BALANCING REDOX REACTIONS

Whrer there is a oxidation, there

is always reduction - Chemistry
is more or less a study of redox
JEE SYLLABUS reactions.

Definitions, Oxidations number , common oxidising and reducing agents and balancing of rexdox
reactions.

Definitions

The term oxidation was first used to mean the addition of oxygen to an element or compound, or the
removal of hydrogen from a compound. Reduction meant the addition of hydrogen to an element or
compound , or the removal of oxygen from a compound. Such definitions have been extended and
now-a- days many oxidation- reduction, or redox, reactions are best interpreted in terms of transfer of
electrons.

Oxidation is the loss of electrons by an atom, ion or moleccule.

Reduction is the gain of electrons by an atom, ion or molecule .

An oxidising agent takes electrons ; it is an electron acceptor & undergoes reduction.

A reducing agent gives electrons; it is an electron donor & undergoes oxidation.

When Fe2+(aq) ions are being oxidised they are acting as reducing agents, and when Fe3+ (aq) ions
are being reduced they are acting as oxidising agents, In general

reduction
O.A + electrons R. A
Oxidation

Fe 2  ( aq)   Fe 3 ( aq)  e  Fe3 ( aq)   Fe2  ( aq)

oxidation reduction

(R.A) (O. A)

Oxidation Number or Oxidation state

When an element is oxidised it must be acting as a reducing agent and it , therefore, loses electrons;
when reduced, it gains electrons . The oxidation state or oxidation number of an elements is the
number of electrons it might be considered to have lost or gained.

All elements in the elementary, uncombined state are given oxidation numbers of zero. When sodium,
for example, is oxidised it loses one electron , and the Na+ ion is said to have an oxidation number
of +1 . Similarly, the Cu2+ and Al3+ ions have oxidation numbers of +2 and +3 , whilst F- and O 2- have
oxidation numbers of -1 and -2 . For simple ions, the oxidation number is equal to the ionic charge
, e. g

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 Na  Na   e  Al  Al3  3e  Cl  e  Cl
0 +1 0 +3 0 -1
The oxidation number for an element in a covalent compound is decided, on an arbitrary basis, by
taking the oxidation number to be equal to the charge that the element would carry, if all the bonds
in the compound were regarded as ionic instead of covalent . In doing this, a shared pair or
electrons between two atoms is assigned to the atom with the greater electronegativity . Or, if the
two atoms are alike. the shared pair is split between the two, one electron being assigned to each
atom. The resulting charge on the various atoms when the bonding electrons are so assigned are
the oxidation numbers of the atoms.
a) The agebraic sum of the oxidation number of all the atoms in an uncharged compound
is zero. In an ion, the algebraic sum is equal to the charge on the ion, e. g.
N H4 O H- S O2-4 A l F63+
-3 +1 -2 + 1 +6 -2 +3 - 1

b) All elements in the elmentary state have oxidation numbers of zero, shared pairs
between like atoms being split equally.

c) As fluorine is the most electronegative elements it always has an oxidation number

of -1 in any of its compounds.
2-
d) Oxygen, second only to fluorine in electronegattivity, has an oxidation number of -2 in
almost all its compounds , e. g. .

Mg O Fe2 O3 C O2 Mn2 O 7 CrO 3

+2 -2 +3 - 2 +4 -2 +7 - 2 +6 - 2
Exceptions are provided by oxygen difluoride and the peroxides
F2 O
-1 + 2
.. ..
:O : O:
.. ..
-1 -1

the oxidation numbers in the peroxide ion being calculated by splitting the shared
pair equally between the two oxygen atoms.

e) In all compounds except ionic metallic hydrides ,the oxidation number of hydrogen is
+ 1 e. g.
HCl H2 O NH3 Li H Ca H2
+1 -1 +1 - 2 -3 + 1 +1 -1 +2 -1

f) In compounds containing more than two elements, the oxidation number of any one of them
may have to be obtained by first assigning reasonalbe oxidation numbers to the others
elements . In sulphuric acid, H2SO4, for example, the most reasonalbe oxidation numbers
for hydrogen and oxygen are +1 and -2 , given sulphur has oxidation number of +6 . Other
examples are.
H2SO3 KMNO4 K2Cr 2O 7 KClO4
+ 1 +4 -2 +1 +7 -2 +1 +6 -2 +1 + 7 - 2

g) Some elements may have widely different oxidation numbers in different compounds
as is shown by the following compounds of manganese, chromium, nitrogen and chlorine.

