STOICHIOMETRY

The concept of atoms and molecules; Dalton's atomic theory; Mole concept;
Chemical formulae; Balanced chemical equations; Calculations (based on mole
concept) involving common oxidation-reduction, neutralisation, and displacement
reactions; Concentration in terms of mole fraction, molarity, molality and
normality.

CONTENTS INTRODUCTION
 Mole concept Mole concept is an important tool for
 Concentration dealing with chemical calculations.
Chemical equations are composed of
 Gravimetric analysis
symbols and formulae which have
 Concept of oxidation number quantitaitve significance also. Chemical
 Volumetric analysis equations therefore, help in solving number
of problems dealing with the weights and
 Volume strength of H2O2 solution
volumes of substances reacting and those
 Water hardness and its determination produced in a chemical change in this
chapter, we will consider calculations
based on chemical equations.
 Chemistry : Stoichiometry

1. MOLE CONCEPT
This topic includes the various basic concepts around which the whole of the chemistry
revolves.
We can classifyexisting substances into following categories keeping mole concept in view.

Elements Compounds Ionic species

(made up of atoms (made up of molecules) (made up of ions)
or molecules)
Atomic weight is Molecular weight is Ionic weight is
used for elements used for compound used for ions

According to mole concept

Gram atomic weight (i.e. atomic weight in grams) of any element contains Avogadro
number of atoms.
weight of element in grams
No. of gram atoms =  w/A
Atomic weight
If w = A i.e. weight of an element in gram taken is equal to it’s atomic weight then number
of gram atoms = 1 and we have already seen that when w = A then Avogadro no. of atoms
are present so from here it is concluded that one gram atom of any element contains
Avogadro number of atoms.
So,
56 g Fe = 1 g atom Fe = 6.023  1023 Fe atoms.
Like wise
23 g Na = 1 g atom Na = 6.023  1023 Na atoms
Similarly
Gram molecular weight (i.e. molecular weight in grams) of any compound contains
Avogadro number of molecules.
Weight of compound in grams
No. of moles   w /M
Molecular weight
If w = M then no. of moles = 1.
But in the definition we have seen that when w = M then 6.023  1023 molecules are
present. So from here it is concluded that 1 mole of any compound contains Avogadro
number of molecules.
58.5 g NaCl = 1 mole NaCl = 6.023  1023 NaCl molecules.

98 g N2SO4 = 1 mole H2SO4 = 6.023  1023 H2SO4 molecules

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Chemistry : Stoichiometry

Note : Moles of elements are referred as gram atoms and moles of ionic species is referred as
weight of ion
gram ions. For ionic species no. of gram ions  .
ionic weight
1 gram ion = Avogadro number of ions
Ionic weight is taken to be equal to ion formula weight. Why ?
It has been observed that one mole of any gas at S.T.P occupies a volume of 22.4 litres.
S.T.P corresponds to 0°C and 1 atm pressure.
volume of gas in litre at S.T.P
So number of moles of gas =
22.4
Similarly,
volume of gas in ml at S.T.P.
No. of moles of gas =
22400

1.1 VAPOUR DENSITY AND IT’S PHYSICAL SIGNIFICANCE

Vapour density: It is the number of times a gas is heavier than hydrogen
Mass of a definite volume of a gas
Vapour density =
Mass of same volume of hydrogen
under same conditions of pressure
and temperature
For our convenience we take the definite volume as 22.4 l and conditions of temperature
and pressure are taken as of S.T.P.
Mass of 22.4 l of gas at S.T.P
So V.D 
Mass of 22.4 l of Hydrogen at S.T.P
M (Molar Mass of gas)
 .
2(Molar Mass of Hydrogen)
Illustration 1: Calculate the following for 49 g H2SO4.
a) Moles (b) Molecules (c) Total H atoms (d) Total S atoms
e) Total O atoms (f) Total electrons.
Solution : Molecular weight of H2SO4 = 98
a) No. of moles = w/m = 49/98 = 1/2
b) Since 1 mole of any compound contains.
6.023 × 1023 molecules.
So 1
2 mole will contain  1
2  6.023  1023  3.0 1023
c) 1 molecule of H2SO4 contains 2H atoms
So total H atoms  2  3 1023  6  1023
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 Chemistry : Stoichiometry

d) Total S atoms  3.0  1023

e) Total O atoms = 3.0 1023  4  12  10 23
f) Electrons present in 1 molecule 1 2  16  8  4  50
So Total electron present  50  3.0 1023  150 1023
Illustration 2 : Calculate total ions present in 4.2 g of N3–
Solution : Weight of N3– = 4.2 g
Ionic weight = 14
No. of gram ions = weight/ionic weight
= 4.2/14 = 0.3
Since one gram ion contains 6.023 1023 ions.
So 0.3 gram ion will contains 0.3  6.023  1023
 1.8069  10 23 ions.
Illustration 3 : The vapour density of metal chloride is 85. If equivalent weight of metal is 7.01.
Calculate atomic weight of metal.

Solution : Molecular weight of metal chloride  2  V.D.

 85  2  170
Let formula of Metal chloride be MClx. [valency of metal = x]
xE + 35.5x = 170
7x + 35.5x = 170
x = 4.
Atomic weight = Equivalent weight × valency. = 28.

Illustration 4: Insulin contains 3.4% sulphur. Calculate minimum molecular weight of

insulin.
Solution : For minimum molecular weight, one mole of insulin should contain one mole of S
atom i.e. 32 g S
3.4 g S is present in 100 g insulin
If 32 g S is present then wt. of insulin
100  32
  941.17
3.4

4
Chemistry : Stoichiometry

EXERCISE 1 :
1. A sample of NH3 contains 3.3 × 1021 H atoms. How many ammonia molecules are in this
sample.
2. Sodium chloride has a density of 2.165g/cm3 at 25°C. Calculate the number of atoms in
1.000 cm3 of sodium chloride at 25°C.
3. A mixture of Al and Zn weighing 1.67g was completely dissolved in acid evolving 1.69L of
pure H2 measured at STP. What was the weight of Al in the original mixture.

2. CONCENTRATION
Solution is a homogenous mixture of two or more components. A solution consists of a
dissolved substance known as solute and a substance in which the solute is dissolved is
known as solvent. The concentration of a solution reflects the relative proportion of solute
and solvent present in the solution. The various concentration terms are
1. % w/W (Weight percent or mass percent)
Weight of solute
% w/ W =  100
Weight of solution
10% H2SO4 w/w means 10 grams of pure H2SO4 is present in 100 gram of H2SO4
solution.
2. % w/V (Weight/volume)
Weight of solute
% w/V =  100
Volume of solution
10% w/V H2SO4 solution means 10 gram of pure H2SO4 is present in 100 ml of H2SO4
solution.
3. % v/V (volume/volume)
This concentration term is defined for a solution of liquid into liquid
volume of solute
% v/v   100
volume of solution
42.8% v/V ethanol solution means that 42.8 ml pure ethanol is present in 100 ml of
ethanol solution.
4. Molality (m): It is defined as no. of moles of solute present in 1 kilogram of solvent.
No. of moles of solute
m=
Mass of solvent in kilogram
5. Mole Fraction (X): Suppose a solution of A and B contains nA moles of A and nB
nA
moles of B then mole fraction of A(XA) =
nA  n B
nB
Similarly mole fraction of B(XB) =
nA  n B
It is clear that
XA + XB = 1.

5
 Chemistry : Stoichiometry

Out of all the concentration terms we will discuss molarity and normality in detail
because these two concentration terms are related with two important methods of
stoichiometry i.e.
(i) Method of Moles
(ii) Method of Gram equivalents
6. Molarity (M): It is defined as the number of moles of solute dissolved in one litre of
solution
No. of moles of solute
M=
Volume of solution in litre
Suppose w gram solute is dissolved in Vml solution and molecular weight of solute
is m.
w/m w 1000 w
M   ;  Moles of solute
Vml /1000 m Vml m
w v w
1000  millimoles of solute; M  ml   moles of solute
m 1000 m
So if a substance is in solid form then it’s moles or millimoles can be calculated by
w w
using or 1000 and when the same substance is in solution then M  Vl or
m m
M  Vml will give the mole or mill moles respectively.
7. Parts per million (ppm) : It is defined as the quantity of the solute in grams present in
106 grams of the solution

Mass of solute 6
ppm = ×10
Mass of solution
Atmospheric pollution in cities is also expressed in ppm by volume. It refers to the
volume of the pollutant in 106 units of volume. 10 ppm of SO2 in air means 10 mL of
SO2 in present in 106 mL of air.
Illustration 5 : Calculate the total number of oxalic acid molecules present in a 100 ml of 0.01
M oxalic acid solution.
Solution : No. of millimoles of solute (oxalic acid) present = M  Vml = 0.01100 = 1.
Since 1 mole of any substance contains 6.023  10 23 molecules so 1 millimole will
contain 6.023 1020 molecules.
Illustration 6 :A 2 M aqueous solution of Potash Alum [K2SO4. Al2 (SO4)3 24H2O], an ionic
solid is prepared. Calculate moles of SO 2–
4 present in 800 ml of solution.

