A, D, E only
3) D, E only 4) A, B, E only
LEVEL - II
1. Which one of the following tests is correctly matched?
1) Phenol - Phthalein dye test
2) Benzyl amine - Azo dye test
3) Phthalic acid - 2, 4-DNP test
4) CH3CONH2 - Carbylamine test
2. Which of the following compounds can be detected using neutral FeCl3 solution?
1) C6H5OH 2) CH3COCOCH3
3) H3C CH2OH 4) CH3CHOHC6H5
3. Element not present in Nessler’s reagent is

1) Hg 2) I 3) K 4) N
4. Which of the following will evolve CO2 on reaction with NaHCO3?
1) Salicylic acid 2) Picric acid
3) Benzoic acid 4) All of these
5. 0.01 M KMnO4 solution was added to 20.0 mL of 0.05 M Mohr’s salt solution through a burette. The
initial reading of 50 mL burette is zero. The volume of KMnO4 solution left in the burette after the end
point is
1) 30 mL 2) 20 mL 3) 15 mL 4) 10 mL
Statement I : Methyl orange is a weak acid.
Statement II : The benzenoid form of methyl orange is more intense/deeply coloured than the quinonoid
form.
below.
360

1) A - III, B - I, C - II, D - IV 2) A - II, B - I, C - IV, D - III
3) A - IV, B - I, C - III, D - II 4) A - IV, B - I, C - II, D - III
8. The formula of purple colour formed in Lassaigne’s test for sulphur using sodium nitroprusside is
1) NaFe[Fe(CN)6] 2) Na[Cr(NH3)2(NCS)4]
3) Na2[Fe(CN)5NO] 4) Na4[Fe(CN)5NOS]
Statement I : In redox titration the indicators used are sensitive towards change in pH of the solution.
Statement II : In acid-base titration the indicators used are sensitive to change in oxidation potential.
below.
10. A white precipitate was formed when BaCl2 was added to water extract of an inorganic salt. Further a
gas ‘X’ with characteristic odour was released when the formed precipitate was dissolved in dil. HCl
the anion present in the inorganic salt is
1) I– 2) SO32
3) S2– 4) NO2
11. In base vs Acid titration at the and point methyl orange is present as
1) Quinonoid form 2) Heterocyclic form
3) Phenolic form 4) Benzenoid form
361

