Stoichiometry & Redox Reaction

Amedeo Avogadro
Lorenzo Romano Amedeo Carlo Avogadro, (1776 - 1856) was an Italian savant chemist,
most noted for his contributions to the theory of molarity and molecular weight. As a
tribute to him, the number of atoms of one mole of a substance, 6.02 × 1023 is known as
Avogadro's number.
In honour of Avogadro's contributions to the theory of molarity and molecular weights,
the number of molecules in one mole was renamed Avogadro's number, NA. It is
approximately 6.0221415 × 1023.

Loschmidt first calculated the value of Avogadro's number, now called Avogadro's
constant, which is still sometimes referred to as the Loschmidt number in German-
language countries (Loschmidt constant now has another meaning). Avogadro's number is
commonly used to compute the results of chemical reactions. It allows chemists to
determine the exact amounts of substances produced in a given reaction.

Clausius, by his kinetic theory on gases, was able to give another confirmation of
Avogadro's law. Not long after, in his researches regarding dilute solutions (and the
consequent discovery of analogies between the behaviour of solutions and gases), J. H. van
't Hoff added his final consensus for the triumph of the Italian scientist, who since then has
been considered the founder of the atomic-molecular theory.

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1.1 The Concept of Atoms And Molecules
The Atoms
The smallest particle of an element that takes part in chemical reaction.
Dalton’s Atomic Theory
The main postulates of this atomic theory are
(i) Matter is discrete (i.e., discontinuous) and is made up of atoms. An atom is the
smallest (chemically) indivisible particle of an element, which can take part in a
chemical reaction.
(ii) Atoms of different elements have different properties and different weights.
(iii) Atoms cannot be created or destroyed. So a chemical reaction is nothing but a
rearrangement of atoms and the same number of atoms must be present before and
after the reaction.
(iv) A compound is formed by the union of atoms of one element with atoms of another in
a fixed ratio of small whole numbers (1 : 1, 1 : 2, 2 : 3 etc).
All the postulates of Dalton’s atomic theory have been proved to be incorrect.
An atom is divisible in the sense that it has a structure. Sub-atomic particle are known
as electron, proton and neutron.
The existence of isotopes for most elements show that atoms of the same element
need not have the same mass. The atomic weight of an element is, in fact, a mean of
the atomic masses of the different isotopes of the element.
Atomic Weight
An atom is so minute that it cannot be detected even with the most powerful
microscope, let alone placed on a balance pan and weighed. So there is no question of
determining the absolute weight of an atom. So chemists decided to determine the
relative masses of atoms (i.e., how many times one atom of an element is heavier than
another). Hydrogen atom was first selected as standard. i.e.
Weight of 1 atomof the element
Atomic weight of an element =
Weight of 1 atom of hydrogen
When we state that the atomic weight of chlorine is 35.5, we mean that an atom
of chlorine is 35.5 times heavier than an atom of hydrogen. It was later felt that the
standard for reference for atomic weight may be oxygen, the advantage being that the
atomic weights of most other elements became close to whole numbers.
Weight of 1 atom of the element
Atomic weight of an element =
1
 weight of 1 atom of oxygen
16

2
 The modern reference standard for atomic weights is carbon isotope of mass number
12.
Weight of 1 atom of the element
Atomic weight of an element =
1
 weigth of 1 atom of carbon  12
12
On this basis, atomic weight of oxygen 16 was changed to 15.9994.
Nowadays atomic weight is called relative atomic mass and denoted by amu
(atomic mass unit). The standard for atomic mass is C12.
(i) Atomic weight is not a weight but a number.
(ii) Atomic weight is not absolute but relative to the weight of the standard reference
element (C12).
(iii) Gram atomic weight is atomic weight expressed in grams, but it has a special
significance with reference to a mole.
Dulong and Petit measured the specific heats of a number of metals and found
that the product of the specific heat and the atomic weight is a constant, having an
approximate value of 6.4.
Specific heat (cal/g-deg)  atomic weight (g/g–atom) 6.4 (cal/deg.g.atom).
This correlation has been used to ‘correct’ the atomic weights of some elements
in the periodic table. Dulong and Petit’s law is applicable only to metals.
The Molecule
Avogadro (1811) suggested that the fundamental chemical unit is not an atom but a
molecule, which may be a cluster of atoms held together in some manner causing
them to exist as a unit. The term molecule means the smallest particle of an element
or a compound that can exist free and retain all its properties.
Consider a molecule of sulphur dioxide. It has been established that it contains
one atom of sulphur and two atoms of oxygen. This molecule can split up into atoms
of sulphur and oxygen. So the smallest particle of sulphur dioxide that can exist free
and retain all its properties is the molecule of sulphur dioxide.
The term molecule is also applied to describe the smallest particle of an element
which can exist free. Thus a hydrogen molecule is proved to contain two atoms;
when it is split up into atoms, there will be observed a change in properties. The
number of atoms of an element in a molecule of the element is called its atomicity.

Molecular Mass
Molecular mass of a substance is an additive property and can be calculated by adding
the atomic masses of all the atoms of different elements present in one molecule.

3
Methods of determining Molecular Masses
(a) Vapour density method
1 Mass of volatile substance
V. D. = × 22400
2 Volume of vapour of its chloride at STP
Molecular mass = 2 × V.D.
(b) Diffusion method
According to Graham’s law of diffusion, rate of diffusion of a gas is inversely
proportional to the square root of its molecular mass.
r1 M2
=
r2 M1

(c) Victor Meyer method

This method applies to volatile organic liquids. Suppose vapour of an organic liquid
having
mass W g occupies a volume of V mL at STP. Then its molecular mass is,
W
Mol. mass = × 22,400.
V
Avogadro Number (NA). The number of carbon atoms present in one gram-atom
(1 mole atom) of C–12 isotope is called Avogadro’s number. One gram-atom (12
grams) of C–12 contains 6.02 × 1023 atoms. Thus the numerical value of Avogadro’s
number (NA) is 6.02 × 1023 per mol. It should be noted that
1
1 a.m.u.= th of mass of a C12 atom
12

Avogadro Hypothesis
It states that equal volumes of gases at the same temperature and pressure contain
equal number of molecules. It means that 1 ml of hydrogen, oxygen, ammonia, or a
mixture of gases taken at the same temperature and pressure contains the same
number of molecules.

Application
(a) To prove that simple elementary gas molecules are diatomic
Consider the experimental result,
1 volume of hydrogen + 1 volume of chlorine 
 2 volumes of hydrogen chloride
at the same temperature and pressure
1 volume contains ‘n’ molecules.

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 Then n molecules of hydrogen + n molecules of chlorine 
 2n molecules of
hydrogen chloride.
Cancelling the common ‘n’, we have 1 molecule of hydrogen + 1 molecule of
chlorine  2 molecules of hydrogen chloride.
A molecule of hydrogen chloride should contain at least 1 atom of hydrogen and 1
atom of chlorine. Two molecules of hydrogen chloride should contain at least 2 atoms
of hydrogen and 2 atoms of chlorine and these should have come from 1 molecule of
hydrogen and 1 molecule of chlorine respectively. Thus Avogadro’s hypothesis
enables us to establish that hydrogen and chlorine molecules must contain at least 2
atoms (Measurement of the ratio of specific heats of these gases at constant pressure
and at constant volume, CP/CV = 1.4, establishes that these gases are diatomic).
(b) [To establish the relationship between molecular weight and vapour density of a
gas. The absolute density of gas is the weight of 1 litre (dm3) of the gas at S.T.P.
[Standard Temperature (0°C and Pressure (1 atmosphere)].
Density of the gas
The relative density or vapour density of gas =
Density of hydrogen
Weight of 1 litre of gas at STP
Vapour density of a gas =
Weight of 1 litre of hydrogen atSTP
Weight of a certain volume of the gas
=
Weight of the same volume of hydrogen at the same temperature and pressure
So the vapour density of a gas is defined as the ratio of the weight of a certain volume
of the gas to the weight of the same volume of hydrogen at the same temperature
and pressure.
 Vapour density (V.D.) of a gas
Weight of 'V' litres of the gas
=
Weight of 'V' litres of hydrogen at the same temperature and pressure
Let ‘V’ litres of the gas contains ‘n’ molecules.
Weight of 'n ' moleculesof the gas Weight of 1 molecule of the gas
V.D. of a gas = 
Weight of 'n ' molecules of hydrogen Weight of 1 molecule of hydrogen
Weight of 1 molecule of the gas 1 Weight of 1 molecule of the gas
V.D. of a gas =  
Weight of 2 atoms of hydrogen 2 Weight of 1 atom of hydrogen
1
V.D. of a gas =  Molecular weight of the gas
2
 Molecular weight of the gas = 2  Vapour density of the gas.
(c) The volume occupied by a gram molecular weight of any gas is called a molar
volume and it is 22.4 L at STP.

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1.2 Mole Concept
A mole of any substance is related to :
(a) mass of a substance
(b) number of particles
(c) volume of the gaseous substance

Mole-Particle Relationship
A mole is a collection of 6.023 × 1023 particles, ions, atoms etc.
i.e. (i) 6.023 × 1023 atoms of Na constitute one mole atom of Na.
(ii) 6.023 × 1023 molecules of oxygen constitutes 1 mole of oxygen molecules.
(iii) 6.023 × 1023 electrons constitute one mole of electrons.
Mole-Weight Relationship
One mole of every substance weighs equal to the gram atomic weight of the substance
or to the gram molecular weight of the substance.
e.g. (i) 1 mole of sodium weighs 23 g of Na.
(ii) 1 mole of CaCO3 weighs 100 g.
Mole-Volume Relationship
One mole of every gas occupies 22.4 lit. of volume at STP.
i.e. 1 mole of O2 occupies 22400 ml of volume at STP.
1 mole of He occupies 22400 ml of volume at STP.

ILLUSTATIONS
Illustration 1
Determine the number of moles of H2 in 0.224 litre of hydrogen gas at STP (assuming
ideal gas behaviour).
Solution
22.4 litres of H2 at STP contain 1 mole of H2.
0.224 litre of H2 at STP has = 0.01 mole
Illustration 2
What will be the number of moles in 13.5 g of SO2Cl2 ?
Solution
Molecular mass of SO2Cl2 = 32 + 32 + 71 = 135 g mol–1
Mass in gram 13.5
No. of moles = = = 0.1 mole
gram mol. wt. 135

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Illustration 3
What will be the number of moles of oxygen in one litre of air containing 21% oxygen by
volume
under standard conditions.
Solution
100 ml of air at STP contains 21 ml of O2
21
1000 ml of air at STP contains = × 1000 = 210 ml O2
100
Vol. in litres under STP conditions
 No. of moles =
22.4 litre
210
= = 0.009 mole.
22400
PRACTICE EXERCISE
1. Calculate the total number of electrons present in 1.6 g of methane. Molecular wt. of
methane = 16 a.m.u.
2. 0.24 gm of a volatile substance upon vaporisation gives 45 ml vapours at STP. What
will be the vapour density of the substance ?

Answers
1. 6.023  10 23
2. 59.

