Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)

CHAPTER - 04
REDOX REACTION
I. Classical concept
A) Oxidation :

Addition of O2 : 2Mg  O 2 
 2MgO

Addition of electronegative element : Mg  Cl 2 

 MgCl 2

Removal of H2 : Zn  2HCl 
 ZnCl 2  H 2

Removal of electropositive element : 2NaI  H 2 O 2 

 2NaOH  I 2
B) Reduction

Addition of Hydrogen : H 2  Cl 2 
 2HCl

Addition of electropositive element : CuCl 2  Cu 

 Cu 2 Cl 2

Removal of O2 : Fe 2 O3  2Al 
 Al2 O3  2Fe

Removal of electronegative element : 2FeCl3  H 2 

 2FeCl 2  2HCl
II. Electron transfer concept of oxidation and reduction
OXIDATION
The reaction in which an atom or an element or an ion or molecule loses electrons is called oxidation

1.  Na   1e  ;
Neutral atom : Na   Mg 2   2e 
Mg 
2. Cation : When a cation loses electrons. There is an increase in positive charge.

Sn 2 
 Sn 4  2e 

Fe 2  
 Fe3  1e 
3. Anion : When an anion loses electron equal to its negative charge, it gets converted to a neutral
atom.

2O 2  
 O 2  4e 

2N 3 
 N 2  6e 

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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)

4. Complex anion : When a complex anion loses electron, its negative charge decreases.
4 3
 Fe  CN 6    Fe  CN 6   e 

5. When a molecule loses electrons, its breaks up into its constituents

 O 2  2H   2e 
H 2 O 2 
REDUCTION
The reawction in which an element or an atom or an ion or a molecule accepts electrons, is called
reduction.
1. Neutral atom : When a neutral element or atom accepts electrons, it get converted into an
anion.

O  2e  
 O 2

 N 3
N  3e 
2. Cation : When a cation accepts electrons equal to its charge, it gets converted into a neutral
atom.

Mg 2   2e  
 Mg

Al3  3e  
 Al
3. Similarly, when a cation accepts electrons then, its positive charge decreases.

Cu 2   1e  
 Cu 1

Fe3  1e  
 Fe 2 
4. Anion : When an anion accepts electrons, its negative charge increases.
3 4
 Fe  CN 6   1e  
  Fe  CN 6 
5. Molecule : When a molecule accepts electron, it is a reduction reaction.

O 2  4e  
 2O 2 

Cl 2  2e  
 2Cl 

Oxidation : loss of electrons by any species

Reduction :Gain of electrons by any species
Oxidising agent:Acceptor of electrons
Reducing agent:Donor of electron

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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)
Competitive Electron Transfer Reactions
Dip zinc rod in copper nitrate solution taken in a beaker A and a copper rod in silver nitrate solution in
another beaker B. After few minutes we can see that in beaker A, zinc rod partially dissolves and its
surface is coated with metallic copper. The blue colour of CuSO4 solution takes and finally it becomes
colourless. This is due to the following reaction taking place in beaker A.

 Zn 2  2e  oxidation 
Zn 
Cu 2  2e    Cu  Re duction 
2 2
Zn  Cu   Zn  Cu (Over all reaction)

In this reaction Zn acts as a reducing agent and Cu2+ acts as a oxidising agent.
In beaker B copper rod dissolves partially and its surface is coated with metallic silver from silver
nitrate solution, the solution develops blue colour due to the formation of Cu2+ ions.

 Cu 2  2e   oxidation 
Cu 
2Ag   2e  2Ag  Re duction 

Cu  2Ag   Cu  2Ag  Overall reaction 
2

Conclusion : In the above reactions, Zn releases electrons to copper and copper releases electrons
to Ag and electron releasing tendency of them is in the order Zn > Cu > Ag. These types of reactions
are called competitive electron transfer reaction.
Oxidation number : Oxidation number is the charge present on the atom of the element when it is in
combination
Rules for assigning oxidation number
1. Oxidation state of any element in the free state is zero.
For example : The oxidation state of H, P, S, O, Fe and Br in H2, P4, S8, O2, Fe and Br2, respectiely is
equal to zero.
2. In all hydrogen compounds the oxydation number per atom of hydrogen is taken to be +1. The exception
occurs when hydrogen forms compounds with strong metals [metallic hydrides].
For example : KH, NaH, MgH2, CaH2 etc. In all of these, the oxidation state of hydrogen is –1.
3. Oxidation number of oxygen is –2 in most of its compounds.
Exceptions :
 In peroxides oxidation number of oxygen is –1. Eg : H2O2, BaO2, SrO2
 In superoxides oxidation state of oxygen is –1/2. Eg : KO2, RbO2
 In OF2 oxidation number of oxygen is +2
 In O2F2 oxidation number of oxygen in +1
4. Oxidation number of halogens in halides is always –1
5. Oxidation number of fluorine is always –1
6. Oxidation number of alkali metal is always +1
7. Oxidation number of alkaline earth metal is always +2

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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)
8. In inter halogen compounds the more electronegative atom of the two halogens gets the oxidation
number of –1.