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 -3 -2 -1 0 1 2 3 4 5 6 7
Mn MnCl2 MnCl3 MnO2 MnO42- MnO4-
Mn2O3 Mn2O7
Cr CrCl2 CrCl3 CrO 3
Cr2O3 CrO42-
Cr 2O 72-
NH3 N2H4 NH2OH N2 N2O NO N2O3 NO2 N2O 5
NH4+ HNO2 HNO3

HCl Cl2 HClO HClO2 ClO2 HClO3 HClO4

h) When an element is oxidised its oxidation number is increased .When an element is

reduced its oxidation number is decreased. Change in oxidation number can be used to decide
whether an oxidation or a reduction has taken place. In the change from chloromethane to
dichloromethane, in following example the oxidation number of carbon is increased from -2 to 0.
The carbon is therefore being oxidised. C H3 Cl C H2 Cl2
-2 +1 -1 0 +1 -1
Common Oxidising and Reducing Agents.
Oxidising agent Effective Change Decrease in O.N.
KMnO4 in acid solution MnO 4  Mn2  5

KMnO4 in alkaline solution MnO 4  MnO 2 3

K2Cr2O7 in acid solution Cr2 O 72   Cr 3 3

dilute HNO3 NO 3  NO 3

concentrated HNO3 NO 3  NO 2 1

concentrated H2SO4 SO 24   SO 2 2

manganese (IV) oxide MnO 2  Mn 2  2

chlorine Cl  Cl 1
chloric (l) acid ClO   Cl 2
KlO3 in dilute acid lO 3  l 5

KlO3 in concentrated acid lO 3  l  4

Reducing agent Effective Change Increase in O.N.
iron(II) salts (acid) Fe2   Fe3 1
tin (II) salts (acid ) Sn2   Sn4  2
ethanediotes (acid ) C 2 O 42   CO 2 1

sulphites (acid) SO 23   SO 24  2
hydrogen sulphide S2  S 2
iodidies (dilute acid) l  l 1
iodides (concentrated acid ) l  l  2
metals,e. g.Zn Zn  Zn2  2
hydrogen H  H 1

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Balancing of Redox Equations:

Oxidation Number /State Method :

This method is based on the principle that the number of electrons lost in oxidation must be equal to
the number of electrons gained in reduction. The steps to be followed are :

i) Write the equation (if it is not complete ,then complete it ) representing the chemical
changes.

ii) By knowing oxidation number of elements , identify which atoms (s) is (are) under going
oxidation and reduction. Write down separate equations for oxidation and reduction.

iii) Add respective electrons on the right of oxidation reaction and on the left of reduction
reaction. Care must be taken to ensure that the net charge on both the sides of the equaiton
is same.

iv ) Multiply the oxidation and reduction reactions by suitable numbers to make the number of
electrons lost in oxidation equal to the number of electrons gained in reduction .

v) Transfer the coefficient of the oxidizing and reducing agents and their products to the main
equation.

vi) By hit & trial, arrive at the co-efficients of the species not undegoing oxidation or reduction.

