Mole Concept & Stoichiometry

MOLE CONCEPT & STOICHIOMETRY XI-CMI-1
Mole Concept & Stoichiometry

1. MOLE CONCEPT
1.1 THE ATOM
The fact that all substances obeyed the laws of chemical combination by weight made the scientists
to speculate about the ultimate particles of matter.
The most common of these speculations is due to John Dalton.
DALTON’S ATOMIC THEORY
The main postulates of this atomic theory are
  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 change.
  Atoms of the same element are identical in all respects: size, shape, structure etc. and
especially weight.
 Atoms of different elements have different properties and different weights.
 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.
 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 been proved that atom consists of a number of
sub atomic particles.
 The existence of isotopes for most elements shows 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.
 Parts of atomic mass can be destroyed and an equivalent amount of energy is released
during nuclear fission.
 Atoms combine in fixed integral ratios; however, there are instances where atoms combine
in non-integral ratios. e.g., in zinc oxide, zinc and oxygen have not combined in exactly an
integral ratio. The atomic ratio of Zn: O = (1 + x): 1, where x is a very small fraction.
Compounds of this kind are called non-stoichiometric compounds or Berthollide
compounds.
1.2 ATOMIC WEIGHTS
 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.,
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Weight of 1 atom of 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.
1
 weight of 1 atom of oxygen
16
 The modern reference standard for atomic weights is carbon isotope of mass number 12.
1
 weight 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.
 Atomic weight is not a weight but a number.
 Atomic weight is not absolute but relative to the weight of the standard reference element
(C12).
 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 heavier metals.
 Average/Mean Atomic Mass
The weighted average of the isotopic masses of the element’s naturally occuring isotopes.
a1x1  a 2 x 2  .....  a n x n
Mathematically, average atomic mass of X (Ax) =
100
Where : a1, a2, a3 ........... atomic mass of isotopes and x1, x2, x3 ........... mole % of isotopes.
1. 3 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 trioxide. It has been established that it contains one atom of
sulphur and three atoms of oxygen. So, the smallest particle of sulphur trioxide that can exist
free and retain all its properties is the molecule of sulphur trioxide. A compound molecule
should contain at least 2 different atoms.
 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 2 atoms; when it is split up into
atoms, there will be observed a change in properties.
 Molecules of elementary gases like hydrogen, oxygen, nitrogen, chlorine, etc., contain 2 atoms
in a molecule; they are diatomic.
 Molecules of noble gases like helium, neon, argon, krypton and xenon are monoatomic.
Molecules of phosphorus contain 4 atoms (tetratomic) while those of sulphur contain 8 atoms.
The number of atoms of an element in a molecule of the element is called its atomicity.
1.4 MOLECULAR WEIGHT
1
 It is the number of times a molecule is heavier than th of an atom of C–12.
12
Weight of 1 molecule
 Molecular weight =
1
 weight of 1 carbon  12 atom
12
 Molecular weight is not a weight but a number.
 Molecular weight is relative and not absolute.
 Molecular weight expressed in grams is called gram-molecular weight.
 Molecular weight is calculated by adding all the atomic weights of all the atoms in a molecule.
Thus, the molecular weight of oxygen which contains 2 atoms in a molecule would be (2 × 16)
= 32. The molecular weight of carbon dioxide, which contains 1 atom of carbon and 2 atoms of
oxygen would be [12 + (2 × 16)] = 44. Molecular weight of sulphuric acid, which contains 2
atoms of hydrogen, 1 atom of sulphur and 4 atoms of oxygen is [(2 × 1) + (1 × 32) + (4 × 16)]
= 98.
 Molecular weight is now called relative molecular mass.
 Mean Molar Mass or Molecular Mass
The average molar mass of the different substance present in the container
n1M1  n 2 M 2  ......n n M n
= .
n1  n 2  ....n n
Where: M1, M2, M3 ........... are molar masses and n1, n2, n3 ........... moles of substances.
1.5 AVOGADRO’S HYPOTHESIS
 According to this “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 of Avogadro’s hypothesis
(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. 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 old S.T.P. [Standard
Temperature (0°C) and Pressure (1 atmosphere)].
Density of the gas
The relative density or vapour density of a gas =
Density of hydrogen
Weight of 1 litre of gas at STP

Vapour density of a gas =
Weight of 1 litre of hydrogen at STP
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 ' molecules of gas Weight of 1 molecule of gas
V.D. of a gas = =
Weight of 'n ' molecules of H 2 Weight of 1 molecule of H 2
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) Gram-Molecular volume or Molar Volume
Weight of 1 L of the gas at old STP
Molecular weight of a gas = 2 ×
Weight of 1 L of hydrogen at old STP
Weight of 1 L of the gas at old STP
Molecular weight of a gas = 2 ×
0.089 g
2
Gram-Molecular weight of a gas = × weight of 1 L of the gas at old STP
0.089
Gram-Molecular weight of a gas = 22.4 × weight of 1 L of the gas at old STP
= Weight of 22.4 L of the gas at old STP
This establishes that gram-molecular weight of any gas (or vapour) occupies the same volume
of 22.4 L at old S.T.P. The volume occupied by a gram-molecular weight of any gas is called
molar volume and its value is 22.4 L at old STP.
1.6 EMPIRICAL FORMULA, % COMPOSITION OF A GIVEN COMPOUND BY MASS, % BY
MOLE, MINIMUM MOLECULAR MASS DETERMINATION.
Percentage Composition
Here we are going to find out the percentage of each element in the compound by knowing the
molecular formula of compound.
We know that according to law of definite proportions any sample of a pure compound always
possess constant ratio with their combining elements.
Empirical and molecular formula
We have just seen that knowing the molecular formula of the compound we can calculate percentage
composition of the elements. Conversely if we know the percentage composition of the elements
initially, we can calculate the relative number of atoms of each element in the molecules of the
compound. This gives us the empirical formula of the compound. Further if the molecular mass is
known then the molecular formula can easily be determined.
 The empirical formula of a compound is a chemical formula showing the relative number of
atoms in the simplest ratio. An empirical formula represents the simplest whole number ratio of
various atoms present in a compound.
 The molecular formula gives the actual number of atoms of each element in a molecule. The
molecular formula shows the exact number of different types of atoms present in a molecule of
a compound.
 The molecular formula is an integral multiple of the empirical formula.
i.e. molecular formula = empirical formula × n
molecular formula mass
where n =
empirical formula mass
Illustration-1
Acetylene and benzene both have the empirical formula CH. The molecular masses of acetylene and
benzene are 26 and 78 respectively. Deduce their molecular formulae.
Solution:
 Empirical Formula is CH
Step-1: The empirical formula of the compound is CH
 Empirical formula mass = (1 × 12) + 1 = 13.

Molecular mass = 26
Step-2: To calculate the value of ‘n’
Molecular formula mass 26
n= = =2
Empirical formula mass 13
Step-3: To calculate the molecular formula of the compound.
Molecular formula = n × (Empirical formula of the compound)
= 2× CH = C2H2
Thus the molecular formula is C2H2.
Similarly for benzene
To calculate the value of ‘n’
Molecular formula mass 78
n= = = 6,
Empirical formula mass 13
Thus the molecular formula is 6 × CH = C6H6.
2. STOICHIOMETRY
 Chemical stoichiometry deals with the determination of quantities of reactants or products of a
chemical reaction.
 The word “stoichiometry” is derived from greek work “stoichion” means element and “metry”
means measure.
 Stoichiometry is divided into two subsections.
 Gravimetric analysis and
 Volumetric analysis.
  The problems on gravimetric and volumetric analysis can be solved using two well known
concepts i.e. mole concept and equivalent concept. But generally, the problems on gravimetric
analysis are solved using mole concept while problems on volumetric analysis are solved
making use of equivalent concept since it does not require the use of a balanced chemical
reaction.
2. 1 THE MOLE
 Let us take elements Ag, Mg and Hg with masses equal to their atomic masses in grams, and
then to our surprise, each element contains equal number of atoms.
 This is not only limited to atoms but also applicable to molecules. For example, if we have
molecules like CO2, NO2 and SO2 with masses equal to their molecular masses in grams, then
they would also contain equal number of molecules. This specified number of atoms or
molecules is referred as a “mole”.
 Thus a system containing a specified number (6.023 × 1023) of elementary entities is said to
contain 1 mole of the entities. Thus 1 mole of an iron sample mean that the sample contain
6.023 × 1023 atoms of iron. Similarly, 1 mole of NaCl crystal contains 6.023 × 1023 ion paris
(Na+ Cl–).
 This specific number 6.023 × 1023 elementary entities is called Avogadro number or constant
(NAV). The SI unit for amount of substance is the mole. One mole of any substance contains
the same number of elementary entities as there are carbon atoms in exactly 12 g of carbon–
12.
 The mass of specific number (6.023 × 1023) of elementary entities is equal to atomic mass for
atoms and molecular mass for molecules.
 Let M g/mole be the molecular mass of a species. Thus M g be the mass of 1 mole (equal to the
mass of 6.023 × 1023 molecules) of the species. Then, x g of the species contain   x 
1
M 
mole. Hence
weight (grams) w
Number of moles of a species = 
Atomic or molecular mass (g / mole) M
 It is also known that one mole of a gas at old STP occupies a volume of 22.4 litres. Thus, if a
gas occupies x L at old STP, then the number of moles of the gas can be calculated by dividing
the actual volume occupied by the gas at old STP with the volume occupied by 1 mole of the
gas at old STP.
Volume occupied by gas at old STP
Thus, number of moles of a gas =
Volume occupied by 1 mole of the gas at old STP
 The volume of gas and the number of moles of gas at temperature and pressure other than the
old STP can be related by ideal gas equation, PV = nRT.
2.2 CHEMICAL EQUATIONS AND STOICHIOMETRY

 Let the balanced chemical equation be
MnO2 + 4HCl 
 MnCl2 + 2H2O + Cl2
 The quantitative information drawn from this balanced chemical equation is
 The molar ratio in which two reactants (MnO2 and HCl) reacting is 1:4.
 The molar ratio between two products can also be known i.e. moles of H2O produced
would be double the moles of MnCl2 produced.
 The initial moles of MnO2 and HCl (to be taken in vessel) for the reaction to occur not
necessarily be 1 and 4, respectively or in the molar ratio of 1:4.
 We can start reaction with MnO2 and HCl taken in any molar ratio, but the moles of two
reacting will always be in the molar ratio of 1:4.
 The balanced chemical equation should follow the law of conservation of mass.
 Let us consider the same chemical system with initial composition (in terms of mole) as
      
n MnO , n HCl , n MnCl , n H O , and n Cl . The n HCl is four times of n MnO . When the reaction occurs,
2 2 2 2 2
these mole numbers change as the reaction progresses.

Let after time ‘t’ from the commencement of reaction, the moles of MnO2 reacting be x, then
the moles of HCl reacting in the same time interval be 4x since MnO2 and HCl react in the
molar ratio of 1:4.
 Thus, after time t, the composition of the system would be
 
n MnO  n MnO  x , n HCl  n HCl  4x ,
2 2
  
n MnCl  n MnCl  x , n H2O  n MnO2  2x , n Cl2  n Cl2  x
2 2
 The algebric signs, + and – indicates that the reactants are consumed and products are formed.
In general, mole numbers of various species at any time would be given as
ni  ni  i x
 Where n i is the initial amount, x is the degree of advancement and  i is the stoichiometric
coefficient which will be given a negative sign for reactants and a positive sign for products.
 After long time interval from the commencement of reaction i.e. after  time, the composition
of the system would be
n MnO  o, n HCl  0
2
 
   n HCl    n HCl
n Mn Cl  n MnCl  n MnO  n MnCl  , nH  nH  2n M nO  n H 
2 2 2 2 4 2O 2O 2 2O 2

   n HCl
n Cl  n Cl  n MnO  n Cl 
2 2 2 2 4
2.3 THE LIMITING REAGENT AND EXCESS REAGENT

 Let the initial moles of MnO2 and HCl be n MnO and n HCl respectively and n HCl  4n MnO .
2 2
 Thus, in the given chemical reaction, after  time, one of the reactant will be completely
consumed while the other would be left in excess.
 Thus, the reactant which is completely consumed when a reaction goes to completion and
which decides the yield of the product is called limiting reagent.
 For example, if in the given case n HCl  4n MnO and there is no MnCl2, Cl2 and H2O in the
2
beginning, then
MnO2 + 4HCl 
 MnCl2 + Cl2 + 2H2O
 
Initially n MnO n HCl 0 0 0
2
    
After  time 0 n HCl  4n MnO n MnO n MnO 2n MnO
2 2 2 2
 Thus, MnO2 is the limiting reagent and the yield of all the products is governed by the amount
of MnO2 taken initially. HCl is the excess reagent in this reaction.
 Similarly, if in the given case n HCl  4n MnO and no MnCl2, Cl2 & H2O are present initially,
2
then
MnO2 + 4HCl 
 MnCl2 + Cl2 + 2H2O
 
Initially n MnO n HCl 0 0 0
2
   
 n n HCl n HCl n HCl
After  time n MnO  HCl 0
2 4 4 4 2
 Here, HCl would become limiting reagent & the products yield are decided by the amount of
HCl taken initially. MnO2 is the excess reagent in this case.
2.4 THE YIELD OF PRODUCT

n HCl
 Let us suppose that the amount of MnCl2 produced in the last case actually be less than
4

n HCl
while the theoretical yield should be . This means that the yield of the product is not
4
100%. Thus, percentage yield of the product is given as ratio of actual yield by theoretical
maximum yield multiplied by 100.
Actual yield
  % yield of the product =  100
Theoretical max imum yield
3. GRAVIMATRIC ANALYSIS
 Gravimetric analysis is an analytical technique based on the measurement of mass of solid
substances and/or volume of gaseous species.
 The gravivimetrmetric analysis is broadly classified into three heads.
 Masstance-mass relationship
 Mass gravi-volume relationship and
 VoluMass-me-volume relationship
3.1 MASS – MASS RELATIONSHIP
 This relates the mass of a species (reactant or product) with the mass of another species
(reactant or product) involved in a chemical reaction.
 Let us consider a chemical reaction,