Eg : I 7 F71 , Cl 3 F31
9. The algibraic sum of all the oxidation numbers of elements in a compound is equal to zero.
Eg : KMnO4
Oxidation number of K + Oxidation number of Mn + 4 (Oxidation number of oxygen) = 0
10. The algebraic sum of all the oxidation numbers of elements in a radical is equal to net charge on the
radical.

Eg : Cr2 O7  dichromate ion 

2

2  oxidation number of Cr  7  oxidation number of O  2

11. Variable oxidation number is most commonly shown by transition elements as well as by p-block
lements.
Transition elements
Fe : +2, +3
Cu : +1, +2
Mn : +1, +2, +3, +4, +5, +6, +7
Ni : +2, +4
Co : +2, +3
p-Block elements
As : +3, +5
Sb : +3, +5
Sn : +2, +4
1. Calculate the oxidation number of all atoms in the following compounds and ions:

a. PbSO4 b. CrO 24  c. Sb2O5 d. (NH4)2SO4

a. In PbSO4 or Pb2+ (SO4)2–
Oxidation number of Pb = +2
Oxidation number of each O atom = –2
Let oxidatino number of S = x

 2  x  4  2   0  2  x  8  0  x  6
Hence, oxidation number of S in PbSO4 = +6

b. In CrO 24 
Oxidation number of each O atom = –2
Let oxidation number of Cr = x
x + 4(–2) = –2  x– 8 = –2  x = 6

Hence, oxidation number of Cr in CrO 24  = +6

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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)
c. In Sb2O5
Oxidation number of each O atom = –2
Let oxidation number of Sb = x
2x + 5(–2) = 0  2x – 10 = 0  x + +5
Hence, oxidation number of Sb in Sb2O5 = +5

d. In (NH4)2 SO4 or NH4 2 SO 24 

Let oxidation number of N in NH4 = x

Oxidation number of each H atom = +1

x + 4 (+1) = +1 (Taking NH4 )

x = –3
Hence, oxidation number of N in (NH4)2 SO4 = –3 and oxidation number of each O atom = –2
Let oxidation number of S = x
2
 x + 4 (–2) + 2 (taking SO 4 )
x – 8 = –2  or x = 6
Hence, oxidation number of S is (NH4)2SO4 = 6
1. Determine the oxidation number of following underlined elements:

a) HCN b) HNC c) HNO3 d) KO2

e) Fe3O 4 f) KI3 g) N 3 H h) Fe  CO 5

i) Fe0.94 O j) NH 2 NH 2 k) FeSO 4  NH 4 2 SO 4 6H 2 O

l) NOCl m) NOClO 4 n) Na 2  Fe  CN 5 NO 

o)  Fe  NO  H 2 O 5  SO 4 p) Na 2 S4 O6 q) (CH3)2SO

r) Na 2 S2 O3 s) CaOCl2

a) HCN : The evaluation cannot be made directly in some cases, eg. HCN, by using rules proposed
earlier as we have no rule for the evaluation of the oxidation nuber of both N and C. In all such
cases, evaluation of oxidation number should be made using indirect concept or using
fundamentals by which following rules have been formed.
i. Each covalently bond contributes one unit for oxidation number.
ii. Covalency bonded atoms with less electronegativity acquire positive oxidation number whereas
other atoms with more electronegativity acquire negative oxidatino number
iii. In case of a coordinate bond, give +2 value for oxidation number to the aotm from which
coordinate bond is directed to a more electronegative atom.

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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)

If coordinate bond is directed from a more electronegative to a less electronegative atom, then
neglect the contribution of coordinate bond for both atoms in which coordinate bond exists.
Thus, H  C  N
Three bonds on N atom implies more electronegative 1 + a + 3( –1) = 0
Oxidation number of N = 3(–1) = –3
Oxidation number of C, a = +2
b. HNC : H  C  N
Oxidation number of H = +1
Oxidation number of N

 [ 2  (1)  0]   3
[For cov alent [For cov alent [No contribution
bond with C] bond with C] for coordinate bond]
According to fundamental concept = –3
 1 + (–3) + a = 0  a = +2
c. HNO3 : By rules, 1 + a + 3 (–2) = 0  a = +5

O
By fundamental approach H O N
O
Oxidation number of H = +1
Oxidation number of N

 1]  (2)  (2)   5

[C ov alent [Two cov alent [coordinate bond]
bond with O] bond with O;
N being less
electronegative
than O]

d. KO 2 : A superoxide of K
Oxidation number of K = +1
Oxidation number of O = a
1 + 2(a) = 0 and a = -1/2

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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)

e. Fe3O 4 : 3(a + b(–2) = 0  a = +8/3

Fe3O4 is a mixed oxide of FeO.Fe2O3
Therefore, Fe has two oxidation numbers +2 and +3, respectively. However, factually speaking,
oxidation number in Fe3O4 is an average of two values, ie. +2 and +3

2    3  8
Therefore, average oxidation number = 
3 3

f. KI3 : 1 + 3 (a) = 0  a = –1/3

Since KI3 is KI + I2, therefore, I has two oxidation numbers –1 and 0, respectively.
However, oxidation number of I in KI3 is an average of two values –1 and 0.