1.3 Concept of Limiting Reagent

In reactions involving more than one reactant, one has to identify first, of all the reactant,
which is completely consumed (limiting reagent), one can identify the limiting reagent as
follow
N 2  3H 2 
 2NH3
Initial mole 5 12 
If N2 is the limiting reactant moles of NH3 produced = 10. If H2 is the limiting
3
reactant moles of NH3 produced =  12  8 . The reactant producing the least number of
2
mole of the product is the limiting reactant, hence H2 is the limiting reactant.
The limiting reactant can also be ascertained by knowing the initial number of
equivalents or milli equivalents of each reactant. The reactant with least number of
equivalents or milli equivalents is the limiting reactant. The equivalent methods to identify
the limiting reactant used not require balancing of chemical equation.
1.4 Gravimetric Analysis
Calculation involving in mass – mass relationship
In general, the following steps are adopted in making necessary calculations

7
1. Write down balanced molecular equation for the chemical change
2. Write down the no of moles below the formula of each of the reactant and product
3. Write down the relative masses of the reactants and the products with the help of
formula below the respective formula. These shall be the theoretical amounts of
reactants and product.
4. By the applications of unitary method, mole concept or proportionality method, the
unknown factor or factors are determined.

Calculation involving percent yield

In general, when a reaction is carried out in the laboratory we do not obtain actually
the theoretical amount of the product. The amount of the product that is actually
obtained is called the actual yield. Knowing the actual yield and theoretical yield the
percentage yield can be calculated as
Actual yield
% yield =  100
Theoretical yield

Weight-Volume Relationship
2Mg(s)  O2 (g) 
 2MgO(s)
In the above reaction, one can find out the volume of O2 at STP required to react with 10
10
gm of Mg. The moles of Mg is . The moles of O2 required would be 1/2 the moles of
24
1 10
Mg. Therefore moles of O2   . Since 1 mole of gas (ideal) occupies 22.4 L at STP,
2 24
1 10 1 10
therefore  moles of O2 would occupy,   22.4 L = 4.67 L.
2 24 2 24

Volume-volume Relationship
Let us consider the reaction H2(g) + ½ O2(g)  H2O(l). We are given 10 L of H2 at a
given temperature and pressure. How many litres of O2 would react with hydrogen at
the same temperature and pressure?
From the ideal gas equation [PV = nRT] it is clear that the volume of an ideal
gas is directly proportional to its no. of moles. Therefore under the same conditions
VH2 n H2
of P and T,  . Since the molar ratio is 2 : 1 (H2 : O2),  the volume ratio
VO2 n O2

would also be 2 : 1. Therefore the volume of O2 required would be 5L. On the other
hand if we need to calculate the volume of O2 at a different T and P, then
PH2 VH2 n H2 TH2
PH2 VH2  n H2 R TH2 , PO2 VO2  n O2 RTO2 , and dividing we get  ,
PO2 VO2 n O2 TO2

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 PH2 VH2 n O2 TO2
 VO2   .
PO2 n H2 TH2

1.5 Concentration Units

There are several methods to express the concentration of solution. We are going to
describe some very important terms used to represent the concentration of solution.
(a) Percent by weight
(b) Percent by volume
(c) Percent by weight/volume
(d) Mole fraction
(e) Molarity
(f) Molality
(g) Normality
(h) ppm
Percent by Weight (w/w)
It is the weight of the solute as a per cent of the total weight of the solution. That is,
weight of solute
%by weight of solute   100
weight of solution
For example, if a solution of HCI contains 36 % HCI by weight, it has 36 g of HCI in 100
g of solution.
Percent by Volume (v/v)
volume of solute
% by volume =  100
volume of solution
For example, it we have 35% C2H5OH solution by volume means 25 ml C2H5OH is present
per 100 ml of the solution.
Percent by weight/volume (w/v)
weight of solution
%=  100
volume of solution
i.e.30% HCl solution, means 30 g of HCl is present per 100 ml of solution
Mole Fraction (X)
A simple solution is made of two substances; one is the solute and the other is solvent.
Mole fraction, X, of solute is defined as the ratio of the number of moles of solute and the
total number of moles of solute and solvent. Thus,
molesof solute
X solute 
 molesof solute  moles of solvent 
If n represents moles of solute and N number of moles of solvent,
n
X solute 
nN

9
Notice that mole fraction of solvent would be
N
X solvent 
nN
Mole fraction is unitless and  Xsolute  Xsolvent   1

Molarity (M)
In current practice, concentration is most often expressed as molarity. Molarity is defined
as the number of moles of solute per litre of solution.
moles of solute w / M w  1000
Molarity  or M  
volume in litres v /1000 MV
w = Mass of solute in grams
M = molecular weight of solute in gm/mol.
V = value of solution in ml.
It’s unit is mol/L.
Molality (m)
Molality of a solution is defined as the number of moles of solute per kilogram of solvent:
moles of solute
Molality 
mass of solvent in kilog rams
w
w  1000
or M M 
W MW
1000
where
w = mass of solute in grams
M = molecular wt of solute
W = mass of solvent in gram.
Normality (N)
Normality of a solution is defined as number of equivalents of solute per litre of the
solution:
w
Normality 
Number of gramequivalents of solute E  w  1000
or N  V
Volume of solution in litres VE
1000
w = mass of solute in gram
V = volume of solution in ml
E = equivalent wt of solute
ppm (parts per million)
It is the mass of solute in grams present per 10 6 grams of solution.

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  weight of solute 
  106  ppm
 weight of solution 
 volume of particular gas 
and also   106  ppm
 volume of gaseous mixture 

ILLUSTRATIONS
Illustration 1
A solution of NaCl 0.5% by wt. If the density of the solution is 0.997 g/ml, calculate the
molality, molarity, normality and mole fraction of the solute.
Solution
mass of NaCI
Number of moles of NaCI 
Molecular mass of NaCI
0.5
  0.0085
58.5
By definition,
No. of moles of solute  1000 0.00854  1000
Molality  =  0.086m
Mass of solvent ingrams 99.5
Mass of solution in grams
Volume of the solution 
Density in gm per ml
100
  100.3
0.997
Nimber of moles of soloute
Now Molarity 
Volume of solution in litres
0.00854  1000
=  0.08514M
100.3
Number of gram equivalents of solute
and Normality 
volume of solution in litres
0.5  1000

100.3  58.5
= 0.0852
To calculate mole fraction of the solute
99.5
No. of moles of water in 99.5g = = 5.5277
18
0.5
Moles of NaCl =  8.547  10 3
58.5
n NaCl
X NaCl 
n NaCl  nH2O

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 8.547  103
=  1.5433  10 3 M
5.5277  8.547  10 3
XH2O  1  XNaCl  0.9984

1.6 Law of Equivalents

Before heading for the law of equivalents, let us first discuss certain definitions.
Molarity (M)
It is defined as the number of moles of solute present in one litre of solution.
number of molesof solute
Molarity (M) =
Volume of solution (in litres)
Let the weight of solute be w g, molar mass of solute be M1g./mol and the volume of
weight of solute w
solution be V litre. Number of moles of solute = 
Atomic or molar mass of solute M1
w 1
 M 
M1 V(in litres)
w
 Number of moles of solute =  M  V (in litres)
M1
Normality (N)
It is defined as the number of moles of equivalents of a solute present in one litre of
solution. Equivalent is also the term used for amount of substance like mole with the
different that one equivalent of a substance in different reactions may be different as
well as the one equivalent of each substance is also different.
number of equivalents of solute
Normality (N) =
Volume of solution (in litres)
Let the weight of solute be w g, equivalent mass of solute be E g/eqv. And the
volume of solution be V litre.
weight of solute w
Number of equivalents of solute = 
Equivalent mass of solute E
w 1
 N 
E V(in litres)

 Number of equivalents of solute = N  V (in litre)

Equivalent Mass
Atomic or molecular mass M1
Equivalent mass = 
'n ' factor n
w w wn
 Number of equivalents of solute =  
E M1 / n M1

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  Number of equivalents of solute = n  number of moles of solute
w 1 w 1
Also, N     n
M1 / n v (in litre) M1 V (in litre)

N=Mn
 Normality of solution = n  molarity of solution.

ILLUSTRATIONS
Illustration 4
1.60 g of a metal were dissolved in HNO3 to prepare its nitrate. The nitrate was strongly
heated to give 2 g oxide. Calculate equivalent weight of metal.
Solution
HNO 
M 3
 M(NO3 )n   M2 On
where n is valency of metal
 neq. of metal = neq. of nitrate = neq. of metal oxide = neq. of oxygen
wmetal w oxygen
=
Emetal Eoxygen
1.60 2  1.60
=
E 8
E = 32
Illustration 5
1.0 g of metal nitrate gave 0.86 g of metal sulphate. Calculate the equivalent weight of
metal.
M(NO3)n  M2(SO4)n
 neq. of M(NO3)n = neq. of M2(SO4)n
1
= 0.86
EM  62 E  48
1 0.86
=
E  62 E  48
 E = 38
Illustration 6
1.5276 g of CdCl2 was found to contain 0.9367 g of Cd. Calculate atomic weight of Cd.
Weight of Cd = 0.9367 g
 Weight of Cl = 1.5276 – 0.9367 = 0.5909 g
For CdCl2; neq. of cadmium = neq. of chlorine
0.9367 0.5909
=
E 35.5
 E = 56.275
 Atomic weight = Eq. wt. × Valency
= 56.275 × 2 = 112.55.

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 PRACTICE EXERCISE
3. 1.8 g of an element displaces 2.04 g copper from CuSO4 solution. If equivalent weight
of Cu = 31.7, what is equivalent weight of iron ?

4. 2 g of a metal in H2SO4 gives 4.51 g of the metal sulphate. The specific heat of metal
is 0.057 cal/g. Calculate the valency and atomic weight of metal.

5. A hydrated sulphate of metal contained 8.1% metal and 43.2% SO4–2 by weight. The
specific heat of metal is 0.24 cal/g. What is hydrated sulphate ?

