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MOLE CONCEPT

LECTURE NOTES OF MOLE CONCEPT- I, II, III & IV

LECTURE # 1
Basic definition, amu, NA & Mole, Moles of atoms and molecules :

Introduction :
There are a large number of objects around us which we can see and feel.
Anything that occupies space and has mass is called matter.
Ancient Indian and Greek Philosphers beleived that the wide variety of object around us are made from
combination of five basic elements : Earth, Fire, Water, Air and Sky.
Ancient Greek Philosphers also believed that all matter was composed of tiny building blocks which were
hard and indivisible.The Greek philosphere Democritus named these building blocks as atoms, meaning
indivisible.All these people have their philosphical view about matter, they were never put to experimental
tests, nor ever explain any scientific truth.It was John Dalton who firstly developed a theory on the
structure of matter, later on which is known as Daltons atomic theory.

DALTONS ATOMIC THEORY :

1.

Matter is made up of very small indivisible particle called atom.

2.

All the atoms of a given element is idenctical in all respect i.e. mass, shape, size, etc.

3.

Atoms cannot be created or destroyed by any chemical process or physical process.

4.

Atoms of different elements are different in nature.

Page No. # 1

Classification of matter

on the basis of physical behaviour


Solids

Liquids

on basis the of chemical behaviour

Gases

Pure substances
Element

Mixtures

Compound

III Some Definitions


I.
RELATIVE ATOMIC MASS :
It is the ratio of the mass of 1 atom of a substance and 1/12 of mass of 1 atom of C12 isotope. For atoms
this is done by expressing mass of one atom with respect to a fixed standard. Dalton used hydrogen as the
standard (H = 1). Later on oxygen (O = 16) replaced hydrogen as the reference.

C-12 ISOTOPE OF CARBON IS LATEST CHOSEN STANDARD SINCE 1961


Therefore relative atomic mass is given as

Relative atomic mass (R.A.M) =

mass of one atom of the element


1
mass of one C12 atom
12

total number of nucleons mass of 1 nucleon


= Total Number of nucleons
1
12 mass of 1 nucleon
12

On Hydrogen scale :
Relative atomic mass (R.A.M) =

mass of one atom of the element


mass of one H atom

Oxygen scale :
Relative atomic mass (R.A.M) =

II.

mass of one atom of the element


1
mass of one O 16 atom
16

ATOMIC MASS UNIT (OR AMU)


1
The atomic mass unit (amu) is equal to one twelfth of the mass of one atom of carbon-12 isotope.
12

1
mass of one C-12 atom
12
~ mass of one neucleon in C-12 atom.
= 1.66 1024 gm or 1.66 1027 kg

1 amu =

one amu is also called one Dalton (Da).TODAY , AMU HAS BEEN REPLACED BY u WHICH IS
KNOWN AS UNIFIED MASS

Page No. # 2

III.

ATOMIC MASS
It is the mass of 1 atom of a substance it is expressed in AMU.
Atomic mass = R.A.M 1 amu

Note : Relative atomic mass is nothing but the number of nucleons present in the atom.
Example :
Find the relative atomic mass of O atom and its atomic mass.
Sol.
The number of neucleons present in O atom is 16.

relative atomic mass of O atom = 16.


Atomic mass = R.A.M 1 amu = 16 1 amu = 16 amu
Q.
Ans.

Find the relative atomic mass, atomic mass of the following elements.
(i) Na (ii) F
(iii) H
(iv) Ca (v) Ag
(i) 23, 23 amu (ii) 19, 19 amu (iii) 1, 1.008 amu (iv) 40, 40.078 amu (v) 108, 107.87 amu

Q.
Ans.

How many neucleons are present in 5 atoms of an element which has atomic mass 14 amu
= 70

IV.

MOLE :THE MASSNUMBER RELATIONSHIP


Mole is a chemical counting S unit and defined as follows :
A mole is the amount of a substance that contains as many entities (atoms, molecules or other
particles) as there are atoms in exactly 0.012 kg (or 12 gm) of the carbon-12 isotope.
From mass spectrometer we found that there are 6.023 1023 atoms are present in 12 gm of C-12 isotope.
The number of entities in 1 mol is so important that it is given a separate name and symbol known as
Avogadro constant denoted by NA.
i.e. on the whole we can say that 1 mole is the collection of 6.02 1023 entities. Here entities may
represent atoms, ions, molecules or even pens, chair, paper etc also include in this but as this number (NA)
is very large therefore it is used only for very small things.
1 mole x mass of 1 atom of C12 isotope
1 mole x 12 x mass of one nucleon

= 12g
= 12 g

Alternatively value of NA can be


found in this fashion

1 mole =

V.

1.66 x 10 24

= 6.023 x 1023

Note : In modern practice gram-atom and gram-molecule termed as mole.

GRAM ATOMIC MASS :


The atomic mass of an element expressed in gram is called gram atomic mass of the element.
For example for oxygen atom :
Atomic mass of O atom = mass of one O atom = 16 amu
gram atomic mass = mass of 6.02 1023 O atoms
= 16 amu 6.02 1023
= 16 1.66 1024 g 6.02 1023 = 16 g
24
(
1.66 10 6.02 1023 ~ 1 )

Q.

How many atoms of oxygen are their in 16 g oxygen.

x 1.66 x 10 24 = 16 g
1

x=

1.66 x 10 24

= NA
Page No. # 3

or
It is also defined as mass of 6.02 1023 atoms.
or
It is also defined as the mass of one mole atoms.

Now see the table given below and understand the definition given before.
Element

R.A.M.
(Relative Atomic Mass)

Atomic mass
(mass of one atom)

Gram Atomic mass/weight

14

14 amu

14 gm

He

4 amu

4 gm

12

12 amu

12 gm

Example :
What is the weight of 3-g atoms of sulphur R.A.M. of s = 32.
Ans.
96 g
Example :
How many g atoms are present in 144 g of sulphur
Ans.
4.5 g atoms
Example :
The ratio of mass of a silver atom to the mass of a carbon atom is 9 : 1. Find the mass of 1 mole of C atom
if molar mass of Ag is 108.
Ans.
12
Example :
Calculate mass of sodium which contains same number of atoms as are present in 4g of calcium. Atomic
masses of sodium and calcium are 23 and 40 respectively.
Ans. 2.3 g

VI.

MOLECULES :
It is the smallest particle of matter which has free existence. Molecules can be further divided into its
constituents atoms by physical & chemical process.
Number of atoms presents in molecule is called its atomicity.
Element :
H2, O2, O3 etc.
Compound :
KCl, H2SO4, KClO4 etc.
Molecule
KCl
H2SO4
O3
H2

VII.

Atomicity
2
7
3
2

MOLECULAR MASS :
It is the mass of one molecule
Ex.
Molecule
H2
KCl
H2SO4

Molecular mass
2 amu
(39 + 35.5) = 74.50 amo
(2 + 32 + 64) = 98 amu.

VIII. GRAM MOLECULAR MASS :

Page No. # 4

The molecular mass of a substance expressed in gram is called the gram-molecular mass of the substance.
or
23
It is also defined as mass of 6.02 10 molecules
or
It is also defined as the mass of one mole molecules. (molar mass)
For example for O2 molecule :
Molecular mass of O2 molecule = mass of one O2 molecule
= 2 mass of one O atom
= 2 16 amu
= 32 amu
gram molecular mass = mass of 6.02 1023 O2 molecules = 32 amu 6.02 1023
= 32 1.66 1024 gm 6.02 1023 = 32 gm

Use the Y-map in the following example.


Example:
Find the mass in grams of 3 mol of zinc. (GMM = 65)
Sol.
Mass = mol At. wt. = 3 65 gm = 195 gm
Example :
How many atoms of copper are present in 0.5 mol of pure copper metal?
Sol.
No. of atoms = no. of moles NA = 0.5 6.02 1023 = 3.01 1023
Example :
The molecular mass of H2SO4 is 98 amu. Calculate the number of moles of each element in 294 g of H2SO4.
Solution
Gram molecular mass of H2SO4 = 98 gm
moles of H2SO4 =
H2SO4
One molecule
1 NA
one mole
3 mole

294
= 3 moles
98

H
2 atom
2 NA atoms
2 mole
6 mole

S
one atom
1 NA atoms
one mole
3 mole

O
4 atom
4 NA atoms
4 mole
12 mole

Example :
A sample of (C2H6) ethane has the same mass as 107 molecules of methane. How many C2H6 molecules
does the sample contain ?
Ans.
n = 5.34 106
Example :
How many molecules of water are present in 252 mg of (H2C2O4.2H2O)

Page No. # 5

Ans.

2.4 1021

Example :
From 48 g of the He sample ,6.023 x 1023 atoms of He are removed. Find out the moles of He left.Also
Calculate the mass of carbon which contains same number of atoms as left over in this sample.
Ans.
11 mole, 132 g of C.

LECTURE # 2
Laws of chemical combination, Molar volume of ideal gasses at STP, Average
molar mass.
II

THE LAWS OF CHEMICAL COMBINATION


Atoine Lavoisier, John Dalton and other scientists formulate certain law concerning the composition of
matter and chemical reactions.These laws are known as the laws of chemical combination.

1.

THE LAW OF CONSERVATION OF MASS :( ANTOINE LAVOISIER)


It states that matter can neither be created nor destroyed in chemical reaction i.e .
In a chemical change , total mass remains conserved.i.e.
mass of all reactants = mass of products after reaction. ( In a closed system )
1
O2 (g) H2O (l )
Example :
H2 (g) +
2
1
mole
Before reaction
1 mole
2
After the reaction
0
0
1 mole
1
mass before reaction = mass of 1 mole H2 (g) +
mole O2 (g)
2
= 2 + 16 = 18 gm
mass after reaction = mass of 1 mole water = 18 gm

2.

LAW OF CONSTANT OR DEFINITE PROPORTION :{JOSEPH PROUST}


A given compound always contains exactly the same proportion of elements by weight irrespective of their
source or method of preparation .

Ex.

In water (H2O), Hydrogen and Oxygen combine in 2 : 1 molar ratio, this ratio remains constant whether it
is tap water, river water or sea water or produced by any chemical reaction.

Ex.

1.80 g of a certain metal burnt in oxygen gave 3.0 g of its oxide. 1.50 g of the same metal heated in steam
gave 2.50 g of its oxide. Show that these results illustrate the law of constant proportion.
In the first sample of the oxide,
Wt. of metal = 1.80 g,
Wt. of oxygen = (3.0 1.80) g = 1.2 g

Sol.

wt. of metal
1.80g

1.5
wt. of oxygen
1.2g

In the second sample of the oxide,


Wt. of metal = 1.50 g,
Wt. of oxygen = (2.50 1.50) g = 1 g.

wt. of metal
1.50 g

1.5
wt. of oxygen
1g

Thus, in both samples of the oxide the proportions of the weights of the metal and oxygen are fixed. Hence,

Page No. # 6

the results follow the law of constant proportion.

3.

THE LAW OF MULTIPLE PROPORTION : {JOHN DALTON}


When one element combines with the other element to form two or more different compounds, the mass of

one elements, which combines with a constant mass of the other, bear a simple ratio to one another.
Note : Simple ratio here means the ratio between small natural numbers, such as 1 : 1, 1 : 2, 1 : 3, later on this
simple ratio becomes the valency and then oxidation state of the element.
Ex.

Carbon and oxygen when combine, can form two oxides viz CO (carbonmonoxide), CO2 (Carbondioxides)
In CO, 12 gm carbon combined with 16 gm of oxygen.
In CO2, 12 gm carbon combined with 32 gm of oxygen.
Thus, we can see the mass of oxygen which combine with a constant mass of carbon (12 gm) bear simple
ratio of 16 : 32 or 1 : 2
Note : See oxidation number of carbon also have same ratio 1 : 2 in both the oxide.

4.

THE LAW OF RECIPROCAL PROPORTION (RITCHER) :


When two elements combine separately with a fixed mass of a third element, then the ratio of their masses
in which they do so is either same or some whole number multiple of the ratio in which they combine with
each other.

The Law of Conservation of Mass :


In a chemical change total mass remains conserved. i.e., mass before reaction is always equal to mass
after reaction.

CONCEPTS RELATED TO DENSITY :


It is of two type.
1.
Absolute density
2.
Relative density
For liquid and solids
mass
volume
density of the subs tance
specific gravity = density of water at 4C
For gases :

Absolute density =

Page No. # 7

*
Ex.
Ans.

Molar mass of the gas


Absolute density (mass/volume) = Molar volume of the gas
For simplification, we can conclude that the density and specific gravity of any substance is numerically
same, but density has a definite unit, but specific gravity has no unit. (dimension less)
Specific gravity of a solution is 1.8 then find the mass of 100 ml of solution.
180 gm.

RELATIVE DENSITY :
Ex.

It is the density of a substance with respect to any other substance.


What is the V.D. of SO2 with respect to CH4

M.W . SO 2
V.D. = M.W . CH
4
V.D =
Ex.

64
=4
16

Find the density of CO2(g) with respect to N2O(g).