Solution : Moles of solute (Potash Alum) present in 800 ml of solution

800
= M  Vl  2   1.6 .
1000
Since potash alum is an ionic solid. So it will split into ions in solution.

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Chemistry : Stoichiometry

 2K   2Al3  4SO 42–

K 2SO 4 .Al2 (SO 4 )3 

it is apparent from balanced equation than 4 moles of SO 2–

4 are produced from 1
mole of potash alum.
So moles of SO 2–
4 present = 1.6  4  6.4

2.1 METHOD OF MOLES

This is an important method for solving stoichiometry problems
Steps for solving the problems
1. Write balanced chemical equation of the reaction taking place between reactants.
2. Check stoichiometric ratio and the ratio of amounts taken.
3. If both ratio matches than any of the reactant with give the amount of products formed.
4. If ratio doesn’t matches then find the limiting reactant. Now the amount of product
formed will be governed by the limiting reactant.

Illustration 7 : 0.5 moles of BaCl2 is mixed with 0.2 moles of Na3PO4. Calculate maximum
number of moles of Ba3(PO4)2 which can be formed.
Solution : Step 1 : 3 BaCl2 + 2Na3 PO4 
 Ba3(PO4)2 + 6NaCl
Step 2 : By viewing the balanced chemical equation we may well conclude that
3 moles of BaCl2 react with two moles of Na3PO4 and 1 mole of
Ba3(PO4)2 is formed i.e. stoichiometric ratio among reactants is of 3 : 2
and we have taken 0.5 moles of BaCl2 and 0.2 moles of Na3PO4 i.e.
ratio of amounts taken is of 5 : 2.
Step 3 : If these two ratio’s would have matched than any of the reactants will
give the amount of product formed because if two ratio’s matches than
both reactants are fully consumed.
Step 4 : Since ratio does not matches so one reactant is fully consumed
(limiting reactant) and other is left (excess reactant).
2.1.1 Process for Finding Limiting Reactant
Assume any of the reactant to be limiting reactant. Our assumption may be right or wrong.
Let BaCl2 is limiting
3BaCl2 + 2Na3PO4 
 Ba3 (PO4)2 + 6NaCl.
Initial Moles 0.5 0.2 0 0
Since BaCl2 is assumed to be limiting so it is fully consumed i.e. 0.5 moles of BaCl2 are
consumed.
3 moles of BaCl2 requires 2 moles of Na3PO4.
2
1 moles of BaCl2 will require moles of Na3PO4.
3
7
 Chemistry : Stoichiometry

1
0.5 moles of BaCl2 will require moles of Na3PO4.
3
But we don’t have 13 moles of Na3PO4 so our assumption that BaCl2 is limiting is wrong.
Now we will check for Na3PO4. Now we are assuming Na3PO4 to be limiting i.e. 0.2 moles
of Na3PO4 are fully consumed.
Since 2 moles of Na3PO4 requires 3 moles of BaCl2.
So 0.2 moles of Na3PO4 will require 0.3 moles of BaCl2.
And we have 0.5 moles of BaCl2 (far more than the requirement) so our assumption that
Na3PO4 is limiting is right.
3BaCl2 + 2Na3PO4 
 Ba3(PO4)2 + 6NaCl.
Initial Moles 0.5 0.2 0 0.
Since Na3PO4 is limiting so it will govern the amount of products formed.
Moles after reaction 0.2 0 0.1
So moles of Ba3(PO4)2 formed = 0.1

Note : Whenever two or more substances react their number of moles reacting might or
might not be same depending upon the stoichiometry of the reaction.

Normality (N): It is the number of gram equivalents of solute dissolved in one litre of
solution.
No. of gram equivalents of solute
N=
volume of solution in litres
Suppose w gram of solute is dissolved in Vml solution and equivalent weight of solute is E.
So number of gram equivalents of solute = w/E
Volume of solution in litres = Vml /1000
w/E w 1000
N=  
Vml /1000 E Vml
w
N  Vml  1000  milligram equivalents of solute
E
Vml w
N  N  Vl   gram equivalents of solute
1000 E
If weight of substance is known that it’s gram equivalent or milligram equivalents can be
w w
calculated by using relation or  1000 respectively and when a substance is in
E E
solution it’s gram equivalents or milligram equivalents can be calculated by using relation
N  vl or N  Vml respectively.

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Chemistry : Stoichiometry

2.2 METHODS FOR FINDING EQUIVALENT WEIGHT

Unless we don’t known equivalent weight we can not calculate normality or gram
equivalents.
Equivalent Weight: It is part’s by weight of a substance that combines with or displaces
1 part by weight of hydrogen, 8 parts by weight of oxygen or 35.5 part by weight of
chlorine.
But from this basic definition we can calculate the equivalent weight of substances that
combines with or displaces hydrogen, oxygen or chlorine. In order to find the equivalent
weight of various substances we categorize our substances in three categories.

Acids Bases Salts

Eq. wt. of acid = Eq. wt. of base = Eq. wt. of salt =
Molecular wt. Molecular wt. Molecular wt.
Basicity Acidity Total anionic or cationic charge
Where basicity is number Where acidity is the number
of replaceable H+ present of replaceable OH– present
in the acid. in the base
HCl, E = M/1 NaOH, E = M/1 NaCl , E = M/1
H2SO4 , E = M/2 Ca(OH)2 , E = M/2 Na2SO4, E = M/2
HNO3 , E = M/1 NH4OH , E = M/1 BaCl2, E = M/2
(COOH)2.2H2O, E = M/2 NaHCO3 , E = M/1 Na3PO4 , E = M/3
CH3COOH, E = M/1 Na2CO3 , E = M/2 Fe2(SO4)3 , E = M/6
Where M is the molar mass of corresponding acid, base or salt. It is clear that equivalent
weight of any substance is related to it’s molecular weight through certain relation. So in
general we can say that
Molecular weight
Equivalent weight =
n factor
nf for acids is the basicity of acid
nf for bases is the acidity of base
nf for salts is the total anionic or cationic charge
nf in redox reaction is change in oxidation number per mole. (To be discussed in oxidation-
Reduction).
It has been discussed that nf for acids will be equal to it’s basicity and basicity is nothing
but number of replaceable H+. Point to be remembered is that basicity can not be predicted
just by viewing the molecular formula of the acid.
1. H2PO2 (Hypo phosphorus acid).
9
 Chemistry : Stoichiometry

O
H—O—P—H

H
Basicity = 1.
Since H atom attached to oxygen is ionized and H atoms attached to phosphorous do not
ionise.
H 3 PO 2 H   H 2 PO 2–
2. H3PO3 (Phosphorus acid).
O
H—O—P—O—H

H
Basicity = 2
H 3 PO 2 H   H 2 PO 3–

H 2 PO3– H   HPO32–
3. H3PO4 (ortho phosphoric acid).
O
H—O—P—O—H

H
H3PO4 + Ca(OH) 2 
 CaHPO4 + 2H2O
In this reaction H3PO4 is furnishing only two H+ so basicity of H3PO4 = 2 = nf
M
E H 3PO4  .
2
Law of Equivalence: Two substances react in such a way that their gram equivalents are
always equal.
Relation between gram equivalents and Moles
Gram equivalents = w/E
= w/M/nf
w
= nf 
M
Gram equivalents = nf  Moles … (4)

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Chemistry : Stoichiometry

Similarly
Milli equivalents = nf  millimoles dividing equation (4) by Vl
N  nf  M … (5)

2.3 METHOD OF EQUIVALENTS

In stoichiometry each and every problem can be analysed by two parallel paths. One is the
method of moles and other is the method of equivalents.

Illustration 8 :0.5 moles of BaCl2 is mixed with 0.2 moles of Na3PO4. Calculated maximum
number of moles of Ba3(PO4)2 which can be formed.
Solution : nf = 2 nf = 3 nf = 6 nf = 1.
3BaCl2 + 2Na3PO4 
 Ba3(PO4)2 + 6NaCl.