BaCO3(s)   BaO(s) + CO2(g)
 Let the mass of BaCO3 taken be x g and we want to calculate the mass of BaO obtained by
x
heating x g BaCO3. Then the moles of BaCO3 taken would be (where M1 represents the
M1
molar mass of BaCO3). According to the balanced reaction, the molar ratio of BaCO3 and BaO
 x 
is 1:1, so same number of moles   of BaO would be formed. Now for converting the
 M1 
moles of BaO into mass of BaO obtained, we need to multiply the moles of BaO with the
molar mass of BaO.
 Let the molar mass of BaO be M2, so the mass of BaO obtained by heating x g of BaCO3 would
 x 
be   M2  g.
 M1 
3.2 MASS – VOLUME RELATIONSHIP
 This establishes the relationship between the mass of a species (reactant or product) and the
volume of a gaseous species (reactant or product) involved in a chemical reaction. Let us take x
g of BaCO3 in a vessel of capacity V L and the vessel is heated so that BaCO3 decomposes as

BaCO3(s)   BaO(s) + CO2(g)
 We want to find out the volume of CO2 evolved at old STP by heating x g of BaCO3. Then
x
Moles of BaCO3 =
M1
x
Moles of CO2 evolved = (since molar ratio of BaCO3 and CO2 is 1:1)
M1
 x 
 Volume of CO2 evolved at old STP =   22.4  L
 M1 
 But, if the volume of CO2 evolved is to be calculated at pressure P atm and temperature TK.
x
Then, moles of CO2 evolved = .
M1
x RT
 Volume of CO2 evolved at pressure P and temperature T =  (Using PV = nRT)
M1 P
3.3 VOLUME – VOLUME RELATIONSHIP
 This relationship deals with the volume of a gaseous species (reactant or product) with the
volume of another gaseous species (reactant or product) involved in a chemical reaction.
 Let us consider the reaction, N2(g) + 3H2(g) 
 2NH3(g). We are given x L of N2 at
pressure P atm and temperature TK and we want to know the volume of H2 required to react
with it at the same pressure and temperature.
Px
Moles of N2 =
RT
3 P  x
Moles of H2 required = (since molar ratio of N2 & H2 is 1:3)
RT
3  P  x  RT
 Volume of H2 required at same pressure & temperature = =3xL
RT  P
 This result could also have been obtained by knowing that for a gaseous relation, at the same
pressure and temperature, the moles of gas is directly proportional to volume of the gas (V  n
since P & T are constant) or molar ratio and volume ratio are same.
 Thus, when x L of N2 is taken at Pressure P atm and temperature TK, then at the same pressure
and temperature, the volume of H2 required would be 3 x L (since the volume ratio of N2 & H2
would be same as molar ratio i.e. 1:3). But if the volume of H2 required is to be calculated at
another pressure ‘P’ atm and temperature T’K, then
3 P  x
Moles of H2 required =
RT
 Volume of H2 required at pressure P’ atm & temperature T’K
3  P  x  RT   3x  PT 
=  L
RT  P   P T 
 Calculate the volume of NH3 evolved by reacting x L of N2 with excess of H2 at pressure P’ atm and
temperature T’K.
Illustration-2
How much zinc should be added to 0.01 mol AgNO3 solution to displace all the silver in the solution?
Solution:
The involved balanced reaction would be
Zn + 2AgNO3 
 Zn(NO3)2 + 2Ag
Moles of AgNO3 in the solution = 0.01
Moles of Zn to be added to solution = 0.005
(since AgNO3 and Zn are reacting in the molar ratio of 2 : 1)
 Mass of Zn to be added to solution = 0.005 × 65.4 = 0.327 g
Illustration-3
NaCl of 95% purity is used to prepare salt cake (Na2SO4) by the reaction,
2NaCl + H2SO4 
 Na2SO4 + 2HCl
If the product (Na2SO4) is only 85% pure, what weight of NaCl is used up in producing 1 kg of the
impure salt cake?
Solution:
Let the weight of NaCl used up in producing 1 kg of impure product be x g.
x  95
Mass of pure NaCl =
100
x  95
Moles of pure NaCl =
100  58.5
x  95 1
Moles of pure Na2SO4 = 
100  58.5 2
x  95 1 1000  85
Mass of pure Na2SO4 =   142 =
100  58.5 2 100
 x = 737.2 g
Illustration-4
KClO3 decomposes on heating in two possible ways as

KClO3   KCl + 3/2 O2

4KClO3   KCl + 3KClO4
When 15 g of KClO3 were heated in an experiment, analysis of the product showed that 5.21 g of KCl
and 4.59 g of KClO4 were formed. What was the weight of KClO3 remaining undecomposed? What
fraction of the KClO3 decomposed yielded KClO4?
Solution:
In order to calculate the weight of KClO3 remaining undecomposed, we need to find out the total
weight of KClO3 that decomposes. The weight of KClO3 that decomposes in second reaction would
be known using the KClO4 data. Using KClO4 data, we would also calculate the weight of KCl
obtained in second reaction. Since, total weight of KCl obtained is known to us, so the weight of
KCl obtained in first reaction would also be known, using this we will find out the weight of KClO3
decomposed in first reaction.
4.59
Moles of KClO4 obtained =
138.5
4.59 1
Moles of KCl obtained in IInd reaction =  = 0.011 (since molar ratio of KClO4 and KCl
138.5 3
in IInd reaction is 3:1).
4.59 4
Moles of KClO3 that decomposes in IInd reaction =  (since molar ratio of KClO4 and
138.5 3
KClO3 in IInd reaction is 3:4)
4.59 4
 Mass of KClO3 that decomposes in IInd reaction =   122.5 = 5.41 g
138.5 3
Moles of KCl obtained in Ist reaction =  

5.21
 0.011  = 0.07 – 0.011 = 0.059
 74.5 
Moles of KClO3 that decomposes in Ist reaction = 0.059
(since molar ratio of KCl and KClO3 in Ist reaction is 1:1)
Mass of KClO3 that decomposes in Ist reaction = 0.059 × 122.5 = 7.23 g
Total mass of KClO3 that decomposes in both the reactions = (5.41 + 7.23) = 12.64 g
 Mass of KClO3 that remain undecomposed = 15 – 12.64 = 2.36 g
3
Moles of O2 evolved in Ist reaction = 0.059 ×
2
3
Volume of O2 evolved at STP in Ist reaction = 0.059 × × 22.4 = 1.98 L
2
5.41
Fraction of KClO3 decomposed yielding KClO4 = = 0.36
15
4. CONCENTRATION TERMS
4.1 MOLARITY (M)
 It is defined as the number of moles of solute present in one litre of solution.
number of moles of 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 solution
weight of solute w
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
4.2 MOLALITY (m)

 The number of moles of solute dissolved in1000 g (1 kg) of a solvent is known as the molality
of the solution.
number of moles of solute
i.e., molality = × 1000
mass of solvent in gram
Let Y g of a solute is dissolved in X g of a solvent. The molecular mass of the solute is M0.
Then Y/M0 mole of the solute are dissolved in X g of the solvent. Hence
Y
Molality = × 1000
M0  X
Molality is independent of temperature changes.
4.3 MOLE FRACTION (x)
 The ratio of number of moles of the solute or solvent present in the solution and the total
number of moles present in the solution is known as the mole fraction of substances concerned.
Let number of moles of solute in solution = n
Number of moles of solvent in solution = N
n
 Mole fraction of solute (x1) =
nN
N
 Mole fraction of solvent (x2) =
nN
Also x1 + x2 = 1
Mole fraction is a pure number. It will remain independent of temperature changes.
4.4 % WEIGHT BY WEIGHT (w/w) :
 It is given as mass of solute present in per 100 g of solution.
mass of solute in g
i.e. % w/w = × 100
mass of solution in g
4.5 % WEIGHT BY VOLUME (w/v)
 It is given as mass of solute present in per 100 ml of solution.
mass of solute in g
i.e., % w/v = × 100
volume of solution in ml
4.6 % VOLUME BY VOLUME (v/v)
 It is given as volume of solute present in per 100 ml solution.
volume of solute in ml
i.e., % v/v = × 100
volume of solution in ml
4.7 PARTS PER MILLION (ppm)
 When the solute is present in very less amount, then this concentration term is used. It is
defined as the number of parts of the solute present in every 1 million parts of the solution.
ppm can both be in terms of mass or in terms of moles. If nothing has been specified, we take
ppm to be in terms of mass. Hence, a 100 ppm solution means that 100 g of solute is present in
every 1000000 g of solution.
mass of A
ppmA = × 106 = mass fraction × 106
Total mass
4.8 NORMALITY (N)

 It is defined as the number 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 difference 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)
w
 Number of equivalents of solute = = N × V (in litre)
E
4.9 EQUIVALENT MASS
Atomic or molecular mass M
 Equivalents mass = = 1
'n ' factor n
w w wn
 Number of equivalents of solute =  =
E M1 / n M1
 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
4.10 DILUTION EFFECT
 When a solution is diluted, the moles and equivalents of solute do not 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.
4.11 DILUTION & MIXING OF TWO LIQUIDS
 If a particular solution having volume V1 and molarity = M1 is diluted upto volume V2 mL than
M1V1 = M2V2
M2 : Resultant molarity
If a solution having volume V1 and molarity M1 is mixed with another solution of same solute
having
volume V2 mL & molarity M2 then M1V1 + M2V2 = MR (V1 + V2)
M1V1  M 2 V2
MR = Resultant molarity =
V1  V2
5. LAW OF EQUIVALENTS
 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 provides 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,
 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 has 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 and M1 are
E M1 / n M1
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 (which we will be dealing in
section–II)
6. n-FACTOR CALCULATION
6.1 ACIDS
 Acids are the species which furnish H+ ions when dissolved in a solvent. For acids, nfactor is
defined as the number of H+ ions replaced by 1 mole of acid in a reaction. Note that the
nfactor for acid is not equal to its basicity; i.e. the number of moles of replaceable H+ atoms
present in one mole of acid.
For example, nfactor of HCl = 1,
nfactor of HNO3 = 1,
nfactor of H2SO4 = 1 or 2, depending upon extent of reaction it
undergoes.
H2SO4 + NaOH 
 NaHSO4 + H2O
 Although one mole of H2SO4 has 2 replaceable H atoms but in this reaction H2SO4 has given
only one H+ ion, so its nfactor would be 1.
H2SO4 + 2NaOH 
 Na2SO4 + 2H2O
The nfactor of H2SO4 in this reaction would be 2.

Similarly, nfactor of H2SO3 = 1 or 2
nfactor of H2CO3 = 1 or 2
nfactor of H3PO4 = 1 or 2 or 3
 nfactor of H3PO3 = 1 or 2 because one of the H is not replaceable in H3PO3. This can be seen
using its structure . The H atoms which are linked to oxygen are replaceable
while the H atom linked directly to central atom (P) is non-replaceable.
 nfactor of H3BO3 = 1
In H3BO3, although all three H are linked to oxygen, yet all 3 H are not replaceable. Here,
boron atom is electron deficient, so it acts as a Lewis acid. When H3BO3 is added to water, then
oxygen atom of H2O through its lone pair attack the boron atom, as follows
 [B(OH)4] + H3O+.
The net reaction is H3BO3 + 2H2O 
Thus, one mole of H3BO3 in solution gives only one mole of H+, so its nfactor is 1.
6.2 BASES
 Bases are the species, which furnish OH ions when dissolved in a solvent. For bases, nfactor
is defined as the number of OH ions replaced by 1 mole of base in a reaction. Note that
nfactor is not equal to its acidity i.e. the number of moles of replaceable OH ions present in 1
mole of base.
For example, nfactor of NaOH =1
nfactor of Zn(OH)2 = 1 or 2
n–factor of Ca(OH)2 = 1 or 2
n–factor of Al(OH)3 = 1 or 2 or 3
n–factor of NH4(OH) = 1.
6.3 SALTS WHICH REACT SUCH THAT NO ATOM UNDERGOES CHANGE IN
OXIDATION STATE
 The nfactor for such salts is defined as the total moles of cationic /anionic charge replaced in
1 mole of the salt. For the reaction,
Na3PO4 + BaCl2 
 NaCl + Ba3(PO4)2
 To get one mole of Ba3(PO4)2, two moles of Na3PO4 are required, which means six moles of
Na+ are completely replaced by 3 moles of Ba2+ ions. So, six moles of cationic charge is
replaced by 2 moles of Na3PO4, thus each mole of Na3PO4 replaces 3 moles of cationic charge.
Hence, nfactor of Na3PO4 in this reaction is 3.
 Similarly, find the n–factor of BaCl2 in the given reaction.
6.4 SALTS WHICH REACT IN A MANNER THAT ONLY ONE ATOM UNDERGOES
CHANGE IN OXIDATION STATE AND GOES IN ONLY ONE PRODUCT
 The nfactor of such salts is defined as the number of moles of electrons exchanged (lost or
gained) by one mole of the salt.
 Let us have a salt AaBb in which oxidation state of A is +x. It changes to a compound, which
has atom D in it. The oxidation state of A in AcD be +y.
A a x Bb 
 A c y D
The nfactor of AaBb is calculated as

n = | ax  ay |
 To calculate nfactor of a salt of such type, we take one mole of the reactant and find the
number of mole of the element whose oxidation state is changing. This is multiplied with the
oxidation state of the element in the reactant, which gives us the total oxidation state of the
element in the reactant. Now, we calculate the total oxidation state of the same element in the
product for the same number of mole of atoms of that element in the reactant. Remember that
the total oxidation state of the same element in the product is not calculated for the number of
mole of atoms of that element in the product.
For example, let us calculate the nfactor KMnO4 for the given chemical change.
H
 Mn 2 .
KMnO 4 
 In this reaction, oxidation state of Mn changes from +7 to +2. Thus, KMnO4 is acting as
oxidising agent, since it is reduced.
 nfactor of KMnO4 = |1  (+7)  1  (+2)| = 5
Similarly,
H 2O
(a) KMnO4   Mn+4
nfactor of KMnO4 = |1  (+7)  1  (+4)| = 3