GAY-LUSSACS LAW OF COMBINING VOLUME :


Gases combine in a simple ratio of their volumes provided all measurements should be done at the same
temperature and pressure
H2 (g)

1 vol

Cl2 (g)

2HCl

1 vol

2 vol

AVOGADROS HYPOTHESIS :
Equal volume of all gases have equal number of molecules (not atoms) at same temperature and
pressure condition.
mathematically, for ideal gases, V n (CONSTANT T & P)
S.T.P. (Standard Temperature and Pressure):
At S.T.P. / N.T.P. condition :
temperature = 0C or 273 K
pressure = 1 atm = 760 mm of Hg
volume of one mole of an ideal gas = 22.4 litres (experimentally determined)
NOTE FOR FACULTY : The gas equation PV = nRT should never be used in this chapter.
Ex.
Sol.

Calculate the volume in litres of 20 g hydrogen gas at STP.


20 gm
No. of moles of hydrogen gas = mass atomic weight = 2 gm = 10 mol
volume of hydrogen gas at STP = 10 22.4 lt.
Number

N
A

Mole

mol. wt.
At. wt.

lt
2.4
2

lt
2.4
2

Volume at STP

mol. wt.
At. wt.

Mass

Page No. # 8

Ex.
Ans.

Calculate the volume in litres of 142 g chlorine gas at STP.


44.8 lt.

Ex.

Find the volume at STP occupied by 16 g of ozone at STP.


22 . 4
= 7.5
3
From 160 g of SO2 (g) sample, 1.2046 x 1024 molecules of SO2 are removed then find out the volume of left
over SO2 (g) at STP.
Ans.
11.2 Ltr.

Ans.
Ex.

Ex.

14 g of Nitrogen gas and 22 g of CO2 gas are mixed together. Find the volume of gaseous mixture at STP.
Ans.
22.4 Ltr.

Ex.
Ans.

672 ml of ozonized oxygen (mix of O2 and O3) at N.T.P. were found to weight one gram. Calculate the
volume of ozone in the ozonized oxygen.
56 ml

6.

AVERAGE/ MEAN ATOMIC MASS :


The weighted average of the isotopic masses of the elements naturally occuring isotopes.
Mathematically, average atomic mass of X (Ax) =

a1x 1 a 2 x 2 ..... an x n
100

Ex.

Naturally occuring chlorine is 75% Cl35 which has an atomic mass of 35 amu and 25% Cl37 which has a
mass of 37 amu. Calculate the average atomic mass of chlorine (A) 35.5 amu
(B) 36.5 amu
(C) 71 amu
(D) 72 amu

Sol.

(A) Average atomic mass =

% of isotope x its atoms mass % of I isotope x its atomic mass


100
75 x 35 25 x 37
100

= 35.5 amu
Note : (a) In all calculations we use this mass.
(b) In periodic table we report this mass only.

MEAN MOLAR MASS OR MOLECULAR MASS:


The average molar mass of the different substance present in the container =
Ex.

n1M1 n 2M2 ......nnMn


n1 n 2 ....nn

The molar composition of polluted air is as follows :


Gas
At. wt.
mole percentage composition
Oxygen
16
16%
Nitrogen
14
80%
Carbon dioxide 03%
Sulphurdioxide 01%
What is the average molecular weight of the given polluted air ? (Given, atomic weights of C and S are 12
and 32 respectively.
jn

n M
j

Sol.

Mavg =

j1
jn

j1

Page No. # 9

j n

Here

= 100

j1

Mavg =

16 x 32 80 x 28 44 x 3 64 x 1
2948
512 2240 132 64
=
=
= 29.48 Ans.
100
100
100

LECTURE#3
Empirical formula, % Composition of a given component by mass, % By mole,
Minimum molecular mass determination.
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.
Thus, the empirical formula of a compound is a chemical formula showing the relative number of atoms in
the simplest ratio, the molecular formula gives the actual number of atoms of each element in a molecule.
The molecular formula is generally an integral multiple of the empirical formula.
i.e.
molecular formula = empirical formula n
where
Ex.
Sol.

molecular formula mass

n = empirical formula mass

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.

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 mass
26
n = Empirical formula mass =
=2
13
Step-3
To calculate the molecular formula of the compound.
Molecular formula
= n (Empirical formula of the compound)
= 2 CH = C2 H2
Thus the molecular formula is C2 H2
Similarly for benzene
To calculate the value of n
Molecular mass
78
=6
n = Empirical formula mass =
13

Ex.

Sol.

thus the molecular formula is 6 CH = C6H6


An organic substance containing carbon, hydrogen and oxygen gave the following percentage composition.
C = 40.684% ; H = 5.085% and O = 54.228%
The molecular weight of the compound is 118. Calculate the molecular formula of the compound.
Step-1
Page No. # 10

To calculate the empirical formula of the compound.

Percentage At. mass Relative no.


Percentage
of element of element of atoms =
At. mass

Element

Symbol

Carbon

40.687

12

Hydrogen

5.085

Oxygen

54.228

16

Simplest
atomic ratio

Simplest whole
no. atomic ratio

40.687
= 3.390
12
5.085
= 5.085
1

3.390
3.389

=1

5.085
3.389

=1.5

54.228
= 3.389
16

3.389
3.389

=1

Empirical Formula is C2 H3 O2

Step-2
To calculate the empirical formula mass.
The empirical formula of the compound is C2 H3 O2 .

Empirical formula mass


= (2 12) + (3 1) + (2 16) = 59.
Step-3
To calculate the value of n
Molecular mass
118
=2
n = Empirical formula mass =
59
Step-4
To calculate the molecular formula of the salt.
Molecular formula
= n (Empirical formula) = 2 C2 H3 O2 = C4 H6 O4
Thus the molecular formula is C4 H6 O4.
Ex.

Ans.
Ex.

An oxide of nitrogen gave the following precentage composition :


N = 25.94
and
O = 74.06
Calculate the empirical formula of the compound.
N2O5
Hydroquinone, used as a photographic developer, is 65.4%C, 5.5% H, and 29.1%O, by mass. What is the
empirical formula of hydroquinone ?
Ans.
C3H3O

% 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

Page No. # 11

constant ratio with their combining elements.


Ex.

Every molecule of ammonia always has formula NH3 irrespective of method of preparation or sources. i.e.
1 mole of ammonia always contains 1 mol of N and 3 mole of H. In other wards 17 gm of NH3 always
contains 14 gm of N and 3 gm of H. Now find out % of each element in the compound.
Mass % of N in NH3 =

Mass of N in 1 mol NH3


100 = 14 100 = 82.35 %
Mass of 1 mol of NH3
17

Mass of H in 1 mol NH3


3
Mass % of H in NH3 = Mass of 1 mol e of NH 100 =
100 = 17.65 %
3
17

Ex.
Ans.

What is the percentage of calcium and oxygen in calcium carbonate (CaCO3) ?


40%, 48%.

Ex.
Ans.

A compound of sodium contains 11.5% sodium then find the minimum molar mass of the compound.
200 gm/mole.

LECTURE # 4
Stoichiometry Law of conservation of mass (LOCM) ,Equation based calculations
(Elementary Level Single Equation or 2).
CHEMICAL REACTION :
It is the process in which two or more than two substances interact with each other where old bonds are
broken and new bonds are formed.

VI CHEMICAL EQUATION :
All chemical reaction are represented by chemical equations by using chemical formule of reactants and
products. Qualitatively a chemical equation simply describes what the reactants and products are. However,
a balanced chemical equation gives us a lot of quantitative information mainly the molar ratio in which
reactants combine and the molar ratio in which products are formed.
Example :
When potassium chlorate (KClO3) is heated it gives potassium chloride (KCl) and oxygen (O2).

KClO3
KCl + O2 (unbalanced chemical equation )

2KClO3
2 KCl + 3 O2 (balanced chemical equation)
Attributes of a balanced chemical equation: (From NCERT PAGE - 17)
(a) It contains an equal number of atoms of each element on both sides of equation.(POAC)
(b) It should follow law of charge conservation on either side.
(c) Physical states of all the reagents should be included in brackets.
(d) All reagents should be written in their standard molecular forms (not as atoms )
(e) The coefficients give the relative molar ratios of each reagent.
Balancing a chemical equation
According to the law of conservation of mass, a balanced chemical equation has the same number of
atoms of each element on both sides of the equation. Many chemical equations can be balanced by
Page No. # 12

trial and error. Let us take the reactions of a few metals and non-metals with oxygen to give oxides
4 Fe(s) + 3O2(g) 2Fe2O3(S)
(a) balanced equation
2 Mg(s) + O2(g) 2MgO(S)
(b) balanced equation
P4(s) + O2(g) P4O10(S)
(c) unbalanced equation
Equations (a) and (b) are balanced since there are same number of metal and oxygen atoms on each
side of equations. However equation (c) is not balanced. In this equation. phosphorus atoms are
balanced but not the oxygen atoms. To balance it, we must place the coefficient 5 on the left of oxygen
on the left side of the equation to balance the oxygen atoms appearing on the right side of the equation.
P4(S) + 5O2(g) P4O10(S)
balanced equation
Now let us take combustion of propane, C3H8, This equation can be balanced in steps.
Step 1. Write down the correct formulas of reactants and products. Here propane and oxygen are reactants, and
carbon dioxide and water are products.
C3H8(g) + O2(g) CO2 (g) + H2O (l)
unbalanced equation
Step 2. Balance the number of C atoms : Since 3 carbon atoms are in the reactant, therefore, three CO2
molecules are required on the right side.
C3H8(g) + O2 (g) 3CO2 (g) + H2O (l)
Step 3. Balance the number of H atoms : on the left there are 8 hydrogen atoms in the reactants however, each
molecule of water has two hydrogen atoms , so four molecules of water will be required for eight
hydrogen atoms on the right side.
C3H8 (g) + O2 (g) 3CO2 (g) + 4H2O (l)
Step 4. Balance the number of O atoms : There are ten oxygen on the right side (3 2 = 6 in CO2 and 4 1 =
4 in water). Therefore, five O2 molecules are needed to supply to supply the required ten oxygen atoms.
C3H8 (g) + 5O2 (g) 3CO2 (g) + 4H2O (l)
Step 5. Verify that the number of atoms of each element is balanced in the final equation.
Always remember that subscripts in formula of reactants and products cannot be changed to balance
an equation.

INTERPRETATION OF BALANCED CHEMICAL EQUATIONS :


(STOICHIOMETRY AND STOICHIOMETRIC CALCULATIONS, NCERT, PAGE - 17)
3.

Mole-mole analysis :
This analysis is very much important for quantitative analysis point of view. Students are advised to
clearly understand this analysis.
Now consider again the decomposition of KClO3 .
2KClO3 2KCl + 3O2
In very first step of mole-mole analysis you should read the balanced chemical equation like
2 moles KClO3 on decomposition gives you 2 moles KCl and 3 moles O2. and from the stoichiometry
of reaction we can write
Moles of O 2
Moles of KClO 3
Moles of KCl
=
=
3
2
2
Now for any general balance chemical equation like

a A + b B c C + d D
you can write.
Mole of A reacted
moles of B reacted
moles of C reacted
moles of D reacted
=
=
=
a
b
c
d

Ex.
Sol.

3 moles (367.5 gm) of KClO3 when heated how many moles KCl and O2 is produced.
The reaction is
Page No. # 13

2KClO3 2KCl + 3O2


Moles of KClO 3
Moles of KCl
=
2
2
Now,

Moles of KCl produced = 3

Moles of O 2
Moles of KClO 3
=
3
2

33
= 4.5 moles
2
CH4 + 2O2 CO2 + 2H2O (from NCERT Page - 18)
following conclusions can be drawn from above reaction by observing its stoichiometry
mole of O2 produced =

Ex.

One mole of CH4 (g) reacts with two moles of O2 (g) to give one mole of CO2 (g) and two moles of H2O (g)
One molecule of CH4 (g) reacts with 2 molecues of O2 (g) to give one molecule of CO2 (g) and 2 molecules
of H2O (g)
22.4 L of CH4 (g) reacts with 44.8 L of O2 (g) to give 22.4L of CO2 (g) and 44.8 L of H2O (g)
16 g CH4 (g) reacts with 232 g of O2 (g) to give 44 g of CO2 (g) and 2 18 g of H2O (g).
Note : In fact mass-mass and mass-vol analysis are also interpreted in terms of mole-mole analysis you can use
following chart also.

Mass

At. wt. / Mol. Wt.

Mole-mole
relationship
of equation

Mole

Mole

t.
.w
/At
.
t
w
ol.
m

22.4 lt

Mass

Ex.

Sol.

Volume at STP

367.5 gm KClO3 (M = 122.5) when heated


(a) How many grams O2 is produced
(b) How many litre of O2 is produced at STP
Now consider the balanced chemical equation
2KClO3 2KCl + 3O2
Now go with the above chart

367.5 gm
KClO3

122.5 gm

Mole of O2
Mole of KClO3
=
3
2

3 mole
KClO3

(Mole-mole relationship of equation)

(a) 144 gm

(b) 100.8 lt

Ex.

32
g
(mol. m
wt.)

9/2 mole of O2

lt
22.4 at STP)
me
lu
o
v
(

Iron in the form of fine wire burns in oxygen to form iron (III) oxide
4Fe(s) + 3O2(g) 2Fe2O3(s)
How many moles of O2 are needed to produce 5 mol Fe2O3 ?

Page No. # 14

Ans.

7.5 mol O2

Ex.

Ans.

Nitric acid, HNO3, is manufactured by the Ostwald process, in which nitrogen dioxide, NO2, reacts with
water.
3NO2(g) + H2O(l ) 2HNO3(aq) + NO(g)
How many grams of nitrogen dioxide are required in this reaction to produced 6.3 g HNO3 ?
6.9g NO2

Ex.

