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in

OXIDATION AND REDUCTION

Let us begin with the chapter (A) Oxidation Reduction and use of mole concept.
In this chapter we intend to cover the following subtitles:
I. Concepts of oxidation and reduction and calculation of oxidation number
II. Balancing of ionic equations dealing with redox reactions and use of mole
concept in solving problems.
III. Solution of some typical problems based on H2O2 free SO3 in oleum, available Cl2
from bleaching powder, hardness of water, iodometric titrations etc.

Let us start to do a detailed study of

A. Concepts of oxidation reduction and calculation of oxidation number.
1. Classical Concepts:

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Before the development of electronic view of reactions, oxidation was defined as:
A reaction which leads to the addition of oxygen or electronegative element to a
ee
substance or removal of hydrogen or electropositive element from a substance.
For example:
2Mg(s) + O ( ) 2MgO(s)
itj
S(s)+ O ( ) SO ( )
CH ( ) + 2O ( ) CO ( ) + 2H2O(l)
ki

2H2S(g) + O ( ) 2S(s)+ 2H2O(l)

ac

Mg(s) + F ( ) MgF ( )
2K4[Fe(CN)6] +H2O2 2K3 [Fe(CN)6](aq.) + 2KOH(aq.)
cr

A close study of the above reactions reveals that in first two reactions, oxygen is
being added. In the next two reactions addition of oxygen as well as removal of
hydrogen is taking place. In the last but one reaction an electronegative element
fluorine is being added, while in the last reaction an electropositive element
potassium is removed from K4Fe(CN)6 [potassium ferrocyanide] when it is
converted into K3Fe(CN)6 [potassium ferricyanide].
Similarly reduction was defined as:
A reaction which leads to the removal of oxygen or electronegative element
from a substance, or addition of hydrogen or electropositive element to a
substance.
For example:
2HgO(s) 2H ( ) + O ()

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2FeCl ( .) + H ( ) 2FeCl ( .) + 2HCl( .)

CH2= CH ( ) + H ( )
CH3- CH ( )

Let us now examine the following chemical reaction with the help of concepts of
oxidation and reduction which we have just gone through.
2HgCl ( .) + SnCl ( .) Hg2Cl ( ) + SnCl ( .)
(mercuric chloride) (stannous chloride) (mercurous chloride (stannic chloride)
or calomel)
We find that conversion of SnCl2 into SnCl4 leads to the addition of
electronegative element chlorine to SnCl2. Hence SnCl2 is oxidized to SnCl4.
Simultaneously conversion of HgCl2 into Hg2Cl2 leads to the addition of
electropositive element mercury to HgCl2. Hence HgCl2 is reducing to HgCl2. It
means oxidation and reduction always occur simultaneously in all oxidation
reduction reactions. Hence a new word REDOX was coined for this class of
chemical reactions.

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2. Modern Concepts for Redox reactions
i. Redox reactions in terms of election transfer reactions (electronic concept)
ee
Let us examine the following reaction
2Na(s) + Cl ( ) 2Na+Cl-(s) Sodium chloride (ionic compd.)
Here we see that two Na atoms are converted into two Na+ with the loss
itj
of two electrons i.e. one electron per atom as is clear from their electronic
ki

configurations
Na (atom) Na (ion)

ac

(ls , 2s p , 3s ) e (ls , 2s p )
On the other hand these two electrons are taken up by two chlorine atoms
to form two chloride ions i.e. each Cl atom gains a electron which is clear
cr

from their electronic configurations.

