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OXIDATION
REDUCTION
 MARKS 3

1 OXIDAT
ATIION REDUCTION

1 .1 FORM A L CH A RGE
The formal charge of an atom in a molecule is the hypothetical charge the atom would have if we
could redistribute the electrons in the bonds evenly between the atoms in the bond. Formal charge (F)
is determined using

s
F = v u
2
where v = valence electrons
s = shared electrons (forming bonds)
u = unshared electrons

Cl Br Cl
Ć In BrCl 3 |
Cl
v s u Formal charge
Br 7 6 4 0
Cl 7 2 6 0

Ć In ICl4

v s u Formal charge
I 7 8 4 (one extra) ă1
Cl 7 2 6 0

Ć In NH 4

v s u Formal charge
N 5 8 0 +1
H 1 2 0 0

Ox i d a t i o n Re d u c t i o n
In many cases, we can draw more than one structure for a molecule, with different arrangement
of atoms. We can use the following guidelines involving formal charge to decide between two or more
possible structures for a molecule or ion.
(a) A molecular structure that gives a Lewis structure in which all formal charges are zero is
preferable to one in which some formal charges are not zero.

OXIDATION REDUCTION
 4 MARKS

(b) If the Lewis structure must have non-zero formal charges, the structure with the lowest
number of non zero formal charge is preferable and a Lewis structure with no more than one
large formal charge (ă 2, + 2 and so on) is preferable to a structure with several formal
charges.
(c) Lewis structures should have adjacent formal charges of zero of opposite sign.
(d) When we must choose among several Lewis structure with similar distribution of formal
charges, the structure with the negative formal charges on the more electronegative atom is
preferable.
Thiocyanate ion can be assign as three structures.
Formal Charges
N C S Total Charge

 .. ..  
I  : N  C  S: ă1 0 0 ă1
 

 .. ..  
II  : C N  S:  +1 ă2 0 ă1
 

 .. ..  
III  : C S  N: ă1 ă2 +2 ă1
 

In all these cases total formal charge is ă 1. But we prefer structure I because it has the lowest
number of atoms with non zero formal charges (guideline (b)).

1 .2 T H E OX I DA T I ON ST A T E OF A N EL EM EN T
To describe the changes that occur in oxidationăreduction reactions and to write the correctly
balanced equations for such reactions, it is helpful to know the concept of the oxidation state (or
oxidation number) of an atom).
For monoatomic ions, the oxidation state is simply the charge on the ion. For example, oxidation
states of Na+, Mg 2+, Clă and N3ă are + 1, + 2, ă 1 and ă 3 respectively. For covalently bonded substances,
the charge on an atom would be so small that it is impossible to calculate the exact charge on each atom
in the molecule. Thus, oxidation state for covalently bonded molecule is defined as „the charge an atom
would possess if all the bonds associated with that atom are broken heterolytically considering them to
be completely ionic‰. For example, in NH 3 there are three NăH bonds. If we consider all three NăH
bonds to be ionic, then each H will possess a charge of + 1 while N has the charge ă 3 (because N is
more electronegative than H). In H2O 2, there are two OăH bonds and one OăO bond as evident from
the structural formula HăOăOăH. Assuming each OăH bond to be ionic, each H atom would possess
+ 1 charge while each O possess ă 1 charge. The OăO bond is not ionic as the bond is between atoms
of similar electronegativity.
It is not necessary to know the structure of a molecule in order to calculate the oxidation state of
an atom in a molecule. The following set of rules are used to assign oxidation states to atoms in ions
or molecules.

OXIDATION REDUCTION
 MARKS 5

1. Each pure element has an oxidation state of zero. This is true whether the element is a
monoatomic gas, a metallic solid or a polyatomic molecule. Thus, Fe(s), N 2(g), P4(s) and S8(s)
are all in the zero oxidation state.
2. In monoatomic ions, the oxidation state of the element is equal to the charge of the ion. Thus,
oxidation state of all alkali metals is + 1 and that of alkaline earth metals is + 2 in all their
compounds. In ionic solid K2S, the oxidation stateÊs of potassium and sulfur are + 1 and ă 2
respectively. In AgCl, the oxidation state of silver and chlorine are + 1 and ă 1 respectively.
3. The oxidation state of hydrogen in any molecule in which it is combined with another element
is + 1, except in the metallic hydrides such as LiH or CaH2, where the oxidation state of
hydrogen is ă 1.
4. The oxidation state of oxygen in any molecule or ion in which it is combined with another
element is ă 2, except in the peroxides, the superoxides and in OF2. The peroxides (H2O 2,
Na 2O2, BaO2 etc.) are compounds in which there is an OăO covalent bond and the peroxide ion
is O22  . The oxidation state of oxygen in peroxides is ă 1. The superoxides (like KO2, CsO2 etc.)