(b) OH
KMnO4   Mn+6
nfactor of KMnO4 = |1  (+7)  1  (+6)| = 1

 It can be seen that in all the above chemical changes, KMnO4 is acting as oxidising agent, yet
its nfactor is not same in all reactions. Thus, the nfactor of a compound is not fixed, it
depends on the type and the extent of reaction it undergoes.
Illustration-5
Calculate the nfactor of reactants in the given chemical changes?
C2O42 

(a) K2Cr2O7 
H
Cr3+ (b)  CO2
(c) S 2O32  

alkaline
 SO42  (d) I– 
 ICI
Solution:
6 
(a) H
K 2 Cr2O7  Cr3
The oxidation state of Cr changes from +6 to +3.
 n = | 2  (+6) 2  (+3) | = 6
3 4
(b) C 2 O42 
 CO2
Carbon get oxidized from +3 to +4.

 n = | 2  (+3)  2  (+4) | = 2
2 alkaline 6
(c) S 2O32 
 SO42
The oxidation state of sulphur changes from +2 to +6.
 n = | 2  (+2) 2  (+6) | = 8
1
(d) I  
 ICl
I get oxidized to I+.

 n = | 1  (1) 1  (+1) | = 2
 Calculate the nfactor of reactants in the given chemical changes?
(a) S 2 O32  

acidic
 S 4 O62  (b) I  
 I2
(c) I
I 2  (d) IO3 
 ICl
(e) FeSO4 
 Fe2O3
 Also calculate the nfactor of reactants in the given chemical changes?
(a) Fe2 O3 
 FeSO4 (b)  Cu 2   SO2
CuS 
(c) NO3 
 N 2O (d) As2 S 6 
 H 2 SO4  H 3 AsO4
(e) As2 O3 
 As2 O5
6.5 SALTS THAT REACT IN A MANNER THAT ONLY ONE ATOM UNDERGOES CHANGE
IN OXIDATION STATE BUT GOES IN TWO PRODUCTS WITH THE SAME OXIDATION
STATE.
 Let us have a salt AaBb in which oxidation state of A is x. It undergoes a reaction such that
element A changes it oxidation state and goes in more than one (two) products with the same
oxidation state (but different oxidation state than in the reactant). In such case, the nfactor is
calculated in the same manner as in case 4.
Let the chemical change be
A a x B b 
 A c y D  A e y F
 In such cases, the number of products in which element A is present is of no significance since
the oxidation state of A in both the products is same. The point of importance is not the number
of products containing that element which undergoes change in oxidation state but the
oxidation state of the element is of importance. The nfactor of AaBb is calculated in the same
way as in case 4.
 nfactor of AaBb = |ax  ay|
For example, let us calculate the nfactor of K2Cr2O7 for the given chemical change.
Cr2 O 72  
 Cr 3  Cr 3
In this reaction, oxidation state of Cr changes from +6 to +3 in both products.

 nfactor of K2Cr2O7 = | 2  (+6) 2  (+3)| = 6
6.6 SALTS THAT REACT IN A MANNER THAT TWO TYPE OF ATOMS IN THE SALT
UNDERGO CHANGE IN OXIDATION STATE (BOTH THE ATOMS ARE EITHER
GETTING OXIDISED OR REDUCED).
 Let the change be represented as
Aa x Bb 
 Ac yD  Ef B z
 In this reaction, both A and B are changing their oxidation states and both of them are either
getting oxidised or reduced. In such cases, the nfactor of the compound would be the sum of
individual nfactors of A and B.
nfactor of A = |ax  ay|
  nfactor of B = | ax  bz| because the total oxidation state of ‘b’ B’s in the reactant is ax (as
the total oxidation state of ‘a’ A’s in the reactant is +ax) and the total oxidation state of
y B’s in the product is bz.
 nfactor of AaBb = |ax  ay| + |ax  bz|
 In general, the nfactor of the salt will be the total number of mole of electrons lost or gained
by one mole of the salt.
4
For example, we have a reaction, Cu 21S2 
 Cu 2  SO 2
in which Cu+ and S2 both are getting oxidised to Cu2+ and S+4 respectively.
 nfactor of Cu2S = |2  (+1)  2  (+2)| + | 1  (2) 1  (+4)| = 8
 Calculate the nfactor of reactants in the given reactions.
(a)  Fe3  Cr 6
FeCr2O4  (b)  Fe3  CO2
FeC2 O4 
(c) [ Fe(CN ) 6 ]4  
 Fe3  CO2  NO3 (d)  Fe 2   NO
Fe( NO3 )3 
(e) Fe2  SO4 3 

 Fe 2   SO2
6.7 SALTS THAT REACT IN A MANNER THAT TWO ATOMS IN THE SALT UNDERGOES
CHANGE IN OXIDATION STATE (ONE ATOM IS GETTING OXIDISED AND THE
OTHER IS GETTING REDUCED).
 If we have a salt which react in a fashion that atoms of one of the element are getting oxidised
and the atoms of another element are getting reduced and no other element on the reactant side
is getting oxidised 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 KClO3 is represented as
5 2 1 0
K ClO3 
 K Cl O2
  In this reaction, O2 is getting oxidised 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
 Calculate nfactor of FeCl3 and (NH4)2Cr2O7 in the respective reactions.
(i) 
FeCl3   Fe2+ + 1/2Cl2 + 2Cl

(ii) (NH4)2Cr2O7   N2 + Cr2O3 + 4H2O
6.8 SALTS OR COMPOUNDS WHICH UNDERGOES DISPROPORTIONATION REACTION

  Disproportionation reactions are the reactions in which oxidising and reducing agents are
same or the same element from the same compound is getting oxidised as well as reduced.
nfactor of a disproportionation reaction can only be calculated using a balanced chemical
reaction. We will categorize disproportionation reactions into two types.
(a) Disproportionation reactions in which moles of compound getting oxidised and reduced
are same i.e. moles of oxidising agent and reducing agent are same. The nfactor for
such compounds is calculated by either the number of mole of electrons lost or gained by
one mole of the compound because in such a case, nfactor of the compound acting as
oxidizing agent or as reducing agent would be same.
For example, 2H2O2 
 2H2O + O2
Out of the 2 mole of H2O2 used in reaction, one mole of H2O2 gets oxidised to O2
(oxidation state of O changes from 1 to 0) while the other mole of H2O2 gets reduced to
H2O (oxidation state of O changes from 1 to 2). When 1 mole of H2O2 gets oxidised to
O2, the halfreaction would be O 22  
 O 02  2e  and when 1 mole of H2O2 gets
reduced to H2O, the halfreaction would be O 22   2e  
 2O 2 
Thus, it is evident that one mole of H2O2 (which is either getting oxidised or reduced)
will lose or gain 2 mole of electrons. Therefore, nfactor of H2O2 as oxidizing as well as
reducing agent in this reaction is 2. Thus,
Or when the reaction is written as

2H2O2  2H2O + O2
Where, H2O2 is not distinguished as how much of it functions as oxidizing agent and
how much as reducing agent, then nfactor calculation can be done in the following
manner. Find the number of electrons exchanged (lost or gained) using the balanced
equation and divide it by the number of moles of H2O2 involved in the reaction. Thus, the
nfactor of H2O2 when the reaction is written without segregating oxidising and reducing
2
agent is =1.
2
2H 2 O 2 
 2H 2 O  O 2
(n 1) (n 1) (n  2)
 Calculate nfactor of HCuCl2 in the given reaction,

dil . with
2HCuCl2   Cu + Cu2+ + 4Cl + 2H+.
H 2O
(b) Disproportionation reactions in which moles of compound getting oxidised and reduced
are not same i.e. moles of oxidising agent and reducing agent are not same.
For example,
 10Br + 2BrO3 + 6H2O
6Br2 + 12 OH 
In this reaction, the mole of electrons lost by the oxidation of some of the moles of Br2
are same as the number of mole of electrons gained by the reduction of rest of the moles
of Br2. 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 electron
(as oxidizing agent).
 2Br+5 + 10e–
Br2 
5Br2 + 10e– 
 10Br
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 Br2.
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 oxidising and reducing agent is 5/3.
10Br   2Br 5
6Br2 
(n  5/3) (n 1) (n  5)

 Calculate nfactor of KClO3 in the following reaction, 4KClO3   3KClO4 + KCl.
7. VOLUMETRIC ANALYSIS
 The volumetric analysis is an analytical method of estimating the concentration of a
substance in a solution by adding exactly same number of equivalents of another substance
present in a solution of known concentration.
  This is the basic principle of titration. Volumetric analysis is also known as titrimetric
analysis.
 The substance whose solution is employed to estimate the concentration of unknown solution
is called titrant and the substance whose concentration is to be estimated is called titrate.
 The volumetric analysis is divided into following types:
(a) Simple titrations (b) Back titrations (c) Double titrations
7.1 SIMPLE TITRATIONS
  The aim of simple titration is to find the concentration of an unknown solution with the help of
the known concentration of another solution.
 Let us take a solution of a substance ‘A’ of unknown concentration. We are provided with
solution of another substance ‘B’ whose concentration is known (N1). We take a certain known
volume (V2 litre) of ‘A’ in a flask and start adding ‘B’ from burette to ‘A’ slowly till all the ‘A’
is consumed by ‘B’. This can be known with the aid of suitable indicator, which shows colour
change after the complete consumption of ‘A’. Let the volume of B consumed is V1 litre.
According to the law of equivalents, the number of equivalents of ‘A’ would be equal to the
number of equivalents of ‘B’.
 N1V1 = N2V2, where N2 is the concentration of ‘A’.
Thus using this equation, the value of N2 can be calculated.
There are four types of simple titrations, namely
(a) Acidbase titrations (b) Redox titrations
(c) Precipitation titrations and (d) Complexometric titrations
7.1.1 ACIDBASE TITRATIONS

 In this type of titration, the concentration of an acid in a solution is estimated by adding a
solution of standard base and vice versa. The equivalence point is detected by 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.
7.1.2 REDOX TITRATIONS
 In a redox titration, an oxidant is estimated by adding reductant or viceversa. For example,
Fe2+ ions can be estimated by titration against acidified KMnO4 solution when Fe2+ ions are
oxidised to Fe3+ ions and KMnO4 is reduced to Mn2+ in the presence of acidic medium. KMnO4
functions as self-indicator as its purple colour is discharged at the equivalence point.
MnO 4  8H   5e  
 Mn 2  4H 2 O
Fe 2  
 Fe3  e  ]  5
MnO 4  8H   5Fe 2  
 Mn 2   5Fe3  4H 2 O
(n 5) (n 1)
 In addition to acidified KMnO4, acidified KCr2O7 can also be employed. Other redox titrations
are iodimetry, iodometry etc.
7.1.3 PRECIPITATION TITRATIONS
 In a titration of this kind, cations and anions combine to form a compound of very low
solubility. Thus, a solid residue separates out. For example,
AgNO3  NaCl 
 AgCl   NaNO3
white
BaCl2  H 2SO4 
 BaSO4  2HCl
white
7.1.4 COMPLEXOMETRIC TITRATIONS
 In this type of titration, the titrate combines with the titrant to form complex salts. The complex
salts may or may not be soluble. For example,
CuSO4 + 4NH4OH 
 [Cu(NH3)4]SO4 + 4H2O
AgNO3 + 2KCN 
 K[Ag(CN)2] + KNO3
7.2 BACK TITRATIONS

 Let us assume that we have an impure solid substance ‘C’, weighing ‘w’ g and we are required
to calculate the percentage purity of ‘C’ in the sample. We are also provided with two solutions
‘A’ and ‘B’, where the concentration of ‘B’ is known (N1) and that of ‘A’ is unknown. For the
back titration to work, following conditions are to be satisfied (a) Compounds ‘A’, ‘B’ and ‘C’
should be such that ‘A’ and ‘B’ react with each other. (b) ‘A’ and pure ‘C’ also react with each
other but the impurity present in ‘C’ does not react with ‘A’. (c) Also the product of ‘A’ and
‘C’ should not react with ‘B’.
 Now we take out certain volume of ‘A’ in a flask (the equivalents of ‘A’ taken should be 
equivalents of pure ‘C’ in the sample) and perform a simple titration using ‘B’. Let us assume
that the volume of ‘B’ used be V1 litre.
Equivalents of ‘B’ reacted with ‘A’ = N1V1
 Equivalents of ‘A’ initially = N1V1
 In another flask, we again take same volume of ‘A’ but now ‘C’ is added to this flask. Pure part
of ‘C’ reacts with ‘A’ and excess of ‘A’ is back titrated with ‘B’. Let the volume of ‘B’
consumed is V2 litre.
Equivalents of ‘B’ reacted with excess of ‘A’ = N1V2
 Equivalents of ‘A’ in excess = N1V2
Equivalents of ‘A’ reacted with pure ‘C’ = (N1V1  N1V2)
Equivalents of pure ‘C’ = (N1V1  N1V2)
Let the nfactor of ‘C’ in its reaction with ‘A’ be x,
then the moles of pure ‘C’ =