Answers
3. 27.97 4. 114.72 5. M2(SO4)3.18H2O

Dilution Effect
When a solution is diluted, the moles and equivalents of solute donot change but
molarity and normality changes while on taking out a small volume of solution from a
larger volume, the molarity and normality of solution do not change but moles and
equivalents change proportionately.
In stoichiometry, the biggest problem is that for solving a problem we need to
know a balanced chemical reaction. Since the number of chemical reactions are too
many, it is not possible to remember all those chemical reactions. So, there is need to
develop an approach which does not require the use of balanced chemical reaction.
This approach makes use of a law called law of equivalence. The law of equivalence
provide us the molar ratio of reactants and products without knowing the complete
balanced reaction, which is as good as having a balanced chemical reaction. The
molar ratio of reactants and products can be known by knowing the n-factor of
relevant species.
According to the law of equivalence, whenever two substances react, the
equivalents of one will be equal to the equivalents of other and the equivalents of any
product will also be equal to that of the reactant.
Let us suppose we have a reaction, A + B  C + D. In this reaction, the
number of moles of electrons lost by 1 mole of A are x and the number of mole of
electrons gained by 1 mole of B are y. Since, the number of mole of electrons lost and
gained are not same, the molar ratio in which A & B react cannot be 1 : 1. Thus, if we
take y moles of A, then the total moles of electrons lost by y moles of A would be (x
 y). Similarly, if x moles of B are taken, then the total mole of electrons gained by x
moles of B would be (y  x). Thus, the number of electrons lost by A and number of
electrons gained by B becomes equal. For reactant A, its n-factor is x and the number
of moles used are y. So,

14
 The equivalents of A reacting = moles of A reacting  n-factor of A = y  x.
Similarly, for reactant B, its n-factor is y and the number of moles used are x. So,
The equivalents of B reacting = moles of B reacting  n-factor of B
=xy
Thus, the equivalents of A reacting would be equal to the equivalents of B
reacting. Thus, the balancing coefficients of the reactant would be as
yA  xB 
 C D
(n  factor  x ) (n  factor  y)

The n-factor of A & B are in the ratio of x : y, and their molar ratio is y : x.
Thus, molar ratio is inverse of the n-factor ratio.
In general, whenever two substances react with their n-factors in the ratio of a :
b, then their molar ratio in a balanced chemical reaction would be b : a.
To get the equivalents of a substance, its n-factor is to be known. Let the weight
of the substance used in the reaction be w g.
W w w
Then, equivalents of substance reacted would be or   n (where E
E M1 / n M1
and M1 are the equivalent mass and molar mass of the substance) Thus, in order to
calculate the equivalents of a substance, knowledge of n-factor is a must.

ILLUSTRATIONS
Illustration 7
Calculate normality and molarity of the following?
(a) 0.74 g of Ca(OH)2 in 5 ml of solution.
(b) 3.65 g of HCl in 200 ml of solution.
(c) 1/10 moles of H2SO4 in 500 ml of solution.
Solution
0.74  w
(a) Eq. of Ca(OH)2 =  Eq.  
74 / 2  E

Volume of solution = 5/1000 litre

0.74  1000  2
 N=
74  5
N 4
N= 4  M  2
Total charge on anion or cation 2
3.65
(b) Eq. of HCl =
36.5

and Volume of solution = 200 / 1000 litre

15
 3.65  1000
 N=  0.5
36.5  200
N 0.5
and M   0.5
Valency 1
1
(c) Eq. of H2SO4 = × 2 ( Meq. = N × V in ml)
10

= 0.2 Molar H2SO4

= 0.4 Normal H2SO4.
Illustration 8
What volume of water is required to make 0.20 N solution from 1600 ml of 0.2050 N
solution.
Solution
Meq. of conc. solution = 1600 × 0.2050 = 328
Let after dilution volume becomes V ml
Meq. of dil. solution = 0.20 × V
 328 = 0.20 × V
 V = 1640 ml
Thus volume of water used to prepare 1640 ml of 0.20N solution = 1640 – 1600 = 40ml
Illustration 9
What is the normality and nature of a mixture obtained by mixing 0.62 g of Na2CO3 .H2O
to
100 ml of 0.1 N H2SO4 ?
Solution
0.62
neq. of =  1000 = 0.01
62
100
neq. of H2SO4=  0.1 = 0.01
1000
Na 2 CO 3  H 2 SO 4  Na 2 SO 4 H 2 O  CO 2 
n eq. added 0.01 0.01 0 0 0
Meq. left 0 0 0.01 0.01 0.01

0.01
 N Na 2SO4  1000  0.1
100
Solution becomes neutral since both acid and base are used up and Na2SO4 does not show
hydrolysis.

16
Illustration 10
How much AgCl will be formed by adding 200 ml of 5N HCl to a solution containing
1.7 g AgNO3 ?
Solution
AgNO3  HCl  AgCl  HNO3
1.7
n eq. initially 200  5 0 0
170
102  1 eq 0 0

n eq. after reaction 0 1  0.01 .01 .01

 neq. of AgCl formed = 0.01

 Amount of AgCl formed = 0.01 × 143.5 = 1.435 g
 wAgCl = 1.435 g.

Illustration 11
Find the weight of H2SO4 in 1200 ml of a solution of 0.2N strength.
Solution
0.2  1200
neq. of H2SO4 = = 0.24 ( Meq. = N × V in ml)
1000
amount of H2SO4 = neq. × neq. wt. of H2SO4
= 0.24 × 49 = 11.76 g
w = 11.76g

PRACTICE EXERCISE

6. The density of 3M solution of Na2S2O3 is 1.25g ml–1. Calculate

(a) the % by weights of Na2 S2 O3
(b) mole fraction of Na2 S2 O3

(c) the molalities of Na+ and S2 O32 ions.

7. A sample of H2SO4 (density 1.787g ml–1) is labelled as 86% by weight. What is

molarityof acid ? What volume of acid has to be used to make 1 litre of 0.2M H2SO4?
8. What weight of AgCl will be precipitated when a solution containing 4.77 g NaCl is
added to a solution of 4.77 g of AgNO3 ?
9. How much BaCl2 would be needed to make 250 ml of a solution having same
concentration of Cl– as the one containing 3.78 g of NaCl per 100 ml ?

17
 Answers
6. (a) 37.92 (b) 0.065 (c) 3.865 7. 12.75 ml 8. 4.87 g 9. 16.80

1.7 ‘n’ Factors

In Non Redox Change
(i) n-factor for element: Valency of the element
(ii) For Acids: Acids will be treated as species which furnish H+ ions when dissolved in a
solvent. The n factor of an acid is the no. of acidic H+ ions that a molecule of the acid
would give when dissolved in a solvent (Basicity).
e.g. for HCl (n = 1), HNO3 (n = 1), H2SO4 (n = 2), H3PO4 (n = 3) and H3PO3 (n = 2)
(iii) For Bases: Bases will be treated as species which furnish OH– ions when dissolved
in a solvent. The n factor of a base is the no. of OH– ions that a molecule of the base
would give when dissolved in a solvent (Acidity).
e.g. NaOH (n = 1), Ba(OH)2 (n = 2), al(OH)3 (n = 3), etc.
(iv) For Salts: A salts reacting such that no atom of the salt undergoes any change in
oxidation state. e.g. 2AgNO3 + MgCl2  Mg(NO3)2 + 2AgCl
In this reaction it can be seen that the oxidation state of Ag, N, O, Mg and Cl remains
the same even in the product. The n factor for such a salt is the total chare on cation or
anion.

ILLUSTRATIONS
Illustration 12
Calculate the n-factor in the following chemical changes.

(i) KMnO4 
H
 Mn 2 (ii) KMnO4 
H2O
 Mn 4
 
(iii) KMnO4 
OH
 Mn 6 (iv) K2Cr2O7 
H
Cr3

(v) C2O42 
 CO2 (vi) FeSO4 ¾ Fe2O3
(vii) Fe2O3 ¾ FeSO4
Solution
(i) In this reaction, KMnO4 which is an oxidizing agent, itself gets reduced to Mn2+
under acidic conditions.
n = |1  (+ 7) – 1  (+ 2)| = 5
(ii) In this reaction, KMnO4 gets reduced to Mn4+ under neutral or slightly (weakly basic
conditions.
n = |1  (+ 7) – 1  (+ 4)| = 3

18
(iii) Here KMnO4 gets reduced to Mn6+ under basic conditions.
n = |1  (+ 7) – 1  (+ 6) = 1
(iv) Here K2Cr2O7 which acts as an oxidizing agent gets reduced to Cr+3 under acidic
conditions. (It does not react under basic conditions).
n = +1  (+7) – 1  (+ 6)| = 1
(v) C2O42– (oxalate ion) gets oxidized to CO2 when it is reacted with an oxidizing agent.
N = |2  (+ 3) – 2  ( 4) = –2
(vi) Ferrous ions get oxidized to ferric ions
n = |1  (+ 2) –1  (+ 3) = 1
(vii) Here ferric ions are getting reduced to ferrous ions
N = |2  (+ 3) – 2  (+ 2)| = 2
Illustration 13
Predict the molar ratio in which the following two substances would react if they are
assumed to be salts Ba3(PO4)2 and AlCl3
Solution
N factor of Ba3 (PO4) = 3  (+2) = 6 = n1
While n factor of AlCl3 = 1  (+ 3) = 3 = n2
n1 6

n2 3
n1 x
If 
n2 y
y
Molar ratio = (inverse of equivalent ratio)
x
 molar ratio in which Ba3 (PO4) and AlCl3 will react = 3 : 6 = 1 : 2.
Illustration 14
Find the n-factor for the reactants in each of the following cases
(i) I–  I2 (ii) I2  I–
(iii) S2O32–  S4O62– (iv) IO3–  Cu2+ + SO2
Solution
(i) n factor = 1  |0 – (–1)| = 1 (ii) n factor = 2  |–1 – 0| = 2
(iii) n factor = 2  |2.5 – 2| = 1 (iv) n factor = 1  |1 – 5| = 4

19
Illustration 15
Calculate the n-factor in the following redox change
 Fe3  CO2
FeC2O4 
Solution
Here Fe2+ is getting oxidized to Fe3+ and C3+ is getting oxidized to C4+. The n factor w.r.t.
Fe is +1 and w.r.t. C2O42– is 2 (as calculated earlier). Therefore total n factor is 3.
In Redox Change
For oxidizing agent or reducing agent n-factor is the change in oxidation number per
mole of the substance.
(i) If we have a salt which react in a fashion that atoms of one of the element are getting
oxidized and the atoms of another element are getting reduced and no other element
on the reactant side is getting oxidized or reduced, than the n–factor of such a salt can
be calculated either by taking the total number of moles of electrons lost or total
number of mole of electrons gained by one mole of the salt.
For example, decomposition reaction of KClO 3 is represented as
 5 2 1 0
KClO 3 
 KCl  O 2

In this reaction, O2– is getting oxidized to O2 and Cl+5 is getting reduced to Cl–1. In
each case, 6 mole of electrons are exchanged whether we consider oxidation or
reduction.
n-factor of KClO3 considering oxidation = |3 (–2) – 3 (0)| = 6
or n–factor of KClO3 considering reduction = |1  (+5) –1  (–1)| = 6.
(ii) Disproportionation reactions in which moles of compound getting oxidsed and
reduced are not same i.e. moles of oxidizing agent and reducing agent are not same.
For example,
6Br2 + 12 OH¯ 
 10 Br¯ + 2BrO3 + 6H2O
In this reaction, the mole of electrons lost by the oxidation of some of the moles of
Br3 are same as the number of mole of electrons gained by the reduction of rest of the
moles of Br3. Of the 6 moles of Br2 used, one mole is getting oxidized, loosing 10
electrons (as reducing agent) and 5 moles of Br2 are getting reduced and accepts 10
moles of electrons (as oxidizing agent).