1  2  0  1
Therefore, average oxidation number = 
3 3

g. N 3 H : 3(a) + 1 = 0  a = –1/3

h. Fe  CO 5 : Sum of oxidation number of CO = 0;  a + 5(0) = 0  a = 200/94

i. Fe0.94O : 0.94 (a) + (–2) = 0  a = 200/94

j. NH 2 NH 2 : Both N have same nature, therefore each N has oxidation number –2.

k. FeSO4  NH 4 2 SO4 6H 2 O
Oxidation number of Fe = a
Sum of oxidation number for (NH4)2 SO4 = 0
Sum of oxidation number of H2O = 0

Sum of oxidation number of SO 24  = –2

 a + (–2) + 0 + 6 (0) = 0  a = +2
l. NOCl : Cl – N = O or use NO Cl
Oxidatin number of N = +1 (for covalent bond with Cl)
Oxidation number of N = +2 (for two covalent bonds with O)
Therefore, oxidation number of N in NOCl = +3

m. NOClO 4 : The compund may be written as NO+ ClO4 for ClO4

For ClO4 , let the oxidation number of Cl = a

 a + 4 (–2) = –1  a = +7

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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)

n. Na 2  Fe  CN 5 NO  : NO in iron complex has NO nature

 2 × 1 + [a + 5(-1) + (+1)] = 0
 a = +2

o.  Fe  NO  H 2 O 5  SO 4 : a + 1 + 5 × 0 + (–2) = 0  a = +1

p. Na 2 S4 O6 : 2(+1) + 4a + 6 (-2) = 0

 a = +5/2
Here also, this value is the average oxidation number 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 cordinate bond is +5, whereas oxidation number
of each S atom involved in pure covalent bonding is zero. Therefore, average oxidation number
5  5  0  0 5
= 
4 2
q. ( C H ) SO or Dimethyl sulphoxide
3 2

Oxidation number of CH3 = +1

Oxidation number of O = –2
 2 (+1) + a + (-2) = 0  a = 0

r. CaOCl2 : In bleaching powder, two Cl atoms are as Ca(OCl) Cl, i.e., one as Cl having oxidation
number –1 and other as OCl having oxidation number +1
OXIDATION STATE OF OXYGEN IN DIFFERENT FORMS
1. Oxidation state of oxygen in Peroxides and Peracides : Oxidation state (oxidation number) of oxygen
in peroxides (–O–O–), eg : H2O2, and peroxoacids is –1.
For example:
+1 -1 -1 +1
a. Hydrogen peroxide (H2O2) : H O O H
+1 -1 -1 +1
b. Sodium peroxide (Na2O2) : Na O O Na
-1
+2 O
c. Strontium peroxide (SrO2) : Sr
-1
O

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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)

-1
+2 O
d. Barium peroxide (BaO2) : Ba
-1
O
e. Peroxosulphuric acid or peroxy sulphuric acid or permonooxo sulphuric acid or persulphuric
acid or Caro’s acid (H2SO5)

Structure:

i. Calculation of oxidation state of S in H2SO5 and their anions:

Two oxygen in peroxide bond are in –1 oxidation state = –1 × 2 = –2
Three oxygen in –2 oxidation state = –2 × 3 = –6
 H2SO5 = 2 + x –2 – 6 = 0  x = 6
Oxidation number of S = +6

ii. HSO5 ( monohydroperoxo sulphate ion)

HSO5 = 1 + x – 2 – 6 = –1  x = 6
Oxidation number of S = 6

iii. SO 52  (peroxosulphate ion)

SO 52  = x – 2 – 6 = –2  x = 6
f. Peroxodisulphuric acid or peroxydisulphuric acid or permonooxodisulphuric acid or per disulphuric
acid or Marshall’s acid (H2S2O8):
Structure

-2
O O -2
-1 -1 -2 +1
+1 -2 +6
H O S O O S +6 O H

O
O -2
-2

i. Oxide state and oxidation number of S in H2S2O8 and their anions:

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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)
Two oxygen in peroxide bond are in –1 oxidation state = –1 × 2 = –2
Six oxygen in H2S2O8 are in –2 oxidation state = –2 × 6 = –12
 H2S2O8 : 2 +2 x – 2 – 12 = 0; 2x = 12  x = 6
Oxidation number of S in H2S2O8 = +6

ii. Monohydroperoxodisulphate ion or hydro-persulphate ion HS2O8

1 + 2X – 2 – 12 = –1
2x = 12  x = 6

Oxidation number of S in S2 O82   6

g. Peroxophosphoric acid or peroxyphosphoric acid or permonooxophosphoric acid or
perphosphoric acid (H3PO)5:
Structures:

O -2
+1 -2 +5 -1 -1 +1
H O P O O H

O H
-2 +1

h. Oxidation state (oxidation number) of P in H3PO5 and their anions:

Two oxygen in peroxide bond are in –1 oxidation state = –1 × 2 = –2
Three oxygen in H3PO5 PO5 are in –2 oxidation state = –2 × 3 = –6
H3PO5 = 3 + x – 2 – 6 = 0  x  5
Oxidation number of P = +5
i. Chromium pentaoxide (butterfly structure) (CrO5) :