 N1V1  N1V2 
x
 Mass of pure ‘C’ =

 N1V1  N1V2   Molar mass of ‘C’.
x
 Percentage purity of ‘C’ =

 N1V1  N1V2  
Molar mass of ' C '
 100
x w
7.3 DOUBLE TITRATIONS
 The purpose of double titration is to determine the percentage composition of an alkali mixture
or an acid mixture. In the present case, we will find the percentage composition of an alkali
mixture. Let us consider a solid mixture of NaOH, Na2CO3 and some inert impurities, weighing
‘w’ g. We are required to find the % composition of this alkali mixture. We are also given an
acid reagent (HCl) of known concentration M1 that can react with the alkali sample.
 We first dissolve this mixture in water to make an alkaline solution and then we add two
indicators, (Indicators are substances that indicate colour change of solution when a reaction
gets completed), namely phenolphthalein and methyl orange to the solution. Now, we titrate this
alkaline solution with standard HCl.
 NaOH is a strong base while Na2CO3 is a weak base. So it is obvious that NaOH reacts first
with HCl completely and Na2CO3 reacts only after complete NaOH is neutralized.
NaOH + HCl 
 NaCl + H2O …(i)
Once NaOH has reacted completely, then Na2CO3 starts reacting with HCl in two steps, shown
as
Na2CO3 + HCl  NaHCO3 + NaCl …(ii)
NaHCO3 + HCl  NaCl + CO2 + H2O …(iii)
 It is clear that when we add HCl to the alkaline solution, alkali is neutralized and the pH of the
solution decreases. Initially the pH decrease would be rapid as strong base (NaOH) is
neutralized completely. When Na2CO3 is converted to NaHCO3 completely, the solution is still
weakly basic due to the presence of NaHCO3 (which is weaker as compared to Na2CO3). At
this point, phenolphthalein changes colour since it requires this weakly basic solution to show
its colour change. When HCl is further added, the pH again decreases and when all the
NaHCO3 reacts to form NaCl, CO2 and H2O the solution becomes weakly acidic due to the
presence of the weak acid (H2CO3). At this point, methyl orange changes colour as it requires
this weakly acidic solution to show its colour change.
Thus in general, phenolphthalein shows colour change when the solution contains weakly
basic NaHCO3 along with other neutral substances while methyl orange shows colour
change when solution contains weakly acidic H2CO3 along with other neutral substances.
 Let the volume of HCl used up for the first and the second reaction be V1 litre (this is the
volume of HCl used from the beginning of the titration up to the point when phenolphthalein
shows colour change) and the volume of HCl required for the third reaction be V2 litre (this is
the volume of HCl used from the point where phenolphthalein had changed colour upto the
point when methyl orange shows colour change). Then,
Moles of HCl consumed by NaHCO3 = Moles of NaHCO3 reacted = M1V2
Moles of NaHCO3 formed from Na2CO3 = M1V2
Moles of Na2CO3 in the mixture = M1V2
Mass of Na2CO3 in the mixture = M1V2  106
M1V2  106
% of Na2CO3 in the mixture =  100
w
Moles of HCl used in the reaction (i) and (ii) = M1V1
Moles of HCl used in reaction (ii) = M1V2
Moles of HCl used in reaction (i) = (M1V1  M1V2)
 Moles of NaOH = (M1V1  M1V2)
Mass of NaOH = (M1V1  M1V2)  40
(M1V1  M1V2 )  40
% of NaOH in the mixture =  100
w
 Here, we have determined the percentage composition of the mixture using mole concept, as
the balanced reactions were available. If we were to solve this by equivalent concept, then the
procedure adopted would be
NaOH + HCl  NaCl + H2O …(i)
Na 2 CO3  HCl 
 NaHCO3  NaCl …(ii)
(n 1) (n 1) (n 1)
Phenolphthalein shows end point after reaction (ii)

NaHCO3  HCl 
 NaCl  CO 2  H 2 O …(iii)
(n 1) (n 1)
and methyl orange shows end point after reaction (iii).

At Phenolphthalein end point,
(Equivalents of HCl)1 = Equivalents of NaOH + Equivalents of Na2CO3 (n = 1) …(iv)

= M1V1
or (Equivalents of HCl)1 = Equivalents of NaOH +½ Equivalents of Na2CO3 (n = 2) …(iv)
At methyl orange end point,
(Equivalents of HCl)2 = Equivalents of NaHCO3 reacted (n = 1)
= Equivalents of NaHCO3 produced (n = 1) = Equivalents of Na2CO3 (n = 1)
 M1V2 = Equivalents of Na2CO3 (n = 1) = ½ Equivalents of Na2CO3 (n = 2) …(v)
Substracting equation (v) from equation (iv),
Equivalents of NaOH = (M1V1  M1V2)
 Moles of NaOH = (M1V1  M1V2) (Since nfactor of NaOH is 1)
 % of NaOH in the mixture =

 M1V1  M1V2   40  100
w
Equivalents of Na2CO3 (n = 1) = M1V2
and moles of Na2CO3 = M1V2 (Since nfactor of Na2CO3 is 1)
M1V2  106
 % of Na2CO3 in the mixture =  100
w
 In the above case, we have taken alkali mixture of NaOH & Na2CO3. But other alkali mixtures
can also be taken. For example,
(i) If a mixture of NaOH and NaHCO3 has been taken
(a) Equivalents of NaOH = Equivalents of HCl required upto phenolphthalein end
point
(b) Equivalents of NaHCO3 = Equivalents of HCl required from phenolphthalein end
point to methyl orange end point.
(ii) If a mixture of Na2CO3 and NaHCO3 has been taken
(a) ½ Equivalents of Na2CO3 (n = 2)
= Equivalents of HCl required upto phenolphthalein end point
(b) ½ Equivalents of Na2CO3 (n = 2) + Equivalents of NaHCO3 initially (n = 1)
= Equivalents of HCl required from phenolphthalein end point to methyl orange
end point.
(iii) If a mixture of NaOH, Na2CO3 and NaHCO3 has been taken
(a) Equivalents of NaOH + ½ Equivalents of Na2CO3 (n = 2)
= Equivalents of HCl required upto phenolphthalein end point
(b) ½ Equivalents of Na2CO3 (n = 2) + Equivalents of NaHCO3 initially (n = 1)
= Equivalents of HCl required from phenolphthalein end point to methyl orange
end point.
Illustration-6
A solution contains a mixture of Na2CO3 and NaOH. Using phenolphthalein as indicator, 25 ml of
mixture required 21 ml of 1.1 N HCl for the end point. With methyl orange as indicator, 25 ml of
solution required 25 ml of the same HCl for the end point. Calculate grams per litre of each
substance in the mixture.
Solution:
Since, the volume of HCl required in titration using methyl orange is greater than the volume of
HCl required using phenolphthalein, this means that the titration is carried out separately two
times using phenolphthalein and methyl orange indicators, respectively.
NaOH + HCl 
 NaCl + H2O …(i)
Na2CO3 + HCl 
 NaHCO3 + NaCl …(ii)
NaHCO3 + HCl 
 NaCl + CO2 + H2O …(iii)
Thus, the volume of HCl used in third reaction = (25  21) = 4.0 ml
 Moles of HCl used in third reaction = 4.0  103  1.1
Moles of NaHCO3 reacted = 4.4  103
Moles of NaHCO3 produced = 4.4  103
 Moles of Na2CO3 present in 25 ml = 4.4  103
 Mass of Na2CO3 present in 1 litre = 4.4  103  106  40 = 18.656 g
Moles of HCl reacted in second reaction = 4.4  103
Moles of HCl used in first two reactions = 21  103  1.1 = 23.1  103
 Moles of HCl used in first reaction = (23.1  4.4)  103 = 18.7  103
Moles of NaOH present in 25 ml = 18.7  103
 Mass of NaOH present in 1 litre = 18.7  103  40  40 = 29.92 g
8. VOLUME STRENGTH OF H2O2 SOLUTION

 When a solution of H2O2 is labeled as ‘x volumes’, it means that 1 volume (1 ml or 1 litre) of
H2O2 solution would liberate x volumes (x ml or x litre) of O2 at STP on complete
decomposition.

H2O2  H2O + ½ O2 …(i)
 If a H2O2 solution (acting as reducing agent) has normality N and it is to be reacted with
KMnO4 solution (acting as oxidising agent), we can say that there are N equivalents of H2O2
present in 1 litre of this H2O2 solution.
N
 1 ml of H2O2 of this solution would contain equivalents.
1000

H
H 2 O 2  KMnO4  O 2  Mn 2 …(ii)
(n  2) (n  2 )
1 N
 Moles of H2O2 in 1 ml of this solution =  [from equation (ii)]
2 1000
 When these many moles of H2O2 in 1 ml of solution are allowed to decompose according to the

reaction, H2O2   H2O + ½O2, the volume of O2 released (in ml) by them at STP will give
the volume strength of H2O2 solution.
1 1 N
Moles of O2 given by 1 ml of this solution =   [from equation (i)]
2 2 1000
1 1 N
 Volume of O2 at STP given by 1 ml of this solution =    22400 = 5.6  N
2 2 1000
 Volume strength of H2O2 = 5.6  Normality of H2O2
9. PERCENTAGE LABELING OF OLEUM
 Oleum contains H2SO4 and SO3 only. When oleum is diluted (by adding water), SO3 reacts
with H2O to form H2SO4, thus increasing the mass of the solution.
SO3 + H2O 
 H2SO4
 The total mass of H2SO4 obtained by diluting 100 g of oleum sample with required amount of
water, is equal to the percentage labeling of oleum.
 Percentage labeling of oleum = Total mass of H2SO4 present in oleum after dilution.
= mass of H2SO4 initially present + mass of H2SO4 produced on dilution.
 If we have a sample of oleum labeled as 109%, this means that 100 g of oleum on dilution
gives 109 g of H2SO4.
Let us calculate the composition of oleum, which is labeled as 109%.
Let the mass of SO3 in the sample be x g, then the mass of H2SO4 would be (100  x) g. On
dilution,
SO3 + H2O 
 H2SO4
x
Moles of SO3 in oleum = = Moles of H2SO4 formed on dilution
80
x  98
 Mass of H2SO4 formed on dilution =
80
x  98 
Total mass of H2SO4 present in oleum after dilution =   + (100  x) = 109
 80 
 x = 40
Thus, oleum contained 40% SO3 & 60% H2SO4.
Alternatively,
Let the mass of oleum sample be 100 g, which on dilution becomes 109 g. This implies that 9 g of
H2O was added.
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.
10. SOME IMPORTANT CHEMICAL REACTIONS
 There are some chemical reactions, which a student should remember in order to solve
problems on stoichiometry. These are categorised as
10.1 COMBINATION OF ELEMENTS WITH OXYGEN
(i) Heating mercury at its boiling point in air.
Hg + O2 
 2HgO (red mercuric oxide)
(ii) Heating magnesium in air. It forms mostly magnesium oxide and some magnesium nitride.
2Mg + O2 
 2MgO
3Mg + N2 
 Mg3N2
(iii) Calcium behaves similarly.

2Ca + O2 
 2CaO
3Ca + N2 
 Ca3N2
(iv) Silver does not combine with oxygen, as Ag2O is unstable to heat.
(v) Many non-metals burn in O2 forming their respective oxides.
2H2 + O2 
 2H2O; S + O2 
 SO2
C + O2 
 CO2; P4 + 5O2 
 P4O10

3000 C
N2 + O2  
 2NO
Cl2, Br2 and I2 do not directly combine with oxygen.

10.2 ACTION OF HEAT ON CERTAIN OXIDES
(i) Mercuric oxide and silver oxide are unstable to heat and decompose readily.
  2Hg  O ; 2Ag O 
2HgO    4Ag  O
2 2 2
(ii) Various higher oxides, dioxides, mixed oxides and peroxides are decomposed to oxygen and a
lower oxide.
2Pb3O4 
 6PbO + O2; 2PbO2 
 2PbO + O2
3MnO2 
 Mn3O4 + O2; 2BaO2 
 2BaO + O2
10.3 COMPOUNDS RICH IN OXYGEN DECOMPOSE TO GIVE OXYGEN

(i)  2KNO2 + O2 
2KNO3 
(ii) 2KMnO 4 
 K 2 MnO 4  MnO 2  O 2 
(purple) (green) (black )
(iii) 4K 2 Cr2 O 7 
 4K 2 CrO 4  2Cr2 O3  3O 2 
(orange  red) ( yellow ) (green )
Potassium chlorate when heated just above its melting point decomposes into potassium
perchlorate and potassium chloride. This reaction is called disproportionation or auto-oxidation and
auto-reduction. On heating further, KClO decomposes to KCl and oxygen.
4
(iv) 4KClO3 
 3KClO4 + KCl
KClO4 
 KCl + 2O2
10.4 ACTION OF HEAT ON NITRATES

Generally heavy metal nitrates decompose to metal oxide, reddish brown nitrogen dioxide gas and
oxygen.
(i) Lead nitrate decomposes to PbO, NO2 & O2.
2Pb(NO3)2 
 2PbO + 4NO2  + O2
litharge or lead (II) oxide
(red when hot and yellow when cold)
(ii) Cupric nitrate decomposes to CuO + 4NO2 & O2.
2Cu  NO3 2 
 2CuO 4NO 2  O 2
(black)
(green)
(iii) Zinc nitrate decomposes to ZnO, NO2 & O2.