Observation: Balancing coefficients of reactants are in the reverse ratio of nf of reactants

similarly balancing coefficients of products are in the reverse ratio of nf of products. Why ?
Now we will prove law of equivalence.
According to stoichometry of reaction 3 moles of BaCl2 reacts with 2 moles of Na3PO4 and
forms 1 mole of Ba3(PO4)2 and 6 moles of NaCl.
No. of gram equivalents = nf  no. of moles.
For BaCl2 (3 moles)
Gram equivalents = 2  3 = 6
For Na3PO4 (2 moles)
Gram equivalents = 3  2 = 6
For Ba3(PO4)2 (1 moles)
Gram equivalents = 6  1 = 6
For NaCl (6 mole)
Gram equivalents = 1  6 = 6
So when 6 gram equivalents of each reactant reacts, 6 gram equivalent of each product is
formed.
3BaCl2 + 2Na3PO4 
 Ba3(PO4)2 + 6NaCl.
Initial Moles 0.5 0.2 0 0
Initial gram 1 0.6 0 0
Equivalents
Na3PO4 will be limiting since it’s gram equivalents are less.
Gram equivalents 0.4 0 0.6 0.6

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 Chemistry : Stoichiometry

After reaction
Gram equivalents of Ba3(PO4)3 formed = 0.6
Gram equivalents 0.6
Moles of Ba3(PO4)2 formed   = 0.1
nf 6

2.4 INTER CONVERSION OF VARIOUS CONCENTRATION TERMS

2.4.1 Weight percent (w/W) to Molarity

Illustration 9 :A 49% (w/W) solution of H2SO4 has a density of 1.294 g/ml. Calculate molarity.
Solution : Since weight percent is given so we will take 100 g of solution into consideration.
Basis : 100 g of solution
Mass of solute (H2SO4) = 49 g.
Molecular mass of solute = 98
Moles of solute = 49/98
Mass 100
Volume of solution (in ml) = 
density 1.294
100
Volume in litres =
1.294 1000
49 / 98 10  49 1.294
Molarity =  = 6.47M
100 /1.294 1000 98
10 Pd 10  % by wt.  density
Molarity = 
M Molecular weight
2.4.2 Weight percent (w/V) to molarity

Illustration 10 : Calculate morality of a 10% (w/v) H2SO4 solution

Solution : Basis : 100 ml of solution
Mass of solute (H2SO4) = 10g.
Molecular Mass of solute = 98
Moles of solute = 10/98
100
Volume of solution = 100 ml = litres.
1000
10 / 98
Molarity = = 1.02M
100 /1000
2.4.3 Molarity to Molality

Illustration 11 : A 3M solution of Na2S2O3 (M.Wt. 158) has a density of 1.25 g/ml. Calculate
molarity.

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Chemistry : Stoichiometry

Solution : Since molarity is given so we will take the basis as 1 litre of solution.
No. of moles of solute = 3
Mass of solute = 3 158  474 g

 M
Mass of solution      1250 g
 V
Mass of solvent = Mass of solution – Mass of solute
= 1250 – 474
= 776 g
No. of Moles of solute
Molality =
Mass of solvent in kg
3
 = 3.86
776 /1000

Note : For dilute aqueous solution molality molarity because solution is dilute so density
will not fluctuate much and it will be very near to 1 g/ml. i.e. volume and mass will remains
same.

2.4.4 Molarity to Mole Fraction

In the above problem
Moles of solute = 3
Mass of solvent = 776 g
Moles of solvent = 776/18
no. of moles of solute
Mole of fraction =
no. of moles of solute no. of moles of solvent
3
 = 0.065
776
3
18

2.4.5 Mole fraction to Molality

Illustration 12 :A solution of Iodine in Benzene has a mole fraction of 0.2. Calculate molality.
n I2 n I2  n B
Solution :  0.2 or 5
n I2  n B n I2

nB
or 1 5
n I2

13
 Chemistry : Stoichiometry

nB
or 4
n I2

n I2 1
or 
nB 4
n I2 1 n I  78 1
or   2  [Molecular weight of Benzene  78] .
WB / M B 4 WB 4
n I2 1
  78 
WB 4
 1000
1000
1 1000
 Molality   = 3.20
4 78
EXERCISE 2 :
1. What will be the final conc. of the ions in a solution made by mixing 0.0-15 moles of
Sr(NO3)2 and 0.003 moles of NaF in enough water to make 0.2L of solution. Assuming that
SrF2 is completely insoluble.
2. Calculate the number of moles of CuSO4 contained in 100 mL of 1 M CuSO4 solution.
Also, find the number of SO 24 ions in it.
3. A drop (0.05 mL) of 12 M HCl is spread over a thin sheet of aluminium foil (thickness 0.10
mm and density of Al = 2.70 g/mL). Assuming whole of the HCl is used to dissolve Al,
what will be the maximum area of hole produced in foil?

3. GRAVIMETRIC ANALYSIS
The analysis of a chemical reaction is generally carried out in the form of mass of reacting
species taking part in chemical reaction.
In gravimetric analysis we generally analyse reactions such as decomposition of
compounds under heat to produce a residue and a gas, or displacement reactions, action of
acids on metals. Problems include.
a) Weight (solid) — weight (solid) relationships.
b) Weight (solid) — volume (gas) relationships.
c) Volume (gas) — volume (gas) relationships.

Note : Methods of moles as well as method of gram equivalents can be applied to solve
problems on gravimetric analysis; however it is convenient to apply method of moles.

Illustration 13 :A mixture NaCl and Na2CO3 is given. On heating 12 gm of the mixture with
dil. HCl, 2.241 gm of CO2 is evolved at normal temperature. Calculate the
percentage composition of the mixture.

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Chemistry : Stoichiometry

Solution : Consider the effect of heat on the mixture:

NaCl + HCl 
 nothing happens
Na 2 CO3  2 HCl 
 2NaCl  CO 2  H 2 O
Let x gram of Na 2 CO 3 are there in the mixture :
Moles of Na 2CO3  x /106 (moles = w/M)
From stoichiometry, we have :
1 mole of Na 2CO3  1 mole of CO2
x/106 moles of Na 2 CO3 =x/106 mole of CO2
x 2.241
 
106 44
 x = 5.398 gm.
Hence grams of NaCl in the mixture = 12 –x = 6.60 gm

Illustration 14 : Brass is an alloy of Cu-Zn. A sample of brass weighing 5.793 g, when treated
with excess of dil. H2SO4 gives 324 ml of dry H2 at 20°C and 750 mm pressure.
What is the percentage of Cu by weight in the alloy ?
Solution : Only Zn reacts with dil. H2SO4 and produces H2.
Zn(s) + H2SO4 
 ZnSO 4  H 2 (g)
1 mol of Zn  1 mol of H2
Using the gas equation, find moles of H2.
PV
Moles of H2 evolved 
RT
750  0.324
n  0.0133
760  0.082  293
The amount of Zn in the alloy = 0.0133 × 65.4 = 0.871 g
4.922
% of Cu  100  85% .
5.793

Illustration 15 : Igniting MnO2 in air converts it quantitatively to Mn3O4. A sample of

pyrolusite is of the following composition : MnO2 = 80%, SiO2 and other inert
consitituents = 15% and rest bearing H2O. The sample is ignited to constant
weight. What is the % of Mn in the ignited sample ?
Solution : 3MnO 2 
 Mn 3O 4
From stoichiometry;
3 moles of MnO 2  1 mole of Mn 3O 4  3 mole of Mn

15
 Chemistry : Stoichiometry

 1 moles of MnO 2  1 /2 mole of Mn 3O 4

Let 100 gm of pyrolusite sample be taken
 gms of MnO 2  80
80
 moles of MnO2 
87
From stoichiometry :
80
Moles of Mn 3O 4  1/ 3 
87
80
Moles of Mn 
87
80
Grams of Mn   55  50.57gm
87
80
Grams of Mn 3O 4  1/ 3   229  70.19
87
Total wt. of ignited sample = 70.19 + 15 ( SiO2 & inert matter) = 85.19
50.57
 % Mn  100  59.36%
85.19
3.1 EFFECT OF HEAT ON SOME COMPOUNDS
1. Effect of heat on carbonates and bicarbonates

a) Na2CO3   no effect

b) K2CO3   no effect

c) (NH4)2 CO3   2NH3  + H2O  + CO2 
d) Other carbonates decomposes to give oxides and CO2.

CaCO3   CaO + CO2.

MgCO3   MgO + CO2.

ZnCO3   ZnO + CO2.
e) All bicarbonates decomposes to give CO2 and H2O.

2NaHCO3   Na2CO3 + CO2  + H2O 
2. Effect of heat on nitrates

a) NH4NO3   N 2 O   2H 2 O

b) NaNO3   NaNO2  1
2 O2 

c) AgNO3   Ag   NO2   1
2 O2 

HgNO3   Hg   NO 2   1
2 O2 

16
Chemistry : Stoichiometry


d) Mg(NO3)2   MgO   2NO 2   1
2 O2 
 1
Pb(NO3 )2   PbO   2NO 2   O 2 
2
3. Effect of heat on sulphates
Sodium and potassium sulphate are thermally stable.

a) MgSO4 7H2O   MgSO4 + 7H2O 

b) 2FeSO4 7H2O   Fe2O3   SO 2   SO3   7H 2O 

c) CuSO 4 .5H 2O   CuSO 4 .H 2O  4H 2O 

d) CuSO 4 .H 2O   CuO   SO3   H 2O 

e) Fe2 (SO 4 )3   Fe2 O3  3SO3 
4. Effect of heat on halides

a) 2FeCl3   2FeCl2 + Cl2 

b) 2CuCl2   Cu2Cl2 + Cl2 

c) NH4Cl   NH3  + HCl 

d) MgCl2 . 6H2O   MgO  + 2HCl  + 5H2O 

4. CONCEPT OF OXIDATION STATE OR OXIDATION NUMBER

Definition : It is the charge which an atom of an element in a compound appears to have
when shared electrons are counted according to following two rules.
Rule 1: an electron pair shared between two similar atoms is counted with both the atoms.
x
H H
o.s of H is 0 o.s of H is 0

o.s of H is 0.
Rule 2: An electron pair shared between two dissimilar atoms is counted with the more
electronegative element

H x Cl
o.s of H is +1 o.s of Cl is –1

Calculation of Oxidation state of some elements in their compounds using basic

definition of oxidation state
1. Oxidation no. of O in H2O2.