20
 Br2 2Br+5 + 10e¯

5Br2 + 10 e¯ 10 Br¯

Br2 + 5Br 2 10 Br¯ + 2Br +5

Thus, n-factor of Br2 acting as oxidizing agent is 2 and that Br2 acting as reducing
agent has n-factor 10.
Or when the reaction is written as
 10Br  2Br5
6Br2 

where, Br2 is not distinguished as how much of it functions as oxidizing agent and
how much as reducing agent, then for calculating n-factor of compound in such
reactions, first find the total number of mole of electrons exchanged (lost or gained)
using the balanced equation and divide it with the number of mole of Br2 involved in
the reaction to get the number of mole of electrons exchanged by one mole of Br 2.
In the overall reaction, the number of mole of electrons exchanged (lost or
gained) is 10 and the moles of Br2 used in the reaction are 6. Thus, each mole of Br2
has exchanged 10/6 or 5/3 mole of electrons. Therefore, the n-factor of Br2 when the
reaction is written without segregating oxidizing and reducing agent is 5/3.
 10Br  2Br 5
6Br2 
(n  5/ 3) (n 1) (n  5)

1.8 Application of The Law of Equivalence

Simple titration
In this, we can find the concentration of a substance with the help of the concentration
of another substance which can react with it.
For example: Let there be a solution of a substance A of unknown concentration. We
are given another substance B whose concentration is known (N1). We take a certain
known volume of A in a flask (V2) and then we add B to A slowly till all the A is
consumed by B. (This can be known with the help of indicators). Let us assume that
the volume of B consumed is V1. According to the law of equivalents, the number of
gm equivalents of A is equal to the number of gm equivalents of B.
 N1V1 = N2V2, where N2 is the concentraton of a.
From this we can calculate the value of N2.
Acid Base titration
In this type of titration, the concentration of an acid in a solution is estimated by
adding solution of standard base and vice versa. The equivalence point is detected by

21
 adding a few drops of a suitable indicator to the solution whose concentration is to be
estimated. An acid-base indicator gives different colours with acids and bases. The
choice of indicator in a particular titration depends on the pH-range of the indicator
and the pH change near the equivalence point. For example.
(i) Strong Acid-Strong Base Titration
In the titration of HCl Vs NaOH, the equivalence point lies in the pH-range of 4–10.
Thus, methyl red (pH-range 4.2 to 6.3), methyl orange (pH-range 3.1 to 4.4) and
phenolphthalein (pH-range 8.3 – 10) are suitable indicators of such titrations.
(ii) Weak Acid–Strong Base Titration
In the titration of CH3COOH and NaOH, the equivalence point lies between 7.5 and
10. Thus, phenolphthalein is the suitable indicator.
(iii) Weak Base-Strong Acid Titration
In the titration of NH4OH and HCl, the equivalence point lies in the pH range of 4 to
6.5. Thus, methyl orange and methyl red are suitable indicators.
(iv) Weak Acid-Weak Base Titration
In the titration of CH3COOH and NH4OH, the equivalence point lies between 6.5 and
7.5 and the pH change is not sharp at the equivalence point. Thus, no simple indicator
can be employed to detect the equivalence point.
Iodometric and Iodimetric titration
The reduction of free iodine to iodide ions and oxidation of iodide ions to free iodine
occurs in these titration’s.
I2  2e 
 2I (reduction)
2I 
 I2  2e (oxidation)
These are divided into two types
(i) Iodometric titration: In iodometric titrations, an oxidizing agent in allowed to react
in neutral medium or in acidic medium with excess of potassium iodide to liberate
free iodine.
KI + oxidizing agent  I2
Free iodine is titrated against a standard reducing agent usually with sodium
thiosulphate Halogen, dichroamtes, cupric ion, peroxides, etc can be estimated by this
method.
I2 + 2Na2S2O3  2NaI + Na2S4O6
2CuSO4 + 4KI  Cu2I2 + 2K2SO4 + I2
K2Cr2O7 + 6KI + 7H2SO4  Cr2(SO4)3 + 4K2SO4 + 7H2O + 3I2

22
(ii) Iodimetric titration: These are the titrations in which free iodine is used as it is
difficult to prepare the solution of iodine (volatile and less soluble in water) it is
dissolved in KI solution.
KI + I2  KI3 (Potassium triiodide)
This solution is first standardizes before use with the standard solution of I2 substance
such as sulphite, thiosulphate, arsenite etc. are estimated.
The iodimetric and iodometric titrations, starch solution is used as indicator. Starch
solution gives blue or violet colour with iodine. At the end point the blue or violet
colour disappears when iodine is completely changed to iodide.
Back titration
Back titration is used to calculate % purity of a sample. Let us assume that we are
given an impure solid substance C weighing w gms and we are asked to calculate the
percentage of pure C in the sample. We will assume that the impurities are inert. We
are provided with two solutions A and B, where the concentration of B is known (N1)
and that of A is not known. This type of titration will work only if the following
conditions are satisfied A, B and C should be such compounds that A and B can react
with each other, A and C should not react with B.
Now we take a certain volume of A in a flask (the A taken should be such that
the gm equivalents of A taken should be  gm equivalents of C in the sample. (This
can be done by taking A in excess). Now we perform a simple titration using B. Let
us assume that the volume of B used is V1. In another beaker, we again take the
solution of A in the same volume as taken earlier. Now, C is added to this and after
the reaction is complete, the solution is being titrated with B. Let us assume that the
volume of B used up is V2.
Gram equivalents of B used in the first titration = N1V1
 gm. Equivalents fo A inititally = N1V1
gm. Equivalents of B used in the second titration is N1V1
 gm. Equivalents of A left in excess after reacting with C = N1V2
gm. Equivalents of A that reacted with C = N1V1 – N1V2
gm. Equivalents of pure C = N1V1 – N1V2.
N1V1  N1V2
If the n factor of C is x, then the moles of pure C =
x
N1V1  N1V2
 the weight of C =  Molecular weight of C.
x
N1V1  N1V2 Molecular wt. of C
 percentage of C =  100 .
x w

23
 Double titration
The method involves two indicator (indicators are substance that change their colour
when a reaction is complete) phenolphthalein and methyl orange. This is a titration of
specific compounds. Let us consider a solid mixture of NaOH, Na2CO3 and inert
impurities weighing w g. You are asked to find out the % composition of mixture.
You are also given a reagent that can react with the sample, say, HCl along with its
concentration (M1).
We first dissolve the mixture in water to make a solution and then we add two
indicators in it, namely phenolphthalein and methyl orange. Now, we titrate this
solution with HCl.
NaOH is a strong base while Na2CO3 is a weak base. So it is safe to assume that
NaOH reacts with HCl first, completely and only then does Na2CO3 react.
NaOH + HCl  NaCl + H2O
Once NaOH has reacted, it is the turn of Na2CO3 to react. It reacts with HCl in two
steps.
Na2CO3 + HCl  NaHCO3 + NaCl and then,
NaHCO3 + HCl  NaCl + CO2 + H2O
As can be seen, when we go on adding more and more of HCl the pH of the
solution keeps on falling. When Na2CO3 is converted to NaHCO3, completely, the
solution is weakly basic due to the presence of NaHCO3 (which is a weaker base as
compared to Na2CO3). It this instant phenolphthalein changes colour since it requires
this weakly basic solution to change its colour. Therefore, remember that
phenolphthalein changes colour only when the weakly basic NaHCO3 is present. As
we keep adding HCl, the pH again falls and when also the NaHCO3 reacts to form
NaCl, CO2 and H2O the solution becomes weakly acidic due to the presence of the
weak acid H2CO3(CO2 + H2O). At this instance methyl orange changes colour since it
requires this weakly acidic solution to do so. Therefore, remember methyl orange
changes colour only when H2CO3 is present.
Now, let us assume that the volume of HCl used up for the first and the second
reaction.
i.e., NaOH + HCl  NaCl + H2O and Na2CO3 + HCl  NaHCO3 + NaCl
be V1 (this is the volume of HCl from the beginning of the titration up to the point
when phenolphthalein changes colour). Let the volume of HCl required for the last
reaction, i.e., NaHCO3 + HCl  NaCl + CO2 + H2O be V2 (this is the volume of HCl
from the point where phenolphthalein had changed colour upto the point when methyl
orange changes (colour). Then,

24
 moles of HCl used for reacting with NaHCO3 = moles of NaHCO3 reacted =
M1V2
moles of NaHCO3 produced by the Na2CO3 = M1V2
moles of Na2CO3 that gave M1V2 moles of NaHCO3 = M1V2
Mass of Na2CO3 = M1V2  106
M1V2 106
% Na2CO3 = 100
w
moles of HCl used for the first two reactions = M1V1
moles of Na2CO3 = M1V2
moles of HCl used for reacting with Na2CO3 = M1V2
moles of HCl used for reacting with only NaOH = M1V1 – M1V2
 moles of NaOH = M1V1 – M1V2
Mass of NaOH = (M1V1 – M1V2)  40
(M1V1  M1V2 )  40
% NaOH = 100
w

ILLUSTRATIONS
Illustration 16
50 mL of a solution, containing 1 g each of Na2CO3, NaHCO3 and NaOH, was titrated with
1(N) HCl. What will be titre reading if
(a) only phenolphthalein is used as indicator
(b) only methyl orange is used as indicator from the very beginning?
(c) methyl orange is added after the first end point with phenolphthalein?
Solution
(a) The titration reactions in this case are
Na2CO3 + HCl  NaHCO3 + NaCl
and NaOH + HCl  NaCl + H2O
Thus, we have
m.e. of Na2CO3 + m.e. of NaOH = m.e. of v1 mL (say) of 1(N) HCl
1 1
 1000   1000 = 1  v1 ;  v1 = 34.4 mL.
106 40

(b) The reactions in this case are,

Na2CO3 + HCl  NaHCO3 + NaCl
NaHCO3  HCl  NaCl  H2 O  CO2
(produced)

25
 NaHCO3  HCl  NaCl  H2 O  CO 2
(originally present)

and NaOH + HCl  NaCl + H2O

Thus, we have,
m.e. of Na 2 CO3  m.e. of NaHCO 3  m.e. of NaHCO 3  m.e. of NaOH
(produced) (originally present)

= m.e. of v2 mL (say) of N HCl

1 1 1 1
 1000   1000   1000   1000  1 v 2
106 106 84 40

 v2 = 55.8 mL.
(c) The reaction in this case are
NaHCO3 (produced) + HCl  NaCl + H2O + CO2
and NaHCO3 (originally present) + HCl  NaCl + H2O + CO2
Thus we have,
m.e. of NaH2 CO3  m.e. of NaHCO3  m.e. of v 3 mL (say) of 1(N) HCl
(produced) (originally present)

or m.e. of Na2 CO3 + m.e. of NaHCO3 = m.e. of v3 mL (say) of 1(N) HCl

1 1
 1000   1000  1  v 3
106 84

 v3 = 21.3 mL.
PRACTICE EXERCISE

10. A solution contained Na2CO3 and NaHCO3. 25 mL of this solution required 5 mL of

0.1 N HCl for titration with phenolphthalein as indicator. The titration was repeated
with the same volume of the solution but with methyl orange. 12.5 mL of 0.1 N HCl
was required this time. Calculate the amount of Na2CO3 and NaHCO3 in the solution.