Illustration1 : Balance the equation : P + HNO3  HPO3 + NO + H2O

Solution : P+ H N O3  H P O3 + N O + H2O
Oxidation 0 + 1 + 5 -2 -1 +5 - 2 +2 -2 +1 -2
numbers
P 0  P 5 ;
N5  N2
P 0  P 5  5e  (1) x 3

N5  3e   N2 (2) x 5

3P 0  3P 5  15e  ; 5N5  15e  5N2

Therefore coefficient of P is 3, that of HPO3 is 3, that of HNO3 is 5 and that of NO is 5.
The equation becomes.
3P + 5HNO3  3HPO3 +5NO + H2O
The equation is thus balanced.

Illustration 2 :Balance the equation : K2Cr2O7 + HCl  KCl + CrCl3 + H2O + Cl2

Solution : K2 Cr2 O7 + H Cl  K Cl + Cr Cl3 + H2 O + Cl2

+1 +6 -2 +1 - 1 +1 -1 +3 - 1 +1 - 2 0
Cr2  2 Cr 3; 2 C l  C l2

6e   Cr2  2 Cr 3; 2 Cl   Cl 2  2 e  x 3

Cr2  6e   2Cr 3 6Cl   3Cl2  6e 

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 Therefore coefficients of K2Cr2O7 is 1, that of CrCl3 is 2, that of HCl is 6 and that of Cl2
is 3
K2Cr2O7 + 6 HCl  2CrCl3 + 3Cl2
For complete balancing it can be seen that there must be 7 H2O in the product
to account for 7 oxygen in the reactant . This would make hydrogens on the right
side as 14, so we must have 14 HCl in the reactant . This would make the
coefficient of KCl as 2. Therefore
K2Cr2O7 + 14 H Cl  2 KCl + 2CrCl3 + 3Cl2 + 7 H2O

Illustration 3 : Balance the equation :

KMnO + H2SO4 + FeSO4  K2SO4 + MnSO4 + Fe2(SO4)3 + H2O

Solution : Mn+7  Mn+2 ; Fe+2  Fe2+3

Mn+7 + 5e-  Mn+2 (1) x 2 ; 2Fe+2  Fe2+3 + 2e- (2 ) x 5
2Mn+7 + 10e-  2Mn+2 ; 10 Fe2+2  5Fe2 + 3 + 10 e-
Therefore coefficient of KMnO4 is 2, that of MnSO4 is 2, that of FeSO4 is 10
and that of Fe2(SO4) is 5.
Therefore 2 KMnO4 + 10 FeSO4  2MnSO4 + 5Fe2(SO4)3
Coefficient of K2SO4 should be 1 .
2KMnO4 + 10 FeSO4  K2SO4 + 2MnSO4 + 5Fe2(SO4)3
To balance SO42- so that left hand side must have 8 H2SO4, thus H2O also
be comes 8 H2O.
2KMnO4 + 10 FeSO4 + 8 H2SO4  K2SO4 + 2Mn(SO4) + 5Fe2(SO4)3 + 8H2O

Illustration 4 : Balance the equation :

MnO4- + C2O42- + H+  CO2 + Mn+2 + H2O

Solution : Mn+7  Mn+2 ; C2  C+4

5e- + Mn+7  Mn+2 (1) x 2 ;
C2  2C+4 + 2e- ( 2 ) x 5
10e-+ 2Mn+7  2Mn+2 ; 5C2  10C+4 + 10 e-
Therefore 2MnO4- + 5C2O4-2  10 CO2 + 2Mn+2
There must be 8H2O on the right to balance O.Therefore there must be 10H+
to balance H.
2MnO4- + 5C2O4-2 + 16 H+  10 CO2 + 2Mn+2 8 H2O

Half -Reaction or Ion- Electron Method

This method involves the following steps :
i) Divide the complete equation into two half reactions, one representing oxidation and the
other reduction.

ii) Balance the atoms in each half reaction separately according to the following steps:
a) First of all balance the atoms other than H and O

b) In a reaction taking place in acidic or neutral medium, oxygen atoms are balanced by
adding molecules of water to the side deficient in oxygen atoms while hydrogen
atoms are balanced adding H+ ions to the other side deficient in hydrogen atoms.
On the other hand, in alkaline medium (OH-) ,every excess of oxygen atom on one side
is balanced by adding one H2O to the same side and 2OH- to the other side . In case
hydrogen is still unbalanced, then balance by adding one OH- for every excess of H
atom on the same side as the excess and one H2O onthe other side

c) Equalize the charge on both sides by adding a suitable number of electrons to the side

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 deficient in negative charge.

iii) Multiply the two half reactions by suitable integers so that the total number of electrons gained
in one half reaction is equal to the number of electrons lost in the other half reaction.

iv) Add the two balanced half equations and cancel any term common to both sides.