are ionic compounds involving the superoxide ion, O2 . The oxidation state of oxygen is ă óin
superoxide in OF 2, the oxidation state of oxygen is + 2 since fluorine is more electronegative
than oxygen.
5. The oxidation state of all the halogens is ă 1 in all their compounds except where they are
combined with an element of higher electronegativity or in interhalogn compounds. Oxidation
state of fluorine is always ă 1, since it is the most electronegative element.
6. In covalent compounds not involving hydrogen or oxygen, the more electronegative element is
assigned negative oxidation state while less electronegative element is assigned positive oxidation
state.
7. The algebraic sum of the oxidation numbers of all the atoms combined in a molecular or
complex ion must equal the net charge on the molecule or ion.
Until the form of radical changes, the O.N of an element in a compound remains same.
For Example
(1) O.N. of nitrogen in HNO 3, NaNO3 , Ca(NO3)2 is same, i.e. + 5.
(2) O.N. of sulphur in H2 S, CaS, Na2S & Al 2S3 is equal.
(3) Oxidation number of a metal in carbonyl complex is always zero.
e.g. Fe in Fe (CO)5
Ni in Ni (CO)4
Here the O.N. of CO is taken to be zero.
(4) Oxidation number can be zero, + ve, ă ve (integer or fraction).
e.g. O.N. of O in KO 2 is ă ó
.
(5) Maximum O.N. of an element is = Group No.
(Except O & F)
(6) Minimum O.N. of an element = Group No. ă 8
(Except metals)

OXIDATION REDUCTION
 6 MARKS

Ex a m p l e 1
Calculate the oxidation state of the underlined atoms in the given species.
(a) NO2 (b) NO3

(c) KMnO 4 (d) Cr 2O27 

Solution :
(a) Let the oxidation state of N in NO2+ be x.
x + [2(ă 2)] = + 1
x =+5
Thus, oxidation state of N in NO2 is + 5.

(b) Let x be the oxidation state of N in NO 3 .

x + [3(ă 2)] = ă 1
x =+5

Thus, oxidation state of N in NO3 is + 5.

(c) Let the oxidation state of KMnO 4 be x.

[1 (+ 1)] + x + [4 (ă 2)] = 0
x =+7

(d) Let the oxidation state of Cr in Cr2O 72 be x.

2x + [7(ă 2] = ă 2
x =+6

Thus, oxidation state of C in Cr2O27 is + 6.

Ex a m p l e 2
Determine the oxidation no. of following elements given in bold letters.
(a) H2SO 5 :
Oxidation number of H = + 1
Oxidation number of O = ă 2
Oxidation number of S = a
2 ï 1 + a + 5 ï (ă 2) = 0
a = + 8 (wrong)
But this can not be true as maximum Oxidation number for S (VI gp) stands + 6. The exceptional
value is due to the fact that two O atoms in H2SO5 show peroxide linkage, i.e.,

O

H O O  S O H

O
OXIDATION REDUCTION
 MARKS 7

Thus, evaluation of oxidation number of S should be made as

2 ï 1 + a + 3 ï (ă 2) + 2 ï (ă 1) = 0
 a = + 6
(b) H2S2O 8 : Here too, O atoms form per oxide linkage. i.e.,

O O
 
H O S O O S O H
 
O O

 2 ï 1 + 2a + 6 ï (ă 2) + 2 ï (ă 1) = 0
a = + 6
(c) NH 4NO 3 : 2 ï a + 4 ï 1 + 3 ï (ă 2) = 0 by rules
a = + 1 (wrong)
No doubt there are two N atoms in NH4 NO3, but one N atom has negative ox. no. (attached
to H) and the other has positive oxidation number (attached to O). Therefore, evaluation should
be made separately as

oxidation number of N in NH4 and oxidation number of N in NH 3

a |+ 4 ï (+ 1) = + 1 a + 3 ï (ă 1) = ă 1
 a = ă3  a = + 5
(d) K 4Fe(CN) 6 : By rules, oxidation number of K= + 1
oxidation number of CNă1 = ă 1
oxidation number of Fe = a
 4 ï 1 + a + 6 ï (ă 1) = 0
 a =+ 2
(e) O SO4 : a + 4 ï (ă 2) = 0
 a =+ 8
Note : 1. The element Os and Ru show highest oxidation state i.e., + 8.
2. Recently Ba2XeO6 has been reported in which ox. no. of Xe is + 8.
(f) HCN : The evaluation can not be made directly in some cases, e.g., HCN by using rules
proposed earlier since we have no rule for oxidation number of both N and C.
In all such cases evaluation of oxidation number should be made using indirect concept or using
fundamentals by which rules have been framed.
(1) Each covalent bond contributes one unit for oxidation number
(2) Covalently bonded atoms with less electronegativity acquires positive ox. no. whereas other
with more electronegativity acquires negative oxidation number
(3) In case of co-ordinate bond, give + 2 value for oxidation number to atom from which co-
ordinate bond is directed to a more electronegative atom and ă 2 value to more electronegative
atom.