Answers
10. .053 g, .021 g

1.9 Volume of Strength of H2O2

x volume of H2O2 means x litre of O2 is liberated by 1 litre of H2O2 on decomposition at
STP
2H2O2 
 2H2O  O2
68 gm 22.4 lit

22.4 lit (at STP) of O2 is given by 68 gm of H2O2

68x 17x
x litre of O2 is released from gm of H2O2 =
22.4 5.6

26
 68x 17x
 x lit of O2 is given by =  (strength)
22.4 5.6
17x
Strength, S=
5.6
S 17x x
Normality =   [x = N  5.6]
E 5.6  34 / 2 5.6
1 x
Molarity = Normality = .
2 11.2

1.10 Strength of Oleum

Oleum means mixture of conc. H2SO4 and SO3
Thus, Oleum = x H2SO4 + y SO3
(x H2SO4 + y SO3) + y H2O  (x + y) H2SO4
Strength of oleum is expressed in terms of percentage which is equal to weight of
H2SO4 obtained when water is added to 100 gms of oleum.
e.g. 109% oleum means
100 gm oleum + water  109 gm H2SO4
SO3 + H2O 
 H2SO4
9
Moles of H2O added = = Moles of SO3 present in oleum sample.
18
9
Mass of SO3 in oleum =  80 = 40 g
18
Thus, oleum sample contained 40% SO3 and 60% H2SO4.

1.11 Oxidation and Reduction

Oxidation is
(i) the gain of oxygen
(ii) the loss of hydrogen
(iii) the loss of electrons (de-electronation)
(iv) the increase of O.N.
Reduction is
(i) the loss of oxygen
(ii) the gain of hydrogen
(iii) the gain of electron
(iv) the decrease in O.N.
Fe  Fe2  2e

O.N.  0 2

27
  Fe loses electrons
 There is increase in O.N.
 Hence Fe is said to be oxidized
 It is a source of electron hence it can act as a reducing agent (R.A.)
 Any species that can be oxidized is a reducing agent (R.A.)
 Cu 2   2e 
O.N. 2
 Cu
0

 Cu2+ gains electron

 There is decrease in O.N.
 Hence Cu2+ is said be reduced.
 Since it can gain electrons, hence it can act as an oxidizing agent (O.A.)
 Any species that can be reduced is an oxidizing agent (O.A.), or oxidant. Above
examples represent half reactions.
A complete reaction showing oxidation and reduction together is called a Redox reaction.
Fe + Cu2+ Cu + Fe2+

R
O

Now that you are clear on what is oxidation – reduction, we are now in the right position to
know how to balance a redox (oxidation – reduction) reaction. This is important because
many of the problems of stoichiometry would be based on such redox eractions.

Oxidation State/Oxidation Number

There are several chemical reactions in which oxidation – reduction takes place.
Oxidation refers to a reaction in which electrons are removed from an atom and
reduction refers to a reaction in which electrons are added to an atom. To describe
these changes, the concept of oxidation state becomes necessary. For ionic species,
the charge on each ion is said to be the oxidation state for that atom. For example in
NaCl, Na exists as Na+ and Cl exists as Cl . Therefore the oxidation state of Na in
NaCl is +1 and that of Cl is –1. But in covalent molecules, the charge on an atom
would be so small that sometimes it becomes impossible to calculate the exact charge
on each atom of a molecule. Therefore, the Oxidation State (O.S.) or Oxidation
Number (O.N.) is defined as the charge, an atom would have in a molecule if all the
bonds associated with this atom in the molecule are considered to be completely
ionic. For example in H2O there are two O–H bonds. If we assume both the O–H

28
 bonds to be completely ionic, then each H would possess a charge of + 1, while O
possess a charge of –2. This is because oxygen is more electronegative than
hydrogen. On the other hand, in H2O2 there are two OH bonds and one O–H bond (H–
O–O–H). Considering each O–H bond to be ionic both the oxygen atoms acquire a
charge of –1 and both the H, +1. This is because O – O bond can not be assumed to
be ionic as both the atoms have the same electronegativity.
To calculate the oxidation state of an element in a molecule you need not always
know the structure of the molecule. There are certain set of rules used to assign
oxidation states in polyatomic molecules.
(i) The O.S. of all elements (in any allotropic form) is zero.
(ii) O.S. of oxygen is –2 in all its compounds except peroxides like H2O2 and Na2O2
where it is
–1 and superoxides like KO2 where it is –1/2. In OF2 and O2F2, oxygeneous +2, +1
respectively.
(iii) O.S. of hydrogen is +1 in all of its compounds except those with the metals where it is
–1.
(iv) O.S. of all alkali metals is +1 and alkaline earth metals is +2 in all their compounds.
(v) O.S. of all the halogens is –1 in all their compounds except where they are combined
with an element of higher electronegativity. Since fluorine is the most electronegative
of all elements, its O.S. is always –1.

ILLUSTRATIONS
Illustration 17
Calculate the O.S. of the atoms in the following species:
(i) In ClO¯ (ii) NO2¯ (iii) NO3¯ (iv) CCl4 (v) K2CrO4 (vi) KMnO4
Solution
(i) In ClO¯, the net charge on the species is –1 and therefore the sum of the oxidation
states of Cl and O must be equal to –1. Oxygen will have an O.S. of –2 and if the O.S.
of Cl is assumed to be ‘x’ then x – 2 should be equal to –1.
 x is + 1
(ii) NO2¯ : (2  –2) + x = –1 (where ‘x’ is O.S. of N)
x=+3
(iii) NO3¯: : x + (3  –2) = –1 (where ‘x’ is O.s. of N)
x+ 5

29
(iv) In CCl4, Cl has an O.S. of –1
 x + 4  –1 = 0
 x = + 4 (where ‘x’ is O.S. of C)
(v) K2CrO4: K has O.S. of + 1 and O has O.S. of –2 and let Cr has O.S. ‘x’ then,
2  + 1 + x + 4  –2 = 0
x=+6
(vi) KMnO4 : + 1 + x + (4  –2) = 0
 x = + 7 (where x is O.S. of Mn).

Balancing Redox Equations

Some examples of redox reactions are
Sn2+ + 2Hg2+ Hg22+ + Sn4+

(a) R
O

MnO4¯ + 5Fe2+ + 8H+ 5Fe3+ + Mn2+ + 4H2O

(b) O
R

Cr2O72+ + 6Fe2+ + 14H+ 6Fe3+ + 2Cr3+ + 7H2O

(c) O
R

3Cu + 2NO3¯ + 8H+ 2NO + 3Cu2+ + 4H2O

(d) R
O

If one of the half reactions does not take place, other half will also not take place. We
can say oxidation and reduction go side by side.
3Cl2 + 6OH¯ 5Cl¯ + ClO3¯ + 3H2O
O.N. = 0 –1 +5

In this we find the Cl2 has been oxidized as well as reduced. Such type of redox
reaction is called Disproportionation reaction.

30
 Examples are
Disproportionates
2Cu+ Cu + Cu2+

R
O

2HCHO + OH¯ CH3OH + HCOO¯

R
O

4ClO3¯ 3ClO4¯ + Cl¯

O
R

3MnO42- + 2H2O MnO2 + 2MnO4- + 4OH-

R
O

How to Balance a Redox Reaction

Ion Electron Method
This method involves the following steps
(i) Divide the complete equation into two half reactions, one representing oxidation and
the other reduction.
(ii) Balance the atoms in each half reaction separately according to the following steps
(a) First of all balance the atoms other than H and O.
(b) In a reaction taking place in acidic or neutral medium, oxygen atoms are
balanced by adding molecules of water to the side deficient in oxygen atoms
while hydrogen atoms are balanced by adding H+ ions to the other side deficient
in hydrogen atoms. On the other hand, in alkaline medium (OH¯), for every
excess of oxygen atom on one side is balanced by adding one H2O to the same
side and 2OH¯ to the other side. In case hydrogen is still unbalanced, then
balance by adding one OH¯, for every excess of H atom on the same side
and one H2O on the other side.
(c) Equalize the charge on both sides by adding suitable number of electrons to the
side deficient in negative charge.

31
(iii) Multiply the two half reactions by suitable integers so that the total number of
electrons gained in one half reaction is equal to the number of electrons lost in the
other half reaction.
(iv) Add the two balanced half equations and cancel any term common to both sides.

ILLUSTRATIONS
Illustration 18

(a) NO3  H2S  H
acidic medium
 HSO4  NH4

(b) Fe  N2 H4  OH
alkaline medium
 Fe(OH)2  NH3

Solution
(a) Step 1 N5+ + 8e  N3–
Step 2 S2–  S6+ + 8e
Step 3 NO3¯ + H2S  NH4+ + HSO4¯
Step 4 No other atom (except H and O) is unbalanced therefore no need for this
step.
Step 5 Balancing O atom. This is made by using H2O and H+ io ns. Add desired
molecules of H2O on the side deficient in O atom and double H+ on
opposite side. Therefore
NO3  H2S  H2O 
 NH4  HSO4  2H
Step 6 Balancing charge by H+
NO3  H2S  H2O  3H 
 NH4  HSO4  2H

 Balanced equation is
NO3  H2S  H2O  H 
 NH4  HSO4

(b) Step 1 Fe  Fe2+ + 2e

Step 2 N22– + 2e  2N3–
Step 3 Fe + N2H4  Fe(OH)2 + 2NH3
Step 4 No other atom (except H and O) is unbalanced and therefore no need for this
step.
Step 5 Fe  N2 H4  4OH 
 Fe(OH)2  2NH3  2H2O
Step 6 Balance charge by H+
 Fe + N2H4 + 4OH¯ + 4 H+  Fe(OH)2 + 2NH3 + 2H2O
Finally Fe + N2H4 + 2H2O  Fe(OH)2 + 2NH3

32
 PRACTICE EXERCISE
11. Balance the redox equation, HNO3 + H2S 
 NO + S
12. Balance the following redox equation,
FeC2O4 + KMnO4 + H2SO4 
 Fe2(SO4)3 + CO2 + MnSO4 + K2SO4.

Answers
11. 2HNO3 + 3H2S 
 3S + 2NO + 4H2O
12. 10FeC2O4 + 6KMnO4 + 24H2SO4 
 5Fe2(SO4)3 + 6MnSO4 + 3K2SO4 + 20CO2 +
24H2O

Oxidation Number Method

This method is based on the principle that the number of electrons lost in oxidation must be
equal to the number of electrons gained in reduction. The steps to be followed are
(i) Write the equation (if it is not complete, then complete it) representing the chemical
changes.
(ii) By knowing oxidation number of elements, identify which atom(s) is(are) undergoing
oxidation and reduction. Write down separate equations for oxidation and
reduction.
(iii) Add required electrons on the right hand side of oxidation reaction and on the left
hand side of reduction reaction. Care must be taken to ensure that the net charge on
both the sides of the equation is same.
(iv) Multiply the oxidation and reduction reactions by suitable numbers to make the
number of electrons lost in oxidation reactions equal to the number of electrons
gained in reduction reactions.
(v) Transfer the coefficient of the oxidizing and reducing agents and their products to the
main equation. By inspection, arrive at the co-efficient of the species not
undergoing oxidation or reduction.

ILLUSTATIONS
Illustration 19
Balance the equation K2Cr2O7 + HCl  KCl + CrCl3 + H2O + Cl2
Solution
6 1 3 0
K2 Cr2 O7  HCl 
 KCl  CrCl3  H2O  Cl2

Thus here cr of K2Cr2O7 is reduced to CrCl3*(+6  + 3) and Cl of HCl is oxidized to Cl2

(–1  0). In short.