Illustration 5 :Balance the equation :

H2S + HNO3  NO + S + H2O

Solution : Oxidation : H2S  S Reduction : HNO3  NO

Balancing oxidation reaction :
H2S  S + 2H+ Balancing the charges H2S  S + 2H+ + 2e- (1)(oxidation half eq. )
Balancing reduction reaction :
3e- + 3H+ + HNO3  NO + 2H2O (2) (reducing half- reaction )
Mulitply (1) by 3 and (2) by 2 and adding (To cancel out the electrons )
3H2S  3S + 6H+ + 6e-
6e+ + 6H+ + 2HNO3  2NO + 4H2O
2HNO3 + 3H2S  3S + 2NO + 4H2O

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Solved Problems

Problem 1 : Arrange the following in order of

a) Increasing oxidation number : MnCl2 , MnO2, Mn(OH)3 ,KMnO4
b) Increasing oxidation number : HlO 4, lCl, Hl , l2
c) Decreasing oxidation number : HXO4, HXO , HXO3, HXO2

Solution : a) MnCl2 < Mn(OH)3 < MnO2 < KMnO4

Ox. no. +2 +3 + 4 +7
Hl < l2 < lCl < HlO4
b) Ox. no. +7 +5 +3 +1
HXO4 > HXO3 > HXO2 > HXO
c) Ox. no. -1 0 +1 +7

Problem 2: The composition of a sample of wustite is Fe0,93O. What percentage of iron is

present in the form of Fe(III) ?
200
Solution : Ox. no. of Fe in wustite 
93
It is an intermediate value in between the oxidation state of Fe(II) and Fe(III). let
percentage of Fe(III) in wustite be x, then
200
2 x(100  x)  (3 x x) x 100  x  15.05%
93
Problem 3 : One mole of N2H4 loses 10 mole electrons to form a new compound Y.
Assuming that all the N2 appears in new compound, what is the oxidation state of
Nitrogen in Y ?( There is no change in the oxidation state of H )
Solution : N2H4  ( Y )  10e 
( Y contains all N atoms)

 N22   ( 2N) x  10e 

b g
2 x  4  10
x = +3
 oxidation state of N in Y is + 3

Problem 4 : Balance the equation :

Cr2O72- + C2O42- + H+  Cr+3 +CO2 + H2O

Solution : Reduction : Cr2 O 72   Cr 3 Oxidation : C 2 O 42   CO 2

Balacing atoms other than O and H : Cr2 O 27   2 Cr 3

Reaction is taking place in acidic medium
Balancing O
Cr2 O 27   2 Cr 3  7H2 O
Balancing H
14  Cr2 O 27   2Cr 3  7H2 O
Balancing charges we get reduction half- reaction .
6e  14H  Cr2O27  2Cr 3  7H2O (1)
Balancing oxidation reaction:

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 Balancing C C 2 O 42   2CO 2
Balancing O C 2 O 42   2CO 2
Balancing charges, we get oxidation half-reaction
C 2 O 24   2 CO 2  2e  (2)
Multiplying (2) by 3 and adding to (1) (To cancel out the electrons )
C 2 O 27   14H  3C 2 O 24   2 Cr 3  7H2 O  6CO 2