-2
O
-1
O O -1
Cr
+6
O O -1
-1

Oxidation state (oxidation number) of Cr in CrO5: There are two peroxide (–O–O–) bonds in
CrO5. For oxygen in two peroxide bond are in –1 oxidation state = –1 × 4 = 4
One oxygen in CrO5 is in –2 oxidation state = –2 × 1 = –2
 CrO5 = x – 4 – 2 = 0  x = +6
Oxidation number of Cr = +6

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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)
Oxidation state of oxygen in superoxides
+2 ½ +1 ½
Oxidation number of oxygen in superoxides is –1/2, eg. in K O (potassium superoxides) and Rb O
2 2
(Rubidium superoxide)
Oxidation state of oxygen, when it is bonded to fluorine
+2 -1 +1 -1
In such compounds, eg., oxygen difluodie and dioxygen difluoride O2 F2 , the oxygen is
O F2
assigned an oxidation number of +2 and +1 respectively. The number assigned to oxygen depends
upon the bonding state of oxygen but this number should be a positive figure only.
STOCK NOTATION
The oxidation number state of a metal in a compound is sometimes represented by Stock notation
given by German chemist Alfred Stock. In this notation, the oxidation number is expressed by a roman
numeral such as I, II, III, IV, V, VI, VII etc, indicating the oxidation state of the metal within parenthesis
after the symbol or name of the metal.

For example, nitrogen forms five oxides, ie. N 2 O, NO, NO 2 , N 2 O 4 and N 2 O 5 having the oxidation
number +1, +2, +4, +4 and +5, respectively. Therefore, according to stock notatin, they are represented
a

2
(I)O, N(II)O, N(IV)O2, N2(IV)O4, and N2(V)O5, respectively.
s N

Similarly, aurous chloride and auric chloride are written as Au(I)Cl and Au(III)Cl3. Similarly, stannous
chloride and stannic chloride are written as Sn(II)Cl2 and Sn(IV)Cl4, respectively. This change in oxidation
state explains whether the species is present in oxidised or reduced form.
Thus, Sn(II)Cl2 is the reduced form of Sn(IV)Cl2. Similarly, Hg2(I)Cl2 is the reduced form of Hg(II)Cl2.

 Sn 2  Re duction 
Sn 4  2e 

 Hg 22  Re duction 
2Hg 2  2e 
3. Using stock notations, represent the following compounds:
a) HAuBr4 b) Tl2O c) FeO d) Fe2O3
e) CuBr f) CuO g) MnO h) MnO2

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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)

Compound Stock notation Name of the compound

1 3 1 4
a H Au Br4 Hau(III) Br4 Hydroauric bromide

 1 2  2
b Tl 2 O Tl 2 (I)O Thallous oxide

 2 2
c Fe O Fe(II) O Ferrous oxide

 3 2  2 3
d Fe 2 O 3 Fe2(III) O3 Ferric oxide

1 1
e Cu Br Cu(I)Br Cuprous bromide

2 2
f Cu(II)Br Cupric oxide
Cu O
2 2
g Mn O Mn(II)O Manganese oxide

4  2 2
h Mn O 2 Mn(IV)O2 Manganese dioxide

Difference between valency and oxidation number (these two terms have different meansings
as explained below)

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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)

Oxidation number Valency

It is the combining capacity of an element. It is also
Oxidation number is the residual charge left on the defined as the number of H atoms or twice the
1
atom when other atoms are removed as ions number of O atoms with which an atom of the
element reacts.

It can be zero, eg., oxidation number of C in

2 It cannot be zero
CH2Br2 is zero

It refers to the charge, which can be positive or It is only a number and it is not assigned as
3 negative, eg: in CuCl2, the oxidation number of Cu positive or negative. For example, in CuCl2, the
is +2 and that of Cl is -1 valency of Cu is 2 and that of Cl is 1

It can have fractional value, eg:- oxidation number It is always a whole number, since atoms always
4
of S in K2S2O8 is +5/2 combine in simple whole numbers.

Oxidation number of an element can be different in

It is fixed in all its compounds, eg:- the valency of
different compounds, eg:- oxidation number of C in
5 C is 4 in all its compounds, such as CH4, C2H6,
CH4, C2H6, CH3Br, C2H2, CH2Br2, CCl4 and CHBr3
CH3Br, C2H2, CH2Br2, CCl4 and CHBr3.
are -4, -3, -2, -1, 0, +4 and +2 respectively

FRACTIONAL OXIDATION STATE

Fractional oxidation state is the average oxidation state of the element and the structural parameters
show that the element whose oxidation satte is determined is present in different oxidation state.
Structures and oxidation numbers of the species S4 O 62 (tetrathionate ion), C3O2 (carbon suboxide),
and Br3O8 (tribromooctaoxide) show the following bonding situations.

a. S4 O 62 (4x – 12 = –2, x = 2.5)

Oxidation number of S = 2.5
Structures:
Structure

O O
0 0
+5 +5
O S S S S O

O O

The element marked with asterisk in each species is showing different oxidation state (oxidation
number) from the rest of the atoms of the same element in each of the species.
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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)

In the species S4 O 62 , each of the two extreme S atoms shows oxidation state of +5 and the middle S
atom as 0. The average of oxidation numbers of the four sulphur atoms is 2.5, whereas the reality
being +5, 0, 0 and +5 oxidation number, respectively, for each sulphur.
b. C3O2 (3x – 4 = 0, x = 4/3)
Oxidation number of C = 4.3