Cl (atom) Cl (ion)

(ls , 2s p , 3s p ) e (ls , 2s p , 3s p )
Now in the light of classical concept, we will say that sodium is being
oxidized because it is gaining an electronegative element chlorine but in
this conclude that oxidation must accompany loss of electron/s and
similarly reduction (Cl Cl) must accompany gain of electron/s.
In other words a redox reaction must involve two half reactions, one
involving loss of electrons called oxidation and the other involving gain of
electrons called reduction.
To summarize, we may mention that
Oxidation: means loss of electron(s) by any species
Reduction: means gain of electron(s) by any species
Oxidizing agent: means which oxidizes others but itself is reduced, hence

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it is acceptor of electron(s)
Reducing agent: means which reduces others but itself is oxidized, hence
it is donor of electron(s)
Let us understand a redox reaction with the help of following experiment.
Take a beaker containing some Cu(NO3)2 aqueous solution into it. The
color of the solution is blue due hydrated Cu2+ ions. Now place a Zn rod in
it. Wait for some time. What do you observe? Look in the reddish
deposition of metallic copper on the zinc rod. The overall reaction can be
represented by the following ionic equation.
Zn(s) + Cu2+(aq.) (Blue) Zn2+(aq.)(Colorless) + Cu(s)(reddish)
This is obviously a redox reaction which can be further represented by
following two half reactions
Zn(s) Zn2+(aq.) +2 (oxidation)
Cu2+(aq.)+2 Cu(s) (reduction)
Therefore, in this reaction Zn is behaving as reducing agent and Cu 2+ as

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oxidizing agent.
ii. Concept of oxidation numbers ee
Another method to deal with redox reactions is with the help of oxidation
number or oxidation state of the species involved.
Oxidation number (also called oxidation state) of an element is defined as
itj
the charge calculated per atom with the help of a set of rules. These rules
are formulated on the basis that in a covalent bond, the shared electrons
ki

belong to more electronegative element. Oxidation number may be zero,

(+) ve or (-) ve integer or even a fraction (usually when it is average)
ac

RULES FOR CALCULATION OF OXIDATION NUMBERS

cr

i. O. No. of an element is zero in its free or uncombined state. Thus each

atom in H2, O2, Cl2, O3, P4, S8, Na, Mg, Al, etc. has the oxidation number
equal to zero.
ii. For ions composed of only one atom i.e. elemental ions, the oxidation
number is equal to the change on the ion. Thus O. No. of sodium in Na+ is
+1, for Mg2+ it is +2, for Fe3+ it is +3, for Cl it is -1, for O2-is -2 & so con
iii. Oxidation numbers of alkali metals and alkaline earth metals in all their
compounds are +1 and +2 respectively.
iv. Oxidation number of fluorine (F) in all its compounds is -1.
v. Oxidation number of oxygen is -2 except the following cases:
-1 in peroxides (e.g. H2O2)
-1/2 in superoxides (e.g. KO2)
+2 in OF2 (oxygen difluoride)
+1 in O2F2 (dioxygen difluoride)

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vi. Oxidation number of hydrogen (H) is +1 except in metallic hydrides (e.g.

LiH, NaH, LiAlH4 etc.) where it is -1.
vii. Oxidation number of a metal in pure metal carbonyl (e.g. Ni(CO) 4) is zero.
viii. The algebraic sum of the oxidation numbers of all the atoms in a molecule
must be zero, for example
+1 +7 -8 = 0
KMnO4 (potassium per magnate)
However in case of polyatomic ion this algebraic sum must be equal to the
charge can the ion, for example for
C+4 O = -2
Carbonate ion
Thus oxidation number of carbon in carbonate ion is equal to +4.
ix. Oxidation numbers of metals are usually positive but it can be negative
too, for example

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K [Fe[-2+0 = -2](CO)4]
Thus oxidation number of iron in the complex K2[Fe(CO)4] is equal to -2.
x. Except for the elements covered in the above rules, for all elements
ee
belonging to p block of the periodic table (from Boron family to
Halogens) the possible oxidation numbers for an element can be from +n
to n-8 where n means the group number. Since sulphur (S) belongs to VI th
itj
group of the periodic table hence it can have oxidation numbers from -2 to
ki

+6. Of course in the new pattern of numbering of groups in the periodic

table S belongs to 16th vertical column (group). In this pattern highest
ac

oxidation number will be given by column number minus 10.