Problem 5 : Balance the equation

Cr(OH)3  lO3  I  CrO24

Solution : Oxidation : Cr (OH) 3  CrO 24  Reduction : IO 3  l 

Balancing oxidation reaction : Balancing atoms other than H and O
Cr (OH) 3  CrO 24 
Balancing O ; 2OH  Cr( OH) 3  CrO 24   H2 O
Balancing H; 3OH  2OH  Cr ( OH) 3  CrO 24   H2 O  3H2 O
Balancing charge : 5OH  Cr( OH) 3  CrO 24   4H2 O  3e  (1)
Balancing reduction reaction :
Balancing O; lO 3  3H2 O  6OH  l 
Balance the charge 6e   lO 3  3H2 O  6OH  l ( 2)
Multiply (1) by 2 and adding to (2)
2Cr(OH)3 + IO3- + 4OH-  2CrO2-4 + 5H2O + l-

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ASSIGNEMENTS

1. Calculate the oxidation numbers of the following

i) O in F2O
ii) N in NH2OH
iii) C in CH2O
iv) C in K2C2O6
v) Fe in K3Fe(CN)6
vi) l in HlO3
vii) Mn in MnO42-
viii) Cr in CrO2Cl2
ix) P in Ca3(PO4)2
x) P in P2O74-
xi) Cr in CrO5
xii) Fe in Fe(CO)5
xiii) Cr in [Cr(NH3)6]Cl3
xiv) Fe in Fe3O4
xv) I in kl3

2. Balance the following equations by oxidation number method :

i) KMnO4 +NH3  KNO3 + MnO2 + KOH + H2O
ii) FeCl3 + H2S  FeCl2 + S + HCl
iii) Zn + HNO3  Zn(NO3)2 + N2O + H2O
iv) Cu + HNO3  Cu(NO3)2 + NO + H2O
v) S + HNO3  H2SO4 + NO2 + H2O

3. Balance the following equations by lon-electron method by acidic medium

i) Cd + l2 + HCl  CdCl2 + Hl
ii) C6H5CHO + Cr2O2-7  C6H5COOH + Cr3+
iii) S2O32- +Sb2O5  SbO + H2SO3
iv) lO4- + l- + H+  l2 + H2O
v) H2SO3 +Cr2O72-  H2SO4 + Cr3+ + H2O
vi) N2O4 + BrO3-  NO3- +Br-
vii) Au + NO3- +Cl- + H+  AuCl4- + NO2 + H2O
viii) l2 +Cr2O72- + H+  Cr3+ +lO3- + H2O
ix) Br-+BrO3- + H+  Br2 + H2O
x) SbCl3 + KlO3 + HCl  SbCl5 + lCl + H2O + KCl
xi) MNO2-4  MnO-4 + MnO2
xii) Cl2 + l2  Cl- + IO-3
xiii) KClO3 + H2SO4  KHSO4 + HClO4 + ClO2 + H2O
xiv) Cu2+ +SO2  SO42- + Cu+
xv) Cu2O + H+ +NO3-  Cu2+ +NO + H2O

4. Balance the following equations using basic medium :

(i) AsO 33  MnO 4  AsO 34  MnO 2  OH
ii) HNO 3  As 2 S5  H2 SO 4  H3 AsO 4  NO 2
iii) N2H4  Cu( OH) 2  N2  Cu
2
iv) S + OH-  S  S2 O 32 

v) S2 O 24   Ag2 O  Ag  SO 23 

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 vi) C 2H5OH  MnO 4  C 2H3O   MnO 2  H2 O
vii) FeC 2 O 4  KMnO 4  H2 SO 4  Fe 2 (SO 4 ) 3  CO 2  MnSO 4  K 2 SO 4  H2 O
viii) FeCr2 O 4  K 2 CO 3  KClO 3  Fe 2 O 3  K 2 CrO 4  KCl  CO 2
ix) H2 O 2  Pbs  PbSO 4  H2 O
x) Fe 3O 4  MnO 4  Fe 2 O 3  MnO 2
xi) Zn  NO 3  ZnO 22   NH3
xii) ClO 2  SbO 2  Sb(OH) 6
xiii) H2  Re O 4  Re O 2  H2 O
xiv) S  OH  S2  S2 O32
xv) Cl2  OH  Cl   ClO 