Statement I : Aqueous solution of K2Cr2O7 is preferred as primary standard in volumetric analysis over
Na2Cr2O7 aqueous solution.
Statement II : K2Cr2O7 has a higher solubility in water than Na2Cr2O7.
1) Both statement I and statement II are true
2) Both statement I and statement II are false
3) Statement I is true but statement II is false
4) Statement I is false but statement II is true
13. The dark purple colour of KMnO4 disappears in the titration with oxalic acid in acid medium. The
overall change in oxidation number of manganese in the reaction is
1) 5 2) 1 3) 7 4) 2
14. 20 mL of 0.02 M K2Cr2O7 solution is used for the titiration of 10 mL of Fe2+ solution in acidic medium.
The molarity of the solution is
1) 0.24 M 2) 0.12 M 3) 0.48 M 4) 0.04 M
Reason (R)
Assertion (A) : A mixture contains benzoic acid and naphthalene. The pure benzoic acid can be separated
out by use of benzene.
Reason (R) : Benzoic acid is soluble in hot water.
16. In the titration of KMnO4 and Oxalic acid in acidic medium, the change in Oxidation number of carbon
at the end point is
1) 1 2) 2 3) 0.5 4) 3
17. The plot of pH metric titration of weak base (NH4OH) vs strong acid (HCl) looks like
1) 2)
3) 4)
362
Statement I : In Lassaigne’s test, when both nitrogen and sulphur are present in an organic compound,
sodium thiocyanate is formed.
Statement II : If both nitrogen and sulphur are present in an organic compound, the excess of sodium
used in sodium fusion will decompose the sodium thiocyanate formed to give NaCN and Na2S.
In the light of the above statements choose the most appropriate answer from options given below.
19. Fe2+ cation gives prussian blue precipitate on addition of potassium ferrocyanide solution due to the
formation of
1) [Fe(H2O)6][Fe(CN)6] 2) [Fe2[Fe(CN)6]3
3) Fe3[Fe(OH)2(CN)4] 4) Fe4[Fe(CN)6]3
20. A compound (X) is a weak acid and it exhibits colour change at pH close to the equivalence point
during neutralisation of NaOH with CH3COOH. Compound (X) exists in ionised form in basic medium.
The compund (X) is
1) methyl orange 2) Methyl red
3) Phenolphthalein 4) erichrome Black-T
Reason (R)
Assertion (A) : Phenolphthalein is pH dependent indicator remains colourless in acidic medium and
gives pink colour in basic medium.
Reason (R) : Phenolphthalein is a weak acid, it does not dissociate in basic medium.
22. To an aqueous solution containing the ions, Al3+, Zn2+, Ca2+, Fe3+, Ni2+, Ba2+ and Cu2+, HCl was added
followed by H2S. The number of cations precipitated during this reaction is/are
1) 2 2) 1 3) 3 4) 4
363
23. The hottest region of Bunsen flame shown in the figure below is
1) region 4 2) region 1
3) region 2 4) region 3
Reason (R)
Assertion (A) : Permanganate titrations are not performed in presence of hydrochloric acid.
Reason (R) : Chlorine is formed as a consequence of oxidation of hydrochloric acid.
25. An alkali is titrated against an acid with methyl orange as indicator. Which of the following is a correct
combination?
Base Acid End point
1) Strong Strong Pinkish red to yellow
2) Weak Strong Yellow to pinkish red
3) Pinkish red to yellow Strong Pink to colourless
4) Weak Strong Colourless to pink
Statement I : In the titration between strong acid and weak base methyl orange is suitable as indicator.
Statement II : For titration of acetic acid with NaOH phenolphthalein is not a suitable indicator.
In the light of the above statements choose the most appropriate answer from options given below.
1) Statement I is false but statement II is true
2) Both statement I and statement II are true
3) Both statement I and statement II are false
4) Statement I is true but statement II is false
364
27. Which of the following give a precipitate with Pb(NO3)2, but not with Ba(NO3)2?
1) NaCl 2) Sodium acetate
3) Sodium nitrate 4) Dilute nitric acid
28. There are certain chemical reagents which are used in the qualitative analysis of specific acid i.e.
anionic radicals. Match the reagent listead in column I with acid radicals listed in column II.
ColumnI ColumnII
A) Sulphanilicacid 1  naphthylaminereagent p) CO32
B) Bariumchloridesolution q) SO24
C) Leadnitratesolution r) S2
D) Acidifiedpotassiumpermanganatesolution s) NO2
1) A- r, s ; B- p, q ; C - q, r ; D - r, s 2) A- p, q ; B- r, s ; C - p, q, r ; D - q, r, s
3) A- p, q ; B- r, s ; C - p, q, r ; D - q, r, s 4) A- s ; B- p, q ; C - p, q, r ; D - r, s
29. A dark blue colour is obtained on adding excess of dilute NH4OH solution in aqueous solution of
copper sulphate. The deep blue colour is due to the presence of
1) CuSO4 2) Cu(OH)2 3) [Cu(NH3)4]2+ 4) (NH4)2SO4
30. Which of the following statements regarding precautions in determining the enthalpy of dissolution of
copper sulphate experiment is TRUE?
1) In the determination of calorimeter constant, record the temperature of hot water just after mixing
2) Use very large amounts of copper sulphate
3) Stir the solution vigorously to dissolve the solid and record the temperature
4) In the determination of calorimeter constant, record the temperature of hot water just before mixing
365
KEY WITH HINTS