xi. Maximum variations in oxidation numbers are found in case of transition
(d-block) elements for example for Mn (atomic number 25) the various
cr

oxidation states can be

+2 in MnO +3 in K3 [Mn(CN)6)]
+4 in MnO2
+6 in K2MnO4
+7 in KMnO4 etc.
xii. If a molecule or ion has more than one atom of an element in it, then the
oxidation number of that element calculated with the help of above rules
is average oxidation number for example average oxidation number of
carbon in carbon sub oxide (C3O2) is +4/3. It means all the carbon atoms
must not be in the same oxidant state in this molecule. Such problems can
be solved with the help of structure of molecule or ion involved. In such a
case oxidation number of an individual atom can be calculated using the
following formula:

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O. No. of an atom = number of electrons in its valence shell number of

electrons left after bonding (assigning electrons to more negative atom)
The structure of C3O2 is

Oxidation number of each oxygen atom = 6-8 = -2

O. No. for C = 4-2 = +2
C = 4-4 = 0
C = 4-2 = +2
xiii. Sometimes oxidation number or state is represented by Stock notation
in which oxidation number is expressed by putting a Roman numeral in
parenthesis after the symbol of the metal in the molecular formula, for
example
Oxidation number of gold in AuCl3 is +3, hence it can be written as
Au(III)Cl3. Similarly SnCl4 can be written as Sn(IV)Cl4 and so con.

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After studying all the above rules now we are in a position to define
the following terms in terms of oxidation number.
OXIDATION: means an increase in the oxidation number of the element in the given
ee
substance.
Thus if in a reaction K2MnO4 is converted into K2MnO4, we see that oxidation number of
itj
Mn increases from +6 to +7. Hence it becomes a case of oxidation.
REDUCTION: means decrease in the oxidation number of the element in the given
ki

MnO MnO
substance for example
+7 +4
ac

OXIDIZING AGENT OR OXIDANT: means a reagent which can increase the oxidation
number of an element in a given substance. For example in acid medium KMnO 4
cr

oxidizes Fe2+ into Fe3+.

REDUCING AGENT OR REDUCTANT: means a reagent which lowers the oxidation
number of an element in a given substance.

Now before we solve some numerical regarding calculation of oxidation numbers, it is

worth to note the following two important types of redox reactions:
a) Disproportionation reactions: In such reaction an element in one oxidation state
is simultaneously oxidized and reduced. For example in alkaline medium P 4 is
converted into PH3 (phosphine) and H2PO (hypophosphite ion)
o 3 +1
+ 3OH( .) + 3H2O(l) + 3[H2 ]
P () PH ( ) PO ( .)
We see that Phosphorous from zero oxidation state has gone up into +1 in
H2PO and down to -3 in PH3

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b) Comproportionation
It is reverse of disproportionation In such a reaction two species with the
same element in different oxidation states form a product in which the
element is in an intermediate oxidation state. For example
Ag ( .) + Ag ( ) 2Ag ( .)

USE OF MOLE CONCEPT

Now we shall learn, how to use mole concept for solving problems related to redox
reactions or titrations. But before we do so let us revise the following elementary

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ideas related to MOLE.
ee
In SI system, mole (symbol, mol) was introduced as seventh base quantity for
the amount of a substance.
itj
One mole is the amount of a substance that contains as many particles or
entities as there are atoms in exactly 12g of the C 12 isotope. Since the mass of a C12
ki

atom as determined by a mass spectrometer comes out to be 1.992648 x 10 -23g.

12
ac

Hence the number of atoms in 12g of C12 isotope will be equal to =

1.992648 x10 23
6.0221367 x 1023 atoms
cr

This figure which is usually used as 6.022 x 10 23 is called Avogadros Number It

means 1 mole of substance will have 6.022 x 1023 molecules (or atoms if the
substance is in atomic state) in it.

Thus number of moles for any mass of a substance can be calculated using the
formula

mass of the substance in grams

moles =
its moles mass (or usually known as molecular weight)

However if the substance is in the atomic state then molar mass means atomic mars
(atomic weight) and if in the form of ion then molar mars means molar mars of the
ion.