2Zn(NO3)2 
 2ZnO + 4NO2 + O2
(zinc oxide, yellow when hot and white when cold)

Knowing the colours of some oxides will be useful in qualitative analysis.
(iv) Nitrates of mercury and silver, whose oxides are unstable, decompose into the metal, NO2 and
O2.
Hg(NO3)2 
 Hg + 2NO2 + O2
2AgNO3 
 2Ag + 2NO2 + O2
(v) Alkali metal nitrates decompose to give the metal nitrite and O2 (No reddish brown NO2 gas).
2KNO3 
 2KNO2 + O2
2NaNO3 
 2NaNO2 + O2
(vi) Ammonium nitrate on heating leaves no residue and forms nitrous oxide and steam.
NH4NO3 
 N2O + 2H2O
10.5 ACTION OF HEAT ON AMMONIUM COMPOUNDS

Generally an ammonium compound decomposes into ammonia and an acid or acidic oxide if the acid
is unstable to heat.
(i) NH4Cl 
 NH3 + HCl
(ii) (NH4)2SO4 
 2NH3 + H2SO4
(iii) (NH4)3PO4 
 3NH3 + H3PO4
(iv) (NH4)2CO3 
 2NH3 + CO2 + H2O
(v) Ammonium compounds which do not give ammonia on heating are ammonium nitrate,
ammonium nitrite and ammonium dichromate.
NH4NO3 
 N2O + 2H2O
NH4NO2 
 N2 + 2H2O
(NH4)2Cr2O7 
 N2 + 4H2O + Cr2O3
(Green fluffy chromic oxide)

10.6 ACTION OF HEAT ON METALLIC CARBONATES
(i) Generally metallic carbonates decompose to give metal oxide and CO2.

900 C
CaCO3   CaO + CO2 
 MgO + CO2 
MgCO3 
CuCO3 
 CuO  CO 2 
(pale green) (black)
PbCO3 
 PbO  CO 2 
(yellow )
 ZnO + CO2 
ZnCO3 
(ii) Carbonates of strongly electropositive metals (alkali metals except lithium) do not decompose on
heating.
(iii) Silver carbonate decomposes to give the metal, CO2 & O2.
2Ag2CO3 
 4Ag + 2CO2 + O2
(iv) Ammonium carbonate (smelling salt) decomposes to give NH3, H2O & CO2. All the products
are in gaseous phase and there is no residue left.
(NH4)2CO3 
 2NH3 + H2O + CO2
10.7 ACTION OF HEAT ON METALLIC BICARBONATES

Only NaHCO3 and KHCO3 are solids; others are known in solution. All bicarbonates decompose to give the
metal carbonate, H2O & CO2.
 Na2CO3 + H2O + CO2 
2NaHCO3 
 CaCO3 + H2O + CO2 

Ca(HCO3)2 
 MgCO3 + H2O + CO2 

Mg(HCO3)2 
10.8 ACTION OF HEAT ON CERTAIN HYDRATED CHLORIDES

Hydrated halides on heating are converted to oxides, H2O and halo acids.
(i) MgCl26H2O does not get completely dehydrated because MgCl2 is hydrolysed by water to give
basic MgCl2.
(ii) MgCl26H2O 
 Mg(OH)Cl + 5H2O + HCl
(ii) Al2Cl612H2O 
 Al2O3 + 6HCl + 9H2O
(iii) SnCl22H2O undergoes hydrolysis to form basic chloride.

SnCl22H2O 
 Sn(OH)Cl + H2O + HCl
(iv) On heating, certain halides of metal ions in higher oxidation state changes to halides of lower
oxidation state.
2FeCl3 
 2FeCl2 + Cl2
2CuCl2 
 Cu2Cl2 + Cl2
10.9 ACTION OF HEAT ON SOME OTHER COMPOUNDS

(i) When sodium sulphite is heated, it undergoes disproportionation reaction.
4Na2SO3 
 3Na2SO4 + Na2S
(ii) Sodium thiosulphate Na2S2O35H2O loses water of hydration and becomes anhydrous salt,
which on further heating gives a mixture of sodium sulphate, sodium sulphide and sulphur.
Na2S2O3  5H2O 
 Na2S2O3 + 5H2O
4Na2S2O3 
 3Na2SO4 + Na2S + 4S
(iii) When hydrated copper sulphate (blue vitriol) is heated, CuO & SO2 formed.
100 C
CuSO 4  5H 2 O 
 CuSO 4  H 2O  4H 2 O
230 C
CuSO 4  H 2 O 
 CuSO 4  H 2 O
750 C
CuSO 4 
 CuO  SO3
2SO3 
 2SO2 + O2
(iv) Gypsum CaSO42H2O, when heated to 120130C forms a hemihydrate called Plaster of Paris.
CaSO4.2H2O 
 CaSO4.½ H2O + 3/2 H2O
If heated above 200C, it forms anhydrous calcium sulphate which does not set with water.
(v) Green vitriol, FeSO47H2O, when heated forms Fe2O3, SO2, SO3 & H2O.
2FeSO4  7H2 O 
 Fe2 O3  SO2  SO3  14H 2O

(vi) MgSO4 .7H 2 O   MgSO4  7H 2 O
(Epsom salt)

MgSO4   MgO  SO 3
(vii) Al2  SO 4 3 .18H 2 O 


 Al2 O3  3SO3  18H 2 O
(purple) (white)
(viii) Cr2  SO 4 3 .18H 2 O 


 Cr2 O3  3SO 3  18H 2 O
(green )
(ix) Fe 2  SO 4 3 
 Fe 2 O3  3SO3
( yellow) (blackish brown )

(x) 2FeSO 4   Fe2 O3  SO3  SO 2
(light green)
10.10 ACIDBASE REACTIONS

(i) A strong acid liberates a relatively weaker acid from its salt. The common strong acids are
perchloric acid, sulphuric acid, hydrochloric acid and nitric acid. The weaker acids are carbonic
acid, sulphurous acid, hydrocyanic acid and most of organic acids. Thus concentrated sulphuric
acid displaces most other acids from their salts.
KCl  H 2SO4 
 KHSO4  HCl
KNO3  H2SO4 
 KHSO4  HNO3
Ca 3 (PO4 )2  3H 2SO4 
 3CaSO4  2H3 PO4
CH3CO2Na + HCl 
 CH3CO2H + NaCl
(ii) Almost all acids displace carbonic acid from carbonates and bicarbonates. Since carbonic acid
is unstable, it decomposes liberating CO2 with effervescence (Test for acids).
Na 2 CO3  2HCl 
 2NaCl  H 2 O  CO 2 
Na 2 CO3  H 2SO 4 
 Na 2SO 4  H 2 O  CO 2 
KHCO 3  HNO 3 
 KNO 3  H 2 O  CO 2 
(iii) A strong base can displace a weak base from a salt of strong acid and weak base.
NH4Cl + NaOH 
 NaCl + NH4OH
(iv) A salt of strong acid and strong base do not react with any acid or base.
10.11 SOME OTHER USEFUL REACTIONS
(i) O3 + 2KI + H2O 
 2KOH + I2 + O2
(ii) BaCO3 + HCl 
 BaCl2 + CO2 + H2O
(iii) BaCl2 + H2CrO4 
 BaCrO4 + 2HCl
(iv) 2BaCrO4 + 6KI + 8H2SO4 
 3I2 + 2BaSO4 + 3K2SO4 + Cr2(SO4)3 + 8H2O
(v) 2CuSO4 + 4KI 
 Cu2I2 + I2 + 2K2SO4
(vi) 2MnO4  5C2O24 + 16H+ 

 2Mn+2 + 10CO2 + 8H2O
(vii) 2KMnO4 + 10FeSO4 + 8H2SO4 
 2MnSO4 + 5Fe2(SO4)3 + K2SO4 + 8H2O
(viii) Mn3O4 + 2FeSO4 + 4H2SO4 
 3MnSO4 + Fe2(SO4)3 + 4H2O
(ix) 2NH2OH + 4Fe3+ 
 N2O + H2O + 4Fe2+ + 4H+
(x) MnO4 + 5Fe2+ + 8H+ 

 Mn2+ + 5Fe3+ + 4H2O
(xi) KMnO4 + 5KI + 4H2SO4 
 3K2SO4 + MnSO4 + 5/2I2 + 4H2O
(xii) K2Cr2O7 + 6KI + 7H2SO4 
 4K2SO4 + Cr2(SO4)3 + 3I2 + 7H2O
11. HARDNESS OF WATER

 Water that produces lather with soap is called soft water and which does not produce lather
with soap is called hard water.
M 2   C17 H 35 COO 2 M  s   2Na 
 2C17 H35COONa 
Hard water Sodium insoluble scum
M 2   Ca 2  ,Mg 2  Stearate(soap)
 The Ca2+ and Mg2+ ions present in hard water react with soap to form a precipitate of Ca and
Mg salts of fatty acids & hence no lather is formed.
 The hardness of water is due to the presence of bicarbonates, chlorides and sulphates of Ca and
Mg.
 The temporary hardness or carbonate hardness is due to the presence of soluble bicarbonates,
Ca(HCO3)2 & Mg(HCO3)2 and permanent or non-carbonate hardness is due to chlorides and
sulphates of Ca and Mg. i.e. CaCl2, MgCl2, CaSO4 & MgSO4.
 Hard water is harmful to steam boilers due to the formation of boiler scales (CaSO4 & CaCO3).
It reduces the efficiency of boiler & damages it.
 The process of removal of Ca2+ or Mg2+ ions is called softening of water.
 The extent of hardness is known as degree of hardness (DOH) defined as the number of parts
by weight of CaCO3 present in one million parts (106) by weight of water.
 DOH is used in determining the hardness of water due to the presence of bicarbonates
(temporary hardness), chlorides and sulphates (permanent hardness) of Ca and Mg.
g of CaCO 3
Hardness of water =
106 g of water
100
 Equivalent weight of CaCO3 = E CaCO3   50
2
162 146 111
E Ca (HCO3 )2   81, E Mg(HCO3 )2   73, E CaCl2   55.5
2 2 2
95 136 120
E MgCl2   47.5, E CaSO4   68, E MgSO4   60
2 2 2
This means 50 g of CaCO3  60 g of MgSO4  55.5 g of CaCl2  68 g of CaSO4
 The reason of expressing hardness as number of parts by weight of CaCO3, is that it is the most
insoluble salt that can be precipitated in water treatment.
Mass of hardness producing subs tan ce Mass of CaCO 3
 
Eq Mass of hardness producing subs tan ce Eq Mass of CaCO 3
Mass of hardness producing subs tan ce

w CaCO3   50
Eq Mass of hardness producing subs tan ce
Illustration-7
A sample of hard water contains 1 mg of CaCl2 and 1 mg of MgCl2 per litre. Calculate the hardness
of water in terms of CaCO3 present in per 106 parts of water.
(a) 2.5 ppm (b) 1.95 ppm (c) 2.15 ppm (d) 195 ppm
Solution: (b)
wCaCl2 wCaCO3 10 3  10 3 wCaCO3
CaCl2  CaCO3 ;  ; 
ECaCl2 ECaCO3 55.5 50
1  50
wCaCO3   0.9 g
55.5
wMgCl2 wCaCO3 10 3  10 3 wCaCO3
MgCl2  CaCO3 ;  ; 
EMgCl2 ECaCO3 47.5 50
1  50
wCaCO3   1.05 g
47.5
Mass of CaCO3 in 106 g water = (0.9 + 1.05) = 1.95 g
Hardness of water = (0.9 + 1.05) = 1.95 ppm.
EXERCISE-1
MCQs with One Correct Answer type
1. Molarity of H2SO4 (density 1.8 g/mL) is 18 M. The molality of this H2SO4 is
(a) 36 (b) 200 (c) 500 (d) 18
2. The percentage of sodium in a breakfast cereal be labeled as 110 mg of sodium per 100 g of cereal is
(a) 11% (b) 1.10% (c) 0.11% (d) 1.10%
3. 4.4 g of CO2 and 2.24 litre of H2 at STP are mixed in a container. The total number of molecules
present in the container will be
(a) 6.023 × 1023 (b) 1.2046 × 1023 (c) 6.023 × 1022 (d) 6.023 × 1024
4. Two elements A (atomic mass = 75) and B (atomic mass = 16) combine to yield a compound. The %
by weight of A in the compound was found to be 75.08. The formula of the compound is
(a) A2B (b) A2B3 (c) AB (d) AB2
5. What weight of HNO3 is needed to convert 5 g of iodine into iodic acid according to the reaction,
I2 + HNO3 
 HIO3 + NO2 + H2O
(a) 12.4 g (b) 24.8 g (c) 0.248 g (d) 49.6 g

6. In the reaction,
VO + Fe2O3 
 FeO + V2O5
the equivalent weight of V2O5 is equal to its

(a) molecular weight (b) molecular weight /4
(c) molecular weight /6 (d) molecular weight /8
7. 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
8. When a metal is burnt, its weight is increased by 24%. The equivalent weight of the metal will be
(a) 25 (b) 24 (c) 33.3 (d) 76
9. The normality of 0.1 M H3PO3, when it undergoes following reaction,
 HPO32 + 2H2O
H3PO3 + 2OH– 
would be
(a) 0.1 (b) 0.2 (c) 0.3 (d) 0.05
10. How much Cl2 at STP is liberated when 1 mole KMnO4 reacts with HCl?
(a) 11.2 L (b) 22.4 L (c) 44.8 L (d) 56 L
11. The minimum quantity of H2S needed to precipitate 63.5 g of Cu2+ is nearly
(a) 63.5 g (b) 34 g (c) 20.0 g (d) 126.0 g
12. 2 g of CaCO3(s) was treated with 0.1 M HCl (500 ml). The volume of CO2 evolved at STP after
heating the solution is
(a) 0.448 L (b) 0.224 L (c) 4.48 L (d) 44.8 L
13. 10 g of CaCO3 on heating gives 5 g of the residue (as CaO). The percent yield of the reaction is
approximately
(a) 50% (b) 72% (c) 89% (d) 100%
14. 33.6 g of an impure sample of sodium bicarbonate when heated strongly gave 4.4 g of CO2. The
percentage purity of NaHCO3 would be
(a) 25% (b) 50% (c) 75% (d) 100%
15. 0.16 g of dibasic acid required 25 ml of N/10 NaOH for complete neutralization. Molecular weight of
acid is
(a) 32 (b) 64 (c) 128 (d) 256
16. Which of the following is a disproportionation reaction?
(a) CaCO3  2H  
 Ca 2  H 2 O  CO2 (b) 2CrO24  2H  
 Cr2 O72  H2O
(c) Cr2O72  2OH 