How many grams of Fe2 O3 is formed by heating 18 gm FeO with Oxygen.


4FeO + O2 2Fe2 O3

Ans.

20. gm

Ex.
Ans.

How many litre O2 at N.T.P. is required for complete combustion of 1 mole C5 H10.
168 lt.

Ex.

Calculate the weight of residue obtained when CaCO3 is strongly heated and 5.6 litre CO2 is produced at
N.T.P.
14 gm

Ans.
Ex.

When sodium bicarbonate is heated 1.806 x 1024 molecules of water is obtained. Then find the volume of
CO2(g) obtained at STP and amount of NaHCO3 needed for this reaction.

Sol.

2NaHCO3 Na2CO3 + H2O + CO2


So volume of CO2 = 3 22.4 = 67.2 Lt.
Mass of NaHCO3 needed = 6 84 = 504 gm.

Problem 1.3
Solution :

Problem 1.4
Solution:

(NCERT, Page 18)


Calculate the amount of water (g) produced by the combustion of 16 g of methane.
The balanced equation for combustion of methane is :
CH4 (g) + 202 (g) CO2 (g) + 2H2O (g)
(i) 16 g of CH4 corresponds to one mole.
(ii) From the above equation, 1 mol of
CH4 (g) gives 2 mol of H2O (g)
2 mol of water (H2O) = 2 (2 + 16)
=
2 18 = 36 g
(NCERT, Page 18)
How many moles of methane are required to produce 22 g CO2 (g) after combustion?
According to the chemical equation,
CH4 (g) + 202 (g) CO2 (g) + 2H2O (g)
44g CO2 (g) is obtained from 16 g CH4 (g).
[ ] 1mol CO2 (g) is obtained from 1 mol of CH4 (g)
mole of CO2 (g)

1molCO 2 (g)
= 22g CO2 (g) 44gCO (g)
2

= 0.5 mol CO2 (g)


Hence, 0.5 mol CO2 (g) would be obtained from 0.5 mol CH4 (g) or 0.5 mol of CH4 (g) would be required
to produce 22 g CO2 (g).

LECTURE # 5
Limiting Reagent , % Excess , % Yield / Efficiency
LIMITING REAGENT :
The reactant which is consumed first and limits the amount of product formed into the reaction, and is
Page No. # 15

therefore called limiting reagent.


Limiting reagent is present in least stoichiometric amount and therefore controls amount of product.
The remaining or leftout reactant is called the excess reagent.
When you are dealing with balanced chemical equation then if number of moles of reactants are not in the
ratio of stoichiometric coefficient of balanced chemical equation, then there should be one reactant which
should be limiting reactant.
Example :
Three mole of Na2 CO3 is reacted with 6 moles of HCl solution. Find the volume of CO2 gas produced at
STP. The reaction is
Na2 CO3 + 2HCl 2 NaCl + CO2 + H2O
Sol.

From the reaction :

Na2 CO3 + 2HCl 2 NaCl + CO2 + H2O

given moles
given mole ratio
Stoichiometric coefficient ratio

3 mol
1
:
1
:

6 mol
2
2

See here given moles of reactant are in stoichiometric coefficient ratio therefore none reactant left over.
Now use Mole-mole analysis to calculate volume of CO2 prdouced at STP

Moles of Na 2 CO3
Mole of CO 2 Pr oduced
=
1
1
Moles of CO2 produced = 3
volume of CO2 produced at STP = 3 22.4 L = 67.2 L
Example :
6 moles of Na2 CO3 is reacted with 4 moles of HCl solution. Find the volume of CO2 gas produced at STP.
The reaction is
Na2 CO3 + 2HCl 2 NaCl + CO2 + H2O
Sol.

From the reaction :

Na2 CO3 + 2HCl 2 NaCl + CO2 + H2O

given mole of reactant


give molar ratio
Stoichiometric coefficient ratio

6
3
1

:
:
:

4
2
2

See here given number of moles of reactants are not in stoichiometric coefficient ratio. Therefore there
should be one reactant which consumed first and becomes limiting reagent.
But the question is how to find which reactant is limiting, it is not very difficult you can easily find it
according to the following method.

HOW TO FIND LIMITING REAGENT :


Step :
Divide the given moles of reactant by the respective stoichiometric coefficient of that reactant.
Step :
See for which reactant this division come out to be minimum. The reactant having minimum value is limiting
reagent for you.
Step :
Now once you find limiting reagent then your focus should be on limiting reagent
From Step &
Na2 CO3
HCl

Page No. # 16

6
=6
1

HCl is limiting reagent


From Step
From

4
= 2 (division is minimum)
2

Moles of CO 2 produced
Mole of HCl
=
2
1
mole of CO2 produced = 2 moles
volume of CO2 produced at S.T.P. = 2 22.4 = 44.8 lt.

Examples on limiting reagent :


Ex.

Ex.

Ex.

The reaction 2C + O2 2CO is carried out by taking 24g of carbon and 96g O2, find out :
(a)
Which reactant is left in excess ?
(b)
How much of it is left ?
(c)
How many mole of CO are formed ?
For the reaction 2P + Q R, 8 mol of P and 5 mol of Q will produce
(A) 8 mol of R
(B) 5 mol of R
(C*) 4 mol of R
(D) 13 mol of R

Ans.

X + Y X3 Y4
Above reaction is carried out by taking 6 moles each of X and Y respectively then
(A) X is the limiting reagent
(B) 1.5 moles of X3 Y4 is formed
(C) 1.5 moles of excess reagent is left behind
(D) 75% of excess reagent reacted
X + Y X3 Y4
B, C, D

Sol.

3X

4Y

6 mole 6 mole
6 4.5 0
1.5 mole
left
Ex.

X3 Y4
1.5 mole
formed

A + B A3B2 (unbalanced)
A3B2 + C A3B2C2 (unbalanced)
Above two reactions are carried out by taking 3 moles each of A and B and one mole of C. Then
(A) 1 mole of A3B2C2 is formed

(B*) 1 2 mole of A3B2C2 is formed

(C*) 1 mole of A3B2 is formed

(D*) 1 2 mole of A3B2 is left finally

Ans.
Sol.

B, C, D
3A
+
2B A3 B2
3 mole
3 mole
1 mole formed

A3B2
+
2C
A3 B2 C2
1 mole
1 mole
0.5 mole
0
0.5 mole

Ex.

CS2 and Cl2 in the weight ratio 1 : 2 are allowed to react according to equation, find the fraction of excess
reagent left behind.
CS2 + 3Cl2 CCl4 + S2Cl2
mole

w
76

2w
71

w
76

2w
71 3

remaining =

L.R. = Cl2 .
Moles of CS2 =

2w
71 3

w
2w

76 213 x 100
fraction of Cl2 left =
w
76

w
2w

76
213

= 28.6%.

Page No. # 17

Ex.
Ans.
Ex.

Ans.
Ex.

Ans.

27 gm Al is heated with 49 ml of H2SO4 (sp. gr = 2) produces H2 gas. Calculate the volume of


H2 gas at N.T.P. and % of Al reacted with H2SO4
Vol of H2 = 22.4 litre
Al reacted = 66.66%
Equal weights of carbon and oxygen are heated in a closed vessel producing CO and CO2 in a
1 : 1 mol ratio. Find which component is limiting and which component left and what is its
percentage out of total weight taken.
Limiting reagent is O2, carbon will left behind, 50%
Three moles of Phosphorus is reacted with 2 moles of iodine to form P3 according to the reaction
P + 2 P3
P3 formed in the above reaction is further reacted with 27 g of water. According to the reaction.
P3 + H2O H3PO3 + H
HI formed in the above reaction is collected in the gaseous form. At higher temperature HI dissociated 50%
then find the molecules of H2 gas liberated
H H2 + 2
3/8 NA.

Problem 1.5 (NCERT Page - 19)


50.0 kg of N2 (g) and 10.0 kg of H2 (g) are mixed to produce NH3 (g) Calculate the NH3 (g) formed.
Identify the limiting reagent in the production of NH3 in this situation. Take reaction N2 + 3H2 2NH3.
Sol.
A balanced equation for the above reaction is written as follows :
Calculation of moles :
N2 (g) + 3H2 (g) 2NH3 (g)
N2

moles of N2

= 50.0 kg

moles of H2

= 10.00 kg H2

1000 g N2
1 mol H2
1kg N2 28.0 g N2

= 17.86 102 mol

1000 g H2
1 mol H2

1kg H2
2.016 g H2

= 4.96 103 mol

According to the above equation, 1 mol N2 (g) requires 3 mol H2 (g), for the reaction, Hence, for 17.86
102 mol of N2, the moles of H2 (g) required would be
3 mol H2 (g)
17.86 102 mol N2 1molN (g)
2

= 5.36 103 mol H2

But we have only 4.96103 mol H2. Hence, dihydrogen is the limiting reagent in this case. So NH3 (g)
would be formed only from that amount of available digydrogen i.e., 4.96 103 mol
Since 3 mol H2 (g) gives 2 mol NH3 (g)

2 mol NH3 (g)


4.96 103 mol H2 (g) 3 mol H (g)
2

= 3.30 103 mol NH3 (g) is obtained.


If they are to be converted to grams, it is done as follows :
17.0gNH3 (g)
3.30 103 mol NH3 (g) 1molNH (g) .
3
= 56.1 103 g NH3

= 3.30 103 17 g NH3 (g)

= 56.1 kg NH3

PERCENTAGE YIELD DETERMINATION :


If a reaction takes place completely, the amount of product formed will be equal to its theortical amount
(amount determined from the balanced reaction). The percentage yield of any product represents the
amount of product formed in comparison to its theoretical amount. The percentage yield of any product will
Page No. # 18

always be equal to the percentage progress of the reaction.


Ex.

When 3.90 gm Al(OH)3 is reacted with excess of HCl, 6.50 gm AlCl3 is formed. Determine the percentage
yield of product. (Al = 27).

Sol.

Al(OH)3 + 3HCl AlCl3 + 3H2O

1 mole
1 mole
= 78 gm
= 133.5 gm
78 gm Al(OH)3 produce 133.5 gm AlCl3

3.90 gm Al(OH)3 should produce

133 .5
3.90 = 6.675 gm AlCl3.
78

But the amnount formed is only 6.50 gm. Hence, the percentage yield is

6.50
100 = 97.38%.
6.675

LECTURE # 6
POAC, Reactions in sequence, Reactions in parallel , Mixture analysis , % Purity
PRINCIPLE OF ATOM CONSERVATION (POAC) :
POAC is based on law of mass conservation if atoms are conserved, moles of atoms shall also be
conserved hence mass of atoms is also conserved.
This principle is fruitful for the students when they dont get the idea of balanced chemical equation in the
problem. This principle can be under stand by the following example.
Consider the decomposition of KClO3 (s) KCl (s) + O2 (g) (unbalanced chemical reaction)
Apply the principle of atom conservation (POAC) for K atoms.
Moles of K atoms in reactant = moles of K atoms in products
or moles of K atoms in KClO3 = moles of K atoms in KCl.
Now, since 1 molecule of KClO3 contains 1 atom of K
or 1 mole of KClO3 contains 1 mole of K, similarly,1 mole of KCl contains 1 mole of K.
Thus, moles of K atoms in KClO3 = 1 moles of KClO3
and moles of K atoms in KCl = 1 moles of KCl.

moles of KClO3 = moles of KCl


or

The above equation gives the mass-mass relationship between KClO3 and KCl which is important in
stoichiometric calculations.
Again, applying the principle of atom conservation for O atoms,
moles of O in KClO3 = 3 moles of KClO3
moles of O in O2 = 2 moles of O2

3 moles of KClO3 = 2 moles of O2


or

Q.

wt. of KClO3 in g
wt. of KCl in g
=
mol. wt. of KCl
mol. wt. of KClO3

wt. of KClO 3
vol. of O 2 at NTP
3 mol. wt. of KClO = 2 s tan dard molar vol. (22.4 lt.)
3

The above equations thus gives the mass-volume relationship of reactants and products.
Write POAC equation for all the atoms in the following reaction.
(i) N2O + P4 P4O10 + N2
(ii) P4 + HNO3 H3PO4 + NO2 + H2O

Example :

Page No. # 19

Sol.

27.6 g K2CO3 was treated by a series of reagents so as to convert all of its carbon to K2 Zn3 [Fe(CN)6]2.
Calculate the weight of the product.
[mol. wt. of K2CO3 = 138 and mol. wt. of K2Zn3 [Fe(CN)6]2 = 698]
Here we have not knowledge about series of chemical reactions
but we know about initial reactant and final product accordingly
Several
K2CO3 K2Zn3 [Fe(CN)6]2
Steps

Since C atoms are conserved, applying POAC for C atoms,


moles of C in K2CO3 = moles of C in K2Zn3 [Fe(CN)6]2
1 moles of K2CO3 = 12 moles of K2Zn3 [Fe(CN)6]2
( 1 mole of K2CO3 contains 1 moles of C)
wt. of K 2CO 3
wt. of the product
mol. wt. of K 2CO 3 = 12 mol. wt. of product
27.6
698

= 11.6 g
138
12
0.32 mole of LiAlH4 in ether solution was placed in a flask and 74 g (1 moles) of t-butyl alcohol was added.
The product is LiAlHC12H27O3 . Find the weight of the product if lithium atoms are conserved.
[Li = 7, Al = 27, H = 1, C = 12, O = 16]
81.28 g

wt. of K2Zn3 [Fe(CN)6]2 =


Q.1

Ans.