OXIDATION REDUCTION
 8 MARKS

If co-ordinate bond is directed from more electronegative to less electronegative atom, then neglect
contribution of co-ordinate bond for both atoms in which co-ordinate bond exist.
Thus, HăC  N  Three bonds on N atom and N
1 + a + 3 ï (ă 1) = 0 is more electronegative.

a = + 2  Ox. no. of N = 3 ï ( ă 1) = ă 3

(g) HNC : H NC



oxidation number of H = + 1
oxidation number of N = [ă 2 + (ă 1) + 0] = ă 3
for covalent [for covalent No contribution
bond with C bond with H] for co-ordinate bond
= ă3
 1 + (ă 3) + a = 0
 a =+ 2
(h) HNO 3 : By rules
1 + a + 3 ï (ă 2) = 0
 a =+ 5
By fundamental approach
O
H O N
O
oxidation number of H = + 1
oxidation number of N = + 1 + (+ 2) + (+ 2) = + 5
covalent two covalent co-ordinate
bond with O bond with O bond
 N being less electronegative than O.
(i) KO 2 : A super oxide of K;
oxidation number of K = + 1
oxidation number of O = a
1+2ï a =0

1
       a = ă
2
(j) Fe 3O4 :
3 ï a + 4 ï (ă 2) = 0

8
       a =+
3

OXIDATION REDUCTION
 MARKS 9

or Fe3O4 is a mixed oxide of FeO.Fe2 O3.

 Fe has two oxidation no. + 2 and + 3 respectively. However, factually speaking oxidation
number of Fe in Fe3 O4 is an average of two values (i.e., + 2 and + 3)

 2 2 ( 3)
Average ox. no. = 8 / 3
3

(k) KI 3 : 1 + 3 ï (a)

1
a
3

or KI3 is KI + I 2
 I has two oxidation no. ă 1 and 0 respectively. However, factually speaking ox. no. of I in KI3
is an average of two values ă 1 and O.

 1  2 (0) 1
Average ox. no. = 
3 3

(l) N3 H : 3ï a + 1 = 0

1
a = 
3

(m) Fe0.94O : 0.94 ï a + (ă 2) = 0

200
a =
94

(n) FeSO 4.(NH4)SO 4.6H2O

oxidation number of Fe = a
Sum of oxidation number for H2 O = 0

Sum of oxidation number for SO4 2 = ă 2

 a + (ă 2) + 0 + 6 ï (0) = 0
 a =+ 2
(o) NOCl : ClăN = O or use NO+Clă
oxidation number of N =  1 (for covalent bond with Cl)
oxidation number of N = + 2 (for two covalent bonds with O)
 Total ox. no.of N in NOCl = + 3
(p) NOClO4 : The compound may be written as NO+ClO 4ă for ClO4ă.
For ClO4ă, let Ox. no. of Cl = a
a + 4 ï (ă 2) = ă 1
a =+ 7

OXIDATION REDUCTION
10 MARKS

(q) Na2[Fe(CN)5NO] : NO in iron complex has NO+ nature.

 2 ï 1 + [a + 5 ï ( ă 1) + (+ 1)] = 0
 a =+ 2
(r) [Fe(NO)(H2 O) 5]SO4 :
a + 1 + 5 ï 0 + (ă 2) = 0
a =+ 1
(s) Na2S4O6 : 2 ï (+ 1) + 4a + 6 ï (ă 2) = 0

5
 a
2
Here also this value is the average oxidation no. of S. The structure of Na2S4O6 is

O O
 
Na O S  S  S  S O  Na
 
O O

Thus oxidation number of each S atom forming co-ordinate bond is + 5 whereas, oxidation number
of each S atom involved in pure covalent bonding is zero.