17
 Chemistry : Stoichiometry

In order to calculate the oxidation state of O in H2O2 using basic definition, first we
will write its octet structure and then we will break all the bonds which O is forming
with the help of Rule-1 and Rule-2 which ever is applicable. Net gain or net loss of
electrons will be equal to the oxidation state.

H xO Ox H

H xO Ox H
Rule - 2 Rule - 2

This O has net gain of 1 electron This O has net gain of 1 electron
so oxidation state is –1. so oxidation state is –1.

From here it is concluded that where ever the peroxy linkage (—O — O—) is present
the oxidation state of O is –1.
2. Oxidation no. of S in. Perdisulphuric acid (H2S2O8) or marshal’s acid.
O O

H —O—S—O —O—S—O— H

O O
So net loss for sulphur atom (2 electrons from each coordinate bond and 1 electron
from each covalent bond).
Net loss = 6 electrons.
Oxidation state of S = +6.
3. Oxidation state of nitrogen in nitro benzene
O
Rule - 2
N
Rule - 2 O
Rule - 2

Net loss for nitrogen : 2 electrons from coordinate bond

2 electrons from double bond gain of 1 electron from N—C single bond
Net loss 3 electrons.
Oxidation state of nitrogen = +3.
By using above two rules we can calculate the oxidation state of any element in any
compound but for this we will have to draw the correct octet-structure, but this is a time
taking process so we have compiled this basic concept into certain rules in order to
save time.

18
Chemistry : Stoichiometry

4.1 RULES FOR CALCULATING OXIDATION STATE

1. The oxidation state of an element in it’s free state or natural state is zero
Natural state H2 N2 O2 P4 S8
Element H N O P S
o.s . 0 0 0 0 0
2. The oxidation state of any element in it’s simple ion (one atom ion) is equal to charge
on ion.
Ion Na+ Ba2+ Al3+ Cl–
o.s +1 +2 +3 –1
3. The algebraic sum of the oxidation states of all the elements in a molecule is O but in
case of an ion it is equal to charge on the ion.
e.g. in CH4
Oxidation state of C + 4 × oxidation state of H = O
in SO 2–
4 Oxidation state of S + 4 × oxidation state of O = –2.

4. The o.s of fluorine in all of it’s compounds is always –1.

5. The o.s. of halogens in metal halides is –1.
6. The o.s of alkali metals (Li, Na, K, Rb, Cs, Fr) in all of their compounds is +1.
7. The o.s. of alkaline earth metals (Be, Mg, Ca, Sr, Ba, Ra) in all of their compounds
is +2.
8. The o.s. of H is generally +1 except in metal hydrides. (NaH, CaH2) where it is –1.
9. The o.s. of oxygen is generally –2 exceptions are peroxides, superoxides and oxygen
fluorides.
In peroxides o.s. of O is –1. (e.g. H2O2)
In superoxides o.s. of O is –1/2 (e.g. KO2)
In oxygen fluorides o.s. of O is +ve (e.g. OF2, O2F2).

4.2 REDOX REACTION

A redox reaction is one in which certain elements undergo a change in oxidation state
consider the following reaction.
CuSO 4  Pb 
 PbSO 4  Cu
Assign oxidation state to each element
2 6 2 0 2 6 –2 0
Cu S O 4  Pb 
 Pb SO 4  Cu

19
 Chemistry : Stoichiometry

Since S and O are not undergoing a change in oxidation state so they are not a part of our
discussion.
o.s. of Pb and Cu has changed from left to right i.e. these two elements aer taking part in
redox reaction.
We can split this equation into two half, reactions, one for the oxidation (increase in
oxidation state) half and the other for the reduction, (decrease in oxidation state) half.
0 2
Oxidation half : Pb 
 Pb  2e (lo sin g 2e)
2 0
Reduction half : Cu  2e 
 Cu (gaining 2e)
Oxidation state of Pb has increased from 0 to +2.
Oxidation state of Cu has decreased from +2 to 0.
So we can redefine oxidation and reduction as follows :
Oxidation is increase in oxidation state or loss of electrons
Reduction is decrease in oxidation state or gain of electrons.
Pb is oxidized and causes Cu2+ to be reduced, Pb is called as reducing agent. Cu2+ is
reduced and causes the oxidation of Pb, Cu2+ is known as oxidizing agent.

4.3 BALANCING OF REDOX REACTIONS

For balancing of redox reactions, two methods are used
4.3.1 By Oxidation Number method
Step :
a) Determine oxidation state of each atom in the equation.
b) Note the atoms which undergo change in oxidation state.
c) Calculate the change in oxidation state per atom.
d) Calculate the change in oxidation state per mole.
e) Put suitable coefficients to balance change in oxidation state per mole.
f) Finally balance equation by inspection.

Illustration 16 : Balance using oxidation number change method.

FeCl3  H 2 S 
 FeCl2  HCl  S
Solution : Determine oxidation state of each atom.
Fe Cl3  H 2S 
 Fe Cl3  HCl  S
3 1 1 –2 2 1 1 – 1 0

H and Cl are not at all taking part in the redox reaction. Only Fe and S are taking
part in redox reaction.

20
Chemistry : Stoichiometry

3 2 2 0
 e / Fe –2e / S
Fe   Fe S  S
 e / FeCl3 –2e /S
FeCl3   FeCl2 H 2S  S
2e / 2FeCl3 –2e / H 2S
2FeCl3  2FeCl 2 H 2S  S

2FeCl3  H 2S 
 2FeCl2  S
HCl will be balanced by inspection
2FeCl3  H 2S 
 2FeCl 2  S  2HCl

Illustration 17 : Balance using oxidation number change in method

K 2 Cr2 O7  HCl 
 KCl  CrCl3  Cl2  H 2O

Solution : K 2Cr2O7  HCl 

 KCl  CrCl3  Cl 2  H 2O
1  6 –2 1 –1 1 –1 3 –1 0 1 – 2

K, O, H are not taking part in redox reaction.

6 3 –1 0
3e / Cr – e / Cl
Cr   Cr Cl   Cl
6e / K 2Cr2 O7 – e / HCl
K 2 Cr2O7   2 CrCl3 HCl  1 Cl
2 2

This coefficient is This coefficient is

put to balance Cr. put to balance Cl

6e / K 2 Cr2 O 7 –6e / 6HCl

K 2 Cr2 O7   2CrCl3 6HCl   3Cl 2
K 2 Cr2 O7  6HCl 
 2CrCl3  3Cl2
Substances which do not take part in redox reaction are to be balanced by hit and
trial
K 2 Cr2 O7  6HCl 
 2KCl  2CrCl3  3Cl2  H 2O
 2KCl  2CrCl3  3Cl2  7H 2O .
K 2 Cr2 O7  14HCl 

4.3.2 By Ion Electron Method

Steps
a) Break the unbalanced equation into two half reactions one for oxidation half and other
for reduction half
b) Balance each half equation first in terms of atoms and then in terms of charge.
c) First balance atoms other than oxygen and hydrogen just by putting coefficients

Rules for Balancing of Oxygen and Hydrogen in Acidic Medium

21
 Chemistry : Stoichiometry

a) Among oxygen and hydrogen always first balance oxygen and then hydrogen
b) To balance oxygen atom add one H2O to the side deficient in oxygen.
c) To balance hydrogen atom add one H+ to the side deficient in hydrogen.

Rules for Balancing Oxygen and hydrogen in Basic Medium

a) First balance oxygen and then hydrogen
b) To balance an oxygen atom add two OH– to the side deficient in oxygen and one H2O
to the other side.
c) To balance one hydrogen atom add one H2O to the side deficient in hydrogen and one
OH– to the other side.