LEVEL - I
1. 1 Phthalein dye test is characteristic of phenolic group.
2. 3 Fe2+ in FeSO4 is oxidised to Fe3+ NaCNS– present in sodium fusion extract form [FeCNS]2+
with Fe3+ [FeCNS]2+ is blood red in colour.
3. 4 HNO3 decomposes AgCN and Na2S which will interfere with AgNO3 test for halogens.
4. 4 Nitrogen - Fe4[Fe(CN)6]3 (ferric ferrocyanides)
Sulphur - Na2[Fe(CN)5NO] (sodium nitro prusside)
Phosphorus - (NH4)2MoO4 (ammonium molybdate)
Halogen - AgNO3
CHO
5. 4 Benedicts solution -
OH
Neutral FeCl3 -
CHCl3 and alc.KOH - NH2
CHOH – CH3
Iodoform test -
6. 2 Boiling with HNO3 decompose NaCN and or Na2S which will interfere with detection of halogen.
7. 3 KOH absorb CO2, so its concentration should be checked.
8. 1 4NaCl  6H 2SO 4  K 2 Cr2 O7 

 2CrO 2Cl 2  2KHSO 4  4NaHSO4  3H 2 O
 B
CrO 2 Cl2  4 NaOH 
 Na 2 CrO 4  2 NaCl  H 2 O
 C
O
O O
9. 1 CrO5 is Cr OS of Cr is +6.
O O
10. 3 S2aq   H 2SO 4 aq  

 H 2S g   SO 24
H 2S   CH 3COO 2 Pb 
 PbS  2CH 3COOH
366
11. 4 Ni 2  2dmg   Ni  dmg 2 

red precipitate
12. 3 Nessler’s reagent is K2HgI4 in KOH medium with ammonia it forms iodide of millions base
Hg
O NH2 I–
.
Hg
13. 1 KHP is a primary standard. It is a weak acid.

Phenolphthalein is used as indicator in weak acid × strong base titration
14. 2 PbSO4 is white in colour.
15. 4 Ni 2  2 DMG 

NH3  aq 
  Ni  DMG 2  .
Rose red complex
3.15 1000
16. 4 Assertion is correct molality M    0.1M
126 250
Hydrated oxalic acid H2C2O4.2H2O
Molar mass = 126 g mol–1
Reason is also correct
17. 4 2SO 2  Cr2 O72  2H   3SO 4 2  2Cr 3  H 2O .

18. 4 Group II H2S in presence of HCl Pb2+, Cu2+
Group III NH4OH in presence of NH4Cl Al3+, Fe3+
Group IV H2S in presence of NH4OH Co2+, Ni2+
Group V (NH4)CO3 in presence of NH4OH Ba2+, Ca2+

19. 3 Cr2 O72  SO32 
H
 Cr 3  SO 42 .
 green 
20. 1 [Ni(dmg)2] complex has two five membered ring co-valent chelate.
21. 3 Nessler’s reagent is K2HgI4.

22. 4 Lucas test is used to distinguish between primary, secondary and tertiary alcohols. A mixture·of
concentrated HCI and anhydrous ZnCl2 is called Lucas reagent. In Lucas test, tertiary alcohols
immediately give turbidity while secondary alcohols give turbidity after 5 min. Primary alcohols
give no reaction with Lucas reagent at room temperature.
367
23. 3 CuSO4 + B2O3 in non luminous flame Cu (BO2)2 cupric meta borate blue green
2Cu  BO 2 2  NaBO 2  C 

lu min ous
flame
 2CuBO 2  Na 2 B4O 7  CO cuprous metaborate
colourless.
Cu(BO2)2 may be reduced to metallic copper and bead appears red and opaque.
2Cu  BO 2 2  4NaBO 2  2C 
 2Cu  2NO 2 B4O7  2CO
24. 1 Mg(NH4)PO4 - white

K3[Co(NO2)6] - yellow
MnO(OH)2 - brown
Fe4[Fe(CN)6]3 - blue
25. 1   Ni  DMG 2 
Ni 2  DMG  
Bright red precipitate
26. 4 H2N SO3H do not have a –COOH group. It contains both N and S hence gives
red colour in Lassaigne’s test.