33
Oxidation: 2Cl 
 Cl02  2 …(a)
Reduction: Cr26 
 2Cr 3  6 …(b)
Step (iii) 2Cl1 
 Cl02  2e ; Cr26  6e  2Cr3
Step (iv) Multiply equation (a) by 6 and (b) by 2
12Cl1 
 6Cl02  12e 
2Cr26  12e 
 4Cr 3
2Cr26  12Cl1  4Cr 3  6Cl02

or Cr26  6Cl 
 2Cr 3  3Cl02

Step (v) K2Cr2O7 + 6HCl  2CrCl3 + 3Cl2

Step (vi) Making provision of KCl and H2O in the product: Since the reactant has 7
oxygen atoms in the product 7H2O must be present. For accounting 14
hydrogen atoms of water in the product, the reactants must have 12 HCl
molecules (the only H containing species). For accounting the 2K atoms and
14 – 12 = 2 additional Cl atoms in the reactant, the product must have 2KCl.
Hence the balanced equation is K2Cr2O7 + 14HCl  2KCl + 2CrCl3 +
7H2O + 3Cl2

PRACTICE EXERCISE
13. Balance the following oxidation-reduction equationm
KMnO4 + KCl + H2SO4 
 MnSO4 + K2SO4 + H2O + Cl2
14. Balance the following redox equation
K2Cr2O7 + HCl 
 KCl + CrCl3 + Cl2 + H2O
Answers
13. 2KMnO4 + 10KCl + 8H2SO4 
 2MnSO4 + 6K2SO4 + 8H2O + 5Cl2
14. K2Cr2O7 + 14HCl 
 2KCl + 2CrCl3 + 3Cl2 + 7H2O
*****

34
 MISCELLANEOUS PROBLEMS
OBJECTIVE TYPE
(* = Problems of Section-I)

*Example 1
8 g of sulphur is burnt to form SO2, which is oxidized by Cl2 water. The solution is then
treated with BaCl2 solution. The amount of BaSO4 precipitated would be
(a) 1 mole (b) 0.5 mole (c) 0.24 mole (d) 0.25 mole

Solution
S 
O2
SO2 
Cl2 water
SO42 
BaCl2
 BaSO4  2Cl
8 1
Moles of sulphur =  = Moles of SO2
32 4
1
 Moles of BaSO4 precipiatated = (applying principle of atom conservation)
4

 Ans. (d)

*Example 2
The normally of 0.3 M H3PO3 when it undergoes the following reaction,
H3 PO3  2OH  
 HPO32   2H 2 O would be

(a) 0.6 N (b) 0.15 N (c) 0.9 N (d) 0.1 N

Solution
Molar ratio of reactants being 1 : 2, so the n-factor ratio has to be 2 : 1, as n-factor of OH ¯
is 1.
 n-factor of H3PO3 in the given reaction is 2.
 Normally of H3PO3 = 0.3  2 = 0.6 N
 Ans. (a)

*Example 3
The moles of ammonium sulphate needed to react with one mole of MnO2 in acidic
medium in a reaction giving MnSO4 and (NH4)2S2O8 is
(a) 2 (b) 3 (c) 1 (d) 1/3

Solution
MnO 2  (NH 4 ) 2  2H 2SO 4 
 MnSO 4  (NH 4 ) 2 S2 O8  2H 2 O
n2 n 1 n 1

Law of equivalence is not applicable  Ans. (c)

35
*Example 4
The number of moles of Cr2 O72  needed to oxidize 0.136 equivalents of N 2 H 5 by the reaction
N 2 H5  Cr2 O72  
 N 2  Cr 3  H 2 O is
(a) 0.136 (b) 0.272 (c) 0.816 (d)
0.0227

Solution
 6 2 
‘n’ factor of Cr2 O72  ion in the given reaction is 6.  Cr 3 
Cr2 O7  
Equivalents of Cr2O72– needed to oxide N 2 H 5 = Equivalents of N 2 H 5 =0.136
0.136
 Moles of Cr2 O72  needed to oxides N 2 H 5  = 0.0227
6

 Ans. (d)

*Example 5
A 10 g sample of a mixture of calcium chloride and sodium chloride is treated with
Na2CO3 to precipitate calcium as calcium carbonate. This CaCO3 is heated to convert all
the calcium to CaO and the final mass of CaO is 1.62 g. The % by mass of NaCl in the
original mixture is
(a) 15.2% (b) 67.9% (c) 21.8% (d) 32.1%

Solution
CaCl2  Na 2 CO3 
 CaCO3  2NaCl

CaCO3   CaO  CO 2

1.62
Moles of CaO  = Moles of CaCO3 = Moles of CaCl2 [from equation (i) and (ii)]
56
1.62
Mass of CaCl2 =  111  3.21 g
56
3.21
% of CaCl2 =  100  32.1%
10

and % of NaCl = 100 – 32.1 = 67.9 %

 Ans. (d)

*Example 6
Equal volumes of 1 M each of KMnO4 and K2Cr2O7 are used to oxidize Fe(II) solution in
acidic medium. The amount of Fe oxidized would be
(a) more with KMnO4 (b) equal with both oxidizing agents
(c) more with K2Cr2O7 (d) cannot be determined

36
Solution
The ‘n’ factor of KMnO4 in its reaction with Fe(II) would be 5 while that of K2Cr2O7
would be 6. So, for the same number of moles, K2Cr2O7 will have greater equivalents than
KMnO4. So, more equivalents of Fe(II) would be oxidized by K2Cr2O7 than by KMnO4.
 Ans. (c)

*Example 7
It takes 2.56  10–3 equivalents of KOH to neutralize 0.1254 g H2XO4. The number of
neutrons in X would be
(a) 16 (b) 8 (c) 18 (d) 32

Solution
Let ‘a’ be the atomic mass of X.
0.1254
Moles of H2XO4 =
(a  66)

‘n’ factor of H2XO4 = 2 [as H2XO4 is a dibasic acid]

Equivalents of KOH = Equivalents of H2XO4
0.1254
 2.56  10–3 = 2
(a  66)

a = 31.96 g/mol  32 g/mol

 X is sulphur and sulphur has 16 protons and 16 neutrons.
 Ans. (a)

*Example 8
10 ml of a solution of H2O2 requires 25 ml of 0.1 N KMnO4 for complete reaction. The
volume strength of H2O2 would be
(a) 1.4 (b) 1.2 (c) 0.25 (d) 2.5

Solution
In the reaction between KMnO4 and H2O2, KMnO4 acts as oxidizing agent, changing to
Mn2+ and H2O2 behaves as reducing agent oxidizing to O2.
 Mn 2  O2
KMnO4  H2 O2 
(n 5) (n  2)

Equivalents of KMnO4 = Equivalents of H2O2.

25  10–3  0.1 = 10  10–3  N
N = 0.25
 Volume strength of H2O2 = 5.6  0.25 = 1.4
 Ans. (a)

37
 SUBJECTIVE TYPE
Example 1
P and Q are two elements which forms P2Q3 and PQ2. If 0.15 mole of P2Q3 weights 15.9 g
and 0.15 mole of PQ2 weights 9.3 g, what are atomic weights of P and Q?
Solution
Let atomic weight of P and Q a and b respectively
 Molecular weight of P2Q3 = 2a + 3b
and Molecular weight of PQ2 = a + 2b
Now given that 0.15 mole of P2Q3 weight 15.9 g
15.9  wt. 
(2a + 3b) =   mole 
0.15  mol. wt 
9.3
Similarly, (a + 2b) =
0.15

Solving these two equations

b = 18
a = 26
Example 2
Potassium selenate is isomorphous with potassium sulphate and contains 45.52% selenium
by weight. Calculate the atomic weight of selenium. Also report the equivalent weight of
potassium selenate.
Solution
Potassium seleante is isomorphous to K2SO4 and thus its molecular formula of K2SeO4.
Now molecular weight of K2SeO4 = (39  2 + a + 4  16)
where a is atomic weight of Se
(142 + a)g K2SeO4 has Se = ag
a  100
 100 g K2SeO4 has Se =
142  a

% of Se = 45.52
a  100
 = 45.52
142  a

 a = 118.168 = 118.2
Mol.wt. 2  39  118.2  64
Also equivalent of K2SeO4 =  = 130.1.
2 2

38
Example 3
A sample of H2SO4 (density 1.787 g mL–1) is labeled as 86% by weight. What is molarity
of acid? What volume of acid has to be used to make 1 litre of 0.2 H2SO4?
Solution
H2SO4 is 86% be weight
 Weight of H2SO4 = 86 g
Weight of solution = 100 g
100 100
 Volume of solution = mL  litre
1.787 1.787  1000

86
 M H2SO4   15.68
100
98 
1.787  1000

Let V mL of this H2SO4 are used to prepare 1 litre of 0.2 M H2SO4

 mM of H2SO4 conc. = mH of H2SO4 dilute
V  15.68 = 1000  0.2  V = 12.75 mL.
*Example 4
The molecular mass of an organic acid was determined by the study of its barium salt
4.209 g of salt was quantitatively converted to free acid by the reaction with 21.64 ml of
0.477 M H2SO4. The barium salt was found to have two mole of water of hydration per
Ba2+ ion and the acid is mono basic. What is molecular weight of anhydrous acid?
Solution
Meq. of barium salt = meq. of acid
4.290
 1000 = 21.64  0.4777  2
M/2

Molecular weight of salt = 415.61

415.61  137.36
Molecular weight of anion =  121.31
2

 Molecular weight of acid = 121.31.

*Example 5
25 mL of a solution of Na2CO3 having a specific gravity of 1.25 g mL–1 required 32.9 mL
of a solution of HCl containing 109.5 gm of the acid per litre for complete neutralization.
Calculate the volume of 0.84 N H2SO4 that will be completely neutralized by 125 g of
Na2CO3 solution.