Illustration 18 : Balance the following equation by ion electron in basic medium

CrO42  I  
 Cr 3  IO3

Solution : Cr O2– –
 Cr3  IO3–
4  I 
6 –1 3 5

Oxidation Half Reduction Half

I – 
 IO3– CrO 2–  Cr 3
4 

This oxidation half reaction is balanced in terms This reduction half reaction is balanced in
of atoms other than oxygen terms of atoms other than oxygen i.e. Cr.
6OH –  I – 
 IO3–  3H 2 O  Cr 3  8OH –
4H 2O  CrO 42– 
This is balanced in terms of atoms. Now we
will balance this n terms of charge.
6OH –  I – 
 IO3–  3H 2O  6e – [4H 2 O  CrO 2– –
 Cr 3  8OH – ]2.
4  3e 

6OH –  I –  8H 2O  2CrO 2–  IO 3–  3H 2O  2Cr 3  16OH –

4 

 IO3–  2Cr 3  10OH –

I –  2CrO 4–  5H 2 O 

Illustration 19 : Balance the following reaction in acidic medium

CuS  NO3 
 Cu 2  S8  NO

Solution :  Cu 2   S8  NO
CuS  NO3– 
2 –2 5 2 0 2

First of all we will balance these half reaction in terms of atoms other than oxygen
and hydrogen but putting simple coefficients. Then we will balance each half
reaction in terms of oxygen and hydrogen by applying rules. Finaly we will
balance these half reactions in terms of charge.

22
Chemistry : Stoichiometry

Oxidation Half Reaction Reduction Half Reaction

 Cu 2   S8
CuS  NO3– 
 NO

 8Cu 2   S8
8CuS  NO3– 
 NO
This is balanced in terms of atoms We will balance oxygen
2
8CuS 
 8Cu  S8 4H   NO3– 
 NO  2H 2O

3[8CuS  8Cu 2  S8  16e – ] [4H   NO3–  3e –  NO  2H 2 O]16

24CuS 16NO3– 64H 

 24Cu2  3S8  16NO  32H2O

EXERCISE 3 :
1. Find the oxidation state of elements underlined in the following compounds.
KClO3 , HClO 4 , MnO 2 , NH 4 NO3 , K 2 MnO 4 , H 2 SO 5 , CrO5 , Na 2 S2O 3

H 2 C 2O 4 , S4O 62– .

2. Write complete balanced equation for the following in acidic medium by ion-electron
method:
(a) Cl O 3 + Fe+2 
 Cl– + Fe+3 + H2O

(b) CuS + N O 3 
 Cu+2 + S8 + NO + H2O

(c) S2 O 32 + Sb2O5 

 SbO + H2SO3
3. Balance the following reactions by oxidation number method.
Zn + N O 3 
 Zn2+ +N2O + H2O (Acidic Medium)

4.4 CALCULATION OF n FACTOR IN A REDOX REACTION

1. If one element is getting oxidized and other is getting reduced:
e.g.
2N H 2OH  2Fe2 (SO 4 )3 
 N 2 O(g)  H 2O  4FeSO 4  2H 2SO 4
–1 3 1 2

NH 2OH is getting oxidized to N 2O and Fe2 (SO4 )3 is getting reduced to FeSO 4 .

In redox reaction nf = change in oxidation state per mole.
23
 Chemistry : Stoichiometry

–1 1 3 2
N  N Fe   Fe
nf for NH 2 OH  2 nf for Fe2 (SO 4 )3  2
nf for N 2O  4 nf for FeSO 4  1
2. Salts that react in such a way that two types of atoms in the salt undergo change in
oxidation state
a) When both atoms are getting oxidized or reduced
1 –2 2 4
 Cu 2   SO 2
Cu 2 S 
Both Cu  and S2– are getting oxidized
nf for Cu 2S [(2 – 1)2]  [4 – (–2)]  8
2 3 3 4
b) Fe C 2 O 4 
 Fe  CO 2
Both Fe2 and C3 are getting oxidized
nf for FeC 2 O 4  [3 – 2] [(4 – 3)2] = 3.
3 5 2 2
c)  Fe 2   NO
Fe (NO3 )3 
Both Fe3 and N 5 are getting reduced.
nf for Fe(NO3 )3  [(3 – 2)]  [(5 – 2)3] = 10.

4.5 n-FACTOR FOR DISPROPORTIONATION REACTION

In those disproportionation reactions, where the number of moles of the substance getting
oxidized or reduced are same, the n factor is calculated by either the number of moles of
electrons lost gained by 1 mole of that substance. For example,
2H 2 O 2 
 2H 2O  O 2
Of 2 mole of H2O2, one mole of H2O2 gets reduced to H2O (oxidation state of O changes
from –1 to –2) and other gets oxidized to O2 (oxidation state of O changes from –1 to 0).
O 22  2e 
 2O2

or O 22  
 O o2  2e 
Thus, it can be seen that one mole of H2O2 which is either getting oxidized or reduced will
lose or gain 2 moles of electrons. Therefore, n factor H2O2 in this reaction is 2.
When same substance undergoes oxidation as well as reduction then this phenomenon is
known as disproportionation.
When balanced disproportionation reaction is given
0 –1 5
12OH –  6Br2 
 10Br  2BrO3–  6H 2O
nf  1 nf  5

Br2 is getting oxidized as well as reduced.

24
Chemistry : Stoichiometry

i.e. Br2 is getting disproportionate. nf calculation for Br2 is difficult whereas. nf for Br –
and BrO3– can be easily calculated now by viewing the balanced reaction.

6 moles of Br2 produces 10 moles of Br – and 2 moles of BrO3– .

By applying law of equivalence
Gram equivalents of Br – in 10 moles = nf  moles
= 1  10 = 10

Gram equivalents of BrO3– in 2 moles = 5  2= 10

So 6 moles of Br2 will have 10 gram equivalents

10 = nf  6
nf = 10/6 or 5/3.
When unbalanced disproportionation reaction is given
0 –1 5
 Br –  BrO3–
Br2 
nf  1 nf  5

Now we cannot calculate nf for Br2 by applying law of equivalence, in such cases,
Consider reduction half and oxidation half reactions.
Reduction Half Oxidation Half
0 –1 0 5
–
Br2 
 Br  Br O3–
Br2 
nf  2 nf  10

Equivalent weight of Br2 in Equivalent weight of Br2

M M
Reduction half  in oxidation half 
nf nf
M M
 
2 10
Net equivalent weight of Br2 will be sum of equivalent weight of two half reactions.
M M
Net E  
2 10
5M  M 6M M
  
10 10 10 / 6
So nf  10 / 6  5 / 3
When some part of a substance is participitating in redox reaction and some part is
not participating in the redox reaction.

25
 Chemistry : Stoichiometry

4 –1 –1 0
e.g. Mn O 2  4H Cl 
 Mn Cl2  Cl2  2H 2 O
nf  2

nf for MnO 2 can be easily calculated, for HCl some chlorine is remaining in the same
oxidation state and some is going in the higher state (–1 to 0).
1 mole of MnO 2 reacts with 4 moles of HCl. Applying the law of equivalence.

Gram equivalents of MnO 2  nf  Moles .

 2  1 = 2.
So 4 moles of HCl will also contain 2 gram equivalents for HCl.
Gram equivalents  nf  Moles
 nf  4
nf for HCl  12 .

Modifications in the Law of Equivalence :

Suppose a reaction is taking place.
A+BC+D
according to law of equivalence
meq of A reacted = meq of B reated = meq of C produced = meq of D produced
This statement holds god only for simplest tpe of redox reactions in which one substance is
getting oxidized and other is getting reduced.
Thus the equivalents of a substance produced and reacted can be equal only when in the two
reactions its nf is same otherwise some modification is required. So at any point when a
substance is produced in a reaction which further reacts in another reaction. We will explain
the above statement through following illustration.

Illustration 20 : When x g of S is burnt, it forms SO2 which is oxidized by Cl2 water to SO42–
ion. Calculate the weight of SO 2– ion produced.
4

0 4
Solution : S  O2 
 SO2
nf  4
Moles of S = x/32
x
equivalents of SO2 = 4 
32
(with respect to nf = 4)
Cl2
SO 2   SO 42 
nf  2

26
Chemistry : Stoichiometry

x
equivalent of SO2 = 2 
32
(with respect to nf = 2)
2x
equivalents of SO42- =
32
W 2x
=
E 32
W 2x
=
48 32
x
W =  48 = 3x
16
Hence we should keep in mind that the equivalents of same substances can be
added to subsracted only when they are of same n factor.
In a reaction of the type
A+B+CD+E
it is not necessary that the equivalent of A = Equivalent of B = Equivalent of C
for e.g.
0 7 1 2 2 O
Z n  KMnO 4  H 2SO4 
 ZnSO 4  H 2SO 4  MnSO 4  H 2
Here Zn is reducing agnet and (KMnO4 and H2SO4) are oxidizing agents
So equivalents of Zn = Equivalents of KMnO4 + Equivalents of H2SO4.