5 5 0  0
 Average ox. no. =  5/2
4
(t) Na2S2O3 :
2 ï 1 + 2 ï a + 3 ï (ă 2) = 0
 a =+ 2
Here too it is the average oxidation number
The structure of Na2S2O3 is

O

Na  S S  O  Na

O
The oxidation number of S involved in co-ordinate bond i.e. donor S atom is + 5. The oxidation
number of other S atom is ă 1.
(u) CrO5 or CrO(O2 )2 : The structure of CrO5 is
O O
Cr
O O
O
i.e., two peroxide bonds and thus four oxygen atoms have oxidation number = ă 1 and one oxygen
atom has oxidation number = ă 2.
Thus, a + 4 ï (ă 1) + 1 ï (ă 2) = 0
a =+ 6
OXIDATION REDUCTION
 MARKS 11

1 .3 SPECI A L M ET H OD
{If we donot know the number of peroxide linkages}
(1) Oxidation no. H2 SO5 (CaroÊs Acid)
If a is the no. of peroxy linkages.
 No. of O ă atoms attached to peroxy linkage = 2a
O.N. of peroxy linkage = ă 1
Let x be the oxidation no. of S
2 ï 1 + x + (5 ă 2a) (ă 2) + 2a (ă 1) = 0
2 + x ă 2a ă 10 + 4a = 0
x + 2a = 8
a =1
x =+6
Peroxy linkage is formed at maximum of electronegative atom
(2) H 2S2O8
2 ï 1 + 2 ï x + (za) (ă 1) + (8 ă 2a) (ă 2) = 0
2 + 2x ă 2a ă 16 + 4a = 0 O
||
2x + 2a = 14 H  O  S O  OH
||
x+ a =7 O
a =1
x =6

O O
|| ||
H  O  S O  O  S  O  H
|| ||
O O

The compounds containing element which have highest oxidation state always act as oxidant.

+5 +6 +7 7
Example HN O3 , K2 Cr2 O7 , KM nO4 , K ClO4

1 .4 OX I DA T I ON - REA CT I ON
Oxidation is a process that involves the loss of electrons by the atoms or ions. Reduction is a
process that involves the gain of electrons by atoms or ions. Any reaction in which the electrons are
exchanged between atoms or ions, represents simultaneous process of oxidation and reduction is called
as Redox Reaction.
In a Redox Reaction, the species that loses electron (i.e., gets oxidised) is known as reducing
agent or reductant, (since it causes reduction of other species), the species which accepts electrons
from other reductant (i.e., gets reduced) is known as oxidising agent or oxidant (as it causes oxidation
of other species).

OXIDATION REDUCTION
 12 MARKS

To illustrate :
Mg + Zn2+ Mg2+ + Zn is a redox reaction.
Oxidation : Mg ă 2eă  Mg 2+
0

Reduction : Zn2+ + 2eă  Zn0

Mg causes reduction of Zn 2+, so it is Reductant.
Zn 2+ causes oxidation of Mg, so it is oxidant.
Note : A redox reaction involves two half reactions :
Oxidation and Reduction half reactions.
(1) Molecular Reaction : When one molecule gets oxidised and other gets reduced in a chemical
reaction.
reduction
+4 +7 +6
e.g. Mn O  KOH  K Mn O  K Mn O  H O
2 4 2 4 2

oxidation
Here MnO2 is getting oxidised and in KMnO4 is getting reduced (In two different molecules). So
it is intramolecular reaction.
(2) Intramolecular Reaction : When oxidation and reduction takes place in the same molecule.
3 +5 1
e.g. NH4 NO3  N2 O + 2H 2O
In this example one N is getting reduced and other is getting oxidised in the same molecule
NH 4NO3. So it is a intramolecular reaction.
(3) Disproportionation Reaction : When same element gets oxidised and reduced in a reaction.
+3 +5 3
e.g. 4H 3 PO3  3H 3 PO4  PH3
Here only one P is oxidised as well as reduced. So it is disproportionation reaction.

Ex a m p l e 3
Which of the following are examples of disproportionation reactions ?
(a) Ag(NH3)2 + + 2H+  Ag+ + 2NH4 + (b) Cl2 + 2OH ă  ClOă + Clă + H2O
(c) CaCO3  CaO + CO 2 (d) 2HgO  2Hg + O2
(e) Cu2O + 2H+  Cu + Cu 2+ + H2 O (f) CuS + O2  Cu + SO2
(g) 2HCuCl 2 + dilute with H 2 O  Cu + Cu 2+ + 4CIă + 2H+
Solution :
The criteria for disproportionation reaction is :
A reaction in which an oxidising agent and the reducing agent is the same.
Hence among the above reactions,
(b), (e) & (g) are disproportionation reactions.