REACTIONS IN SUCCESSION :
In such problems, the amount of any one of the reaction component belonging from a reaction is to be
determined from the given amount of some other reaciton component belonging from some other reaction
with the help of some common components.
Ex.

How many gram of ethylene can be burnt completely by the oxygen gas produced from complete
decomposition of 49 gm KClO3.

Sol.

2KClO3 2KCl

+ 3O2

C2H4 + 3O2 2CO2 + 2H2O


Relate the moles of the component of given amount with the component of required amount, with the help
of commom compound, with the help of balanced chemical reactions.
2 mole KClO3 = 3 mole O2 = 1 mole C2H4
= 2 122.5 gm
= 28 gm
49 gm

28
49 = 5.6 gm.
2 122 .5

MIXTURE ANALYSIS OR PERCENTAGE COMPOSITION CALCULATION :


Ex.
Sol.

When 4 gm of a mixture of NaHCO3 and NaCl is heated strongly, 0.66 gm CO2 gas is evolved. Determine
the percentage composition of hte original mixture.
CO2 gas will come out only from NaHCO3 according to the reaction :
2NaHCO3 Na2CO3 + CO2 + H2O

2mole
1mole
= 2 84gm
= 44 gm
44 gm CO2 is evolved from 2 84 gm NaHCO3
Page No. # 20

0.66 gm CO2 will evolve from

2 84
0.66 = 2.52 gm NaHCO3.
44

Hence, the percentage composition of the mixture is, NaHCO3 =

2.52
100 = 63%
4

and NaCl = 100 63 =37%.


Ex.
Sol.

2 gm of a mixture of CaCO3 and MgCO3 requires 2 gm of H2SO4 for complete reaction. Determine the
percentage composition of the original mixture.
Let the mixture contains x gm CaCO3. Then the weight of MgCO3 should be (2 x) gm.
CaCO3 + H2SO4

CaSO4 + CO2 + H2O

1mole
1mole
= 100 gm =98 gm
100 gm CaCO3 requires 98 gm H2SO4.
x gm CaCO3 will react with
MgCO3

98
gm H2SO4
100

H2SO4

MgSO4

CO2

H2 O

1mole
1mole
= 84 gm
= 98 gm
84 gm MgCO3 requires 98 gm H2SO4
(2 x) gm MgCO3 will react with

98
(2 x) gm H2SO4
84

Hence, the total weight of H2SO4 required =

98
98
x+
(2 x) gm = 2 gm (from question).
100
84

x = 1.78 gm
Hence, the percentage composition of the mixture is
CaCO3 =

x
100 = 89%.
2

MgCO3 =

2x
100 = 11%.
2

PERCENTAGE PURITY CALCULATION :


In such problems, if the impurity is not given, it is always considered as inert material. Only the substance
takes part in the chemical reaction.
Ex.
Sol.

When 1.25 gm of a sample of chalk is strongly heated, 0.44 gm CO2 gas in produce. Determine the
percentage of pure CaCO3 in the chalk sample.
CaCO3 CaO + CO2
1mole
1mole
=100 gm
= 44 gm
44 gm CO2 is produced from 100 gm CaCO3
0.44 gm CO2 should be produced from

100
0.44 = 1.0 gm CaCO3
44

Page No. # 21

Hence, percentage of pure CaCO3 in the sample =


Ex.
Sol.

1.0
100 = 80%.
1.25

Calculate the amount of 80% pure NaOH sample required to react completely with 21.3 gm chlroine in hot
condition.
6NaOH +

3Cl2 5NaCl + NaClO3 + 3H2O

6mole
3mole
=640 gm =371gm
3 71 gm Cl2 requires 6 40 gm pure NaOH
21.3 gm Cl2 will react with

6 40
21.3 = 24 gm pure NaOH.
3 71

Hence, the weight of NaOH sample required = 24

100
= 30 gm.
80

LECTURE # 7
Basics of oxidation number.
CONCEPT OF OXIDATION NUMBER :
Real or imaginary charge present on an element when it goes from its elemental free state to
combined state.

Rules governing oxidation number :


The following rules are helpful in calculating oxidation number of the elements in their different compounds.
It is remembered that the basis of these rule is the electronegativity of the element .
1.

Fluorine atom :
Fluorine is most electronegative atom yet known and it has always oxidation number equal to 1 in any
compound

2.

Oxygen atom :
In general and in the case of its oxide oxygen atom has oxidation number equal to 2. In case of peroxide
(e.g. H2O2, , Na2O2 ) it is 1, In case of super oxide (e.g KO2) and ozonide (KO3) it is 1/2 and 1/3 , In case
of oxygendiflouride OF2 it is + 2 & in dioxygendiflouride O2F2 it is +1

3.

Hydrogen atom :
In general H atom has oxidation number equal to +1 in all its compounds but in case of metallic hydride
e.g. NaH, KH it is 1

4.

Halogen atom :
In general all halogen atom (Cl,Br ,I) has oxidation number equal to 1 But if halogen atom is attached with
an atom which is more electronegative than halogen atom then it will show positive oxidation number e.g.

Page No. # 22

K ClO3 , HI O 3 , HCIO 4 , KBrO3


5.

Metals :
(a) Alkali metal (Li , Na, K, Rb, .......) always have oxidation number +1 in all its compound.
(b) Alkaline earth metal (Be , Mg , Ca .......) always have oxidation number +2 in all its compound.
Note :- Metal may have negative or zero oxidation number

6.

Oxidation number of an element in free state or in allotropic forms is always zero


0

e.g. O , S , P , O
2
8
4
3
7.
8.
9.

Sum of the charges of all elements in a molecule is zero.


Sum of the charges of all elements in an ion is equal to the charge on the Ion .
If the group no. of an element in periodic table is n then its oxidation number may vary from
n to n 8 (but it is mainly applicable in p-block elements )
e.g. N- atom belongs to v group in the periodic table therefore as per rule its oxidation number may vary
3

from 3 to +5 ( N H ,NO , N 2 O , N O , N 2 O )
3
2
5
3

Calculation of average oxidation number :


Q.
1.

2.

Calculate oxidation number of underlined element


Na2 S2O3 :
Let oxidation number of S-atom is x. now work accordingly with the rules given before .
(+1) 2 + (x) 2 + (2) 3 =0
x=+2
Na2 S 4O6 :
Let oxidation number of s-atom is x
(+1) 2 + (x) 2 + (2) 6 = 0
x = + 2.5
Its important to note here that Na2S2O3 have two s-atom and there are four s-atom in Na2S4O6 but none
sulphur atom in both the compound have + 2 or + 2.5 oxidation number it is the average charge (O.No.)
Which reside on each sulphur atom therefore we should work to calculate the individual oxidation number
of each sulphur atom in these compound.

Calculation of individual oxidation number :


It is important to note that to calculate individual oxidation number of the element in its compound one
should know the structure of the compound and use the following guidelines.
Formula:
Oxidation Number = number of electrons in the valence shell number of electrons left after
bonding
Guidelines :
These guidelines to calculate oxidation number is given on the basis of electronegativity.
1.

If there is a bond between similar type of atom and each atom has same type of hybridisation then bonded
pair electrons are equally shared by each element

Ex.

Calculate oxidation number of each Cl atom in Cl2 molecule

Structure :

Page No. # 23

No. of electrons in the valence shell = 7.


No. of electrons left after bonding = 7.
oxidation number = 7 7 = 0.
:

similarly oxidation number = 7 7 = 0.

2.

If there in a bond between different type of atoms


e.g.
A B (B is more electronegative than A)
Then after bonding bonded pair electrons are counted with B - atom .

Ex.

Calculate oxidation number of each atom in HCl molecule


Structure :

Note : Electron of H-atom is now counted with Cl-atom, because Cl-atom is more E.N. than H-atom
H : number of electrons in the valence shell = 1
number of electrons left after bonding = 0
oxidation number = 1 0 = + 1
Cl : Number of electrons in the valence shell = 7
Number of electrons left after bonding = 8
Oxidation number = 7 8 = 1
Ex.
Calculate individual oxidation number of each s -atom in Na2S2O3 (sodium thio sulphate) with the help of its
structure .

Sol.

Structure :

(central S-atom) is sp 3 hybridised (25% s-character) and (terminal S-atom) is sp 2 hybridised


(33% S-character). Therefore terminal sulphur atom is more electronegative than central sulphur
atom. Now the shared pair electrons are counted with terminal S-atom.

, S-atom : No. of electrons in the valence snell = 6


: No. of electrons left after bonding = 0
Oxidation No. = 6 0 = + 6

, S-atom : No. of electrons in the valence shell = 6


No. of electrons left after bonding = 8
Oxidation No. = 6 8 = 2
62
Now you can also calculate Average Oxidation No. =
= + 2 ( as we have calculated before )
2

1.
Calculate individual oxidation number of each s -atom in Na2S4O6 (sodium tetrathionate) with the
help of its structure .

Page No. # 24

Miscellaneous Examples :
In order to determine the exact or individual oxidation number we need to take help from
the structures of the molecules. Some special cases are discussed as follows:

The structure of CrO5 is

Cr
||
O
O
O

From the structure it is evident that in CrO5 there are two peroxide linkages and one double bond.
The contribution of each peroxide linkage is 2. Let the O.N. of Cr is x.
x + (2)2 + (2) = 0 or x = 6
O.N. of Cr = +6

The structure of H2SO5 is H

From the structure, it is evident that in H2SO5. there are one peroxide linkage, two sulphur-oxygen double
bond and one OH group. Let the O.N. of S = x.
+1 2 + x + (2) 2+ (2) + 1 = 0
or x + 2 8 = 0
or x 6 = 0
or x = 6
O.N. of S in H2SO5 is + 6.

Paradox of fractional oxidation number :


Fractional oxidation state is the average oxidation state of the element under examination and the
structural parameters reveal that the element for whom fractional oxidation state is realised is actually
present in different oxidation states. Structure of the species C3O2, Br3O8 and S4O62 reveal the following
bonding situations :
The element marked with asterisk in each species is exhibiting the different oxidation state (oxidation
number) from rest of the atoms of the same element in each of the species. This reveals that in C3O2, two
carbon atoms are present in +2 oxidation state each whereas the third one is present in zero oxidation
state and the average is 4/3. However the realistic picture is +2 for two terminal carbons and zero for the
middle carbon.

O C C* C O
Structure of C3O2
(Carbon suboxide)
Likewise in Br3O8, each of the two terminal bromine atoms are present in +6 oxidation state and
the middle bromine is present in +4 oxidation state. Once again the average, that is different from reality is
16/3.

O
+6

O = Br

+4 ||

O
+6

Br* Br = O
||
O
O
O
Structure of Br3O8 (tribromooctaoxide)
In the same fashion, in the species S4O62, is 2.5, whereas the reality being +5,0,0 and +5
oxidation number respectively for each sulphur.

Page No. # 25

O
O
|| +5 0
||
0
O S S* S* S O
||
||
O
O
Structure of S4 O62- (tetrathionate ion)
In general, conclude that the idea of fractional oxidation state should be taken with care and the
reality is revealed by the structures only.

1.

Find the average and individual oxidation number of Fe3O4, Mn3O4, Pb3O4 , which are mixed oxides.

2.

Calculate oxidation number of each atom in the following compounds.


(a) H2S2O8
(b) CrO5
(c) Rb4Na[HV10O28]
(e) K2FeO4
(f) Ba2XeO4
(g) HCN
(i) C3O2
(j) S4O62
(k) Br3O8

(d) Na2S2O3
(h) HNC
(l) Fe3O4

OXIDATION & REDUCTION :


Let us do a comparative study of oxidation and Reduction :
Oxidation
1. Addition of oxygen
e.g. 2Mg + O2 2MgO

Reduction
1. Removal of oxygen
e.g. CuO + C Cu + CO

2. Removal of Hydrogen
e.g. H2S + Cl2 2HCl + S

2. Addition of Hydrogen
e.g. S + H2 H2S

3. Increase in positive charge


e.g. Fe2+ Fe3+ + e

3. Decrease in positive charge


e.g. Fe3+ +e Fe2+

4. Increase in oxidation number


(+2)
(+4)
SnCl2 SnCl4

4. Decrease in oxidation number


(+7)
(+2)
MnO4 Mn2+

5. Removal of electron
e.g. Sn2+ Sn4+ + 2e

5. Addition of electron
e.g. Fe3+ + e Fe2+

Oxidation and reduction always take place simultaneously. Such overall reactions which involves
simultaneous oxidation and reduction are called Redox Reaction.

Oxidizing and reducing agents :


Substances that oxidized is called reducing agent and substances that reduced is called oxidizing agent.
For Example :

( 5 )

2 HNO 3
O.A.

( 2 )

( 2)

3 H2 S

2 NO

(0)

3S + 4H2O

R.A.