Illustration 21 :In a raction FeS2 in oxidized by O2 to Fe2O3 and SO2. If the equivalents of O2
consumed are y then calculate the equivalents of Fe2O3 and SO2 produced with
respect to FeS2.
2 1 3 4
11
Solution : 2FeS2  O 2 
 Fe2 O3  4SO 2
nf 1 25 11 2 nf  2 nf  5

Equivalents of O2 = Equivalents of FeS2 = y

y
Moles of FeS2 =
11
y
Moles of Fe2O3 = 2.
11

27
 Chemistry : Stoichiometry

y 2 y
Equivalents of Fe2O3 = =
2  11 11
2y
Moles of SO2 =
11
2y 10y
Equivalents of SO2 = 5=
11 11
i.e. equivalents are divided in the ratio of n factors.
FeS2
nf = 1+2×5 = 11

y 10y
so equivalents of Fe2O3 = and equivalents of SO2 =
11 11
Now we will calculate the equivalents of equivalents of Fe2O3 and SO2 with
respect to O2.
11 0 2 2
2FeS2  O 2   Fe2 O3  4SO2
2 nf  4 nf  6 nf  4

Equivalents of O2 = y
Moles of O2 = y/4
2 y
Moles of Fe2O3 = 
11 4
2 y 3y
Gram equivalents of Fe2O3 =  6 =
11 4 11
4 2 y
Moles of SO2 = 
11 4
8 y 8y
Gram equivalents of SO2 =  4 =
11 4 11
so from above discussion it is apparent for Fe2O3
y
that when nf = 2 then is equivalents are
11
3y
and when nf= 6 for Fe2O3 then its equivalents =
11
10y
Similarly for SO2 (when nf = 5) then gram equivalents =
11
8y
and when (nf = 4) then gram equivalents =
11
So for any substance if nf is same then its gram equivalents will be same.

4.6 SOME IMPORTANT OXIDIZING AND REDUCING AGENTS

28
Chemistry : Stoichiometry

1. Fe2 (SO4 ) 3
act as an oxidizing agent
Fe3  e – 
 Fe2
nf = 2. (per mole change in oxidation state is of 2)
M
E Fe2 (SO4 )3 
2
2. K 2 Cr2 O7
acts as an oxidizing agent in acidic medium
Cr2O72–  14H   6e – 
 2Cr 3  2H 2O
6 3
nf 6

M
E K 2Cr2O7 
6
3. KMnO4
acts as oxidizing agent in acidic and alkaline medium
a) In acidic medium
MnO 4–  8H   5e – 
 Mn 2   4H 2 O
7 2

nf = 5
M
E KMnO4 
5
b) In neutral medium
2H 2O  Mn O 4–  3e – 
 Mn O 2  4OH –
7 4

nf  3
M
E KMnO4 
3
c) In alkaline medium
–
OH
MnO4–  e –   MnO 2–
4

nf = 1
M
E KMnO4 
1
4. HNO3
It acts as an oxidizing agent
NO3– 2H   e – 
 NO2  H 2O
5 4
nf  1

29
 Chemistry : Stoichiometry

M
E HNO3  .
1
5. FeSO4
It acts as a reducing agent
Fe2  
 Fe3  e –
nf  1

M
E FeSO 4 
1
6. H 2C 2O 4
It acts as a reducing agent
C 2O 42– 
 2CO2  2e –
3 4

nf = 2
M
E H 2 C 2 O4 
2
7. SO 2
It acts as a reducing agent
 SO 42–  4H   2e –
SO 2 2H 2 O 
4 6

nf = 2
M
ESO2 
2
8. HI
It acts as a reducing agent
 I 2  2H   2e –
2HI 
–1 0

nf = 1
M
E HI  .
1
EXERCISE 4
1. i) What is the weight of sodium bromate and molarity of solution necessary to prepare
85.5 mL of 0.62 N solution when the half cell reaction is
BrO3  6H   6e 
 Br   3H 2O?
ii) What would be the weight as well as molarity if the cell reaction is
2BrO3  12H   10e 
 Br2  6H 2O
2. 9.824g of FeSO4(NH4)SO4xH2O were dissolved in 250 mL of solution. 20 mL of this
solution required 20 mL of KMnO4 containing 3.52g of 90% by weight KMnO4 dissolved
per litre. Calculate value of x.

30
Chemistry : Stoichiometry

3. What is molarity and normality of a MnO 4 solution if 32.00 mL of the solution is required
to react with 40.00 mL of 0.4500 N Fe2+?

5. VOLUMETRIC ANALYSIS
In volumetric analysis we deal with the reacting substances which are in solution form.
Each and every problem of volumetric analysis can be solved by using method of moles.
( M  V  Moles ) or method of equivalents ( N  V gram equivalents).
Titration: It is an experimental method of determining the concentration of a substance. In
volumetric analysis we will encounter following types of titrations.

5.1 SIMPLE TITRATION

It is the simplest form of titration in which one solution is taken in the burette and definite
volume of other in the conical flask, off course the two substances are reactive. Now the
reaction is carried out by drop by drop addition of a solution which is in burette into the
conical flask. When the gram equivalents or milligram equivalents of two substances
becomes equal i.e. equivalence point or end point is achieved the titration is over.
Equivalence point or end point is indicated by a substance known as indicator, very little
amount of which is added into the conical flask before starting the titration : Although in
most of the cases it is the end point which is achieved and not the equivalence point. Why?
Let us understand simple titration through an illustration.
Suppose we have a 20 l stock of a NaOH solution, the concentration of which is not known
to us. We adopted the method of titration to find the concentration of this NaOH (base)
solution with the help of a standard (concentration of which is known) HCl (acid) solution.
Let concentration of HCl solution is 0.1 M.
We filled this HCl solution in the burette. From the 20 l NaOH stock, we withdrew 10 ml
with the help of pipette and transferred into the conical flask one drop of suitable indicator
is added to the conical flask, after which the NaOH solution will possess a distinct colour.
Now we started adding HCl drop by drop into the conical flask upto a situation, when
colour change takes place, now end point is achieved. The volume of HCl required to
achieve end point is noted and say it is 10 ml.
At End point
Milligram equivalent of HCl = Milligram equivalents of NaOH.
N  Vml  N  10
0.1  10  N  10
N = 0.1
So normality of NaOH = 0.1 N
If the constituents are acid and base then titration is known as Acid-base titration. If redox
reaction takes place between the constituents then the titration is known as redox titration.
If precipitation of a substance takes place the titration is known as precipitation titration.
31
 Chemistry : Stoichiometry

Working of indicator and difference between end point and equivalence point will be
discussed in ionic equilibria.
Illustration 22: 25 ml of N/10 caustic soda solution exactly neutralizes 20 mL of an acid
solution containing 7.875g of acid per litre. Calculate the equivalent mass of the
acid.
Solution : N1V1  N 2 V2
(NaOH) (Acid)

1
 25  N 2  20
10
25
N2   0.125
10  20

Strength = Normality × Eq. mass

7.875
Eq. mass of the acid = = 63.00
0.125

5.2 BACK TITRATION

Let us assume that we are given a definite weight of an impure substance C and percentage
purity of C in the sample is to be calculated. We are provided with two solutions A and B
concentration of both solutions are known to us. This type of titration will work, If the
following conditions are satisfied.
i) A and B should react with each other.
ii) A and pure C can react with each other.
iii) Product of A and C should not react with B.
Since we have to calculate percentage purity of C. So it should not be left unreacted i.e. in
reaction of C with A, C should be limiting and A should be in excess, excess amount of A
is determined by titrating the resulting mixture with B.
Illustration 23 :1.5 g of chalk were treated with 10 ml of 4N HCl. The chalk was dissolved and
the solution made to 100 ml 25 ml of this solution required 18.75 ml of 0.2 N
NaOH solution for complete neutralization. Calculate percentage of pure
CaCO3 in the sample of chalk.
Solution : Here C is impure CaCO3. A is HCl which is added in excess. Pure A and pure C
reacts with each other and product of A and C i.e. CaCl2 does not react with B i.e.
NaOH.
Initially chalk reacts with HCl
CaCO3  2HCl 
 CaCl2  H 2 O  CO 2
So meq. of pure CaCO3 present in chalk = meq. of HCl reacted with chalk.
Since HCl is in excess, some part of HCl reacts with a base NaOH
= Total meq. of HCl – meq. of HCl reacted with NaOH.
 10  4 – 4 18.75  0.2  25

32
Chemistry : Stoichiometry

W  M 
but meq 
E
1000  E CaCO3  2  50 
25  50
W  1.25g
1000
1.25
% purity  100  83.33 .
1.5

5.3 DOUBLE TITRATION

For studying the titrations of alkali mixtures such as NaOH and Na 2CO3 ; NaHCO3 and
NaOH; Na 2 CO3 and NaHCO3 ; NaOH, Na 2 CO3 and NaHCO3 , two indicators
phenolphthalein and methyl organe are used.
Phenolphthalein is a weak organic acid and gives end point between pH range 8–10 i.e.
above pH 10 indicator will exist in one particular colour and below pH 8 it will exist in
another colour and in between 8–10 intermediate colour of both will be obtained.
Methyl orange, a weak base gives end point between pH range of 3–4.5.
Above mixtures are bases so they are to be titrated by standard solution of any acid.
When methyl orange is used as an indicator for studying, neutralisation titrations for above
mixtures, it indicates complete neutralization for these mixtures i.e. at the end point the
above mixtures are completely neutralized.
When phenolphthalein is used as an indicator for above mixtures.
a) It indicates complete neutralization of NaOH or KOH (strong alkali).
b) It indicates half neutralization of Na 2 CO3

c) It fails to indicate neutralization of NaHCO 3 at all.