OXIDATION REDUCTION
 MARKS 13

Ex a m p l e 4
H2 SO4 acts as an oxidising agent, a dehydrating agent and an acid. Among the each of
following reactions, which behaviour is shown by H2SO4 ?
(a) C6H12 O6 + H2 SO4(conc.)  6C + H2 O
(b) 5H2 SO 4(conc.) + 4zn  H 2S + 4Zn2+ + 4SO 42ă + 4H2O
(c) H2 SO4 (dil) + Zn  Zn 2+ + H2 + SO4 2ă
(d) H2 SO4 (dil) + ZnCO3  Zn2+ + CO 2 + SO 42ă + H2 O
Solution :
(a) as a dehydrating agent since it simply removes water from glucose.
(b) H2SO 4 (S in + 6 state)  H2 S (S in ă 2 state), i.e. acid is reduced. So it acts as an oxidising
agent.
(c) all strong acids liberate H2 with an active metals like Zn (i.e. it is reduced) unless SO 42ă is
reduced. In this case, H + is reduced to H2 . So it acts as an oxidising agent. We can also call
it as an acidic property.
(d) simply an acid.

Ex a m p l e 5
One mole of N2 H4 loses 10 mole electrons to form a new compound Y. Assuming that all the
N2 appears in new compound, what is oxidation state of N in Y? There is no change in
oxidation state of H.
Solution : N2H 4  (Y) + 10e
 Y contains all N atoms
 N2ă2  (2N) a + 10e
Therefore, 2a ă (ă 4) = 10
a = + 3

Ex a m p l e 6
In the reaction Al + Fe3 O4  Al2O3 + Fe
(a) Which element is oxidized and which is reduced?
(b) Total no. of electrons transferred during the change.
Solution : 2Al0  Al2+3 + 6eă ...(1)
8e + Fe 3+8/3  3Fe0
ă
...(2)
Multiplying Eq. (1) by 4 and Eq. (2) by 3, then adding
8Al0  4Al2+3 + 24e

24e  3Fe8 / 3  9Fe0

8Al0  3Fe 3 8 / 3  4Al+3
2  9Fe
0

or 8Al + 3Fe3O4  4Al2O3 + 9Fe

Therefore, it is clear that
(a) Al is oxidized and Fe+8/3 is reduced.
(b) Total no. of electrons transferred during change = 24

OXIDATION REDUCTION
 14 MARKS

Pro b l e m 7
The composition of a sample of wustite is Fe0.93O 1.00. What percentage of iron is present in
the form of Fe III ?
Solution :

200
Oxidation no. of Fe in wustite is =  2.15
93

It is an intermediate value in between two oxidation state of Fe as, Fe (II) and (III),
Let percentage of Fe (III) be a, then
2 ï (100 ă a) + 3 ï a = 2.15 ï 100
or a = 15.05
 Percentage of Fe (III) = 15.05%

Pro b l e m 8
Identify the substance acting as oxidant or reductant reduced if any in the following:
(i) AlCl3 + 3K  Al + 3KCl
(ii) SO2 + 2H 2S  3S + H2 O
(iii) BaCl2 + Na 2SO4  BaSO 4 + 2NaCl
(iv) 3l 2 + 6NaOH  NalO 3 + 5Nal + 3H2O
Solution :
In a conjugate pair, oxidant has higher oxidation number
(i) For AlCl3 : Al+3 + 3e  Al0; For K : K 0      K+1 + e
 Oxidant is AlCl3 and reductant is K.
(ii) For SO2 : S+4 + 4e  S0; For H 2S : Să2   S0 + 2e
SO2 is oxidant H2 S is reductant.
(iii) No change in oxidation number of either of the conjugate pair.
 None is oxidant or reductant.
(iv) For I2 : I 2 0  2I +5 + 10e and I 20 + 2e    2I ă1
I2 acts as oxidant and reductant both.

Pro b l e m 9
Arrange the following in order of :
(a) Increasing oxidation no. : MnCl2, MnO2, Mn(OH) 3 , KMnO4
(b) Decreasing oxidation no. : HXO4, HXO3 , HXO2, HXO
(c) Increasing oxidation no. : I2 , HI, HIO4, ICl
OXIDATION REDUCTION
 MARKS 15

Solution :
(a) MnCl2 < Mn(OH)3 < MnO2 < KMnO 4
Ox. No. +2 +3 +4 +7
(b) HXO4 > HXO 3 > HXO2 > HXO 4
Ox. No. +7 +5 +3 +1
(c) HI < I2 < ICl < HIO 4
Ox. No. ă1 0 +1 +7

1 .5 B A L A N CI N G OF REDOX REA CT I ON S
There are 2 common and useful methods to balance redox reactions. These are
(a) Oxidation number method and
(b) Ion-electron method