39
Solution
109.5
NHCl  3
36.5 1
Since Na2CO3 is completely neutralized by HCl
 Meq. of Na2CO3 = Meq. of HCl
N  25 = 32.9  3
 N Na 2CO3 = 3.948

Now Na2CO3 fresh solution reacts with H2SO4

 Volume of Na2CO3 solution =
 Meq. of H2SO4 = Meq. of Na2CO3
0.84  V = 100  3.948
 Volume of H2SO4 = 470 mL.
*Example 6
Borax in water gives
B4 O72  7H 2 O 
 4H 3BO3  2OH 
How many gram of borax (Na2B4O7.10H2O) are required to?
(a) Prepare 50 mL of 0.2 M solution
(b) neutralize 25 mL of 0.1934 M of HCl and H2SO4 separately
Solution
 Normality 
 Molarity   
 No. of replaceable OH 

 N=M2
Thus Meq. of borax in solution = 50  0.2  2 = 20
w
  1000  20
M/2
w
  1000  20  w = 3.82 g
282 / 2
For neutralization of HCl
Meq. of HCl = Meq. of borax
w
25  0.1934 =  1000
382 / 2
 Weight of borax = 0.09235 g
For neutralization of H2SO4

40
Meq. of borax = Meq. of H2SO4
w
 1000 = 25  0.1934  2
382 / 2
 Weight of borax = 1.847 g.
*Example 7
A mixture containing As2O3 and As2O5 required 20.10 mL of 0.05 N iodine for titration.
The resulting solution is then acidified and excess of KI was added. The liberated iodine
required 1.1113 g hypo (Na2S2O3 . 5H2O) for complete reaction. Calculate mass
mixture. The reactions are
As2O3 + 2I2 + 2H2O   As2O5 + 4H+ + 4I¯
As2O5 + 4H+ + 4I¯   As2O3 + 2I2 + 2H2O
Solution
Meq. of I2 used = 20.10  0.05 = 1.005
Let Meq. of As2O3 Meq. of As2O5 in mixture be a and b respectively. On addition of I2 to
mixture. As 23 is converted to As 25 .
 Meq. of As2O5 = Meq. of I2 to mixture used = 1.005 – Meq. of As5+ formed.
or a = 1.005 ...(1)
After the reaction with I2, mixture contains all the arsenic in +5 oxidation state which is
then titrated using KI + hypo. Thus,
Meq. of As2O3 as As+5 + Meq. of As2O5 as As+5 = Meq. of liberated I2
= Meq. of hypo used
1.113
or a + b = 100
248
or a + b = 4.481
By equations (1) and (2),
B = 4.481 – 1.005 = 3.476
Meq.  Eq.Wt 1.005 198
 Wt. of As2O3 =   0.0497g
1000 4 100
3.476  230
and. Wt. of As2O5 =  0.19999g 3
4 1000
 Wt. of mixture = 0.0497 + 0.1999 = 0.2496 g.

*****

41
Exercise - I
OBJECTIVE TYPE QUESTIONS
Multiple choice questions with ONE option correct
1. It takes 2.56 ×10–3 equivalents of KOH to neutralize 0.125 g H 2XO4. The number
neutrons in x is
(a) 16 (b)8 (c) 7 (d) 32
2. 0.1 lit of 0.01 M KMnO4 oxidized 100 ml H2O2 in acidic medium. Volume of same
KMnO4 required in alkaline medium to oxidize 0.1 lit of same H2O2 will be (Mn
changes to Mn+2 in acidic medium and MnO2 in alkaline medium)
(a) 100/3 ml (b) 500/3 ml (c) 300/5 ml (d) None
3. The hydrated salt Na2SO4. nH2O, undergoes 55.9% loss in weight on heating and
becomes anhydrous. The value of n will be
(a) 5 (b) 3 (c) 7 (d) 10
4. 8 g of sulphur is burnt to form SO2 which is oxidized by Cl2 water. The solution is
treated with BaCl2 solution. The amount of BaSO4 precipitated is
(a) 1 mole (b) 0.45 mole (c) 0.24 mole (d) 0.25 mole
5. A 10.0 g sample of a mixture of calcium chloride and sodium chloride is treated with
Na2CO3 to precipitate the calcium as calcium carbonate. This CaCO3 is heated to
convert all the calcium to CaO and the final mass of CaO is 1.62 gms. The % by mass
of CaO is 1.62 gms. The % by mass of CaCl2 in the original mixture is
(a) 15.2% (b) 32.1 % (c) 21.8 % (d) 11.07%
6. How many volumes of 1 M KMnO4 ion will react with 1 mol of ferrous oxalate in
acidic medium
(a) 1/5 (b) 2/5 (c) 3/5 (d) 5/3
7. If equal volumes of 10 M KMnO4 and 10 M K2Cr2O7 solutions are allowed to
oxidize Fe(II) to Fe(III) in acidic medium, then Fe(II) oxidized will be
(a) more by KMnO4 (b)more by K2Cr2O7
(c) equal in both cases (d)can’t be determined
8. When 10 ml of ethyl alcohol (density = 0.7893 g/mol) is mixed with 20 ml of water
(density = 0.9971 g/mol) at 25°C, the final solution has a density of 0.9571 g/ml. The
percentage change in total volume on mixing is
(a) – 3.1 % (b) 2.4 % (c) 1 % (d) 10%

42
9. Calculate the number of oxygen atoms required to combine with 7 g of N2 to form
N2O3 when 80% of N2 is converted into N2O3
(a) 2.3×1023 (b) 3.6 ×1023 (c) 1.8 ×1021 (d) 5.4 ×1021
10. The density of 1 M solution of NaCl is 1.0585 g/ml. The molality of the solution is
(a) 1.0585 (b) 1.00 (c) 0.10 (d) 0.0585
11. 1 mole of Fe2S3, 2 moles of H2O, 3 moles of O2 are allowed to react according to the
equation
2Fe2S3  s   6H 2 O  l   3O 2  g   4Fe  OH 3  s   6S  s 

The number of moles of Fe(OH)3(s) that can be produced is

(a) 1.34 (b) 2 (c) 4 (d) 3
12. In a reaction FeS 2  KMnO4  H  Fe 3  SO2  Mn 2  H 2 O the equivalent mass of FeS2
would be equal to
(a) molar mass (b) molar mass/10 (c) molar mass/11 (d) molar mass/13
13. A molal solution is one that contains one mole of a solute in:
(a) 1000 g of the solvent (b) one litre of the solvent
(c) one litre of the solution (d) 22.4 litres of the solution
14. The equivalent weight of MnSO4 is half its molecular weight when it is converted to:
(a) Mn2O3 (b) MnO2 (c) MnO 4 (d) MnO 24 

15. Which has maximum number of atoms?

(a) 24g of C (12) (b) 56g of Fe (56)
(c) 27g of Al (27) (d) 108g of Ag (108)

Multiple choice questions with MORE THAN ONE option correct

1. for the following balanced redox reaction,

2MnO4¯ + 8H+ + Br2 2Mn+2 + 2 BrO3¯ + 2H2O
If the molecular wt. of MnO4¯, Br2 be Mx, My respectively, then
(a) equivalent wt. of MnO4¯ is Mx/5 (b) equivalent wt. of Br2 is My/10
(c) the n-factor ratio of Mn+2 to BrO3¯ is 1 : 1 (d) none of these

43
*2. When non-stoichiometric compound Fe0.95O is heated in presence of oxygen, then it
converts into Fe2O3, then which of the following statements are correct?
M
(a) Equivalent weight of Fe0.95O is where M is molecular weight of Fe0.95O
0.85

(b) The number of moles of Fe+3 and Fe+2 1 moles Fe0.95O and 0.1 and 0.85
respectively
(c) The number of moles of Fe+3 and Fe+2 in 1 mole of Fe0.95O are 0.85 and 0.10
respectively
(d) The % composition of Fe+2 and Fe+3 in the non stoichiometric compound is 89.47%
and 10.53% respectively
3. Which of the following quantities are dependent on temperature?
(a) Molarity (b) Normality
(c) Molality (d) Mole fraction
4. For the reaction
H3 PO4  Ca(OH)2 
 CaHPO4  2H2 O
1 mole 1 mole

Then which of the following statements are correct?

(a) the equivalent weight of H3PO4 is 49
(b) the resulting solution is neutralized by 1 mole of KOH
(c) 1 mole of H3PO4 is completely neutralized by 1.5 mole of Ca(OH)2
(d) None
5. The density of 3M sodium thiosulphate is 1.25 g mL–1. Identify the correct
statements among the following
(a) % by the weight of sodium thiosulphate is 37.92
(b) The mole fraction of sodium thiosulphate is 0.065
(c) The molality of Na+ is 2.53 and S2O32– is 1.25
(d) All of these
6. Which of the following has same mass
(a) 1.0 mole of O2 (b) 3 × 1023 molecules of SO2
(c) 0.5 moles of CO2 (b)1 g atom of sulphur
7. A solution of KMnO4 to be used in acidic medium is prepared by dissolving 1.58 g
L–1. The solution is
(a) M/100 (b) N/20 (c) M/50 (d) N/50

44
8. The mole fraction of NaCl in aqueous solution is 0.2. The solution is
(a) 13.9 m (b) Mole fraction of H2O is 0.8
(c) Acidic in nature (d) Neutral
9. 0.1 M HCl is used to react with 1g of mixture of Na2CO3 and NaHCO3 containing
equimolar amount of two. The volume of HCl used is
(a) 156.0 mL (b) 0.156 L (c) 1.57 L (d) 15.7 L
10. H3BO3, Boric acid is
(a) Monobasic acid (b) Tribasic acid (c) Dibasic acid (d) Aprotic acid
*****

45
Exercise – II

ASSERTION & REASON , COMPREHENSION & MATCHING TYPE

Assertion and Reason
(a) If both A and R are true and R is the correct explanation of A.
(b) If both A and R are true but R is not the correct explanation of A
(c) If A is true but R is false.
(d) If A is false but R is true.
1. A : In the balanced redox reaction x Cu2O + y NO3– + 14 H+   6 Cu+2 + 2NO +
7H2O, the
–
n-factor of Cu2O and NO3 is 2 and 3 respectively.
R : since reciprocal of n-factor’s ratio is molar ratio and so, x : y = 3 : 2.
2. A : For the redox reaction Cu2S  CuO + SO2, y mole Cu2S in equal to 8y
equivalents of Cu2S
R : Since the n-factor of Cu2S is 8 and number of equivalents = n–factor  number of
moles.
3. A : For the reaction Na2CO3 + HCl  NaCl + NaHCO3 the equivalent weight of
Na2HCO3 is 106.
molecular wt.
R : Because the n-factor Na2CO3 is 1 and equivalent weight =
n  factor
4. A : The lowest-oxidation state or oxidation number of N is –3
R : Because the lowest oxidation number of non-metal = V.E. is valence electron.
5. A : The oxidation number of “S” in H2S2O8 is 7.
R : The maximum oxidation number of S is +6, because the maximum oxidation of
element is its no. of valence electron (s) or, group number.