Suppose we have a mixture of NaOH and Na 2 CO3 initially pH will be around 12 or 13

because strong base is present. We added 1 drop of phenolphthalein. A particular colour
will be observed. We started titrating this with a standard acid solution. Full neutralisation
of NaOH and Half neutralization of Na 2 CO3 will take place at the end point i.e. colour
change point.
Neutralisation of Na 2CO3 takes place in two steps

Na 2 CO3  HCl 
 NaCl  NaHCO 3
NaHCO3  HCl  NaCl  H 2O  CO 2
Na 2CO3  2HCl 
 2NaCl  H 2 O  CO 2
One mole of Na 2 CO 3 for complete neutralization requires 2 moles of HCl; one mole HCl
in 1st step and 1 mole HCl in second step. When one mole of HCl is consumed half of

33
 Chemistry : Stoichiometry

Na 2 CO3 is neutralized and only NaHCO 3 is left in the solution and HCO3– is an
amphoteric species.
PKa  PKa 2
pH of amphoteric species  1 .
2
H 2 CO3 H   HCO3– Pka1  6.38
HCO3– H   CO32– Pka 2  10.26
6.38 10.26
So pH of NaHCO3   8.32 pH is on colour change range, so colour change
2
will take place so neutralization of NaHCO3 in presence of phenolphthalein cannot be
detected.
So in analysis of such alkali mixtures, both indicators are used. These two indicators can be
used
a) one after the other is the same volumetric mixture.
b) two indicators are used separately in two different titrations.

Illustration 24 :25 ml of solution of NaOH and Na2CO3 required (A) 25 ml of 0.1 N HCl using
phenolphthalein indicator (B) 35 ml of 0.1 N HCl using methyl orange
indicator. Calculate the masses of NaOH and Na2CO3 present in one litre of
solution.
Solution : Suppose x meq. of NaOH and y meq. of Na2CO3 are present in 25 ml of solution.
In presence of phenolphthalein indicator full meq of NaOH & 1
2 meq. of Na2CO3
are neutralized.
Full meq of NaOH + 1
2 meq. of Na2CO3 = meq of HCl.
y
x  25  0.1  2.5 … (i)
2
In presence of methyl orange indicator full meq. of NaOH and full meq. of
Na2CO3 are neutralized.
So, full meq. of NaOH + full meq. of Na2CO3 = Meq. of HCl.
X + y  35  0.1  3.5 … (ii)
From (i) and (ii)
y
1
2
y=2
x = 1.5
Meq. of NaOH in 1 litre = 1.5  40  60
w  M 40 
But meq 
E
 1000  E NaOH  nf  1  40 

34
Chemistry : Stoichiometry

w
60   1000
40
w  2.4g
Meq. of Na2CO3 in 1 litre  2  40  80
w  M 106 
But meq 
E
 1000  E Na 2CO3  nf  2  53

w
80  1000
53
w = 4.24 g .

EXERCISE 5 :
1. 5.5g of a mixture of FeSO47H2O and Fe2(SO4)39H2O requires 5.4 mL of 0.1 N KMnO4
solution for complete oxidation. Calculate the number of mole of hydrated ferric sulphate
in the mixture.
2. 4.00g of mixture of NaCl and Na2CO3 was dissolved in water and the volume made up to
250 mL; 25 mL of this solution required 50 mL of N/10 HCl for complete neutralization.
Calculate percentage composition of the original mixture.
3. A commercial sample (2.013g) of NaOH containing Na2CO3 as an impurity was dissolved
to give 250 mL of solution. A 10 mL portion of the solution required 20 mL of 0.1 N
H2SO4 solution for complete neutralization. Calculate the percentage of weight of Na2CO3
in the sample.

5.4 IODIMETRY
This is a method of titration used to calculate the amount of I 2 present. I 2 is titrated with a
standard Na 2S2O3 (sodium thiosulphate). The concerned reaction is
0 2 –1 2.5
I2  2Na 2 S2 O3 
 2 NaI  Na 2 S4O6
nf  2 nf  1

Starch acts as an indicator.

5.5 IODOMETRY
This is an indirect method of estimating the iodine. An oxidizing agent is made to react
with excess of KI. The oxidizing agent oxidizes I – to I2 . The liberated iodine now can be
titrated with Na 2S2 O 3 solution.
Na 2S2 O3
Oxidising agent + KI 
 I 2   NaI  Na 2S4O 6 .

35
 Chemistry : Stoichiometry

Illustration 25 :For estimating ozone in the air, a certain volume of air is passed through an
acidified or neutral Kl solution when oxygen is evolved and iodide is oxidized to
give iodine. When such a solution is acidified, free iodine is evolved which can
be titrated with standard Na2S2O3 solution. In an experiment 10 litre of air at 1
atm and 27°C were passed through an alkaline KI solution, at the end, the
iodine entrapped in a solution on titration as above required 1.5 mL of 0.01 N
Na2S2O3 solution. Calculate volume % of O3 in sample.
Solution : The reactions are
H2O + 2KI + O3  2KOH + I2 + O2
Also 2e+ I2  2I–
And 2S22+  S4+5/2 + 2e
 Meq. of I2 = Meq. of Na2S2O3
= 1.5  0.01 = 1.5  10–2
1.5  10 2
or mM of I2 = = 7.5  10–3
2
 mM of O3 = mM of I2 = 7.5  10–3
( Mole ratio of O3 : I2 :: 1: 1)
7.5  10 6  0.0821  300
 PO 3 
10
= 184.725  10–7 atm
 Volume % of O3 = 184.725  10–7  100
= 1.847  10–3%
Method of gram equivalents
–1 3 1 2
2NH 2 OH  4Fe3 
 N 2O   4Fe2  H 2O  4H 
nf  2 nf 1 nf  4 nf 1

In redox reaction, nf is change in oxidation number per mole. For reactants balancing
coefficients are in ratio of 1 : 2 whereas nf are in the ratio of 2 : 1. For products balancing
coefficients are in the ratio of 1 : 4 whereas nf are in the ratio of 4 : 1 i.e. balancing
coefficients are in the reverse ratio of nf.
–7 2 2 3
MnO4–  5Fe2  8H  
 Mn 2  5Fe3  4H 2O
nf  5 nf 1 nf  5 nf 1

Since normality = nf × Molarity.

Normality of KMnO 4  5  0.02  0.1N
From law of equivalence
Meq. of KMnO4 used for 50 ml diluted solution = meq of Fe2 produced

36
Chemistry : Stoichiometry

= meq of Fe3 reacted = meq of NH 2 OH present = N  Vml = 0.112  1.2

So meq of NH 2OH is 50 ml of dillued solution = 1.2
Meq of NH 2 OH in 1 litre diluted solution = 1.2  20
Meq of NH 2OH in 10 ml original solution  1.2  20
Meq of NH 2 OH in 1 litre original solution  1.2  20 100  2400
w  M 33 
but meq 
E
 1000  E NH2OH  nf  2 

w
2400  1000
33/ 2
w  39.6 gram / litre

EXERCISE 6 :
1. 25 mL of a mixed solution of Na2CO3 and NaHCO3 required 12 mL of N/20 HCl when
titrated using phenolphthalein as an indicator. But 25 mL of the same, when titrated
separately with methyl orange required 30 mL of N/20 HCl. Calculate the amount of
Na2CO3 and NaHCO3 in grams per litre.
2. 50 mL of H2O2 was treated with excess of KI in presence of dilute sulphuric aid I2 so
liberated was titrated with 20mL of 0.1 N hypo solution. Calculate the strength of H2O2 in
grams per litre.
3. Calculate the percentage of available chlorine in a sample of 3.546g of bleaching powder
which was dissolved in 100 mL of water, 25 mL of this solution, on treatment with KI and
dilute acid, required 20 mL of 0.125N sodium thiosulphate solution.

EXERCISE 7 :
1. A sample supposed to be pure CaCO3 is used to standardize a solution of HCl. The
substance really was a mixture of MgCO3 and BaCO3, but the standardization of HCl was
accurate. Find the percentage of BaCO3 and MgCO3 in mixture.
2. On gm of impure sodium carbonate is dissolved in water and the solution is made up to
250 ml. To 50 ml of this made up solution, 50 ml of 0.1 N – HCl is added and the mix
after shaking well required 10 ml of 0.16N – NaOH solution for complete titration.
Calculate the % purity of the sample.
3. One gm of a sample of Ca(OH) is dissolved in 50 ml of 0.5 N HCl solution. The excess of
HCl was titrated with 0.3 N – NaOH. The volume of NaOH used was 20cc. Calculate %
purity of Ca(OH)2.