 2CrO24  H2O (d) Cu 2O  2H 
 Cu  Cu 2  H 2 O
17. NX is produced by the following step of reactions
M + X2 
 M X2 , 3MX2 + X2 
 M3X8 , M3 X8 + N2CO3 
 NX + CO2 + M3O4
How much M (metal) is consumed to produce 206 g of NX. (Take at wt. of M = 56, N=23, X = 80)
14 7
(a) 42 g (b) 56 g (c) g (d) g
3 4
18. Decreasing order of mass of pure NaOH in each of the aqueous solution.
(I) 50 g of 40% (W/W) NaOH
(II) 50 ml of 50% (W/V) NaOH (dsol = 1.2 g/ml).
(III) 50 g of 15 M NaOH (dsol = 1 g/ml).
(a) I, II, III (b) III, II, I (c) II, III, I (d) III = II = I
19. When the same amount of zinc is treated separately with excess of H2SO4 and excess of NaOH, the
ratio of volumes of H2 evolved is
(a) 1:1 (b) 1:2 (c) 2:1 (d) 9:4
20. The red pigment in blood contains 0.32% iron by weight. Molecular mass of the pigment is 70,000 g
mol–1. The number of iron atoms in each molecule of the pigment would be
(a) 1 (b) 2 (c) 3 (d) 4
21. 27 g of Al will react completely with how many grams of oxygen?
(a) 8g (b) 16g (c) 32g (d) 24g
22. A compound was found to contain nitrogen and oxygen in the ratio 28 gm and 80 gm respectively.
The formula of compound is
(a) NO (b) N2O3 (c) N2O5 (d) N2O4
23. The largest number of molecules are in
(a) 36 g of water (b) 28 g of carbon monoxide
(c) 46 g of ethyl alcohol (d) 54 g of nitrogen pentoxide
24. The total number of electrons in one molecule of carbon dioxide is
(a) 22 (b) 44 (c) 66 (d) 88
25. A gaseous mixture contains oxygen and nitrogen in the ratio of 1 : 4 by weight. Therefore the ratio of
their number of molecules is
(a) 1:4 (b) 1:8 (c) 7 : 32 (d) 3 : 16
26. 2. 76 g of silver carbonate on being strongly heated yields a residue weighing
(a) 2.16g (b) 2.48g (c) 2.32 g (d) 2.64 g
27. If 0.50 mole of BaC12 is mixed with 0.20 mol of Na3PO4, the maximum number of moles of
Ba3(PO4)2 that can be formed is
(a) 0.70 (b) 0.50 (c) 0.20 (d) 0.10
28. 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
29. The equivalent weight of MnSO4 is half of its molecular weight when it is converted to:
(a) Mn2O3 (b) MnO2 (c) MnO4 (d) MnO 24

30. In which mode of expression, the concentration of a solution remains independent of temperature?
(a) Molarity (b) Normality (c) Formality (d) Molality
31. The normality of 0.3 M phosphorous acid (H3PO3) is:
(a) 0.1 (b) 0.9 (c) 0.3 (d) 0.6
32.  ClO3 (aq) + 2Cl–(aq), is an example of

The reaction, 3ClO–(aq) 
(a) oxidation reaction (b) reduction reaction

(c) disproportionation reaction (d) decomposition reaction
33. An aqueous solution of 6.3 g oxalic acid dihydrate is made up to 250 ml. The volume of 0.1 N NaOH
required to completely neutralize 10 ml of this solution is
(a) 40 ml (b) 20 ml (c) 10 ml (d) 4 ml
34. How many moles of electron weigh one kilogram?
1
(a) 6.023 × 1023 (b)  1031
9.108
6.023 1
(c)  1054 (d)  108
9.108 9.108  6.023
35. Which has maximum number of atoms?
(a) 24 g of C (12) (b) 56 g of Fe (56)
(c) 27 g of Al (27) (d) 108 g of Ag (108)
36. Mixture X = 0.02 mol of [Co(NH3)5SO4] Br and 0.02 mol of [Co(NH3)5Br]SO4 was prepared in 2
litre of solution.
1 litre of mixture X + excess AgNO3 

Y
1 litre of mixture X + excess BaCl2 

Z
No. of moles of Y and Z are
(a) 0.01, 0.01 (b) 0.02, 0.01 (c) 0.01, 0.02 (d) 0.02, 0.02
37. In a gravimetric determination of P, an aqueous solution of dihydrogen phosphate ion H 2 PO 4 is

treated with a mixture of ammonium and magnesium ions to precipitate magnesium ammonium
phosphate, Mg(NH4)PO4.6H2O. This is heated and decomposed to magnesium pyrophosphate,
Mg2P2O7, which is weighed. A solution of H 2 PO 4 yielded 1.054 g of Mg2P2O7. What weight of
NaH2PO4 was present originally?
(a) 1.14 g (b) 1.62 g (c) 2.34 g (d) 1.33 g
38. 10.78 g of H3PO4 in 550 mL solution is 0.40 N. Thus, this acid
(a) has been neutralised to HPO24 (b) has been neutralised to PO34
(c) has been changed to H3PO2 (d) has been neutralised to H 2 PO 4
39. 20 mL of x M HCl neutralizes completely 10 mL of 0.1 M NaHCO3 and a further 5 mL of 0.2 M

Na2CO3 solution to methyl orange end point. The value of x is
(a) 0.167 M (b) 0.133 M (c) 0.150 M (d) 0.200 M
40. When a solution of NaOH and Na2CO3 is titrated against standard HCl, the end point due to
phenolphthalein is obtained after the reaction
(a) NaOH + HCl 

 NaCl + H2O (b) Na2CO3 + HCl 
 NaCl + NaHCO3
(c) NaHCO3 + HCl 

 NaCl + H2CO3 (d) Na2CO3 + 2HCl 
 2NaCl + H2CO3
41. A metal oxide is reduced by heating it in a stream of hydrogen. It is found that after complete
reduction 3.15 g of the oxide have yielded 1.05 g of the metal. We may conclude that
(a) atomic mass of the metal is 4 (b) atomic mass of the metal is 8
(c) equivalent mass of the metal is 4 (d) equivalent mass of the metal is 8
42. The n-factor of FeS2 in the following reaction,
 Fe3+ + SO2
FeS2 
would be
(a) 5 (b) 6 (c) 10 (d) 11
43. A solution contains Na2CO3 and NaHCO3. 10 mL of the solution required 2.5 mL of 0.1M H2SO4 for
neutralisation using phenolphthalein as indicator. Methyl orange is then added when a further 2.5 mL
of 0.2 M H2SO4 was required. The amount of Na2CO3 and NaHCO3 in 1 litre of the solution is
(a) 5.3 g and 4.2 g (b) 3.3 g and 6.2 g (c) 4.2 g and 5.3 g (d) 6.2 g and 3.3 g
44. Hydrogen peroxide in aqueous solution decomposes on warming to give oxygen according to the
equation,
2H2O2(aq) 
 2H2O(l) + O2(g)
Under conditions where 1 mole of gas occupies 24 dm3. 100 cm3 of X M solution of H2O2 produces 3
dm3 of O2. Thus X is
(a) 2.5 (b) 1 (c) 0.5 (d) 0.25
45. 12 g of alkaline earth metal gives 14.8 g of its nitride. Atomic weight of metal is
(a) 12 (b) 20 (c) 40 (d) 14.8
46. How many liters of CO2 at STP will be formed when 0.01 mol of H2SO4 reacts with excess of
Na2CO3.
Na2CO3 + H2SO4 
 Na2SO4 + CO2 + H2O
(a) 22.4 L (b) 2.24 L (c) 0.224 L (d) 1.12 L

47. What volume of O2 measured at standard condition will be formed by the action of 100 mL of 0.5 N
KMnO4 on hydrogen peroxide in an acid solution? The skeleton equation for the reaction is,
KMnO4 + H2SO4 + H2O2 

 KHSO4 + MnSO4 + H2SO4 + H2O + O2
(a) 0.12 litre (b) 0.028 litre (c) 0.56 litre (d) 1.12 litre
48. 100 mL of a sample of hard water requires 25.1 mL of 0.02 N H2SO4 for complete reaction. The
hardness of water (density 1 g/mL) based on CaCO3 is
(a) 200 ppm (b) 250 ppm (c) 251 ppm (d) 258 ppm
49. Equal weight of 'X' (At. wt. = 36) and 'Y' (At. wt. = 24) are reacted to form the compound X2Y3.
Then:
(a) X is the limiting reagent
(b) Y is the limiting reagent
(c) No reactant is left over and mass of X2Y3 formed is double the mass of ‘X’ taken
(d) none of these
50. If the equivalent weight of a compound ‘A’ is MA/4 when it reacts with compound ‘B’ whose
equivalent weight is MB/5, then 4 mol of ‘A’ requires (where MA and MB are molecular weights of A
& B respectively)
(a) 4 mol of ‘B’ (b) 5 mol of ‘B’
(c) less than 4 mol of ‘B’ (d) more than 5 mol of ‘B’
EXERCISE-2
MCQs with One or More Correct Answer(s) Type
1. In the following redox reaction 2MnO4  10Cl  16H  
 2Mn 2  5Cl2  8H 2O. Pick up the
correct statements.
(a) MnO4 is reduced (b) Cl– is oxidising agent
(c) MnO4 is an oxidising agent (d) Cl– is reduced
2. 0.1 M of MnO4 (in acidic medium) can
(a) oxidise 0.25 M C2O24 (b) oxidise 0.5 M Fe2+
(c) oxidise 0.166 M FeC2O4 (d) oxidise 0.6 M Cr2O72

3. Which of the following represents redox reaction(s)?
(a) Cu  Cu 2   2Cu  (b) MnO4  Mn 2  OH –  MnO2  H 2 O
(c) Cr2O72  2OH  2CrO24  H 2O (d) 2CrO24  2H   Cr2O72  H 2O

4. Which of the following reaction is disproportionation?
(a) 2Cu+ 
 Cu + Cu2+ (b)  ClO3 + 5Cl– + 3H2O
3Cl2 + 6OH– 
1
(c) 2H2S + 8O2 
 2H2O + 3S (d) Na + Cl2 
 NaCl
2
5. Which of the following changes involve oxidation?
(a) change of Zn to ZnSO4 by reaction with H2SO4
(b) change of Cl2 to chloride ion
(c) change of H2S to S
(d) change of sodium sulphide to sodium sulphate
6. When 16.6 g of KI is treated with excess of KIO3 in the presence of 6 N HCl, ICl is produced. Which
of the following is correct choice?
(a) Moles of KIO3 consumed are 0.1 mol (b) Moles of KIO3 consumed are 0.05 mol
(c) Moles of ICl produced are 0.15 mol (d) Moles of ICl produced are 0.3 mol
7. The concentration of an aqueous solution of NaOCl can be determined by a redox titration with
iodide ion in acidic solution.
OCl–(aq) + 2I–(aq) + 2H+(aq) 

 Cl–(aq) + I2(aq) + H2O(l)
Assume that the concentration of I– ions in the buret is 0.12 M and the volumes in the buret and the
flask are identical. What would be the concentration of the NaOCl in the flask and what fraction of
the I– solution in the buret must be added to the flask to react with all the OCl– ions?
1
(a) 0.06 M NaOCl; th of the I– must be added
2
1
(b) 0.05 M NaOCl; rd of the I– must be added
3
2
(c) 0.04 M NaOCl; rd of the I– must be added
3
2
(d) 0.03 M NaOCl; rd of the I– must be added
3
8. A mixture of 0.84 g of NaHCO3, 4.0 g of NaOH and 10.6 g of Na2CO3 is dissolved in 100 ml H2O.
The solution obtained is thus titrated with 0.5 M HCl solution. Which of the following option is
correct?
(a) The volume of HCl used at phenolphthalein end point is 400 ml.
(b) The volume of HCl used at methyl orange end point is 840 ml.
(c) The volume of HCl used at methyl orange end point after phenolphthalein end point is 220 ml.
(d) The volume of HCl used at phenolphthalein end point after methyl orange end point is 220 ml.
9. 100 ml of 0.1 M KMnO4 solution (acidified) will oxidise
(a) 200 ml of 0.125 M C2O24 solution. (b) 300 ml of 0.167 M Fe2+ solution.
(c) 100 ml of 0.125 M C2O24 solution. (d) 400 ml of 0.125 M Fe2+ solution.
10. Which of the following reaction is not a redox reaction?
(a) 3H2 MnO4 

 MnO4 + 2MnO2 + 2OH– + 2H2O
(b) FeSO4 + 2AgNO3 

 Ag2SO4 + Fe(NO3)2
5
(c) KMnO4 + 8HCl 
 KCl + MnCl2 + Cl2 + 4H2O
2
(d) (NH4)2[Ce(NO3)6] + 2CH3OH 

 2NH4NO3 + [Ce(NO3)4(CH3OH)2]
11. Which of the following reactants in the given half–reactions has n–factor 2?
(a) KI 
 I2 (b) KI 
 ICl
(c) C2O24 
 CO2 (d) Fe2O3 
 FeSO4
12. When 17.4 g of MnO2 is treated with excess of HCl, then

(a) 0.8 mole of HCl are used in the reaction. (b) 25.2 g of MnCl2 will be produced.
(c) 14.6 g of HCl is used in the reaction. (d) 50.4 g of MnCl2 will be produced.
13. An H2O2 solution has volume strength of ‘10’. Which of the following statement is not true?
(a) When 100 ml of the same H2O2 solution is decomposed, the volume of O2 liberated at STP is
1000 ml.
(b) 100 ml of the same H2O2 solution is oxidised by 35.7 ml of 0.1 M KMnO4 solution.
(c) 100 ml of the same H2O2 solution oxidises 17.8 ml of 1 M of Fe2+ solution.
(d) 100 ml of the same H2O2 solution oxidises 89 ml of 1 M C2O24 solution.
14. In which of the following reactions, the reactant has fractional n–factor?
(a) Na2S2O3 
 Na2S4O6 (b) Fe3O4 
 FeO
(c)  2Cl– + Cl2

4HCl  (d)  Fe3+
Fe0.94O 
15. 53 mg of Na2CO3 is dissolved in 500 ml of distilled water. The solution obtained is titrated with 0.01
M HCl solution. Which of the following statements are true?
(a) The volume of HCl used at phenolphthalein end point is 100 ml.
(b) The volume of HCl used at phenolphthalein end point is 50 ml.
(c) The volume of HCl used at methyl orange end point is 200 ml.
(d) The volume of HCl used at methyl orange end point is 100 ml.
16. The density of air is 0.001293 g/cm3 at STP. Identify which of the following statement is correct
(a) Vapour density is 14.48
(b) Molecular weight is 28.96
(c) Vapour density is 0.001293 g/cm3
(d) Vapour density and molecular weight cannot be determined
17. For the following reaction: Na2CO3 + 2HCl 