Page No. # 26

Important oxidizing agents :


O2, O3, X2 (halogens), KMnO4, K2Cr2O7, Na2Cr2O7, CrO3, H2SO4, HNO3, NaNO3, FeCl3, HgCl2, KClO3, MgO,
CuO, CrO3, CO2, P4O10, H2O2, CO2, SO3 etc.
Important reducing agents :
All metals, (ex. Na, Zn, Fe, Al etc), a few nonmetals (ex. C, H2, S, P etc.) Hydra acids (HCl, HBr, HI, H2S
etc), Metallic hydrides (NaH, LiH, CaH2 etc). Organic compounds like HCOOH, (COOH)2 and tartaric acid
and their salts, aldehydes, alkanes etc.
Lithium (Li) is the strongest reducing agent in solution, Cesium is the strongest reducing agent in absence
of water.
Substances which act as oxidising as well as reducing agents are :
H2O2, SO2, H2SO3, HNO2, NaNO2, Na2SO3, O3 etc. Such a molecule is said to autooxidise and the
process (reaction) as autooxidation or disproportionation.
1 1

1 1

1 2

Ex. H 2 O 2 H2 O 2 2 H 2 O O 2
Note : (i)

If an element is in its highest possible oxidation state in a compound, it can function as an


oxidizing agent.
Ex. KMnO4, K2Cr2O7, HNO3, H2SO4, HClO4 etc.

(ii)

If an element is in its lowest possible oxidation state in a compound, it can function as a reducing
agent.
Ex. H2S, H2C2O4, FeSO4, Na2S2O3, SnCl2 etc.

(iii)

If an element is in its intermediate oxidation state in a compound it can function both as an


oxidizing agent as well as reducing agent
Ex. H2O2, H2SO4, HNO2, SO2 etc.

Types of Redox Reactions :


1.

Combination reactions :
A combination reaction may be denoted in the manner:
A + B C
Either A and B or both A and B must be in the elemental form for such a reaction to be a redox reaction. All
combustion reactions, which make use of elemental dioxygen, as well as other reactions involving elements
other than dioxygen, are redox reactions. Some important examples of this category are:
0

4 2

C(s) O 2 (g) C O 2 (g)


0

2 3

3Mg(s) N2 (g) Mg3 N 2 (s)


41

4 2

1 2

CH4 (g) 2 O 2 (g) CO 2 (g) 2H2O( )


2.

Decomposition reactions : Decomposition reactions are the opposite of combination reactions. Precisely,
a decomposition reaction leads to the breakdown of a compound into two or more components at least one
of which must be in the elemental state. Examples of this class of reactions are:
1 2

2H2 O( )
2H2 (g) O 2 (g)

1 1

2NaH(s) 2Na(s) H2 (g)


1 5 2

1 1

2KClO3 (s) 2KCl(s) 3O 2 (g)


3.

Displacement reactions : In a displacement reaction, an ion (or an atom) in a compound is replaced


by an ion (or an atom) of another element. It may be denoted as:

Page No. # 27

(a)

X + YZ XZ + Y
Displacement reactions fit into two categories: metal displacement and non-metal displacement.
Metal displacement: A metal in a compound can be displaced by another metal in the uncombined
state. Metal displacement reactions find many applications in metallurgical processes in which pure
metals are obtained from their compounds in ores. A few such examples are:
2 6 2

2 6 2

CuSO 4 (aq) Zn(s) Cu(s) ZnSO 4 (aq)


5 2

2 2

V2O 5 (s) 5 Ca(s)


2V(s) 5CaO(s)

4 1

2 1

TiCl4 ( ) 2 Mg(s) Ti (s) 2MgCl2 (s)


3 2

3 2

Cr2O 3 (s) 2 Al(s) Al2O 3 (s) 2Cr(s)


In each case, the reducing metal is a better reducing agent than the one that is being reduced which
evidently shows more capability to lose electrons as compared to the one that is reduced.
(b)

Non-metal displacement: The non-metal displacement redox reactions include hydrogen displacement
and a rarely occurring reaction involving oxygen displacement.
All alkali metals and some alkaline earth metals (Ca, Sr, and Ba) which are very good reductants, will
displace hydrogen from cold water.
0

1 2

1 2 1

2Na(s) 2H2O( ) 2NaOH(aq) H2 (g)


0

1 2

2 2 1

Ca(s) 2H2 O( ) Ca(OH)2 (aq) H2 (g)

Less active metals such as magnesium and iron react with steam to produce dihydrogen gas.
0

1 2

2 2 1

Mg(s) 2H2O( ) Mg(OH)2 (s) H2 (g)


0

1 2

3 2

2Fe(s) 3H2 O( )
Fe 2 O 3 (s) 3H2 (g)

Many metals, including those which do not react with cold water, are capable of displacing hydrogen
from acids. Dihydrogen from acids may even be produced by such metals which do not react with
steam. Cadmium and tin are the examples of such metals. A few examples for the displacement of
hydrogen from acids are :
0

1 1

2 1

Zn(s) 2HCl(aq) ZnCl2 (aq) H2 (g)


0

1 1

2 1

Mg(s) 2HCl(aq) MgCl2 (aq) H2 (g)


0

1 1

2 1

Fe(s) 2HCl(aq) FeCl2 (aq) H2 (g)


Above three reactions are used to prepare dihydrogen gas in the laboratory. Here, the reactivity of
metals is reflected in the rate of hydrogen gas evolution, which is the slowest for the least active metal
Fe, and the fastest for the most reactive metal, Mg. Very less active metals, which may occur in the
native state such as silver (Ag), and gold (Au) do not react even with hydrochloric acid.
We already know that the metals - zinc (Zn), copper (Cu) and silver (Ag) through tendency to lose
electrons show their reducing activity in the order Zn> Cu>Ag. Like metals, activity series also exists for
the halogens. The power of these elements as oxidising agents decreases as we move down from
fluorine to iodine in group 17 of the periodic table. This implies that fluorine is so reactive that it can
replace chloride, bromide and iodide ions in solution. In fact, fluorine is so reactive that it attacks water
and displaces the oxygen of water:
1 2

1 1

2H2O( ) 2F2 (g) 4HF(aq) O 2 (g)


It is for this reason that the displacement reactions of chlorine, bromine and iodine using fluorine are not
generally carried out in aqueous solution. On the other hand, chlorine can displace bromide and iodide
Page No. # 28

ions in an aqueous solution as shown below:


0

1 1

1 1

Cl2 (g) 2KBr(g) 2KCl(aq) Br2 ( )


0

1 1

1 1

Cl2 (g) 2K (aq) 2KCl (aq) 2 (s)


As Br2 and I2 are coloured and dissolve in CCI4, can easily be identified from the colour of the solution.
The above reactions can be written in ionic form as:
0

Cl2 ( g) 2Br (aq) 2Cl (aq) Br2 ( )


0

Cl2 ( g) 2 (aq) 2Cl (aq) 2 ( s)

Above two reactions form the basis of identifying Br and I in the laboratory through the test popularly
known as Laye! Test. It may not be out of place to mention here that bromine likewise can displace
iodide ion in solution:
0

Br2 ( ) 2 (aq) 2Br (aq) 2 ( s)

The halogen displacement reactions have a direct industrial application. The recovery of halogens from
their halides requires an oxidation process, which is represented by:

2X X2 + 2e

here X denotes a halogen element. Whereas chemical means are available to oxidise Cl , Br and I , as

fluorine is the strongest oxidising agent; there is no way to convert F ions to F2 by chemical means.

The only way to achieve F2 from F is to oxidise electrolytically, the details of which you will study at a
later stage.
4.

Disproportionation reactions :
Disproportionation reactions are a special type of redox reactions. In a disproportionation reaction an
element in one oxidation state is simultaneously oxidised and reduced. One of the reacting substances
in a disproportionation reaction always contains an element that can exist in at least three oxidation
states. The element in the form of reacting substance is in the intermediate oxidation state; and both
higher and lower oxidation states of that element are formed in the reaction. The decomposition of
hydrogen peroxide is a familiar example of the reaction, where oxygen experiences disproportionation.
1 1

1 2

2H2O 2 (aq) 2H2O ( ) O 2 (g)


Here the oxygen of peroxide, which is present in -1 state, is converted to zero oxidation state in O2 and
decreases to -2 oxidation state in H2O. Phosphorous, sulphur and chlorine undergo disproportionation in
the alkaline medium as shown below:
0

P4 ( s) 3OH (aq) 3H2 O( ) PH3 ( g) 3H2PO 2 (aq)


0

S 8 ( s) 12OH (aq) 4S 2 (aq) 2S 2 O 23 (aq) 6H2 O( )


2

Cl 2 ( g) 2OH (aq) ClO (aq) Cl (aq) H2 O( )

The last reaction describes the formation of household bleaching agents. The hypochlorite ion (CIO-)
formed in the reaction oxidises the colour-bearing stains of the substances to colourless compounds.
It is of interest to mention here that whereas bromine and iodine follow the same trend as exhibited by
chlorine in the last reaction, fluorine shows deviation from this behaviour when it reacts with alkali. The
reaction that takes place in the case of fluorine is as follows:
2F2(g) + 2OH(aq) 2F (aq) + OF2(g) + H2O()
(It is to be noted with care that fluorine in reaction above will undoubtedly attack water to produce some
oxygen also). This departure shown by fluorine is not surprising for us as we know the limitation of
Page No. # 29

fluorine that, being the most electronegative element, it cannot exhibit any positive oxidation state. This
means that among halogens, fluorine does not show a disproportionation tendency.
5.

Comproportionation reactions : Reverse of disproportionation is called comproportionation

For Ex.
Ex.

Sol.

I + IO3 + H I2 + H2O.

Which of the following species, do not show disproportionation reaction and why?
CIO, CIO2, CIO3 and ClO4
Also write reaction for each of the species that disproportionates.
Among the oxoanions of chlorine listed above, CIO4 does not disproportionate because in this oxoanion
chlorine is present in its highest oxidation state that is, +7. The disproportionation reactions for the other
three oxoanions of chlorine are as follows:
1

3ClO 2Cl ClO 3


5

h
6ClO 2
4ClO 3 2Cl
5

4ClO 3 Cl 3ClO 4
Ex.

Suggest a scheme of classification of the following redox reactions.


(a) N2(g) + O2(g) 2NO(g)
(b) Pb(NO3)2(s) PbO(s) + 2NO2(g) +

1
O (g)
2 2

(c) NaH(s) + H2O() NaOH(aq) + H2(g)

(d) 2NO2(g) + 2OH (aq) NO2 (aq) + NO3 (aq) + H2O()


Sol.

In reaction (a), the compound nitric oxide is formed by the combination of the elemental substances,
nitrogen and oxygen ; therefore, this is an example of combination redox reaction. The reaction (b) involves
the breaking down of lead nitrate into three components ; therefore, this is categorised under decomposition
redox reaction. In reaction (c), hydrogen of water has been displaced by hydride ion into dihydrogen gas.
Therefore, this may be called as displacement redox reaction. The reaction (d) involves disproportionation

of NO 2 (+4 state) into NO 2


(+3 state) and NO 3
(+5 state). Therefore
reaction (d) is an example of disproportionation redox reaction.

Ex.

Why do the following reactions proceed differently?


Pb3O4 + 8HCl 3PbCl2 + Cl2 + 4H2O

Sol.

and
Pb3O4 + 4HNO3 2Pb(NO3)2 + PbO2 + 2H2O
Pb3O4 is actually a stoichiometric mixture of 2 mol of PbO and 1 mol of PbO2. In PbO2, lead is present in
+4 oxidation state. Whereas the stable oxidation state of lead in PbO is +2. PbO2 thus can act as an

oxidant (oxidising agent) and, therefore, can oxidise Cl ion of HCI into chlorine. We may also keep in mind
that PbO is a basic oxide. Therefore, the reaction
Pb3O4 + 8HCl 3PbCl2 + Cl2 + 4H2O
can be splitted into two reactions namely:
2PbO + 4HCl 2PbCl2 + 2H2O (acid-base reaction)
4

Pb O 2 4H Cl Pb Cl2 Cl2 2H2O (redox reaction)


Since HNO3 itself is an oxidising agent therefore, it is unlikely that the reaction may occur between PbO2
and HNO3. However, the acid-base reaction occurs between PbO and HNO3 as:
2PbO + 4HNO3 2Pb(NO3)2 + 2H2O
It is the passive nature of PbO2 against HNO3 that makes the reaction different from the one that follows
with HCl.
Page No. # 30

LECTURE # 8
Steps for balancing redox reactions & Practice of balancing redox
reactions.
Balancing of redox reactions :
1.

All balanced equations must satisfy two criteria


Atom balance (mass balance) :
That is there should be the same number of atoms of each kind in reactant and products side.

2.

Charge balance :
That is the sums of actual charges on both sides of the equation must be equal
Two methods are used to balance chemical equations for redox processes. One of these methods is
based on the change in the oxidation number of reducing agent and the oxidising agent and the other
method is based on splitting the redox reaction into two half reactions - one involving oxidation and the
other involving reduction. Both these methods are in use and the choice of their use rests with the individual
using them.

(a)

Oxidation Number Method : In writing equations for oxidation-reduction reactions, just as for other
reactions, the compositions and formulas must be known for the substances that react and for the
products that are formed. The oxidation number method is now best illustrated in the following steps:

Step 1: Write the correct formula for each reactant and product.
Step 2: Identify atoms which undergo change in oxidation number in the reaction by assigning the oxidation
number to all elements in the reaction.
Step 3: Calculate the increase or decrease in the oxidation number per atom and for the entire molecule/ion in
which it occurs. If these are not equal then multiply by suitable coefficients so that these become equal.
(If you realise that two substances are reduced and nothing is oxidised or vice-versa, something is
wrong. Either the formulas of reactants or products are wrong or the oxidation numbers have not been
assigned properly).
Step 4: Ascertain the involvement of ions if the reaction is taking place in water, add H+ or OH ions to the
expression on the appropriate side so that the total ionic charges of reactants and products are equal. If
the reaction is carried out in acidic solution, use H+ ions in the equation; if in basic solution, use OH
ions.
Step 5: Make the numbers of hydrogen atoms in the expression on the two sides equal by adding water (H2O)
molecules to the reactants or products. Now, also check the number of oxygen atoms. If there are the
same number of oxygen atoms in reactants and products. The equation then represents the
balanced redox reaction.
Let us now explain the steps involved in this method with the help of a few problems given below:
Ex.