There are two specific concentration terms. These are

37
 Chemistry : Stoichiometry

6. VOLUME STRENGTH OF H2O2 SOLUTION

H 2 O 2 undergoes self decomposition to H 2 O and O 2 . If a solution of H 2 O 2 is labelled as
`x volumes’, it means that 1 volume of this particular H 2O 2 solution would liberate x
volume of O 2 at S.T.P on complete decomposition.

H 2 O2 
 H2O  1
2 O2
Suppose normality of a H 2 O 2 solution is N i.e. N gram equivalents of H 2 O 2 is present in 1
litre of this solution.
N
1 ml of this would contain equivalents but gram equivalents  nf  moles
1000
(nf for H 2O 2 = 2).
1 N
Moles of H 2 O 2 present in 1 ml  
2 1000
1 1 N
So Moles of O 2 obtained   
2 2 1000
1 N
Volume of O 2 at S.T.P. obtained    22400  5.6 N
4 1000
Volume strength  5.6  Normality

6.1 PERCENTAGE LABELLING OF OLEUM

When SO3 is passed through a H 2SO 4 solution oleum is obtained. Oleum is
(H 2SO4  SO3 ) . In order to dissolve this free SO3 , dilution of oleum is done.

SO3  H 2 O 
 H 2SO 4
If a oleum sample is labeled as 109%, this means that 100 g of oleum on dilution gives
109g H 2SO4 . i.e. in order to dissolve whole of free SO3 present in 100 g of oleum sample,
9g of H 2 O is required.

EXERCISE 8 :
1. Calculate the St. of “20V” of H2O2 in terms of
i) gm/L; ii) N; iii) M; iv) %
2. 0.5g of fuming H2SO4 (oleum) is diluted with water. The solution requires 26.7 mL of 0.4
N NaOH for complete neutralization. Find the % of free SO3 in the sample of oleum.

7. WATER HARDNESS AND ITS DETERMINATION

38
Chemistry : Stoichiometry

The hardness of water is due to soluble salts of Mg 2  and Ca 2 . Soaps are sodium or
potassium slat of long chain fatty acids. They are water soluble. Ca 2 and Mg 2 cause
precipitation of soaps and therefore destroy it’s wasting activity.
Alkali metal soaps are water soluble and soaps of other metals are water insoluble.
Alkali metal soaps are RCOO – Na  or RCOO – K  .
Ca 2 and Mg 2 ions present in hard water cause precipitation.
2RCOO –  Ca 2  
 (RCOO) 2 Ca 
2COO –  Mg 2  
 (RCOO) 2 Mg 
Ca 2 and Mg 2  ions are present in hard water in the form of their bicarbonate, sulphate or
chloride. The hardness due to bicarbonate of Ca 2 and Mg 2 may be removed by boiling
water. This is known as Temporary hardness.
Heat
Ca(HCO3 ) 2   CaCO3   H 2O  CO 2
solub le
Heat
Mg(HCO3 )2   MgCO3   H 2O  CO 2
Addition of lime also causes precipitation of temporary hardness.
Ca(HCO3 )2  CaO   2CaCO3  H 2O
The hardness due to sulphate and chloride of Ca 2 and Mg 2 cannot be removed by boiling
water this is known as permanent hardness
Permanent Hardness   CaSO 4 , MgSO 4
CaCl2 , MgCl 2
Temporary hardness 
 Ca(HCO3 )2 , Mg(HCO3 )2
Determination of Temporary Hardness
For the determination of T.H a definite volume of hard water is titrated against standard
HCl or H 2SO 4 solution
No. of milli equivalents of acid used = No. of meg. Of T.H.
Ca(HCO3 ) 2  2HCl   CaCl 2  2H 2O  2Cl 2
Mg(HCO3 )2  2HCl 
 MgCl2  2H 2O  2CO 2
Determination of permanent Hardness
For the determination of P.H a definite volume of hard water is boiled to precipitated T.H
and then treated with excess of soda reagent (Na 2 CO 3 ) which precipitate P.H.
On boiling
Ca(HCO 3 ) 2 
 CaCO 3   H 2O  CO 2
Mg(HCO 3 ) 2 
 MgCO3   H 2O  CO 2
On adding Na 2CO3

39
 Chemistry : Stoichiometry

CaSO4  Na 2CO3 
 CaCO3   Na 2SO 4
MgSO 4  Na 2CO3 
 MgCO3   Na 2SO4
CaCl2  Na 2 CO3 
 CaCO3   2NaCl
MgCl2  Na 2CO3 
 MgCO3   2NaCl
Soluble Insoluble
The unused amount of Na 2 CO3 is determined by titrating the filterate against HCl or
H 2SO4 solution (Back titration) no. of milliequivalents = No. of milliequivalents of P.H.
Hardness is generally expressed in terms of weight of CaCO3 per 10 6 ml (106 g) water.
Illustration 26 : 10 L of hard water required 0.56 g of lime CaO for removing hardness.
Calculate temporary hardness in ppm.
Solution : The relevant reaction is
Ca(HCO 3 ) 2  CaO 
 CaCO 3  H 2O
56 g 100 g
0.56 1g
Temporary hardness equivalent to 1 g of CaCO3 is present in 10 litre (10 4 g) .
1
So ppm of T.H.  4
 106
10
= 100 ppm
1
Illustration 27 : 50 ml of hard water required 10 ml, N HCl for neutralization. Calculate
50
temporary hardness.
Solution : Meq of T.H = meq of HCl used
= N  Vml
1 1
  10 
50 5
1
i.e. 50 ml (50 g) hard water contains meq T.H. and hardness is expressed in
5
ppm of CaCO3 .
1
i.e. meq of CaCO3 
5
Molecular wt.
Equivalent weight of CaCO3   50
(nf  2) 2
w 1
So meq   1000 
E 5
1 50 1
or w  
5 1000 100

40
Chemistry : Stoichiometry

1
Ppm  100  106  200 ppm.
50
Illustration 28 : A sample of hard water contains 80 ppm Ca 2+ . This sample is passed through
an ion exchange column and Ca 2+ are replaced by H + . Calculate molarity of
H+ .
Solution : 90 ppm of Ca 2 are present in hard water sample i.e. 80 g of Ca 2 are present is
106 g (106 ml) water sample.
No. of moles 80 / 40
So molarity of Ca 2    6
Volume in litre 10 /103
 2  10 –3 M
To maintain electrical neutrality of water sample. 1 mole of Ca 2 will require 2
moles of H  for replacement.
So molarity of H   2  2  10 –3
 4  10 –3 .
1
Illustration 29 : A mixture of 100 ml hard water and 100 ml N Na2 CO3 was boiled and
50
1
filtered. The filtrate required 60 ml of H HCl for titration. Calculate
50
hardness.
Solution: Meq of P.H = meq of Na 2 CO3 used in reacting with P.H.
= total meq of Na 2CO3 – meq. Of Na 2CO3
reacted with HCl.
1 1
 100  – 60 
50 50
 2 – 1.2
 0.8
i.e. permanent hardness equivalent to 0.8 meq CaCO3 is present
w
 1000  0.8
E
E (CaCO3 )  50
0.8  50
w  0.04g
1000
0.04
ppm of CaCO3   106  400 ppm
100

41
 Chemistry : Stoichiometry

EXERCISE 9 :

1. 100 kg hard water contains 5g MgSO4. Find hardness.

2. A sample of hard water contains 20 mg of Ca++ ions per litre. How much of Na2CO3 in
moles would be required to softer 1 L of sample.
N
3. 200 mL of a hard water sample was boiled with 100 mL of soda reagent. After boiling
50
the volume was again made to 200 mL and the solution filtered. 25 mL of filtrate required
N
8.2 mL of HCL for neutralization. Calculate hardness.
50

EXERCISE 10 :

1. A sample of hard water has 20 mg of L Ca2+ ions and 48 mg per L Mg2+ ions, calculate
the total hardness in equivalent per L.
2. A particular water sample contains 88.2 ppm of SO 24 and 149 ppm of HCO3–, with Ca2+
ions as the only cation in 106g.
a) How many ppm of Ca2+ does this water contains
b) How many moles of CaO are consumed in removing HCO3 from 1.00 X 106g of water
described above.
c) What is the concentration Ca2+ remaining in the water after the treatment above.
3. A sample of water has its hardness due only to CaSO4. When the water is passed through
an anion exchange resin, SO34 ions are replaced by OH–. A 25 ml of this water sample so
treated requires 21.58 mL of 1 10 3 M H2SO4 for titration. What is the hardness of water
in ppm of CasO4.

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