 2NaCl + CO2 + H2O
106.0 g of Na2CO3 reacts with 109.5 g of HCl.
Which of the following is/are correct?
(a) The HCl is in excess
(b) 117.0 g of NaCl is formed
(c) The volume of CO2 produced at NTP is 22.4 L
(d) None of these
18. Solutions containing 23 g HCOOH is/are:
46 g of 70%   HCOOH (dsolution = 1.40 g/mL)

W
(a)
V
(b) 50 g of 10 M HCOOH (dsolution = 1 g/mL)
50 g of 25%   HCOOH
W
(c)
W
(d) 46 g of 5 M HCOOH (dsolution = 1 g/mL)
19. If 100 ml of 1M H2SO4 solution is mixed with 100 ml of 9.8%(w/w) H2SO4 solution (d = 1 g/ml)
then:
(a) concentration of solution remains same (b) volume of solution become 200 ml
(c) mass of H2SO4 in the solution is 98 g (d) mass of H2SO4 in the solution is 19.6 g
20. Equal volume of 0.1M NaCl and 0.1M FeCl2 are mixed with no change in volume due to mixing.
Which of the following will be true for the final solution. (No precipitation occurs). Assume
complete dissociation of salts and neglect any hydrolysis.
(a) [Na+] = 0.05 M (b) [Fe2+] = 0.05M (c) [Cl–] = 0.3M (d) [Cl–] = 0.15M
21. Cortisone is a molecular substance containing 21 atoms of carbon per molecule. The mass percentage
of carbon in cortisone is 69.98%. Its molar mass is:
(a) 176.5 (b) 252.2 (c) 287.6 (d) 360.1
22. 0.05 mole of LiAlH4 in ether solution was placed in a flask containing 74g (1 mole) of t-butyl
alcohol. The product LiAlHC12H27O3 weighed 12.7 g. If Li atoms are conserved, the percentage yield
is:
(Li = 7, Al = 27, H = 1, C = 12, O = 16).
(a) 25% (b) 75% (c) 100% (d) 15%
23. The following process has been used to obtain iodine from oil-field brines in California.
Nal + AgNO3 
 Agl + NaNO3; 2AgI + Fe 
 Fel2 + 2Ag
2Fel2 + 3Cl2 
 2FeCl3 + 2l2
How many grams of AgNO3 are required in the first step for every 254 kg I2 produced in the third
step.
(a) 340 kg (b) 85 kg (c) 68 kg (d) 380 kg
24. When 100g of ethylene polymerises entirely to polyethene, the weight of polyethene formed as per
the equation n(C2H4) 
 (–CH2–CH2–)n is:
(a) (n/2)g (b) 100g (c) (100/n)g (d) 100ng
25. If 27 g of Carbon is mixed with 88 g of Oxygen and is allowed to burn to produce CO2, then:
(a) Oxygen is the limiting reagent
(b) Volume of CO2 gas produced at NTP is 50.4 L
(c) C and O combine in mass ratio 3:8
(d) Volume of unreacted O2 at STP is 11.2 L
26. What is the molarity of H2SO4 solution that has a density of 1.84 g/cc and contains 98% by mass of
H2SO4? (Given atomic mass of S = 32)
(a) 4.18 M (b) 8.14 M (c) 18.4 M (d) 18 M
27. A sample of a mixture of CaCl2 and NaCl weighing 4.44 g was treated to precipitate all the Ca as
CaCO3, which was then heated and quantitatively converted to 1.12g of CaO.
(At. wt. Ca = 40, Na = 23, Cl = 35.5)
(a) Mixture contains 50% NaCl (b) Mixture contains 60% CaCl2
(c) Mass of CaCl2 is 2.22 g (d) Mass of CaCl2 1.11 g
28. Which of the following statements is/are correct? 1.0 g mixture of CaCO3(s) and glass beads liberate
0.22 g of CO2 upon treatment with excess of HCl. Glass does not react with HCl.
CaCO3 + 2HCl 
 CO2 + H2O + CaCl2
[M. wt. of CaCO3 = 100, M. wt. of CO2 = 44, [Atomic weight of Ca = 40]
(a) The weight of CaCO3 in the original mixture is 0.5 g
(b) The weight of calcium in the original mixture is 0.2 g
(c) The weight percent of calcium in the original mixture is 40% Ca.
(d) The weight percent of Ca in the original mixture is 20% Ca.
29. 100 g sample of clay (containing 19% H2O, 40% silica, and inert impurities as rest) is partially dried
so as to contain 10% H2O
Which of the following is/are correct statements (s)?
(a) The percentage of silica in paritially dried clay is 44.4%
(b) The mass of paritially dried clay is 90.0 g.
(c) The percentage of inert impurity in paritially dried clay is 45.6%
(d) The mass of water evaporated is 10.0 g
30. 21.2 g sample of impure Na2CO3 is dissolved and reacted with a solution of CaCl2, the weight of
precipitate of CaCO3 is 10.0 g. Which of the following statements is/are correct?
(a) The % purity of Na2CO3 is 50%
(b) The percentage purity of Na2CO3 is 60%
(c) The number of moles of Na2CO3 = CaCO3 = 0.1 mol
(d) The number of moles of NaCl formed is 0.1 mol
EXERCISE-3
Matrix Match Type
1. Match the column. (Note: Each statement in column I has only one match in column II.)
Column-I Column-II
I.  SO24 + HCN
SCN–  (A) Disproportionation reaction
II. KClO3 
 KClO4 + KCl (B) n–factor = 6
III H  (C) Equivalent mass = (mol. mass) / 11

K2Cr2O7  Cr2(SO4)3 + Cr2O3
IV.  Fe3+ + SO2

FeS2  (D) Two elements show change in oxidation
state
Column-I Column-II
I. H3PO4 on reaction with NaOH (A) Iodimetry

completely.
II. HNO2 (B) Oxidation states of most electronegative

atom are 1 and –2
III CrO5 (C) Oxidising as well as reducing agent
IV. Na2S2O3 (D) ‘n’ factor is 3
(E) Only reducing agent.
Column-I Column-II
I. Iodimetry (A) Phenolphthalein, Methyl orange
II. Iodometry (B) I2 + Na2S2O3 

 NaI + Na2S4O3
III Oleum (C) Cu2+ + 2 I 

 Cu+ + I2
I2 + Na2S2O3 
 NaI + Na2S4O6
IV. Double titration (D) Acidified H2O2 solution
(E) H2SO4 + SO3
4. Match the column. (Note: Each statement in column I has one or more matches in column II.)
Column – I Column – II
Zn(s) + 2HCl(aq)  ZnCl2(s) + H2(g)

(A) above reaction is carried out by taking 2 moles each (p) 50% of excess reagent left
of Zn and HCl
AgNO3(aq) + HCl(aq)  AgCl(s) + HNO3(g)

22.4 L of gas at STP is
(B) above reaction is carried out by taking 170 g AgNO3 (q)
liberated
and 18.25 g HCl (Ag = 108)
CaCO3(s)  CaO(s) + CO2(g) 1 moles of solid (product)

(C) (r)
100 g CaCO3 is decomposed obtained.
2KClO3(s)  2KCl(s) + 3O2(g)

(D) (s) HCl is the limiting reagent
2/3 moles of KClO3 decomposed
5. Match the column. (Note: Each statement in column I has one or more matches in column II.)
Column – I Column – II
100 ml of 0.2 M AlCl3 solution + 400 ml of 0.1 M Total concentration of cation(s)

(A) (p)
HCl solution = 0.12 M
(B) 50 ml of 0.4 M KCl + 50 ml H2O (q) [SO42–] = 0.06 M
(C) 30 ml of 0.2 M K2SO4 + 70 ml H2O (r) [SO42–] = 2.5 M
(D) 200 ml 24.5% (w/v) H2SO4 (s) [Cl–] = 0.2 M
Numerical Type
6. Consider the following reaction involved in the preparation of teflon polymer ( CF2  CF2 ) n .
XeF6  ( CH 2  CH 2 ) n 
 ( CF2  CF2 ) n  HF  XeF4 .
Determine the moles of XeF6 required for preparation of 100 g Teflon.

1 1
7. When 1 mole of A reacts with mole of B2 (A + B2  AB), 100 Kcal heat is liberated and when
2 2
1 mole of A reacted with 2 mole of B2 (A + 2B2  AB4), 200 Kcal heat is liberated. When 1 mole of
A is completely reacted with excess, of B2 to form AB as well as AB4, 140 Kcal heat is liberated
calculate the mole of B2 used. [Write your answer as number of mole of B2 used × 10]
8. 92 g mixture of CaCO3, and MgCO3 heated strongly in an open vessel. After complete decomposition
of the carbonates it was found that the weight of residue left behind is 48 g. Find the mass of MgCO3
in grams in the mixture.
9. H3PO4 (98 g mol–1) is 98% by mass of solution. If the density is 1.8 g/ml, calculate the molarity.
10. A student performs a titration with different burettes and finds titre values of 25.2 mL, 25.25 mL, and
25.0 mL. The number of significant figures in the average titre value is
11. Silver (atomic weight = 108 g mol–1) has a density of 10.5 g cm–3. The number of silver atoms on a
surface of area 10–12 m2 can be expressed in scientific notation as y × 10x. The value of x is:
12. The difference in the oxidation numbers of the two types of sulphur atoms in Na2S4O6 is
13. If the value of Avogadro number is 6.023 × 1023 mol–1 and the value of Boltzmann constant is 1.380
× 10–23 J K–1, then the number of significant digits in the calculated value of the universal gas
constant is
14. A solution containing 0.1 mol of a metal chloride MClx requires 500 ml of 0.8 M AgNO3 solution for
complete reaction MClx + xAgNO3  xAgCl + M(NO3)x. Then the value of x is:
15. If 240 g of carbon is taken in a container to convert it completely to CO2 but in industry it has been
found that 280 g of CO was also formed along with CO2. Find the mole percentage yield of CO2. The
reactions occurring are:
1
C + O2  CO2; C + O2  CO
2
Linked Comprehension Type

Comprehension # 1
According to the Avogadro’s law, equal number of moles of gases occupy the same volume at
identical condition of temperature and pressure. Even if we have a mixture of non-reacting gases then
Avogadro’s law is still obeyed by assuming mixture as a new gas.
Now let us assume air to consist of 80% by volume of Nitrogen (N2) and 20% by volume of oxygen
(O2). If air is taken at STP then its 1 mol would occupy 22.4 L. 1 mol of air would contain 0.8 mol of
N2 and 0.2 mol of O2 hence the mole fractions of N2 and O2 are given by X N2  0.8 , XO2  0.2 .
16. Volume occupied by air at NTP containing exactly 11.2 g of Nitrogen:

(a) 22.4 L (b) 8.96 L (c) 11.2 L (d) 2.24 L
17. If air is treated as a solution of O2 and N2 then % W/W of oxygen is:
10 200 700 350
(a) (b) (c) (d)
9 9 9 9
18. Density of air at NTP is:
9
(a) 1 g/L (b) g/L
7
2
(c) g/L (d) can’t be determined
7
Comprehension # 2
The concentrations of solutions can be expressed in number of ways; viz: mass fraction of solute (or
mass percent), Molar concentration (Molarity) and Molal concentration (molality). These terms are
known as concentration terms and also they are related with each other i.e. knowing one
concentration term for the solution, we can find other concentration terms also. The definition of
different concentration terms are given below:
Molarity: It is number of moles of solute present in one litre of the solution.
Molality: It is the number of moles of solute present in one kg of the solvent.
moles of solute
Mole Fraction =
moles of solute  moles of solvent
If molality of the solution is given as ‘a’ then mole fraction of the solute can be calculated by
a a  M solvent
Mole Fraction = ;
1000 (a  M solvent  1000)
a
M solvent
where a = molality and Msolvent = Molar mass of solvent

We can change : Mole fraction  Molality  Molarity
19. 60 g of solution containing 40% by mass of NaCl are mixed with 100 g of a solution containing 15%
by mass NaCl. Determine the mass percent of sodium chloride in the final solution.
(a) 24.4% (b) 78% (c) 48.8% (d) 19.68%
20. What is the molality of the above solution.
(a) 4.4 m (b) 5.5 m (c) 24.4 m (d) none
21. What is the molarity of solution if density of solution is 1.6 g/ml
(a) 5.5 M (b) 6.67 M (c) 2.59 M (d) none
Comprehension # 3
Dissolved oxygen in water is determined by using a redox reaction. Following equations describe the
procedure:
I. 2Mn2+(aq) + 4OH–(aq) + O2(g) 

 2MnO2(s) + 2H2O(l)
II. MnO2(s) + 2I–(aq) + 4H+(aq) 

 Mn2+(aq) + I2(aq) + 2H2O(l)
III. 2S2 O32  + I2(aq) 

 + 2I–(aq)
22. How many moles of S2O32 are equivalent to each mole of O2?
(a) 0.5 (b) 1 (c) 2 (d) 4