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Therefore:
88
88g of CO2(g) means = 2 mole CO2
44
58.5
58.5g of NaCl means = 1 mole NaCl
58.5
[Atomic mass Na = 23, Cl = 35.5]
238
238g of MnO 4 means = 2 mole MnO 4
119
[Atomic mass: Mn = 55, O=16] and so on.

At the same time we must not forget that 1 mole of a gas occupies 22.4L volume at

.in
273 K temp. and 1 atm. pressure (NTP)

With this much knowledge, we are in a position to apply mole concept to any
ee
chemical reaction provided we have a balanced chemical equation representing that
reaction.
itj
Consider a reaction:
ki

m1A + m2B n1C + n2D (balanced equation)

ac

what is the significance of writing a balanced equation?

The answer is that it tells us for example for the above equation (or
cr

reaction) that m1 moles of A combine with m2 moles of B to produce n1

moles of C and n2 moles of D. the same thing can be written mathematically
as:

number of moles of ' A' m

= 1 and so on.
number of moles of ' B' m2

This is the mole concept. Thus with its help if we know the number of moles of one
substance we can calculate the number of moles of the other substance needed to
react with it or to be produced when reaction is complete.

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The following numerical illustrations will make the use of mole concept further clear.

1. A solution containing 2.68 x 10-3 moles of An+ ions require 1.61 x 10-3 moles
of MnO 4 for oxidation of An+ into AO 3 in acid medium. Calculate the value of
n.

Solution As is clear from the text of the question that here MnO 4 is oxidizing agent
oxidizing A n+ into AO 3 . Further we have already learnt that in acid medium MnO 4
is reduced into Mn2+. Hence we can write the following two half equations, balance
them and add to get the net balanced equation for the complete reaction.

5 e + 8H++ MnO 4 Mn2+ + 4H2O ------- (1)

3H2O + An+ AO 3 + 6H+ + (5-n) e ----- (2)

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Multiply equation (1) by (5-n) and (2) by 5 and add them so as to cancel out the
electrons. Thus we get
ee
[8(5-n)-30]H+ + (5-n) MnO 4 + 5An+ (5-n) Mn2+ + 5AO 3 + [4(5-n)-15] H2O.
itj

Now applying mole concept on this balanced equation we can write

ki

number of moles of A n 5
ac

=
number of moles of MnO 4 (5 - n)
cr

Substituting the values of number of moles as given in the question we have

2.68 x 10 -3 5
=
1.61 x 10 -3
(5 - n)

This on solving gives n = 1.996. since n is balance charge on the ion.

Hence n =2 or +2 Ans.

NOTE: Just to save the time, there is no need to write the entire balanced equation,
pick up the molar coefficients of the species for which we want to apply mole
concept.

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2. In an experiment 40mL of 0.1M solution of a metallic salt reacted completely

with 20mL of 0.1M Na2SO3 to oxidize it into Na2SO4 in acid medium. If the
oxidation state of the metal in the salt was +3, what is the oxidation number
of metal after the reaction is over?

Solution: The half reactions and hence their equations are, assuming that metal (m)
is reduced from +3 to + state.

H2O + SO 2 + 2H+ + 2 e x (3- )

4

(3- ) e + M3+ M+ x 2

Using mole concept we can write

.in
no. of moles or mmoles of M 3 2
=
no. of moles or mmoles of SO 2 - (3 - x)
3 ee
Since from the question we have
itj
No. of m.moles of M3+ = 0.1 x 40 = 4
and No. of m.moles of SO 2 = 0.1 x 20 = 2
ki

3
ac

4 2
We have = solving this we get =2 or +2
2 (3 - x)
cr

Hence the new oxidation state of the metal(M) is +2 Ans.

Calculation of equivalent weight of oxidizing and reducing agents.