Ox i d a t i o n N u m b e r M e t h o d
For balancing a redox reaction by oxidation number method, follow the order of steps as listed
below :
(i) Separate the reactants and products into two half-reactions involving the elements that
changes its oxidation number. Write the skeletal equations for each half-reaction.
(ii) For each half-reaction, deduce the oxidation numbers of the element that is changing oxidation
number.
(iii) Then balance the number of atoms of the element changing oxidation number.
(iv) Now find the total oxidation number change by determining the change per atom and
multiplying by the total number of atoms that change oxidation number. Also, decide whether
electrons are lost or gained. An increase in oxidation number is loss of electrons and a
decrease in oxidation number is gain of electrons.
(v) Add the electrons lost or gained to the half equation. Lost electrons are placed on the product
side and gained electrons are kept on the reactant side.
(vi) Now add both the half reactions after multiplying by suitable integers to make the number
of electrons lost and gained same.
(vii) Transfer the coefficient of each reactant and product to the main skeleton equation.
(viii) If the coefficients developed are not correct, then change them by inspection (Such coefficient
changes are required when an element from a compound goes in 2 different compounds, one
with the same oxidation state & the other with changed oxidation state).
(ix) Count the charges on both sides of the equation and balance the charges in the equation by
adding requisite H+ or OHă to the required side. If the reaction occurs in acidic solution, use
H + and if it occurs in basic solution, use OHă. If the reaction occurs in a neutral solution, use
H + or OH ă on any of the side as needed i.e. in a neutral solution, if negative charges are
needed for balancing, use OHă and if positive charges are needed, use H+ .
(x) Balance the hydrogens and oxygens by adding the appropriate number of H 2O molecules on
the required side.

OXIDATION REDUCTION
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Ex a m p l e 1 0
Balance the following oxidation-reduction equation.
KMnO4 + KCl + H 2SO4  MnSO4 + K2SO 4 + H2O + Cl2
by oxidation number method.
Solution :
(i) Identify the oxidation & reduction half equations in ionic form.
Reduction half : MnO4ă1  Mn 2
Oxidation half : Clă  Cl2
(ii) Balance the atoms that undergoes change in oxidation number.
Reduction half : MnO4ă1  Mn 2+
Oxidation half : 2Clă1  Cl 2
(iii) And the electrons lost or gained to each half equation
Reduction half : 5eă + MnO4ă1  Mn 2+ ................ (A)
ă ă
Oxidation half : 2Cl  Cl 2 + 2e ................. (B)
(iv) Multiply equation (A) with 2 and equation (B) with 5 and then add the two half reactions.
5e + MnO4 ă1  Mn2+ ] ï 2
2Cl 1  Cl2  2e ]  5
2MnO4  10Cl  5Cl 2  2Mn 2
(v) Transfer the coefficients to the main equation.
2KMnO 4 + 10KCl + H 2SO 4  2MnSO 4 + K2SO 4 + H2O + 5Cl 2
(vi) Balance H & O atoms
2KMnO 4 + 10KCl + 8H2 SO4  5Cl 2 + 2MnSO4 + 8H2O + K 2SO4
(vii) Finally balance by inspection method
2KMnO 4 + 10KCl + 8H2 SO4  2MnSO 4 + 6K 2SO 4 + 8H 2O + 5Cl 2

Ex a m p l e 1 1
Balance the following redox equation
K2Cr 2O 7 + HCl  KCl + CrCl2 + Cl2 + H 2O
by oxidation number method
Solution :
(i) Identify the oxidation & reduction half equations in ionic form.
Reduction half : Cr2O72  Cr3+
Oxidation half : Cl  Cl2
(ii) Balance the atoms that undergoes change in oxidation number.
Reduction half : Cr2 O72ă  2Cr3+
Oxidation half : 2Clă  Cl 2

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(iii) Add the electrons lost or gained to each half equation

Reduction half : 6eă + Cr 2O72ă  2Cr3+ ............. (A)
Oxidation half : 2Clă  Cl 2 + 2e ă .................... (B)
(iv) Multiply equation (B) by 2 and add it to equation (B)
6eă + Cr2O72+  2Cr3+

2Cl  Cl2  2e  ] 3
Cr2 O72  6Cl  2Cr 3  3Cl2

(v) Transfer the coefficients to the main equation.