Write the net ionic equation for the reaction of potassium dichromate (VI), K2Cr2O7 with sodium sulphite
(Na2SO3) in an acid solution to give chromium(III) ion and the sulphate ion.

Step 1: The skeletal ionic equation is:


Cr2O72(aq) + SO32(aq) Cr3+(aq) + SO42(aq)
Step 2: Assign oxidation numbers for Cr and S.
6

4 2

6 2

Cr2 O 72 (aq) SO 32 (aq) Cr (aq) SO 24 (aq)

This indicates that the dichromate ion is the oxidant and the sulphite ion is the reductant.
Step 3: Calculate the increase and decrease of oxidation number, and make them equal:

Page No. # 31

6 2

4 2

6 2

Cr2 O 72 (aq) 3SO 32 (aq) 2Cr 3 (aq) 3SO 24 (aq)

Step 4: As the reaction occurs in the acidic medium, and further the ionic charges are not equal on both the sides,
add 8H+ on the left to make ionic charges equal
Cr2O72(aq) + 3SO32(aq) + 8H+(aq) 2Cr3+(aq) + 3SO42(aq) + 4H2O()
Step 5: Finally, count the hydrogen atoms, and add appropriate number of water molecules (i.e., 4H2O) on the
right to achieve balanced redox change.
Cr2O72(aq) + 3SO32(aq) + 8H+(aq) 2Cr3+(aq) + 3SO42(aq) + 4H2O()
Ex.

Permanganate ion reacts with bromide ion in basic medium to give manganese dioxide and bromate ion.
Write the balanced ionic equation for the reaction.

Step 1 : The skeleton ionic equation is :

MnO4 (aq) + Br (aq) MnO2(s) + BrO3 (aq)


Step 2 : Assign oxidation numbers for Mn and Br
7

MnO 4 (aq) Br (aq) MnO 2 ( s) BrO 3 (aq)


this indicates that permanganate ion is the oxidant and bromide ion is the reductant.

Step 3: Calculate the increase and decrease of oxidation number, and make the increase equal to the decrease.
7

2MnO 4 (aq) Br (aq) 2MnO 2 ( s) BrO 3 (aq)

Step 4: As the reaction occurs in the basic medium, and the ionic charges are not equal on both sides, add 2
OH- ions on the right to make ionic charges equal.
2MnO4(aq) + Br (aq) 2MnO2(s) + BrO3(aq) + 2OH(aq)
Step 5: Finally, count the hydrogen atoms and add appropriate number of water molecules (I.e. one H2O
molecule) on the left side to achieve balanced redox change.

2MnO4 (aq) + Br (aq) + H2O() 2MnO2(s) + BrO3(aq) + 2OH(aq)


(b) Half Reaction Method (Ion electron method): In this method, the two half equations are balanced
separately and then added together to give balanced equation.
Suppose we are to balance the equation showing the oxidation of Fe2+ ions to Fe3+ ions by dichromate
ions Cr2O72 in acidic medium, wherein, Cr2O72 ions are reduced to Cr3+ ions. The following steps are
involved in this task.
Step 1: Produce unbalanced equation for the reaction in ionic form :
Fe2+(aq) + Cr2O72 (aq) Fe3+(aq) + Cr3+(aq)
Step 2: Separate the equation into half reactions :
2

Oxidation half : Fe 2 (aq) Fe 3 (aq)


6 2

Reduction half : Cr2O 27 (aq) Cr 3 (aq)


Step 3: Balance the atoms other than and H in each half reaction individually. Here the oxidation half reaction is
already balanced with respect to Fe atoms. For the reduction half reaction, we multiply the Cr3+ by 2 to
balance Cr atoms.
2

Cr O (aq) 2Cr3+(aq)
2

Step 4: For reactions occurring in acidic medium, add H2O to balance O atoms and H to balance H atoms.
Thus, we get:

Page No. # 32

Cr2O72(aq) + 14H+ (aq) 2Cr3+(aq) + 7H2O()


Step 5: Add electrons to one side of the half reaction to balance the charges. It need to, make the number of
electrons equal in the two half reactions by multiplying one or both half reactions by appropriate
coefficients.
The oxidation half reaction is thus rewritten to balance the charge:

Fe2+ (aq) Fe3+ (aq) + e


Now in the reduction half reaction there are net twelve positive charges on the left hand side and only six
positive charges on the right hand side. Therefore we add six electrons on the left side.
Cr2O72(aq) + 14H+(aq) + 6e 2Cr3+(aq) + 7H2O()
To equalise the number of electrons in both the half reactions. We multiply the oxidation half reaction by
6 and write as : Fe2+(aq) Fe3+(aq) + 6e
Step 6: We add the two half reactions to achieve the overall reaction and cancel the electrons on each side.
This gives the net ionic equation as :
6Fe2+(aq) + Cr2O72(aq) + 14H+(aq) 6Fe3+(aq) + 2Cr3+(aq) + 7H2O()
Step 7: Verify that the equation contains the same type and number of atoms and the same charges on both sides
of the equation. This last check reveals that the equation is fully balanced with respect to number of atoms
and the charges.
For the reaction in a basic medium, first balance the atoms as is done in acidic medium. Then for each H+
ion, add an equal number of OH- ions to both sides of the equation. Where H+ and OH- appear on the same
side of the equation, combine these to give H2O.
Ex.

Permanganate (VII) ion. MnO4 in basic solution oxidises iodide ion, I to produce molecular iodine (I2) and
manganese (IV) oxide (MnO2). Write a balanced ionic equation to represent this redox reaction.

Step 1: First we write the skeleton ionic equation, which is


MnO4(aq) + I (aq) MnO2(s) + I2(s)
Step 2: The two half-reactions are:
1

Oxidation half : (aq) 2 ( s)


7

Reduction half : MnO 4 (aq) MnO 2 ( s)


Step 3: To balance the 1 atoms in the oxidation half reaction, we rewrite it as:
2I(aq) I2(s)
Step 4: To balance the atoms in the reduction half reaction. We add two water molecules on the right:
MnO4(aq) MnO2(s) + 2H2O()
To balance the H atoms. we add four H+ ions on the left:
MnO4(aq) + 4H+(aq) MnO2(s) + 2H2O()
As the reaction takes place in a basic solution, therefore, for four H+ ions, we add four OH ions to both
sides of the equation :
+

MnO4(aq) + 4H (aq) + 4OH (aq) MnO2(s) + 2H2O() + 4OH(aq)


Replacing the H+ and OH- ions with water, the resultant equation is:
MnO4(aq) + 2H2O() MnO2(s) + 4OH(aq)
Step 5 : In this step we balance the charges of the two half-reactions in the manner depicted as:

2I(aq) I2(s) + 2e

Page No. # 33

MnO4 (aq) + 2H2O() + 3e MnO2(s) + 4OH (aq)


Now to equalise the number of electrons, we multiply the oxidation half-reaction by 3 and the reduction
half-reaction by 2.
6I(aq) 3I2(s) + 6e
2MnO4(aq) + 4H2O() + 6e 2MnO2(s) + 8OH(aq)
Step 6: Add two half-reactions to obtain net reactions after cancelling electrons on both sides.

6I (aq) + 2MnO4 (aq) + 4H2O() 3I2(s) + 2MnO2(s) +8OH (aq)


Step 7: A final verification shows that equation is balanced in respect of the number of atoms and charges on both
sides.
Ex.

FeSO4 + KMnO4 + H2SO4 Fe2(SO4)3 + MnSO4 + H2O

Sol.
Step 1: Assign the oxidation No. to each elements present in the reaction.
2 6 2

1 7 2

1 6 2

6 2

2 6 2

1 2

Fe S O 4 + K MnO 4 + H 2 S O 4 Fe 2 (S O 4 )3 + Mn S O 4 + H 2 O

Step 2: Now convert the reaction in ionic form by eleminating the elements or species which are not going either
oxidation or reduction
7

Fe2+ + Mn O 4 Fe3+ + Mn2+


Step 3: Now Identify the oxidation / reduction occuring in the reaction

Step 4: Spilt the ionic reaction in two half one for oxidation and other for reduction
oxidation

Fe2+ Fe3+

Re duction
MnO 4

Mn 2

Step 5: Balance the atom other than oxygen and hydrogen atom in both half reactions
Fe2+

Fe3+

MnO4 Mn2+

Fe & Mn atom are balanced in both side.


Step 6: Now balance O & H atom by H2O & H+ respectively by the following way. For one excess oxygen atom
add one H2O on the other side and two H+ on the same side.
Fe2+ Fe3+

(no oxygen atom )

8H+ + MnO4 Mn2+ + 4H2O

.................(i)
................(ii)

Step 7: Now see equation (i) & (ii) is balanced atomwise. Now balance both equations chargewise To balance the
charge add electrons to the electrically positive side .
oxidation
Fe2+
............(1)

Fe3+ + e

duction
Mn2+ + 4H2O ............(2)
5e + 8H+ + MnO4 Re
Step 8: The number of electrons gained and lost in each half -reaction are equalised by multiplying suitable factor
Page No. # 34

in both the half reaction and finaly the half reactions are added to give the over all balanced reaction
Here we multiply equation (1) by 5 and (2) by one
Fe2+ Fe3+ + e

..........(1) 5

5e 8H MnO 4 Mn 2 4H2O

.........( 2) 1

5Fe 2 8H MnO 4 5Fe 3 Mn 2 4H2 O


Here at this stage you will get balanced redox reaction in ionic form

Step 9: Now convert the Ionic reaction into molecular form by adding the elements or species which are removed
in step (2). Now by some manipulation you will get
5

5 FeSO4 + KMnO4 + 4H2SO4


Fe2 (SO4)3 + MnSO4 + 4H2O
or
2
10FeSO4 + 2KMnO4 + 8H2SO4 5Fe2(SO4)3 + 2MnSO4 + 8H2O + K2SO4.
Ex.
Sol.

Balance the redox reaction in basic medium


ClO + CrO2 + OH Cl + CrO42 + H2O
By using up to step V we will get
1

Re duction
Cl O

Cl

Oxidation
Cr O 2

Cr O 24

Now student are advised to follow step VI to balance O and H atom


2H+ + ClO Cl + H2O
| 2H2O+ CrO2 CrO42 + 4H+

Now since we are doing balancing in basic medium therefore add as many as OH on both side of equation
as there are H+ ions in the equation
2OH + 2H+ + ClO Cl + H2O +2OH
4OH + 2H2O + CrO2 CrO42 + 4H+ + 4OH
Finally you will get
Finally you will get

H2O + ClO Cl + 2OH ...........(i)


4OH + CrO2 CrO42 + 2H2O ........... (ii)
Now see equation (i) and (ii) in which O and H atoms are balanced by OH and H2O
Now From step VIII
2e + H2O + ClO Cl + 2OH
............. (i) 3
4OH + CrO2
CrO42 + 2H2O + 3e ............. (ii) 2

Adding : 3ClO + 2CrO2 + 2OH 3Cl + 2CrO42 + H2O

Ex.

Balance the following reactions


(a) FeC2O4 + KMnO4 + H2SO4 Fe2(SO4)3 + CO2 + MnSO4 + K2SO4 + H2O
(b) V [HV6O17]3 + H2
Do tell the students that whenever oxygen or hydrogen is coming out from the redox reaction(in aqueous
medium) then the water is taken as source of these.
(c) As2S3 + HNO3 H3AsO4 + H2SO4 + NO ;
(d) FeS2 + O2 Fe2O3 + SO2

LECTURE # 9

Page No. # 35

Units of concentration measurement, Inter conversion of units.


SOLUTIONS :
A mixture of two or more substances can be a solution. We can also say that a solution is a homogeneous
mixture of two or more substances Homogeneous means uniform throughout. Thus a homogeneous
mixture, i.e., a solution, will have uniform composition throughout.

CONCENTRATION TERMS :
The following concentration terms are used to express the concentration of a solution. These are :
1.
strength of solution
2.
Molarity (M)
3.
Molality (m)
4.
Mole fraction (x)
5.
% calculation
6.
Normality (N)
7.
ppm

Remember that all of these concentration terms are related to one another. By knowing one concentration
term you can also find the other concentration terms. Let us discuss all of them one by one.

1.

STRENGTH OF SOLUTION :
The concentration of solution in gram/litre is said to be strength of solution.

(a)

A 65% solution has the following meanings


65% by weight i.e. 100 gm solution contain 65 gm solute
65% by volume i.e. 100 ml of solution contain 65 ml solute
65% by strength i.e. 100 ml of solution contain 65 gm solute
If, anything is not specified, 65% generally mean 65% by mass

(b)

For concentrated acids, like 98% H2SO4, 65% HNO3 etc, if anything is not specified than percentage by
mass/volume is usually considered.