+2 0 +2
Strucutre : O C C C O

In C2O2, two terminal carbon atoms are present in +2 oxidation state each, whereas the third C
atom (middle carbon) is in zero oxidation state and the average is 4/3.
Br3O8 (3x – 16 = 0, x = 16/3)
Oxidation number of Br = 16/3
Structures:

O O
O
+6 +4 +6
O Br Br Br O

O O O

In Br3O8, each of the two terminal Br atoms is present in +6 oxidation state and the middle Br
atom is present in +4 oxidation state. The average that is different from reality is 16/3.
Therefore, in general, the fractional oxidation state reality is revealed by the structures only. It is
concluded that fractional oxidation state is the average oxidation number only. This proves that
the element in that particular species is present in more than one whole number oxidation states.
III. Oxidation and reduction in terms of oxidation number
Oxidation is defined as a chemical process in which oxidation number of the element increases. On
the other hand, reduction is defined as the chemical process in which oxidation number of the element
decreases. For example, let us consider the reaction between hydrogen sulphide and bromine to give
Hydrogen bromide and sulphur.

Decrease of oxidation number

1  2 0 1  1 0
H 2 S  Br2 
 2 H Br  S

Decrease of oxidation number

In the above example, the oxidation number of bromine decreases from 0 to –1, thus it is reduced. The
oxidation number of ‘s’ increases from –2 to 0. Hence, H2S is oxidised. Let us now define the reducing
and oxidising agents in the light of the concept of oxidation number.
Oxidising agent : is a substance which undergoes increase in the oxidation number of one or more
of its elements.
In the above example, H2S is reducing agent while Br2 is oxidising agent.
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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)
Example : Identify the oxidising agent and reducing agent in the following reaction.

Decrease of ON
2 1 3 1 4 1 2 1
Sn Cl 2  2 Fe Cl3 
 Sn Cl 4  2 Fe Cl 2
Increase of ON

Oxidising agent - FeCl3

Reducing agent - SnCl2

3 1 1  2 2 1 1 1 0
Fe Cl3  H 2 S 
 Fe Cl 2  H Cl S
2. ON increases
ON decreases
Oxidising agent - FeCl3
Reducing agent - H2S
Important oxidising agents.
1. Molecule made up of electronegative elements. Eg : O2, O3, X2 (Halogens)
Note : Fluorine is the strongest oxidant
2. Compounds containing an element which is the highest oxidation state.
Eg : KMnO4, K2Cr2O7, Na2Cr2O7, CrO3, H2SO4, HNO3, FeCl3 etc
3. Oxides of elements
Eg: MgO, CuO, CrO3, CO2, P4O10 etc.
Important reducing agents:-
1. Metals : Eg- Na, Zn, Fe, Al etc
2. Few non metals : Eg - C, H2, S etc
3. Hydracids - HBr, HI, H2S etc
4. Few compounds containing an element in the lower oxidation state.
Eg: FeCl2, FeSO4, SnCl2, Cu2O
5. Metallic hydrides Eg : NaH, LiH etc
6. Organic compounds like HCOOH and (COOH)2
Substances which acts as oxidising as well as reducing agents
H2O2, SO2, H2SO3, HNO2, NaNO2, Na2SO3 etc.
Tips for the identification of oxidising and reducing agents:
If an element is in its highest possible oxidation state in a compound, the compound can function as
an oxidising agent.
Eg: KMnO2, K2Cr2O7, HNO3, H2SO4, HClO4 etc
If an element is in its lowest possible oxidation state in a compound, the compound can function only
as a reducing agent.

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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)

Eg: H2O2, H2SO3, HNO2, SO2 etc.

Highly electronegative element is in its highest oxidation state in a compound, that compound can
function as powerful oxidising agent.
Eg: KClO4, KClO3, KBrO3, KIO3 etc.
An electronegative element is in its lowest possible oxidation state in a compound or in a free state, it
can function as powerful reducing agent.
Eg : I–, Br–, N3– etc.

TYPES OF REDOX REACTIONS

1. Combination Reactions : A reaction is which two atoms or molecules combine together to form a
third molecule is called a combination reaction. For example A  B 
C .
Either A or B both A and B must be in the elemental form for such a reaction to be a redox reaction. All
combustion reactions in which elemental oxygen is used and all other reactions that involve elements
other than oxygen are redox reactions. For example.
0 0 3 3
a. 
3M g(s)  N 2 (g)   Mg 3 N 2  s 

0 0 4  2

b. C(s)  O 2 (g)   C O 2 (g)
4 1 0 4 2 1 2
c. 
C H 4 (g)  2 O 2 (g)   C O 2 (g)  2 H 2 O   

0 0 1 3
d. Li  s   N 2 (g) 

 Li3 N  s 
In reaction (c) , there is no change in the oxidation number of hydrogen.
2. Decomposition Reactions : Decomposition reactions are those in which when a molecule breaks
down to form two or more components, at least one of them must be in the elemental state. Thus,
decomposition reactions are reverse of combination reactions. For example:
1 5 2 1 1 0
a. 
2 K Cl O3s    2 K Cl  s   3O 2 (g)