Passage based questions

Passage I
Normality is number of gram equivalents dissolved per litre of solution. It changes with
change in temperature. In case of monobasic acid, normality and molarity are equal but in
case of dibasic acid, normality is twice the molarity. In neutralization and redox reaction
reactions, number of miliequivalents of reactants as well as products are always equal
1. The volume of 0.1 M Ca(OH)2 required to neutralize 10 mL of 0.1 N HCl will be
(a) 10 mL (b) 20 mL (c) 5 mL (d) 40mL
2. Molarity of 0.25 N Na2CO3 is
(a) 0.25 (b) 1.0 (c) 0.5 (d) 0.125

46
3. 6.90 N KOH solution in water contains 30% by weight of KOH. The density of
solution will be
(a) 1.288 (b) 2.88 (c) 0.1288 (d) 12.88

Passage II
1.00 g of a mixture consisting of equal number of moles of carbonates of two alkali metals,
required 44.4 ml of 0.5 N hydrochloric acid for complete reaction. If the atomic weight of
one of the metals is 7.00.
1. The number of equivalents of HCl used is
(a) 0.222 (b) 2.22 (c) 22.22 (d) 0.0222
2. The number of moles of each metal carbonate are
(a) 0.1 (b) 0.0111 (c) 0.0055 (d) 0.00275
3. The molecular weights of the two alkali metal carbonate are
(a) 74 and 60 (b) 134 and 160 (c) 160 and 60 (d) 74 and 106

Matching Type Questions

1. Column I Column II
(a) 1 mole of Na (p) 6.02  1023
(b) 1 mole of H2O (q) At. wt. in g
(c) 1 mole (r) molecular wt. in g
(d) No. of molecules in 16 g CH4 (s) Avogadro’s number
(a) (a-p, q, s), (b-q, r, s), (c-p, s), (d-p, s) (b) (a-p, s), (b-q, r, s), (c-p, s), (d-p, s)
(c) (a-p, q, s), (b-q, r, s), (c-p, r, s), (d-p, s)(d) (a-q, s), (b-q, r, s), (c-p, s), (d-p, s)

2. Column I Column II
(a) Eq. wt. of reducing agent (p) Formula wt./No. of electron gained
per mole
(b) Eq. wt. of oxidizing agent (q) Formula wt./Total change in oxidation
No.
(c) Eq. wt. of salt (r) Formula wt./Negative charge
(d) Eq. wt. of salt (s) Half the molecular weight
(a) (a-p, q, s), (b-q, r, s), (c-p, s), (d-p, s) (b) (a-p, s), (b-q, r, s), (c-p, s), (d-p, s)
(c) (a-p, q), (b-q), (c-r), (d-p, q, s) (d) (a-q, s), (b-q, r, s), (c-p, s), (d-p, s)
*****

47
Exercise - III
SUBJECTIVE TYPE

*1. A 1.00gm sample of H2O2 solution containing X percent H2O2 by weight requires X
ml of a KMnO4 solution for complete oxidation under acidic conditions. Calculate
the normality of the KMnO4 solution.

*2. 4.08 g of a mixture of BaO and an unknown carbonate MCO3 was heated strongly.
The residue weighed 3.64g. This was dissolved in 100 ml of I N HCI. The excess
acid required 16 ml of 2.5 N NaOH solutions for complete neutralization. Identify
the metal M.

(Atomic weight H = 1, C = 12, O = 16, Cl = 35.5, Ba = 138).

3. 2.68 × 10–3 moles of a solution containing an ion An+ required 1.61 x10–3 moles of
MnO 4 for the oxidation of An+ to AO 3 in acid medium. What is the value of n?

*4. An equal volume of a reducing agent is titrated separately with 1 M KMnO4 in acid
neutral and alkaline media. The volumes of KMnO4 required are 20 ml. in acid, 33.4
ml. neutral and 100 ml. in alkaline media. Find out the oxidation state of manganese
in each reduction product. Give the balanced equations for all the three half
reactions. Find out the volume of 1 M K2Cr2O7 consumed; if the same volume of
the reducing agent is titrated in acid medium.

5. Calculate the molality of 1 litre solution of 93% H2SO4 (weight/volume). The

density of the solution is 1.84 g/mI.

*6. A 2.0 g sample of a mixture of Na2 CO3 , NaHCO3 and Na 2 SO4 is gently heated till the
evolution of CO2 ceases. The volume of CO2 at 750 mm of Hg and 298 K is
measured to be 123.9 mL. A 1.5 g of the same sample requires 150 mL of (M/10)
HCl for complete neutralization. Calculate the % composition of the components of
the mixture.

*7. An aqueous solution containing 0.10 g KIO 3 (formula wt. = 214.0) was treated with
an excess of KI solution. The solution was acidified with HCl. The liberated I2

48
 consumed 45.0 mL of thiosulphate solution to decolorize the blue starch-iodine
complex. Calculate the molarity of the sodium thiosulphate solution.

8. How many milliliters of 0.5 M H2 SO4 are needed to dissolve 0.5 g of copper (II)
carbonate?

*9. Hydrogen peroxide solution (20 ml) reacts quantitatively with a solution of
KMnO4 (20 mL) acidified with dilute H2 SO4 . The same volume of the KMnO4
solution is just decolourised by 10 ml of MnSO4 in neutral medium simultaneously
forming a dark brown precipitate of hydrated MnO2 . The brown precipitate is
dissolved in 10 mL of 0.2 M sodium oxalate under boiling condition in the presence
of dilute H2 SO4 . Write the balanced equations involved in the reactions and calculate
the molarity of H2 O2.

10. Calculate the molarity of water if its density is 1000 kg/m3.

*****

49
Exercise - IV
NEET PROBLEMS

1. Balance the following equations.

(i) Cu2O  H  NO3  Cu2  NO  H2O
(ii) K 4 Fe  CN 6   H2 SO4  H2 O  K 2 SO 4  FeSO4  (NH 4 )2 SO 4  CO
(iii) C2 H5OH  I2  OH   CHI3  HCO3  I  H2 O
*2. Hydroxylamine reduces iron (Ill) according to the equation:
2NH2 OH  4Fe3 
 N2 O(g)  H2 O  4Fe2  4H
Iron (II) thus produced is estimated by titration with a standard permanganate
solution. The reaction is:
MnO4  5Fe2  8H 
 Mn2  5Fe3  4H2 O
A 10 ml. sample of hydroxylamine solution was diluted to 1 litre. 50 ml. of this
diluted solution was boiled with an excess of iron (Ill) solution. The resulting solution
required 12 ml. of 0.02 M KMnO4 solution for complete oxidation of iron (II).
Calculate the weight of hydroxylamine in one litre of the original solution. (H = 1, N
= 14, O = 16, K = 39, Mn = 55, Fe 56).
3. The density of a 3 M sodium thiosulphate solution (Na2S2O3) is 1.25 g per ml.
Calculate (i) the percentage by weight of sodium thiosulphate, (ii) the mole fraction of
sodium thiosulphate and (iii) the molalities of Na+ and S 2 O 23 ions.
4. Complete and balance the following reactions:
(i) Zn  NO3   Zn2  NH4 (ii) Cr2O72  C2H4O   C2 H4 O2  Cr 3
(iii) HNO3  HCl 
 NO  Cl2 (iv) Ce3  S2 O82 
 SO42  Ce4
(v) Cl2  OH 
 Cl  ClO (vi) Mn2  PbO2 
 MnO4  H2 O
(vii) S  OH 
 S2  S2 O23 (viii) ClO3  I  H2SO4 
 Cl  HSO4
(ix) Ag  AsH3 
 H3 AsO3  H

5. Five ml of 8N nitric acid, 4.8 ml of 5N hydrochloric acid and a certain volume of

17M sulphuric acid are mixed together and made upto 2 litre. Thirty ml. of this acid
mixture exactly neutralise 42.9 ml of sodium carbonate solution containing one gram
of Na2CO3.10H2O in 100 ml. of water. Calculate the amount in gram of the sulphate
ions in solution.
*6. (i) What is the weight of sodium bromate and molarity of solution necessary to
prepare 85.5 ml of 0.672 N solution when the half-cell reaction is
BrO3  6H  6e 
 Br  3H2 O
(ii) What would be the weight as well as molarity if the half-cell reaction is?
2BrO3  12H  10e 
 Br2  6H2 O

50
*7. A sample of hydrazine sulphate (N2H6SO4) was dissolved in 100 ml. of water, 10 ml
of this solution was reacted with excess of ferric chloride solution and warmed to
complete the reaction. Ferrous ion formed was estimated and it required 20 ml. of
M/50 potassium permanganate solution. Estimate the amount of hydrazine sulphate in
one litre of the solution.
Reaction:
4Fe3  N2 H4 
 N2  4Fe2  4H
MnO4  5Fe2  8H 
 Mn2  5Fe3  4H2 O
*8. A mixture of H2C2O4 (oxalic acid) and NaHC2 O4 weighing 2.02 g was dissolved in
water and the solution made upto one litre. Ten milliliters of the solution required 3.0
ml of 0.1 N sodium hydroxide solution for complete neutralization. In another
experiment, 10.0 ml of the same solution, in hot dilute sulphuric acid medium,
required 4.0 ml of 0.1 N potassium permanganate solutions for complete reaction.
Calculate the amount of H2C2O4 and NaHC2 O4 in the mixture.

*9. A solid mixture (5.0 g) consisting of lead nitrate and sodium nitrate was heated below
600°C until the weight of the residue was constant. If the loss in weight is 28.0
percent, find the amount of lead nitrate and sodium nitrate in the mixture.

*10. A solution of 0.2 g of a compound containing Cu2 and C 2 O 42  ions on titration with
0.02 M KMnO4 in presence of H2 SO 4 consumes 22.6 mL of the oxidant. The resultant
solution is neutralized with Na2 CO3 , acidified with dilute acetic acid and treated with
excess KI. The liberated iodine requires 11.3 mL of 0.050 M Na 2 S2 O3 solution for
complete reduction. Find out the molar ratio of Cu2 and C 2 O 42  in the compound. Write
down the balanced redox reactions involved in the above titrations.

*11. A 1 g sample of Fe 2 O3 solid of 55.2 per cent purity is dissolved in acid and reduced by
heating the solution with zinc dust. The resultant solution is cooled and made upto
100.0 ml. An aliquot of 25.0 ml of this solution requires 17.0 ml of 0.067 M solution
of an oxidant for titration. Calculate the number of electrons taken up by the oxidant
in the reaction of the above titration.

*12. Upon mixing 45.0 ml of 0.25 M lead nitrate solution with 25 mL of 0.10 M chromic
sulphate, precipitation of lead sulphate takes. How many mol of lead sulphate are
formed? Also, calculate the molar concentration of the species left behind in final
solution. Assume that lead sulphate is completely insoluble.
*****

51
 Answers
Exercise - I
Only One Option is correct
1. (a) 2. (b) 3. (d) 4. (d) 5. (b)
6. (c) 7. (b) 8. (a) 9. (b) 10. (b)
11. (b) 12. (c) 13. (a) 14. (b) 15. (a)
More Than One Choice Correct
1. (a, b, c) 2. (a,b,d) 3. (a,b) 4. (a,b,c) 5. (a,b)
6. (a,b,d) 7. (a,b) 8. (a,b,d) 9. (a,b) 10. (a,d)

Exercise - II
Assertion and Reason
1. (a) 2. (a) 3. (a) 4. (a) 5. (d)
Passage I
1. (c) 2. (a) 3. (a)
Passage II
1. (d) 2. (c) 3. (d)
Matching Type Questions
1. (a) 2. (c)
Exercise - III
Subjective Type
1. 0.588 N 2. Ca
3. 2 4. +2, +4, +6, 16.66 ml
5. 10.43 6. Na2CO3 – 26.5%, Na2SO4 – 31.5%
7. 0.062 8. 8.097 ml
9. 0.1 10. 55.55 M

Exercise - IV
NEET Level Problem
2. 39.6 g l–1 3. (i) 37.92; (ii) 0.065; (iii) 7.74, 3.87
5. 6.3648 g 6. (i) 1.446 gm, 0.112 M; (ii) 1.7532 g, 0.1344 M
7. 6.5 g 8. 1.12 g, 0.90 g
9. 3.324 g, 1.676 g 10. 1:2
11. 6
12. 0.0075, Pb2+ = 0.05357 M, NO3  0.3214 M, Cr 3  0.0714 M

*****

52