K2 Cr2 O7 + 6HCl  KCl + 2CrCl 3 + 3Cl2 + H2 O
(vi) By inspection, it is seen that the coefficient of HCl developed is not correct, as the
number of moles of Cl atoms on the product side are 13 while on the reactant side are
only 6. So the coefficient is changed appropriately, seeing that the net reaction is completely
balanced.
K2 Cr2 O7 + 14HCl  2KCl + 2CrCl 3 + 3Cl 2 + 7H2 O

I o n -El e c t r o n M e t h o d
This method of balancing redox reaction involves following steps.
(i) Separate the reactants and products into half-reactions involving the elements that changes
its oxidation number. Write the skeleton equations for each half-reaction.
(ii) Balance each half-reaction separately involving given steps.
1. First balance the atoms of the element undergoing oxidation or reduction.
2. Then balance atoms of the elements other than hydrogen and oxygen.
3. For balancing oxygen atoms in acidic or neutral medium, add suitable number of H 2O
molecules to the side deficient in O while in alkaline medium, add equal number of H 2O
molecules as the excess of O on the side having excess of O atoms and add double the
number of OHă ions on the opposite side of the equation.
4. In order to balance hydrogen atom in acidic or neutral medium, add required number of
H + to the side deficient in H while in alkaline medium, add equal number of OH ă ions
as the access number of atom on the side having access H and add equal number of H 2O
molecule on the opposite side of the equation.
(iii) Multiply each half-reaction by suitable integer to make the number of electrons lost and
gained same and add both the half-equations to get a completely balanced reaction.

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Ex a m p l e 1 2
Balance the redox equation,
HNO3 + H 2S  NO + S
by ion-electron method (acidic medium)
Solution :
(i) Identify the oxidation & reduction halves
Reduction half : HNO3  NO
Oxidation half : H2S  S
(ii) Atoms of the element undergoing oxidation and reduction are already balanced.
(iii) Balancing O atoms,
Reduction half : HNO3  NO + 2H2 O
Oxidation half : H2S  S
(iv) Balancing H atoms,
Reducing half : 3H + + HNO3  NO + 2H2O
Oxidation half : H2S  S + 2H+
(v) Balancing charge,
Reduction half : 3e + 3H+ + HNO3  NO + 2H 2O ............... (A)
Oxidation half : H2S  S + 2H+ + 2eă ................ (B)
(vi) Multiplying equation (A) by 2 and equation (B) by 3 and then adding them
3eă + 3H+ + HNO3  NO + 2H2O] ï 2 ................ (A)

H2 S  S  2H   2e ] 3
................ (B)
2HNO3 3H2 S  2NO+ 4H2 O

Ex a m p l e 1 3
Balance the following redox equation,
FeC 2O4 + KMnO 4 + H 2SO4  Fe 2(SO4) 3 + CO2 + MnSO4 + K 2SO 4
using ion-electron method (acidic medium)
Solution :
(i) Identify the oxidation & reduction halves
Oxidation half : KMnO4  MnSO 4
Reduction half : FeC2O4  Fe2 (SO4)3 + CO2
(ii) In both the half-reactions, all the atoms (other then O and H) are not appearing on both sides
of the reaction. So, in the oxidation half, H2 SO4 and K 2SO 4 are to be to added on reactant
and product side respectively.
(iii) Balancing of the atoms of the element undergoing oxidation & reduction.
Reduction half : H2SO 4 + 2KMnO4  2MnSO4 + K2 SO4
Oxidation half : H2SO4 + 2FeC 2O4  Fe 2(SO 4)3 + 4CO 2

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(iv) Balancing of the atoms of elements other than O and H.

Reduction half : 3H2SO 4 + 2KMnO4  2MnSO4 + K 2SO 4
Oxidation half : 3H2SO 4 + 2FeC2 O4  Fe 2(SO4)3 + 4CO 2
(v) Balancing O atoms,
Reducing half : 3H 2SO4 + 2KMnO4  2MnSO 4 + K2 SO4 + 8H 2O
Oxidation half : 3H2SO 4 + 2FeC2 O4  Fe 2(SO4)3 + 4CO 2
(vi) Balancing H atoms,
Reducing half : 10H+ + 3H2SO 4 + 2KMnO 4  2MnSO4 + K 2SO4 + 8H2O
Oxidation half : 3H2SO 4 + 2FeC2 O4  Fe 2(SO4) 3 + 4CO2 + 6H+
(vii) Balancing charge,
Reduction half : 10e ă + 10H+ + 3H 2SO4 + 2KMnO4  2MnSO4 + K2SO 4 + 8H 2O.... (B)
Oxidation half : 3H2SO 4 + 2FeC2 O4  Fe 2(SO4) 3 + 4CO 2 + 6H+ + 6eă.......... (A)
(viii) Multiply equation (A) by 5 and equation (B) by 3 and then adding them.
10eă + 10H+ + 3H2 SO4 + 2KMnO 4 + K2 SO4 + 8H2O] ï 3