2 1 0 0

b. Ca H 2   Ca(s)  H 2 (g)
1 1 0 0

c. 2Na H   2Na(s)  H 2 (g)
1 2 0 0
d. H 2 O    

 2H 2 (g)  O 2 (g)
3. Displacement Reactions : A reaction in which an atom or ion in a compound is replaced by an atom
or ion of another element is called a displacement reaction. It may be denoted as: X  YZ 
 XZ  Y

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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)

Types of displacement reactions

These are two types :
a. Metal displacement reactions
b. Nonmetal displacement reactions
a. Metal displacement reactions : In these reactions, a metal in the compound is displaced by
some other metal in the uncombined or elemental state.These reactions are used in metallurgical
processes in which pure metals are obtained from their compounds in ores.
For example :

In all the above cases, the reducing metal is a better reducing agent than the one that is being
reduced, which shows more capability to lose electrons as compared to the one that is reduced.
a. Non-metal displacement reactions : In these reactions, a metal or nonmetal displaces another
nonmetal from its compound. These nonmetal displacement redox reactions include hydrogen
displacement and the rarely occurring reaction involving oxygen or halogens displacement.
i. All alkali metals and some alkaline earth metals (Ca, Sr, and Ba) which are very good reductants
displace hydrogen from cold water, for example,

ii. Less reactive metals such as Mg and Fe react with steam to produce dihydrogen gas, for
example,

iii. Many metals, including those which do not react with cold water, displace dihydrogen from
acids, for example,

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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)

The reactions of Z and Mg with HCl are used in the preparation of dihydrogen gas in the
laboratory.
Reactivity of Metals
The reactivity of metals is determined by the rate of evolution of H2 by metals from H2O and aqueous
acids, for example, Na reacts with water at the fastest rate, Mg reacts slowly, Fe reacts at teh slowest
rate while Ag, and Au do not react at all.
Order of reducing acitivty : Z n > Cu > Ag
Reactivity of Nonmetals
The nonmetals, such as halogens, have a tendency to accept electrons, therefore, their reactivity
depends upon their oxidising power.
Order of decreasing oxidising power of halogens is : F2 > Cl2 > Br2 > I2
Thus F2 is the strongest oxidising agent; it displaces Cl2, Br2 and I2 from the solutions of their respective
ions (Cl–, Br– and I–). F2 is very reactive so it displaces O2 from H2O, for example:

F2  2Cl 
 Cl2  2F

F2  2Br 
 Br2  2F

F2  2I 
 I 2  2F
Disproportionation 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 substances is in the intermediate oxidation state, and both lower and higher oxidation states
of that element are formed in the reaction.

For examples
1. Decomposition of H2O2 (hydrogen peroxide) to H2O and O2. In H2O2, –1 oxidation state of O is
converted to zero oxidation state in O2 and decreases to –2 oxidation state in H2O

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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)
2. Phosphorous, sulphur and chloride undergo disproportionation in the basic medium as given below:

3.

4.

5.

6.

Fluone does not show a disproportionation reaction since it is the most electronegative element,
therefore it cannot exhibit any positive oxidation state. The reaction of fluorine takes place as follows
Comproportionation Reaction : Conproportionation reaction is the revers of disproportionation reaction.
For example, Br and BrO3 in acidic medium undergoes oxidation and reduction respectively to give
Br2.

Example :

Intermolecular redox reaction : It is similar to redox in which one molecule is oxidised and other molecule
is reduced. For example,

Reduction

5KI + KIO3 + 6HCl 3I2 + 6KCl + 3H2O

a.
Oxidation

Reduction

NO3 + H2S + H + H2O NH4 + HSO4

b.

Oxidation

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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)

Intramolecular Redox reaction : In this reaction one atom of a molecule is oxidised and another is
reduced. For example,

Oxidation
+7 +4
2Mn2O7 4MnO2 + 3O2
a.
Reduction

Oxidation
-1
+5
b. 2KClO3 2KCl + 3O2
Reduction

BALANCING OF REDOX REACTIONS

Two methods are commonly used for balancing chemical equations involving redox reactions. The
first method is based on the change in the oxidation number of the oxidant and the reductant (oxidation
number method) and the second method is based on splitting the redox reaction into two half reactions,
one involving oxidation and the other involving reduction (ion-electron method)
a. Oxidation number method
The various steps involved are:
i. Write the skeletal equation for all the known reactants and products of the reaction
ii. Indicate the oxidation number of all the atoms in each compound in the skeletal equation and
ignore the atoms or groups in which there is no change of oxidation number. Now identify the
atoms undergoing change in their oxidation number.
iii. Calculate the increase or decrease in the oxidation number per atom and then for the whole
molecule in which it occurs. If these are not equal then multiply by suitable coefficients so that
these become equal.
iv. Balancing the chemical equation with respect to all atoms except H and O.
Finally balance with respect to H and O atoms. For balancing oxygen atoms and water molecules
to the side deficient in it. Balancing of hydrogen atoms will depend on the medium (acidic or
basic) as explained below.
a. If the reaction is in an acidic medium then the deficiency in hydrogen atoms can be made up by
adding H+ ions on the side that is deficient in it.
b. If the reaction is in a basic medium the deficiency in hydrogen atoms can be made up by adding
water molecules on the deficient side and adding equal number of OH– ions on the other side of
the equation.
Finally, the equation is balanced by cancelling common species present on both sides of the
equation.