(c)

For the calculation of strength (% w/w, %w/v etc) the solute must be completely dissolved into the solution,
otherwise, the given terminologies will be invalid. For example, the specific gravity of gold = 19.3 gm/cm3,
if we add 193 gm gol powder in 1 litre of water, its % w/w =

193
x 100 = 16.17 is appears to be
1000 193

correct, but gold is not dissolvable in water, its % w/w in water cannot be calculated.

2.

MOLARITY (M) :
The number of moles of a solute dissolved in 1 L (1000 ml) of the solution is known as the
molarity of the solution.
i.e., Molarity of solution =

number of moles
volume of solution in litre

Let a solution is prepared by dissolving w gm of solute of mol.wt. M in V ml water.

Number of moles of solute dissolved =

V ml water have

1000 ml water have M V


ml

w
M

w
mole of solute
M
w 1000

Page No. # 36

w 1000

Molarity (M) = (Mol. wt of solute) V


ml

Problem 1.7 (NCERT Page - 20)


Calculate the molarity of NaOH in the solution prepared by dissolving its 4 g in enough water to form 250
mL of the solution.
Solution
Since molarity (M)
=

No. of moles of solute


Volume of solution in litr es

4 g / 40 g
0.250L

= 0.4 mol L1

0.1mol
0.250 L

Mass of NaOH/Molar mass of NaOH


0.250 L

= 0.4 M

Note that molarity of a solution depends upon temperature because volume of a solution is temperature
dependent.
Some other relations may also useful.

Number of millimoles

mass of solute
1000 = (Molarity of solution V )
inml
(Mol. wt. of solute)

Molarity is an unit that depends upon temperature .it varies inversely with temperature .
mathematically : molarity decreases as temperature increases.
Molarity

1
1

temperature
volume

Molarity of solution may also given as :


Number of millimole of solute
Total volume of solution in ml

Ex.
Sol.

149 gm of potassium chloride (KCl) is dissolved in 10 Lt of an aqueous solution. Determine the molarity of
the solution (K = 39, Cl = 35.5)
Molecular mass of KCl = 39 + 35.5 = 74.5 gm

149 gm
Moles of KCl = 74 .5 gm = 2

Molarity of the solution =

2
= 0.2 M
10

Q.
Ans.

117 gm NaCl is dissolved in 500 ml aqueous solution. Find the molarity of the solution.
0.4 M

Ex.

Calculate molarity of the following :


(a)
0.74 g of Ca(OH)2 in 5 mL of solution
(b)
3.65 g of HCl in 200 ml of solution
(c)
1/10 mole of H2SO4 in 500 mL of solution

Ex.

[ 2M ]
[0.5M ]
[0.2 M ]

Calculate the molarity of water


H2O 18 gm
= 1 mole
Volume of water = 1 Litre
Page No. # 37

Mass = 1000 gm
mole =

1000
18

Molarity of water =

1000
= 55.55 M
18

Ex.

Find the minimum volume of 0.2 M HCl solution for the complete neutralisation of 0.4 M, 40 ml of NaOH
solution.

Ex.

CaCO3 reacts with aq. HCl to give CaCl2 and CO2 according to reaction
CaCO3(s) + 2HCl(aq) CaCl2 + CO2 + H2O
How much mass of CaCO3 is required to react completly with 100 ml of 0.5 m HCl

Sol.

millimole of HCl
100 0.5 = 50
2 mole of HCl reacts 1 moles CaCO3
1
1 mole of HCl reacts
2
1
50 mmole of HCl reacts
50 = 25 mmole of CaCO3
2
mole of CaCO3 =
mass of CaCO3 =

Ex.

Sol.

25
1000
25
100 = 2.5 gm.
1000

Na2CO3 + 2HCl 2NaCl + CO2 + H2O


(a)
moles of NaCl formed when 10.6 gm of Na2CO3 is mixed with 100 ml of 0.5 M HCl solution.
(b)
Calculate the concentration of each ion in the solution after the reaction
(c)
Volume of CO2 liberated at S.T.P.
molar mass of Na2CO3 = 106 gm
Na2CO3 =

10.6
1000 = 100 m mole
106

HCl = 100 0.5 = 50 milli mole


limiting reagent HCl
2 HCl reacts = 2 NaCl
50 mmole HCl reacts = 50 mmole of Na2CO3
remaining Na2CO3 = 100 25 = 75 mmole
(a)

moles of NaCl =

(c)

volume of CO2
=

50
= 0.05
1000

25
22.4 = 0.556 L
1000

Page No. # 38

[Na+] =

[Cl] =

50 150 200

=2M
100
100
50
= 0.5 M
100

(CO32] =

75
= 0.75 M.
100

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 soulte are present in every 1000000 g of solution.
ppm of A in solution =

mass of A
10 6 = mass fraction 106
Total mass of solution

LECTURE # 10
Dilution, Practice & Mixing of two liquids.
(i)

If a particulars solution having volume V1 and molarity = M1 is diluted to V2 mL then


M1V1 = M2V2
M2 : Resultant molarity

(ii)
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)
MR = Resultant molarity
=

M1V1 M2 V2
V1 V2

Ex.

Calculate the resultant molarity of following :


(a) 200 ml 1M HCl + 300 ml water
(b) 1500 ml 1M HCl + 18.25 g HCl
(c) 200 ml 1M HCl + 100 ml 0.5 M H2SO4
(d) 200 ml 1M HCl + 100 ml 0.5 M HCl

Ex.

Calculate the molarity of H+ ion in the resulting solution when 200 ml 1M HCl is mixed with 200 ml 1M
H2SO4
For
HCl
M1 = 1 M
V1 = 200 mL

Sol.

For

H2SO4
M2 = 1
V2 = 200 mL

nHCl = MHCl VHCl = 1 0.2


Page No. # 39

HCl H+ + Cl

nH = 0.2 (from HCl)


nH2SO 4 MH2SO4 VH2SO4
= 1 0.2 = 0.2 mole
H2SO4 2H+ + SO42

nH = 0.2 2

(from H2SO4)

Total H+ = nH (from HCl) + nH (from H2SO4)


= 0.2 + 0.4 = 0.6
Total volume = 200 + 200 = 400 mL = 0.4 L
MR = Resultant molarity
=

Ex.

nH
Vsolution

0 .6
= 1.5 Ans.
0 .4

What are the final concentration of all the ion when following are mixed
50 ml of 0.12 M Fe(NO3)3 + 100 ml of 0.1 M FeCl3 + 100 ml of 0.26 M Mg(NO3)2

[NO3] =

50 0.12 3 100 0.26 2


250

18 52
70

= 0.28
250
250

[Cl] = 0.12 M
[Mg++] = 0.104 M
[Fe3+] = 0.064 M

MOLALITY (m) :
The number of moles of solute dissolved in1000 gm (1 kg) of a solvent is known as the molality of
the solution.
i.e.,
molality =
number of moles of solute
1000
mass of solvent in gram
Let y gm of a solute is dissolved in x gm of a solvent. The molecular mass of the solute is m. Then Y/m
mole of the solute are dissolved in x gm of the solvent. Hence
Y
1000
Molality =
m x
Ex.
Sol.

225 gm of an aqueous solution contains 5 gm of urea. What is the concentration of the solution in terms of
molality. (Mol. wt. of urea = 60)
Mass of urea = 5 gm
Molecular mass of urea = 60
Number of moles of urea =

5
= 0.083
60

Mass of solvent = (255 5) = 250 gm

Molality of the solution =

Number of moles of solute


0.083
1000 =
1000 = 0.332
Mass of solvent in gram
250

Note : molality is independent of temperature changes.

Page No. # 40

Problem 1.8 (NCERT Page - 21)


The density of 3 M solution of NaCl is 1.25 g mL1. Calculate molality of the solution.
Sol.
M = 3 mol L1
Mass of NaCl in 1 L solution = 3 58.5 = 175.5 g
Mass of 1L solution = 1000 1.25 = 1250 g
(since density = 1.25 mL1)
Mass of water in solution = 1250 175.5
= 1074.5 g

No. of moles of solute


Molaity = Mass of solvent in kg

3 mol
= 1.0745 kg

= 2.79 m

Often in a chemistry laboratory, a solution of a desired concentration is prepared by diluting a solution of


known higher concentration. The solution of higher concentration is also known as stock solution. Note
that molality of a solution does not change with temperature since mass remains unaffected with temperature.
Q.
Ans.

518 gm of an aqueous solution contains 18 gm of glucose (mol.wt. = 180). What is the molality of the
solution.
0.2 m

Q.

Molality of an NaOH solution is 4. Find the wt. of solution if solvent is 500 g.

4.

MOLE FRACTION (x) :

5.

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 solution (x1) =


nN
N

Mole fraction of solvent (x2) =


nN
also
x1 + x2 = 1
Note : mole fraction is a pure number its also independent of temperature changes.

% CALCULATION :
The concentration of a solution may also expressed in terms of percentage in the following way.
(i) % weight by weight (w/w) : It is given as mass of solute present in per 100 gm of solution.
i.e.

mass of solute in gm
% w/w = mass of solution in gm 100

(ii) % weight by volume (w/v) : It is given as mass of solute present in per 100 ml of solution.
i.e.,

% w/v =

mass of solute in gm
100
mass of solution in ml

(iii) % volume by volume (V/V) : It is given as volume of solute present in per 100 ml solution.
i.e.,

% V/V =

Volume of solute in ml
100
Volume of solution

Example
0.5 g of a substance is dissolved in 25 g of a solvent. Calculate the percentage amount of the substance in
the solution.
Solution.
Mass of substance = 0.5 g
Mass of solvent = 25 g

Page No. # 41

percentage of the substance (w/w) =

0 .5
100 = 1.96
0.5 25

Problem 1.6 (NCERT Page - 19)


A solution is prepared by adding 2 g of a substance A to 18 g of water. Calculate the mass per cent of the
solute.
Solution
Mass per cent of A =

Mass of A
100
Mass of solution

2g
2gofA 18gofwater 100

2g
100 = 10 %
20g

Example
20 cm3 of an alcohol is dissolved in80 cm3 of water. Calculate the percentage of alcohol in solution.
Solution
Volume of alcohol = 20 cm3
Volume of water = 80 cm3

percentage of alcohol =

20
100 = 20.
20 80

Interconversion of Concentration units :


Representing solvent and solute in a binary solution by subscripts 1 and 2 respectively, the various
conversion expressions are as follows :
DERIVE THE FOLLOWING CONVERSION :
1.
Sol.

x 2 1000
Mole fraction of solute into molarity of solution M = x M M x
1 1
2 2
Mole fraction into molarity M
mole fraction of solvent and solute are X1 and X2
so X1 + X2 = 1
supposs total mole of solution is = 1
mole of solute and solute and solvent is X2, X1
weight of solute = X2M2 , weight of solvent = X1M1
total wt of solution = X1M1 + X2M2
volume of solution =

volume in L =

X1M1 X 2M2
ml

X1M1 X2M2
1000
X2 1000

molarity (M) = X M X M
1 1
2 2

MM1

2.

Molarity into mole fraction x2 = MM 1000 MM


1
2

Sol.

Molarity into mole fraction


molarity (M) = moles solute in 1000 ml of solution
so moles of solution = M
mass of solution = x 1000

Page No. # 42

wt. of solute = MM2


wt. of solvent = 1000 MM2
moles of solvent =

1000 MM2
M1
MM1

Hence x2 = MM 1000 MM
1
2

x 2 1000
x1M1

3.

Mole fraction into molality m =

Sol.

Mole fraction into molarity


mole fraction of solute X2 and solvent X1
mole is n2 & n1

n2
molality = n M x 1000
1 1
x2
= x M x 1000
1 1
4.
Sol.

n2 x 2

x1
n1

mM1
Molality into mole fraction x2 = 1000 mM
1
Moalrity into mole fraction
molality = moles of solute in 1000 gm of solute = m

1000
mole of solvent = M
1
mM
m
mole fraction X2 = 1000
= 1000 mM
1
m
M1
5.
Sol.

m 1000
Molality into molarity M = 1000 mM
2
Molality in molarity
molality = moles of solute in 1000 gm of solvent
mole of solute = m
wt. of solute = mM2
wt. of solution = 1000 + mM2
volume of solution =
volume in (L) =

1000 mM2

1000 mM2
1000

Page No. # 43

m 1000
molarity = 1000 mM
2
6.

Sol.

M 1000
Molarity into Molality m = 1000 MM
2
M1 and M2 are molar masses of solvent and solute. is density of solution (gm/mL)
M = Molarity (mole/lit.), m = Molality (mole/kg), x1 = Mole fraction of solvent, x2 = Mole fraction of solute
Molarity (M) into molality (m)
molarity = mole of solute in 1000 ml of solution
moles of solute = M
wt. of solute = MM2
wt. of solution = 1000
mass of solvent = 1000 MM2
molality =

moles of solute
wt of solvent x 1000

M 1000
m = 1000 MM
2

LECTURE # 11
HARDNESS OF WATER :
Hard water does not give lather with soap.
A water is said to be soft water if it gives enough lather with the soap .
The water sample is said to be hard if it forms a insoluble scum and gives very little lather with soap.
Generally , all salts ( except the salts of alkali metals Viz Na,K, Li etc) containing Mg2+, Ca2+,Al3+ etc
makes water hard.
Hardness can be grouped primarily under two heads:
I) Temporary hardness
II) Permanent Hardness
I) Temporary Hardness : It is due to presence of bicarbonates of calcium and magnesium.
It is easily removed by boiling which decomposes bicarbonates readily and the insoluble
carbonates settle down.So its named as temporary hardness.
II) Permanent hardness : It is due to chlorides or sulphates of Ca , Mg, Al, Fe etc.
Its permanent hardness because this cannot be removed just by boiling the sample. Although special
methods can be employed to remove the hardness .
There are some method by which we can Softening the water
(a)
by boiling
:
2HCO3 H2O + CO2 + CO32
or, Ca(HCO3)2 CaCO3 + H2O + CO2
(b)

by slaked lime

Ca(HCO3)2 + Ca(OH)2 2CaCO3 + 2H2O

(c)

By Washing Soda

CaCl2 + Na2CO3 CaCO3 + 2NaCl

(d)

By ion exchange resins :

(e)

By adding chelating agents like (PO3)3 etc.