27. 1 Cu2+ green flame with blue centre
Ca2+ brick red
Sr2+ crimson red
Ba2+ pale green
28. 3   Ag  NH 3 2  Cl .
AgCl  2NH 3 
soluble
29. 2 Ring is formed due to nitroso ferrous sulphate complex.

30. 1 Time is recorded immediatly after the appearence of blue colour.
Concentration of Na2S2O3 is kept limited.
LEVEL - II
1. 1 Phthalein dye test is for phenolic –OH group.
2. 1 Neutral FeCl3 detects phenols and enols, by giving coloured solutions. A exists partly in enolic
form as shown below and hence gives a coloured solution with FeCl3.
3. 4 Nessler’s reagent is K2HgI4.
4. 4 Salicylic acid benzoic acid and picric acid liberate CO2 from NaHCO3
368
5. 1 N1V1 = N2V2
0.01 × 5 × V1 = 0.05 × 1 × 20
V1 = vol of KMnO4 used
Volume left = 50 – 20 = 30 mL
6. 3 Methyl orange is a weak base.
Benzenoid structure  Quinonoid structure

Red orange more intense yellow
7. 4 CO32 - CO 2 Brisk effervescence
SO2 - H2S Lead acetate paper black
SO32 - SO 2 Acidified K2Cr2O7 paper green
NO 2 - NO2 Starch KI solution blue
8. 4 Na 2S  Na 2  Fe  CN 5 NO   Na 4  Fe  CN 5 NOS .
9. 4 In redox titration indicators used are sensitive to change in reduction potential and in acid base
titration indicators are sensitive to change in pH.
10. 2 BaCl 2  SO 32  BaSO3  

dil. HCl
 SO 2  .
white
11. 1 Quinonoid form of methyl orange is red orange in colour.

12. 3 K2Cr2O7 is used as a primary standard. Solubility of Na2Cr2O7 is greater than that of K2Cr2O7
7
13. 1  Mn 2 in acid medium.
MnO 4 
14. 1 0.02 × 20 × 6 = M × 10 × 1
Molarity of Fe2+ solution M = 0.24 M.
15. 4 Both benzoic acid and naphthalene are soluble in benzene but in hot water only benzoic acid is
soluble.
16. 1 2KMnO4  5H 2C2O4  3H 2SO4  K 2SO 4  2MnSO4  10CO2  8H 2O
17. 1
369
18. 1 Both statement I and statement II are correct
Na  C  N  S 
 NaSCN
NaSCN  2Na 
 NaCN  Na 2S
4
19. 4 4Fe3  3  Fe  CN 6  
 Fe 4  Fe  CN 6 
3
prussian blue
20. 3 Phenolphthalein is a weak acid. It give colour in aqueous medium.

21. 3 Phenolphthalein is pH dependent indicator and it does dissociate in basic medium.
22. 2 HCl followed by H2S is group II reagent. Only Cu2+ will get precipitated.
23. 3 Region 2 is the hottest region.
24. 1 2KMnO4  16 HCl 

 2MnCl2  2KCl  8H 2O  Cl 2
HCl is oxidised by KMnO4 to Cl2
25. 2 Methyl orange is yellow in alkaline medium and pinkish red in acid medium.
26. 4 For strong acid weak base titration methyl orange is a suitable indicator. For weak acid strong
base titration phenolphthalein is suitable indicator.
27. 1 Because Pb(NO3)2 is an ionic compound, so the reaction is easy.
Pb  NO3 2  2NaCl  2NaNO3  PbCl2 , but Ba  NO3 2 do not give precipitate with NaCl.
28. 4 Sulphanilic acid - 1-naphthylamine - Reagent
Red dye formed when NO2 is present
BaCl2  BaCO3, BaSO4 - Precipitated

Pb(NO3)2  PbCO3, PbSO4, PbS - Precipitated
Acidified KMnO4  decolourised by S2– and NO 2
29. 3 Complex is formed which gives a deep blue colour.