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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)
1. Dichromate ion in aqueous acidic medium reacts with ferrous ion to give ferric and chromic
ions. Write the balanced chemical equation corresponding to the reaction.?

i. The skeletal equation is Cr2 O 72   Fe 2  

 Cr 3  Fe3
ii. Write the oxidation number of each atom.

O.N decreases by 3

+6 -2 +2 +3 +3
Cr2 O 72  Fe 2 
 Cr 3  Fe3

O.N increases by 1

iii. The oxidation number of Cr in chromate ion is +6 and it changes to +3 in Cr3+ and the oxidation
number of Fe2+ is +2 and changes to +3 in Fe3+. Therefore chromate ion acts as the oxidant and
Fe2+ acts as the reductant. The oxidation number of chromium atom decreases by 3 and for
dichromate ion contaiing two chromium ions, the total decrease in 6. The oxidation number of
iron increases by 1. In order to equalise the increase and decrease in oxidation number of the
oxidant and reductant, we must multiply Fe2+ by 6.

Cr2 O 72   6Fe 2  
 Cr 3  Fe 2
iv. Now balancing all elements on both sides except O and H we get

Cr2 O 72   6Fe 2  
 2Cr 3  6Fe3
v. F o r b a l a n c i n g O a t o m s o n b o t h s i d e s a d d 7 H O molecules to the RHS.
2

Cr2 O 72   6Fe 2   14H  

 2Cr 3  6Fe3  7H 2 O

Thus, the balanced equation is Cr2 O 72   6Fe 2   14H  

 2Cr 3  6Fe3  7H 2 O

Thus, the balanced equation is Cr2 O 72   6Fe 2   14H  

 2Cr 3  6Fe3  7H 2 O
2. Permanganate ion reacts with bromide ion in basic medium to give manganese dioxide and
bromate ion. Write the balanced chemical equation for the reaction.
i. The skeletal equation is

MnO 4  Br  
 MnO 2  BrO3
ii. Write the oxidation number of each atom.

O.N decreases by 3

+7 -2 -1 +4 -2 +5 -2
MnO 4  Br  
 MnO 2  BrO3

O.N increases by 6

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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)

iii. The oxidation number of Mn decreases from +7 to +4 and Br increases from –1 to +5. Therefore
permanganate ion acts as the oxidant and Br– acts as the reductant. In order to have equal
increase in oxidation number of reductant and decrease in the oxidation number of oxidant, we
should multiply permanganate ion by 2.

2MnO 4  Br  
 MnO 2  BrO 3
iv. Balance all atoms other than H and O on both sides.

2MnO 4  Br  
 MnO 2  BrO 3
v. Now balancing for oxygen atoms we add one H2O molecule on RHS

2MnO 4  Br  
 MnO 2  BrO 3 + H2O
vi. As the reaction takes place in basic medium for balancing for 2H atom, we add 2 water molecules
on LHS and two OH– ions on RHS.

2MnO 4  Br   2H 2 O 
 2MnO 2  BrO 3  H 2 O  2OH 
Cancel one water molecule from both sides. We get the balanced chemical equation as

2MnO 4  Br   H 2 O 
 2MnO 2  BrO 3  2OH 
B. Ion-electron method (Half reaction method)
In this method first of all identify the oxidant and the reductant in the skeletal equation and then split the
redox reaction into two half reactions corresponding to oxidation and reduction. The balancing of the
equation is carried out systematically in various steps discussed below.
i. Indicate the oxidation number of each atom involved in the reaciton . Identify the elements which
undergo a change in the oxidation number.
ii. Divide the skeletal redox equation into two half reactions, oxidation half and reduction half. In
each half reaction balance the atoms which undergo the change in oxidation number.
iii. Add electrons to the side to make up for the difference in oxidation number in each half reaction.
iv. Balance oxygen atom by adding proper number of H2O molecules to the side which is falling
short of O atoms in each half reaction.
v. In the acidic medium, H atoms are balanced by adding H+ ions to the side deficient in H atoms.
However, in the basic medium, H atoms are balanced by adding H2O molecules equal in number
to the deficiency of H atoms and equal number of OH– ions are included in the opposite side of
the equation.
vi. Multiply the half reaction equations by appropriate coefficients so that the number of electrons
involved in both the equations is same. Add the two equations and cancel the electrons and
other common species on both sides.

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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)

1. Permanganate ion reacts with ferrous ion in acidic medium to give Fe 3+ and Mn2+ ions. Write
balanced chemical equation for the reaction?
i. Write the oxidation number of each element in the skeletal equation.

O.N increases by 1

+7 -2 +2 +2 +3
MnO 4  Fe 2 
 Mn 2  Fe3

O.N. decreases by 5

ii. Since the oxidation number of Mn decreases from +7 to +2 and the oxidation number of Fe
increases from +2 to +3, permanganate ion is reduced and ferrous ion is oxidised. Therefore
we can write the half reactions as

 Mn 2  Re duction half 
Mn 7 O4 

 Fe3  oxidation half 

Fe2 
iii. Add sufficient number of electrons to the half reaction.