23. What amount of I2 will be liberated from 8 g dissolved oxygen?
(a) 127 g (b) 257 g (c) 504 g (d) 1008 g
24. If 3 × 10–3 moles O2 is dissolved per litre of water, then what will be the molarity of I– produced in
the given reaction?
(a) 3 × 10–3 M (b) 4 × 3 × 10–3 M (c) 2 × 3 × 10–3 M (d) ½ × 3 × 10–3 M
25. If 50 ml of water containing dissolved oxygen requires 20 ml of 0.05 N Na2S2O3 for complete
estimation of I2 liberated in the process, what will be the strength of dissolved oxygen in g / L?
(a) 0.08 (b) 0.16 (c) 0.24 (d) 0.32
EXERCISE-4
Previous Years JEE Main /AIEEE
MCQ with One Correct Answer Type
1. In a compound C, H and N atoms are present in 9:1:3.5 by weight. Molecular weight of compound is
108. Molecular formula of compound is
(a) C2H6N2 (b) C3H4N (c) C6H8N2 (d) C9H12N3
2. With increase of temperature, which of these changes?
(a) molality (b) mass fraction (c) molarity (d) mole fraction
3. Number of atoms in 558.5 gram Fe (at. wt. of Fe = 55.85 g mol–1) is
(a) twice that in 60 g carbon (b) 6.023 x 1022
(c) half that in 8 g He (d) 558.5 × 6.023 × 1023
4. What volume of hydrogen gas, at 273 K and 1 atm. pressure will be consumed in obtaining 21.6 g of
elemental boron (atomic mass = 10.8) from the reduction of boron trichloride by hydrogen?
(a) 67.2L (b) 44.8 L (c) 22.4 L (d) 89.6 L
5. 25 ml of a solution of barium hydroxide on titration with a 0.1 molar solution of hydrochloric acid
gave a litre value of 35ml. The molarity of barium hydroxide solution was
(a) 0.14 (b) 0.28 (c) 0.35 (d) 0.07
6. 6.02 × 1020 molecules of urea are present in 100 ml of its solution. The concentration of urea solution
is
(a) 0.02M (b) 0.0l M (c) 0.001 M (d) 0.l M
(Avogadro constant, NA = 6.02 × 1023 mol–1)
7. To neutralise completely 20 mL of 0.l M aqueous solution of phosphorous acid (H3PO3), the value of
0. l M aqueous KOH solution required is
(a) 40mL (b) 20mL (c) 10mL (d) 60mL
8. The ammonia evolved from the treatment of 0.30 g of an organic compound for the estimation of
nitrogen was passed in 100 mL of 0.1 M sulphuric acid. The excess of acid required 20 mL of 0.5 M
sodium hydroxide solution for complete neutralization. The organic compound is
(a) urea (b) benzamide (c) acetamide (d) thiourea
9. Two solutions of a substance (non electrolyte) are mixed in the following manner. 480 ml of 1.5 M
first solution +520 ml of 1.2 M second solution. What is the molarity of the final mixture?
(a) 2.70 M (b) 1.344M (c) 1.50 M (d) 1.20 M
10. If we consider that 1/6, in place of 1/12, mass of carbon atom is taken to be the relative atomic mass
unit, the mass of one mole of the substance will
(a) be a function of molecular mass of substance (b) remain unchanged
(c) increase two fold (d) decrease twice
11. How many moles of magnesium phosphate, Mg3(PO4)2 will contain 0.25 mole of oxygen atoms?
(a) 1.25 × 10–2 (b) 2.5 × 10–2 (c) 0.02 (d) 3.125 × 10–2
12. Density of a 2.05M solution of acetic acid in water is 1.02 g/mL. The molality of the solution is
(a) 2.28 mol kg–1 (b) 0.44 mol kg–1 (c) 1.14 mol kg–1 (d) 3.28 mol kg–1
13. The density (in g mL–1) of a 3.60 M sulphuric acid solution that is 29% H2SO4 (molar mass = 98g
mol–1) by mass will be
(a) 1.45 (b) 1.64 (c) 1,88 (d) 1.22
14. In the reaction,
2Al(s) + 6HCl(aq)  2A13+ (aq) + 6Cl– (aq) + 3H2(g)
(a) 11.2 L H2(g) at STP is produced for every mole HCl (aq) consumed
(b) 6 L HCl(aq) is consumed for every 3 L H2(g) produced
(c) 33.6L H2(g) is produced regardless of temperature and pressure for every mole Al that reacts
(d) 67.2 H2(g) at STP is produced for every mole Al that reacts.
15. A gaseous hydrocarbon gives upon combustion 0.72 g of water and 3.08 g of CO2. The empirical
formula of the hydrocarbon is:
(a) C2H4 (b) C3H4 (c) C6H5 (d) C7H8
EXERCISE-5
Previous Years JEE Advanced
Paragraph for Question Nos. (1) to (3)
Chemical reactions involve interaction of atoms and molecules. A large number of atoms/molecules
(approximately 6.023 × 1023) are present in a few grams of any chemical compound varying with
their atomic/molecular masses. To handle such large numbers conveniently, the mole concept was
introduced. This concept has implications in diverse areas such as analytical chemistry, biochemistry,
electrochemistry and radiochemistry. The following example illustrates a typical case, involving
chemical / electrochemical reaction, which requires a clear understanding of the mole concept.
A 4.0 molar aqueous solution of NaCl is prepared and 500 mL of this solution is electrolysed. This
leads to the evolution of chlorine gas at one of the electrodes
(Atomic mass: Na = 23, Hg = 200; 1 Faraday = 96500 coulombs).
[Hint: At the anode: 2Cl–  Cl2 + 2e–
At the cathode: Na+ + e–  Na
Na + Hg  Na-Hg (sodium amalgam)]
1. The total number of moles of chlorine gas evolved is:
(a) 0.5 (b) 1.0 (c) 2.0 (d) 3.0
2. If the cathode is a Hg electrode, the maximum weight (g) of amalgam formed from this solution is:
(a) 200 (b) 225 (c) 400 (d) 446
3. The total charge (coulombs) required for complete electrolysis is:
(a) 24125 (b) 48250 (c) 96500 (d) 193000
4. A student performs a titration with different burettes and finds titre values of 25.2 mL, 25.25 mL, and
25.0 mL. The number of significant figures in the average titre value is:
5. Reaction of Br2 with Na2CO3 in aqueous solution gives sodium bromide and sodium bromate with
evolution of CO2 gas. The number of sodium bromide molecules involved in the balanced chemical
equation is
6. Dissolving 120 g of urea (mol. wt. 60) in 1000 g of water gave a solution of density 1.15 g/mL. The
molarity of the solution is:
(a) 1.78 M (b) 2.00 M (c) 2.05 M (d) 2.22 M
7. 29.2% (w/w) HCl stock solution has a density of 1.25 g mL–1. The molecular weight of HCl is 36.5 g
mol–1. The volume (mL) of stock solution required to prepare a 200 mL solution of 0.4 M HCl is:
8. A compound H2X with molar weight of 80 g is dissolved in a solvent having density of 0.4 g ml–1.
Assuming no change in volume upon dissolution, the molality of a 3.2 molar solution is
9. The mole fraction of a solute in a solution is 0.1. At 298 K, molarity of this solution is the same as its
molality. Density of this solution at 298 K is 2.0 g cm–3. The ratio of the molecular weights of the
solute and solvent is _______.
10. To measure the quantity of MnCl2 dissolved in an aqueous solution, it was completely converted to
KMnO4 using the reaction,
MnCl2 + K2S2O8 + H2O 

 KMnO4 + H2SO4 + HCl (equation not balanced).
Few drops of concentrated HCl were added to this solution and gently warmed. Further,
oxalic acid (225 mg) was added in portions till the colour of the permanganate ion
disappeared. The quantity of MnCl2 (in mg) present in the initial solution is __________.
(Atomic weights in g mol−1: Mn = 55, Cl = 35.5)
11. The mole fraction of urea in an aqueous urea solution containing 900 g of water is 0.05. If the density
of the solution is 1.2 g cm–3, the molarity of urea solution is __________.
12. 5.00 mL of 0.10 M oxalic acid solution taken in a conical flask is titrated against NaOH from a
burette using phenolphthalein indicator. The volume of NaOH required for the appearance of
permanent faint pink color is tabulated below for five experiments. What is the concentration, in
molarity, of the NaOH solution?
Exp. No. Vol. of NaOH (mL)
1 12.5
2 10.5
3 9.0
4 9.0
5 9.0
13. Aluminium reacts with sulfuric acid to form aluminium sulfate and hydrogen. What is the volume of
hydrogen gas in liters (L) produced at 300 K and 1.0 atm pressure, when 5.4 g of aluminium and 50.0
mL of 5.0 M sulfuric acid are combined for the reaction?
(Use molar mass of aluminium as 27.0 g mol−1, R = 0.082 atm L mol−1 K−1)
ANSWER KEY
Exercise-1
MCQs with One Correct Answer Type
1. (c) 2. (c) 3. (b) 4. (b) 5. (a)
6. (c) 7. (d) 8. (c) 9. (b) 10. (d)
11. (b) 12. (a) 13. (c) 14. (b) 15. (c)
16. (d) 17. (a) 18. (b) 19. (a) 20. (d)
21. (d) 22. (c) 23. (a) 24. (a) 25. (c)
26. (a) 27. (d) 28. (a) 29. (b) 30. (d)
31. (d) 32. (c) 33. (a) 34. (d) 35. (a)
36. (a) 37. (a) 38. (a) 39. (c) 40. (b)
41. (c) 42. (d) 43. (a) 44. (a) 45. (c)
46. (c) 47. (c) 48. (c) 49. (c) 50. (c)
Exercise-2
MCQs with One or More Correct Answer(s) Type
1. (a, c) 2. (a, b, c) 3. (a, b) 4. (a, b) 5. (a, c, d)
6. (b, c) 7. (a, c) 8. (a, c) 9. (a, b, d) 10. (b, d)
11. (b, c) 12. (a, b) 13. (b, c) 14. (c, d) 15. (b, d)
16. (a, b) 17. (a, b, c) 18. (a, b) 19. (a, b, d) 20. (a, b, d)
21. (d) 22. (c) 23. (a) 24. (b) 25. (b, c, d)
26. (c) 27. (a, c) 28. (a, b, d) 29. (a, b, c, d) 30. (a, c)
Exercise-3
Matrix Match Type
1. I. (B), (D) II. (A) III. (B) IV. (C), (D)
2. I. (D) II. (C) III. (B) IV. (A)
3. I. (B) II. (C) III. (E) IV. (A)
4. A. (p, q, r, s) B. (p, s) C. (q, r) D. (q)
5. A. (p, s) B. (s) C. (p, q) D. (r)
Numerical Type
6. 4 7. 11 8. 42 9. 18 10. 3
11. 7 12. 5 13. 4 14. 4 15. 50
Linked Comprehension Type

Comprehension # 1 16. (c) 17. (b) 18. (b)
Comprehension # 2 19. (a) 20. (b) 21. (b)
Comprehension # 3 22. (d) 23. (a) 24. (b) 25. (b)
Exercise-4
Previous Years JEE Main /AIEEE
MCQ with One Correct Answer Type
1. (c) 2. (c) 3. (a) 4. (a) 5. (d)
6. (b) 7. (a) 8. (a) 9. (b) 10. (d)
11. (d) 12. (a) 13. (d) 14. (a) 15. (d)
Exercise-5
Previous Years JEE Advanced
1. (b) 2. (d) 3. (d) 4. (3) 5. (5)
6. (c) 7. 8 mL 8. (8) 9. (9) 10. 126 mg.
11. 2.98 M 12. 0.11 M 13. 6.15 L

Mole Concept & Stoichiometry

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Mole Concept & Stoichiometry

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MOLE CONCEPT & STOICHIOMETRY XI-CMI-1

Mole Concept & Stoichiometry

Cancelling the common ‘n’, we have 1 molecule of hydrogen + 1 molecule of chlorine 

Weight of 1 litre of gas at STP

Weight of a certain volume of the gas

Weight of 1 molecule of the gas 1 Weight of 1 molecule of the gas

 Empirical formula mass = (1 × 12) + 1 = 13.

2.2 CHEMICAL EQUATIONS AND STOICHIOMETRY

these mole numbers change as the reaction progresses.

Moles of KCl obtained in Ist reaction =  

4.2 MOLALITY (m)

4.8 NORMALITY (N)

 Number of equivalents of solute = n × number of moles of solute

The nfactor of H2SO4 in this reaction would be 2.

 Similarly, find the n–factor of BaCl2 in the given reaction.

The nfactor of AaBb is calculated as

nfactor of KMnO4 = |1  (+7)  1  (+4)| = 3

nfactor of KMnO4 = |1  (+7)  1  (+6)| = 1

(c) S 2O32  

Carbon get oxidized from +3 to +4.

I get oxidized to I+.

 Calculate the nfactor of reactants in the given chemical changes?

(a) S 2 O32  

 Also calculate the nfactor of reactants in the given chemical changes?

In this reaction, oxidation state of Cr changes from +6 to +3 in both products.

 Calculate the nfactor of reactants in the given reactions.

(e) Fe2  SO4 3 

 Calculate nfactor of FeCl3 and (NH4)2Cr2O7 in the respective reactions.

6.8 SALTS OR COMPOUNDS WHICH UNDERGOES DISPROPORTIONATION REACTION

Or when the reaction is written as

 Calculate nfactor of HCuCl2 in the given reaction,

7.1.1 ACIDBASE TITRATIONS

7.2 BACK TITRATIONS

then the moles of pure ‘C’ =

 Mass of pure ‘C’ =

 Percentage purity of ‘C’ =

Phenolphthalein shows end point after reaction (ii)

and methyl orange shows end point after reaction (iii).

(Equivalents of HCl)1 = Equivalents of NaOH + Equivalents of Na2CO3 (n = 1) …(iv)

 % of NaOH in the mixture =

8. VOLUME STRENGTH OF H2O2 SOLUTION

(iii) Calcium behaves similarly.

Cl2, Br2 and I2 do not directly combine with oxygen.

10.3 COMPOUNDS RICH IN OXYGEN DECOMPOSE TO GIVE OXYGEN

10.4 ACTION OF HEAT ON NITRATES

(iii) Zinc nitrate decomposes to ZnO, NO2 & O2.

(zinc oxide, yellow when hot and white when cold)

10.5 ACTION OF HEAT ON AMMONIUM COMPOUNDS

(Green fluffy chromic oxide)

10.7 ACTION OF HEAT ON METALLIC BICARBONATES

 CaCO3 + H2O + CO2 

 MgCO3 + H2O + CO2 

10.8 ACTION OF HEAT ON CERTAIN HYDRATED CHLORIDES

(iii) SnCl22H2O undergoes hydrolysis to form basic chloride.

10.9 ACTION OF HEAT ON SOME OTHER COMPOUNDS

(vii) Al2  SO 4 3 .18H 2 O 

(viii) Cr2  SO 4 3 .18H 2 O 

10.10 ACIDBASE REACTIONS

(vi) 2MnO4  5C2O24 + 16H+ 

(x) MnO4 + 5Fe2+ + 8H+ 

11. HARDNESS OF WATER

Mass of hardness producing subs tan ce

(a) 12.4 g (b) 24.8 g (c) 0.248 g (d) 49.6 g