Na2R + Ca2+ CaR + 2Na+

(R = resin)

Page No. # 44

Degree of hardness :
The degree of hardness of water is defined as the number of parts of calcium carbonate or equivalent to
various calcium and magnesium salts present in a million parts of water. ( ppm in terms of CaCO3)
A sample labeled as Hardness 180 ppm in terms of MgSO4 .
It means that the sample contains 180 g of MgSO4 in a 106 g of given water sample.
If this is expressed in terms of CaCO3 ( which is the normal practice ) , we can convert it as follows,
Equiv.mass of CaCO3 = 100/2 = 50
Equiv.mass of MgSO4 = 120/2 = 60
50 g of CaCO3 = 60 g of MgSO4
if any sample that contain 150 ppm of MgSO4 ,then in terms of CaCO3 ,
degree of hardness = 50/60 X180 = 150 ppm
So hardness of water is expressed in terms of ppm of CaCO3 although hard water does not contain CaCO3
.
So we can say that
1 mole CaCl2 1 mole CaCO3
1 mole MgCl2 1 mole CaCO3
1 mole CaSO4 1 mole CaCO3

1 mole MgSO4 1 mole CaCO3

mass of CaCO3

Hardness in ppm =
Ex.
Sol.

Total mass of water

10 6

0.00012% MgSO4 and 0.000111% CaCl2 is present in water. What is the measured hardness of water
and millimoles of washing soda requires to purify water 1000 lt water.
Basis of calculation = 100 g hard water
0.00012
Mole
120

MgSO4 = 0.00012g =
CaCl2 = 0.000111g =

0.000111
mole
111
0.00012

equivalent moles of CaCO3 = 120

0.000111
mole
111

0.00012 0.000111

100 = 2 104 g
111
120

mass of CaCO3 =

2 10 4
10 6 = 2 ppm
100

Hardness (in terms of ppm of CaCO3) =


CaCl2 + Na2CO3 CaCO3 + 2NaCl

NaSO4 + Na2CO3 MgCO3 + Na2SO4


Required Na2CO3 for 100g of water =

0.00012 0.000111

mole
120
111

= 2 106 mole
Required NaCO3 for 1000 litre water =

2 10 6
2
10 6
mole
100
100

=
Ex.

( d = 1g/ml)

20
mole = 20 m mole
1000

Calculate the weight of CaO required to remove the hardness of 1m3 of water containing 1.62 g of calcium
bicarbonate per liter.

Page No. # 45

162

56

Sol.

CaO

Ca(HCO3 )2 CaCO + H O
3
2

56
1.62 10 3 g
162

1.62 103g

= 560 g.

Ex.

A sample of hard water contains 96 ppm of SO42 and 183 ppm of HCO3 with Ca2+ as the only cation. How
many mole of CaO will be required to remove HCO3 from 1000 kg of this water ? If 1000 kg of this water
is treated with the amount of CaO calculated above, what will be the concentration ( in ppm ) of residual
Ca2+ ions (Assume CaCO3 to be completely insoluble in water) ? If the Ca2+ ions in one litre of the treated
water are completely exchanged with hydrogen ions, what will be its pH.

Sol.

2
Sample of hard water contains 96 ppm SO42 and 40 ppm Ca as CaSO4. Also it contains 183 ppm HCO3

and 60 ppm Ca2+ as Ca(HCO3)2.


To remove Ca(HCO3)2 from 103 kg or 106 g sample of hard water which contains 243 g Ca(HCO3)2 or
3/2 mole of Ca(HCO3)2, CaO required is 3/2 mole.
Ca(HCO3)2 + CaO 2CaCO2 + H2O
Thus, mole of CaO required = 3/2 or 1.5
Also Ca2+ ions left in solution are of CaSO4 i.e., 40 ppm
Now 1 litre water contains Ca2+ after removal of Ca(HCO3)2 =

40 10 3
10 6

40 10 3 g

40 10 3
10 3
40
If these Ca2+ are exchanged with H+ then [H+] in solution = 2 103
or

[Ca 2 ]

STRENGTH OF OLEUM :
Oleum is SO3 dissolved in 100% H2SO4. Sometimes, oleum is reported as more than 100% by weight, say
y% (where y > 100). This means that (y 100) grams of water, when added to 100 g of given oleum
sample, will combine with all the free SO3 in the oleum to give 100% sulphuric acid.
80

SO3

80
(y 100)
18

18

H2 O

H2SO4

(y 100)

Hence weight % of free SO3 in oleum = 80(y 100)/18


It means if an oleum is labelled as 109% it means 100 g oleum (SO3 + H2SO4) when dissolved in
(109 100) = 9g of H2O will produce 109 g pure H2SO4.
Ex.

An oleum sample is labeled as 118%. Calculate % of free SO3

Sol.

% of free SO3 =

80
18 = 80%.
18

HYDROGEN PEROXIDE (H 2O 2 ) :

H2O2 can behave both like oxidising and reducing agents in both the medium (acidic and basic).

1.

Oxidising agent : (H 2 O 2 H 2O)


(a) Acidic medium :
2e + 2H+ + H2O2 2H2O
(b) Basic medium :
2e + H2O2 2OH

Page No. # 46

2.

Reducing agent : (H 2 O 2 O 2 )
(a) Acidic medium :
H2O2 O2 + 2H+ + 2e
(b) Basic medium :
2OH + H2O2 O2 + 2H2O + 2e

Volume strength of H2O2 : Volume strength of H2O2 is represented as 10V , 20 V , 30 V etc.

20V H2O2 means one litre of this sample of H2O2 on decomposition gives 20 litre of O2 gas at S.T.P.
Decomposition of H2O2 is given as
H2O2 H2O +
1 mole
= 34g

1
O
2 2

1
22.4 lt O2 at S.T.P
2
= 11.2 lt O2 at S.T.P.
To obtain 11.2 litre O2 at S.T.P. at least 34 gm H2O2 must be decomposed.
34
for 20 lt O2 , we should decompose atleast
20 gm H2O2
11.2
1 lt solution of H2O2 contains

34
20 gm H2O2
11.2

Strength (in g/) :


Strength = molarity mol.wt.= molarity 34

SIGNIFICANT FIGURES
The uncertainty in the experimental or the calculated values is indicated by mentioning the number of
significant figures. Significant figures are meaningful digits which are known with certainty. The
uncertainty is indicated by writing the certain digits and the last uncertain digit. Thus, if we write a
result as 11.2 mL, we say the 11 is certain and 2 is uncertain and the uncertainty would be 1 in the
last digit. Unless otherwise stated, an uncertainty of 1 in the last digit is always understood.
There are certain rules for determining the number of significant figures. These are stated below :

(1)

All non-zero digits are significant. For example in 285 cm, there are three significant figures and in
0.25 mL, there are two significant figures.

(2)

Zeros preceding to first non-zero digit are not significant. Such zero indicates the position of decimal
point.
Thus, 0.03 has one significant figure and 0.0052 has two significant figures.

(3)

Zeros between two non-zero digits are significant. Thus, 2.005 has four significant figures.

(4)

Zeros at the end or right of a number are significant provided they are on the right side of the decimal
point. For example, 0.200 g has three significant figures.
But, if otherwise, the terminal zeros are not significant if there is no decimal point. For example, 100
has only one significant figure, but 100. has three significant figures and 100.0 has four significant
figures. Such number are better represented in scientific notation. We can express the number 100
as 1 102 for one significant figures and 1.00 102 for three significant figures.

(5)

Counting numbers of objects, for example, 2 balls or 20 eggs, have infinite significant figures as
these are exact numbers and can be represented by writing infinite number of zeros after placing a
decimal i.e. 2 = 2.000000 or 20 = 20.000000
In numbers written in scientific notation, all digits are significant e.g., 4.01 102 has three significant
figures, and 8.256 103 has four significant figures.

Page No. # 47

ADDITION AND SUBTRACTION OF SIGNIFICANT FIGURES


The result cannot have more digits to the right of the decimal point than either of the original numbers.
12.11
18.0
1.012
31.122
Here, 18.0 has only one digit after the decimal point and the result should be reported one upto one
digit after the decimal point which is 31.1.

MULTIPLICATION AND DIVISION OF SIGNIFICANT FIGURES


In these operations, the result must be reported with no more significant figures as are there in the
measurement with the few significant figures.
2.5 1.25 = 3.125
Since 2.5 has two significant figures, the result should not have more than two significant figures,
thus, it is 3.1.
While limiting the reuslt to the required number of significant figures as done in the above mathematical
operation, one has to keep in mind the following points for rounding off the numbers.

1.

If the rightmost digit to be removed is more than 5, the preceding number is increased by one, for
example, 1.386 if we have to remove 6, we have to round it to 1.39.

2.

If the rightmost digit to be removed is less than 5, the preceding number is not changed. For example,
4.334 if 4 is to be removed, then the reuslt is rounded upto 4.33.

3.

If the rightmost digit to be removed is 5, then the prceding number is not changed if it is an even
number but it is increased by one if it is an odd number. For example, if 6.35 is to be rounded by
removing 5, we have to increase 3 to 4 giving 6.4 as the result. However, if 6.25 is to be rounded off it
is rounded of to 6.2.

NCERT PROBLEMS
How many significant figures are present in the following ?
(i) 0.0025
(ii) 208
(iii) 5005
(iv) 126,000
(i) 2
(ii) 3
(iii) 4
(iv) 3

1.
Ans.
2.

(v) 500.0
(v) 4

(vi) 2.0034
(vi) 5

Ans.

Round up the following upto three significant figures :


(i) 34.216
(ii) 10.4107
(iii) 0.04597
(iv) 2808
(i) 34.2
(ii) 10.4
(iii) 0.0460
(iv) 2810

3.

How many significant figures should be present in the answer of the following calculations ?
(i)

0.02856 298 .15 0.112


0.5785

(ii) 5 5.364

Ans.

(i) 3

EXAMPLES
Find significant figures in the following observations (i) 0.007 gm
(ii) 2.64 x 1024 kg
(iii) 0.2370 gm/cm3
(v) 6.032 N/m2
(vi) 0.0006032 K1
(i) 1 (ii) 3 (iii) 4 (iv) 4 (v) 4 (vi) 4.

(iv) 6.320 J/K

Round off the following numbers within three significant figures (i) 0.03927 kg
(ii) 4.085 x 108 sec
(iii) 5.2354 m
(i) 0.0393 kg (ii) 4.08 x 108 sec (iii) 5.24 m (iv) 4.74 x 106 kg

(iv) 4.735 x 106 kg

The mass of a ball is 1.76 kg. The mass of 25 such balls is


(A) 0.44 103 kg
(B) 44.0 kg
(C) 44 kg
(B) 44.0 kg.

(D) 44.00 kg

1.

Ans.
2.
Ans.
3.
Ans.

(ii) 4

Page No. # 48


1.

QUESTIONS FROM COMPETITIVE EXAMS


The edge of a cube is a = 1.2 102 m. Then its volume will be recorded as : [JEE 2003 (Scr.), 3/84,1]
(A) 1.72 106 m3

Ans.
Sol.

2.

(B) 1.728 106 m3

(C) 1.7 106 m3


(D) 1.73 106 m3
(C)
V = 3 = (1.2 102 m)3 = 1.728 106 m3
length () has two significant figure, the volume (V) will also have two significance figures. Therefore, the
correct answer is V = 1.7 10-6 m3.

Ans.

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 :
[JEE -2010]
3

Sol.

Average titre value =

25 .2 25.25 25.0
75.45
=
= 25.15 = 25.2 mL
3
3

number of significant figures will be 3.


3.

Ans.
Sol.

The respective number of significant figures for the numbers 23.023, 0.0003 and 2.1 103 are
[AIEEE-2010, 4/144, 1]
(A) 5, 1, 2
(B) 5, 1, 5
(C) 5, 5, 2
(D) 4, 4, 2
(A)
Rule : I. We know all non zero digits are significant.
Rule : II. If zero is between two non-zero digits this is also significant.
Rule : III. If zero left to the non-zero digit they are non-significant.
Significant figures for number 23.023 is 5. Using I & II.
Significant figures for number 0.0003 is 1. Using I, II & III.
Significant figures for number 2.1 103 is 2. Using I.

MOLE CONCEPT : BIBLIOGRAPHY


1.

Mole concept for IIT-JEE (Includes Equivalent Concept and Titration) : Shishir Mittal.
(TMH-2011 Edition)

2.

Text Book of Physical Chemistry (Includes complete General Chemistry) : Shishir Mittal.
(Disha Publication, 6th Edition)

3.

Chemistry Principles and Applications : Sienko & Plane.

4.

Schaums Series : 3000 problems in Chemistry.

Page No. # 49