Before the development of mole concept, calculations were based on the

concept of equivalence which required a knowledge of equivalent weight of an
oxidant or reluctant. But since the equivalent weight of a substance may change
from reaction to reaction depending upon the conditions, hence use the concept of
equivalence has been abandoned by IUPAC. However some times of needed we can
use the following:

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Equivalent weight of an oxidizing agent/reducing agent =

molecular weight or ion formula weight
valence factor

Where valence factor means the number of electrons lost or gained per molecule or
ion in the balanced half equation for reducing or oxidizing agent respectively.
Further do not forget for any solution of an oxidizing or reducing agent that
Normality = molarity x uf
no. of equivalents = no. of moles x uf

Let us consider the following examples

1. Calculate equivalent weight of MnO - 1 in acid medium.

4
[given atomic mass: Mn = 55, O = 16]

.in
Solution: Since the balanced half equation for the conversion of MnO 4 into Mn2+ in
acid medium is: ee
5 e + 8H++ MnO 4 Mn2+ + 4H2O
itj
Hence valence factor for MnO 4 becomes 5
55 64 119
ki

Equivalent weight of MnO 4 = = = 23.8

5 5
ac

However if we wish to calculate equivalent weight for the molecular form K MnO 4 ,
then since K is not involved in oxidation or reduction, hence it becomes a spectator
cr

ion (Atomic mass = 39)

Equivalent weight of K MnO 4 in acid medium

39 55 64 158
as on oxidizing agent = = = 31.6
5 5

2. Calculate equivalent weight of K2Cr2O7 in the reaction in acid medium where

Cr2O72- is reduced to Cr3+. [Atomic mass: Cr = 52, O = 16, K = 39]

Solution 6 e + 14H+ + Cr2O72- 2Cr3+ + 7H2O

39 x 2 52 x 2 16 x 7
Equivalent weight of K2Cr2O7 = 6
= 49 Ans.

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3. Calculate equivalent weight of H2O2 in acid medium behaving as

(i) Oxidizing agent (ii) reducing agent
[Atomic mass: O = 16, H = 1]

Solution: (i) H2O2 as oxidizing agent is reduced into H2O

2 e + 2H+ + H2O2 2 H2O

2 16 x 2
Hence equivalent weight of H2O2 = 2
= 17 Ans.

(ii) H2O2 as reducing agent is oxidized into O2

H2O2 O2 + 2H+ + 2 e

.in
2 16 x 2
Equivalent weight = 2
= 17 Ans. ee
Part (iii) Here we wish to study some typical calculations involving compounds like
H2O2, hypo, bleaching powder etc. involved in some redox reactions.
itj

Let us begin with H2O2

ki

H2O2
ac

Hydrogen peroxide can behave as oxidizing as well as reducing agent. A very

cr

important thing about its aqueous solution is the style of expressing its
concentration which is known as volume strength of H2O2 solution

For example a 20 volume solution of H2O2 means1 litre of such a solution will
liberate 20L of O2(g) at NTP according to the following reaction:

2 H2O2 2H2O + O2.

If its a V volume solution of H2O2 then

68 x V
(i) its concentration in g/L = 22.4
68 x V V
(ii) Molarity = 22.4 x 34 = 11.2

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1. 25mL of H2O2 solution were added to excess of acidified solution of KI. The I 2
so liberated required 20mL of 0.1M Na2S2O3 solution for titration. Calculate
the volume strength of H2O2. Also write the reactions involved.

Solution Reactions:

2 e + 2H+ + H2O2 2 H2O

2 I I2 + 2 e
______________________________________
2H+ + 2 I + H2O2 I2 + 2 H2O

1 m mole

2 2
I2 + 2S2O 3 S4O 6 + 2I

.in
20mL
0.1M ee
m moles = 2

Hence I2 reacted must be one m mole

itj
H2O2 consumed must also be 1 m mole.
ki

m mole 1
ac

molerity of H2O2 solution = mL

= 25
= 0.04M
for H2O2,
cr

' V'
molarity = 11.2 where V is volume strength
V
0.04 = 11.2

V= 0.04 x 11.2 = 0.448 Ans.

Calculation of available Cl2 from Bleaching Powder

When a sample of bleaching powder reacts with dilute acid or CO 2, it liberate

Cl2 that is known as available Cl2. For example

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CaOCl2 + 2HCl CaCl2 + H2O + Cl2

CaOCl2 + CO2 CaCO3 + Cl2

CaOCl2 or Ca(OCl)Cl is taken to be an accepted formula of bleaching powder.