30. 4 Avoid using large amounts of copper sulphate and avoid too much stirring as it may produce
heat due to friction.
370

Chemistry (Study Package - XII)

Uploaded by

Copyright:

Available Formats

Chemistry (Study Package - XII)

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Chemistry (Study Package - XII)

Uploaded by

Copyright:

Available Formats

[Study Package - Chemistry - Class XII]

3. Chemical Kinetics ------------------------------------------------------------------------- 54

4. The d-and f-block Elements ------------------------------------------------------------ 86

5. Co-ordination Compounds ----------------------------------------------------------- 111

6. Haloalkanes and Haloarenes -------------------------------------------------------- 140

7. Alcohols, Phenols and Ethers ------------------------------------------------------- 174

8. Aldehydes and Ketones --------------------------------------------------------------- 205

9. Carboxylic acids ------------------------------------------------------------------------- 233

10. Organic Compounds containing Nitrogen -------------------------------------- 254

11. Biomolecules ------------------------------------------------------------------------------ 277

12. The p-Block elements ------------------------------------------------------------------ 299

13. Principles Related To Practical Chemistry -------------------------------------- 322

Mass of the component in solution

Mass of component in solution

Volume of the component in solution

VAPOUR PRESSURE OF LIQUID SOLUTIONS

Vapour Pressure of Liquid-Liquid Solutions

PA  PA0 x A and PB  PB0 x B

Ptotal  x A PA0  x B PB0

 PA0  (PB0  PA0 ) x B

(i) P = PA  PB  PA0 x A  PB0 x B , i.e., PA = PA0 x A and PB  PB0 x B .

(iv) Entropy change of mixing is always positive; ΔSmix = + ve .

Figure - 02 Vapour pressure-composition curves: i. positive deviation, ii. negative deviation

PA  x A PA0 and PB  x B PB0

(ii) P A > P A0 x A ; P B  P B0 x B  PA  PB  PA0 x A  PB0 x B .

(iii) Volume increases on mixing, Vmix  0 .

(iii) Volume decreases on mixing, Vmix  0 .

Components Weight Boiling points

Relative Lowering of Vapour Pressure

Lowering of vapour pressure = P0 – Ps

Elevation of Boiling Point

Figure - 03 Elevation of boiling point.

Tb  m or Tb  K b m or Tb  molality  K b

Substituting the value of m in equation, Tb  K b m

Depression of Freezing Point

Figure - 04 Depression of freezing point.

Tf  Tf  Tf or Tf  m or Tf  K f m

If m =1, then, Tf  Kf .

Determination of molecular mass of solute from depression of freezing point

Substituting the value of m in the equation, Tf  K f m

Boiling point Molal elevation Freezing point Molal depression

Semipermeable Membrane. A membrane that allows unrestricted movement of solvent molecules

When isotonic solutions are separated by a semipermeable membrane, no osmosis occurs.

4. Applications of osmotic pressure measurement.

Figure - 05 Reverse osmosis (desalination of sea water).

ABNORMAL COLLIGATIVE PROPERTIES

Dissociation of solute molecules : Electrolytes undergo ionisation or dissociation in ionising solvents to

Observed valueof colligative property Normal molecular mass

Tota l n umber of particles after association / dissociation

(iii) Osmotic pressure,   i n 2 RT / V

14. For an ideal solution, the correct option is

1)  mix G = 0 at constant T and P 2)  mix S = 0 at constant T and P

3)  mix V  0 at constant T and P 4)  mix H = 0 at constant T and P

1) Al2  SO4 3 2) AlCl3 3) Al  NO3 3 4) Al  OH 3

2. Which of the following statement(s) is/are correct?

11. Which of the following is not correct for an ideal solution?

1) Hmix  0 2) It obeys Raoult’s law

12. When HNO3 is added to water, the solution

1)  mix H  0,  mix V  0, PTotal  p 0A x A  p 0B x B