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ANSWERS
1. i) +2 ii) -1 iii) 0 iv) +5
v) +3 vi) +5 vii) +6 viii) +6
ix) +5 x) +5 xi) +6 xii) 0
xiii) +3 xiv) +8/3 xv) -1/3

2. i) 8KMnO 4  3NH3  3KNO 3  8MnO 2  5KOH  2H2 O

ii) 2FeCl3  H2 S  2FeCl2  S  2HCl
iii) 4 Zn  10HNO 3  4 Zn(NO 3 ) 2  N2 O  5H2 O
iv) 3Cu  8HNO 3  3Cu(NO 3 ) 2  2NO  4H2 O
v) S  6HNO 3  H2 SO 4  6NO 2  2H2 O

3. i) Cd  l2  2HCl  CdCl2  2Hl

ii) 3C 6H5CHO  Cr2 O 72   8H  3C 6H5COOH  2Cr 3  4H2 O
iii) 3S2 O 23   2 Sb 2 O 5  6H  3H2 O  4SbO  6H2 SO 3
iv) lO 4  7l  8H  4l2  4H2 O
v) 3H2 SO 3  Cr2 O 72   8H  3H2 SO 4  2Cr 3  4H2 O
vi) 3N2 O 4  BrO 3  3H2 O  6NO 3  Br   6H
vii) Au  3NO 3  4Cl  6H  AuCl4   3NO 2  3H2 O
viii) 3l2  5Cr2 O 72  34H  10Cr 3  6lO3  17H2 O
ix) 5Br   BrO 3  6H  3Br2  3H2 O
x) 2SbCl3  KlO 3  6HCl  2SbCl5  lCl  3H2 O  KCl
xi) 3MnO 24   4H  2MnO 4  MnO 2  2H2 O
xii) 5Cl2  l2  6H2 O  2lO 3  10Cl   12H
xiii) 3KClO 3  3H2 SO 4  3KHSO 4  HClO 4  2ClO 2  H2 O
xiv) 2Cu 2   SO 2  2H2 O  2Cu   4H  SO 42 
xv) 2Cu 2 O  14H  2NO 3  6Cu 2   2NO  7H2 O

4. i) 3AsO 33  2MnO 4  H2 O  3AsO 43  2MnO 2  2 OH

ii) 40HNO 3  As 2 S5  5H2 SO 4  2H3 AsO 4  40NO 2  12H2 O
iii) N2H4  2Cu( OH) 2  N2  2Cu  4H2 O
iv) 4S  6OH  2S2   S2 O 23   3H2 O
v) S2 O 42   Ag2 O  2OH  2 Ag  2 SO 23   H2 O
vi) 3C 2H5OH  2MnO 4  OH  3C 2H3O   2MnO 2  5H2 O
vii) 10FeC 2 O 4  6KMnO 4  24H2 SO 4  5Fe2 (SO 4 )3  20CO 2  6MnSO 4  3K 2 SO 4  24H2 O
viii) 6FeCr2 O 4  12K 2 CO 3  7KClO 3  3Fe 2 O 3  12K 2 CrO 4  7KCl  12CO 2

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 ix) 4H2 O 2  PbS  PbSO 4  4H2 O
x) 6Fe 3O 4  2MnO 4  H2 O  9Fe 2 O 3  2MnO 2  2OH
xi) 4 Zn  NO 3  7 OH  4 ZnO 22   2H2 O  NH3
xii) 2ClO 2  SbO 2  2OH  2H2 O  2ClO 2  Sb( OH) 6
xiii) 3H2  2 Re O 4  2 Re O 2  2H2 O  2OH
xiv) 6OH  4S  2S2   S2 O 23   3H2 O
xv) Cl2  2OH  Cl  ClO   H2 O

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