3H2 SO4  2FeC2 O4  Fe2  SO4 3  4CO2  6H  6e ] 5

10FeC2O4 6KMnO4  24H2SO4 5Fe 2 SO4 3  6MnSO4  3K 2SO4  20CO2  24H 2O

Ex a m p l e 1 4
Balance the following redox equation,
 
AsO 33  MnO4  AsO 34  MnO 2
using ion-electron method (alkaline medium).
Solution :
(i) Identify the oxidation & reduction halves

Reduction half : MnO 4  MnO2

Oxidation half : AsO 33  AsO 34

(ii) Atoms of the element undergoing oxidation reduction are already balanced.
(iii) Balancing O atoms,

Reduction half : 2H 2O + MnO 4  MnO 2  4OH 

Oxidation half : 2OH  AsO33  AsO34  H2 O

(iv) Balancing H atoms,
H atoms are already balanced in both the half-reactions.
(v) Balancing charge.
Reduction half : 3eă + 2H2O + MnO 4ă  MnO2 + 4OHă ...............(B)
Oxidation half : 2OH ă + AsO 33ă  AsO 43ă + H2O + 2e ă ................. (A)

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(vi) Multiply equation (A) by 3 and equation (B) by 2 and then add (A) and (B)
3eă + 2H2O + MnO4ă  MnO2 + 4OHă] ï 2

2OH  AsO33  AsO34  H2 O+ 2e ] 3

AsO 33  2MnO4  H 2O  3AsO 43  2MnO 2  2OH 

Mostly, the medium in which a redox reaction is to be balanced is given in the problem but if
the problem does not state the medium explicitly, then the medium is decided by looking at the
reactants or products. If an acid or base is one of the reactants or products, then the medium is the
same. If ammonia is present, the solution would be basic, for example ammonium ion is present, it
would be acidic. If metals which forms insoluble hydroxides are shown in their ionic form, the solution
is acidic.
Although, the oxidation number method and ion-electron method both lead to the correct form of
the balanced redox reaction but ion-electron method is considered superior to oxidation number method
due to following advantages :
(i) In ion-electron method, all reactants and products are completely balanced (i.e. coefficient is
developed for each one of them) whether they participate in the redox change or not, while
in oxidation number method, the balancing coefficient is developed only for the species
involved in redox change.
(ii) The balancing coefficients developed in ion-electron method are always correct and needs
no amendment while such coefficients are to be changed sometimes oxidation number
method.

Ex a m p l e 1 5
Complete and balance the following :
(a) H2O 2 + I 2  Iă + ?? (b) H2 O2 + Sn2+  Sn 4+ + ??
(c) MnO4 2ă + H +  Mn2+ + ?? (d) NO2 + H2O  NO + ??
Solution :
(a) I2 is reduced to Iă, so H 2O 2 must be oxidised, i.e. it acts as a reducing agent. Hence final
product will be O2 gas.
H2O2 + I 2  Iă + O 2
The balanced equation will be :
H2O2 + I 2  2Iă + O 2 + 2H+
(b) Sn2+  Sn4+ , i.e. Sn2+ is oxidised. So H2 O2 acts as an oxidising agent, which means it must
be reduced to H 2O.
H2O2 + Sn2+  Sn4+ + H2O
The balanced equation will be
H2O2 + Sn 2+ + 2H+  Sn4+ + 2H2O

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(c) MnO4 2ă is reduced to Mn2+ , i.e. it is acting as an oxidising agent. Now H + is already in the
maximum oxidation state, so MnO42ă must also be reduced to Mn 7+ state i.e. MnO 4 will be
formed (disproportionation reaction)
MnO4 2ă + H+  Mn2+ + MnO4
The balanced equation will be :
5MnO42ă + 8H+  Mn2+ 4MnO4 + 4H2O
(d) NO2 (+ 4 state) disproportionates (like in last case) to NO (+ 2 state) and NO3ă (+ 5 state).
NO2 + H 2O  NO + NO3ă
The balanced equation will be :
3NO 2 + H2 O  NO + 2NO3 + 2H +

Ex a m p l e 1 6
Predict the products of each of the following reactions.
(a) Na + ZnCl2  ? + ? (b) F2 + NaCl  ? + ?
(c) I2 + Fe  ? + ? (d) Iă + Fe2+  ? + ?
Solution :
(a) 2Na + ZnCl2  Zn + 2NaCl
(b) F 2 + 2NaCl  2NaF + Cl2
(c) I2 + Fe  Fe2+ + 2Iă
(d) no reaction because Fe is a better reducing agent than Iă.

OXIDATION REDUCTION
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