According to this formula (molecular weight = 127) the % of available Cl 2 must be
about 56 but even a very good sample does not give more than 38% Cl 2 Hence it is
necessary to estimate the available Cl2 from a sample of bleaching powder to check
its purity.

For this purpose a weighed sample (say Wg) of bleaching powder is

suspended in water, to that CH3COOH and excess KI is added. The Cl2 liberated
reacts with KI to liberate I2 which is then subjected to iodometric titration using
starch indicator.

.in
The chemical reactions involved are ee
CaOCl2 + 2CH3COH Ca(CH3COO)2 + Cl2 + H2O

Cl2 + 2KI 2KCl + I2

itj

2 2
ki

I2 + 2S2O 3 (Hypo) S4O 6 + 2I (iodometric titration)

ac

Calculation

Let the molarity of hypo solution used is , and its volume used in titration be V
cr

mL.
XxV
moles of Hypo consumed = 1000

XV
Then according to mole concept moles of I2 must be half of this i.e. 2000 and these
XV x 71
must be equal to moles of Cl2 Hence mass of Cl2 liberated = g
2000

XV71
W(g) bleaching powder gives Cl2 = 2000 g

X x V x 71 X x V x 3.55
% of Cl2 = 2000 x W x 100 = W
.

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We can directly apply this formula provided such data are given as is clear from the
following numerical illustration.

1. 1g sample of bleaching powder suspended in water was treated with enough

CH3COOH and KI. I2 thus liberated required 84.5 mL of 0.1M Hypo solution for
titration. Calculate the % of available Cl2.

Solution Directly using the formula

X x V x 3.55
% Cl2 = W

0.1 x 84.5 x 3.55

= 1
= 29.99 or 30% Ans.

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ee
Calculation of % of free SO3 in oleum (H2S2O7) solution

Oleum is actually very highly concentrated sulfuric acid solution containing

itj
excess of SO3 in it. Some times the concentration of such a H2SO4 is expressed in %
ki

from which it becomes desirable to calculate free SO 3 present in that. Let us solve
the following question to understand it.
ac

1. . Calculate % (w/w) of free SO3 in an oleum that is labeled as 109% H2SO4.

cr

Solution A 109% H2SO4 means that if we take 100g of such a oleum solution and
add to that 9g H2O. In other words 9g H2O must combine with free SO3 present in
oleum.

H2O + SO3 H2SO4

1 mol 1 mol
18g 32+48 = 80g
9g H2O will combine with 40g SO3

Hence above solution must have 40% free SO3 Ans.

In general if the sample of oleum given is labeled as % H2SO4, then

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80
% (w/w) of SO3 in the given sample of oleum = 18 ( -100) [ >100]

Calculation of Degree of Hardness in a given sample of water

We know that hard water does not give sufficient lather with soap. Hardness
is due to the presence of salts of Ca and Mg. further the temporary hardness is due
to the presence of bicarbonates of Ca and Mg while permanent is due the presence
of sulphates and chlorides of Ca & Mg.

.in
The extent of hardness in water is expressed in terms of degree of hardness
which is defined as: ee
the number of parts of CaCO3 equivalent to various calcium and magnesium
salts present in a million parts of water by mass.
itj
Thus it is expressed in ppm (w/w) unit. Let us solve the following numerical to
understand it.
ki

Q. Calculate the degree of hardness of a sample of water containing 12mg of MgSO 4

ac

(molecular weight = 120)per kg of water.

cr

Solution It is given that

1kg water= 1000g = 103g contains =12mg MgSO4

106g water will contain = 12000mg MgSO 4
(1 million g) = 12g MgSO4

Further since molecular weights of MgSO4 and CaCO3 are 120 and 100 respectively
hence we can say that
120g MgSO4 is equivalent to 100g CaCO3
12g MgSO4 will be equivalent to 10g CaCO3
Degree of hardness in the given sample of water = 10 ppm. AnS

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