 Mn 2  Re duction half 
MnO4  5e 

 Fe3  1e  Oxidation half 

Fe2 
iv. It can be seen that the half reactions are always balanced with respect to other atoms and now
balancing with respect to oxygen atoms by adding water molecules and for hydrogen by adding
H+ ions (acidic medium) we get

MnO 4  5e   8H  
 Mn 2  4H 2 O (Re duction half ) .............(1)

 Fe3  1e  oxidation half  ...................(2)

Fe2 
v. To balance the number of electrons lost in equation (2) and gained in equation (1), multiply
equation (2) by 5.

5Fe 2  
 5Fe3  5e  (Oxidation half) ..............(3)
vi. Add equation (1) to (3)

MnO 4  5Fe 2  8H   5e  
 Mn 2  5Fe3  4H 2 O  5e 
 The balanced chemical equation is
MnO 4  5Fe 2  8H   
 Mn 2  5Fe3  4H 2 O

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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)

2. Balance the following equation in basic medium. Cl 2  OH  

 Cl   ClO3
i. Write the oxidation number of each element in the skeletal equation

O.N. inccreases by 5

0 -1 +5

 Cl  ClO3
Cl 2  OH 

O.N. decreases by 1

ii. It can be seen that Cl atom has oxidation number 0 in chlorine gas while in chloride ion it is –1
and in chlorate ion it is +5. ie, chlorine undergoes both oxidation and reduction.
 the two half reactions are
0 -1
 Cl 
Reduction half : Cl 
2

0 +5
 ClO3
Oxidation half : Cl 
2

iii. Balance all atoms other than O and H

0
 2Cl 
Reduction half : Cl 2 

 2ClO 3
Oxidation half : Cl 2 
iv. Add sufficient number of electrons to the half reactions

Reduction half : Cl 2  2e  
 2Cl 

 2ClO 3  10e 
Oxidation half : Cl 2 
v. Balance O atoms by adding water molecules on the deficient side

Reduction half : Cl 2  2e  
 2Cl 

 2ClO 3  10e 
Oxidation half : Cl 2  6H 2 O 
vi. The reaction takes place in alkaline medium and for balancing of hydrogen atoms add water
molecules on the deficient side and equal number of OH– ions on the opposite side.

Reduction half : Cl 2  2e  
 2Cl  ...............(1)

Oxidation half : Cl 2  6H 2 O  12OH  

 2ClO 3  10e   12H 2 O............(2)
vii. To balance the number of electron lost in equation (2) and gained in equation (1), multiply equaiton
(1) by 5.

Reduction half : 5Cl 2  10e  

10Cl  ...........(3)

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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)
viii. Add equation (2) to (3)

Cl 2  6H 2 O  12OH   5Cl 2  10e  

 2ClO 3  10e   12H 2 O  10Cl 

6Cl 2  12OH  
10Cl   2ClO 3  6H 2 O
The above equation is balanced but does not have the simplest coefficients. Thus, divide both
sides by 2.

3Cl 2  6OH  
 5Cl   ClO 3  3H 2 O
EQUIVALENT WEIGHT OF OXIDANT AND REDUCTANT
Equivalent weight of oxidant

molar mass
E oxidaant 
Number of electron gained by one molecule
1. Eg : Equivalent weight of KMnO4
Equivalent weight of KMnO4 in acidic medium

M
 Mn 2 ; E 
MnO 4  5e  
5
Equivalent weight of KMnO4 in basic or neutral medium

M
 MnO 2 ; E 
MnO 4  3e  
3

MnO 
Equivalent weight of KMnO4 in strong basic medium  Permanganate4 ion 
 1e  
 MnO 42 ; E = M
 Manganate ion  1
2. Eg : Equivalent weight potassium dichromate (K2Cr2O7) in acidic as well as basic medium

M
Cr2 O 72  6e  
 Cr 3 ; E 
6
Equivalent weight of reductant

molecular mass
E reduc tan t 
No.of electron lost by one molecule
Examples:

M
1. Sn 2 
 Sn 4  2e  ; E 
2

M
2. Fe 2 
 Fe3  1e  ; E 
1
Equivalent weight of the element or compound in disproportionation reaction
Equivalent weight is the sum of the equivalent weights in oxidation and reduction reaction, i.e. (M/n1 +
M/n2), where M is the molecular mass of the compound and n1 and n2 are the number of electrons in
oxidation and reduction reactions, respectively.
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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)
For example, the equivalent weight of P4 in the disproportionation reaction shown below is:

REDOX REACTIONS AS THE BASIS FOR TITRATIONS

Redox titrations can be performed in the same manner as acid-base titrations by titrating one reagent
with the other. The end point is detected with the help of a redox indicator which changes colour on
oxidation of reduction. In some cases, such as oxidation by permanganate ions, the reactant itself
undergoes colour change and functions as an indicator. The usage of indicators in redox titration is
illustrated below.
i. Permanganometric titrations
It involves the use of potassium permanganate (KMnO4) as oxidising agent and reducing agents such
as ferrous salts, oxalate ions, oxalic acid etc in acidic medium.

Eg: MnO 4  5Fe 2   8H  

 Mn 2  5Fe3  4H 2 O




Here permanganate ion MnO 4 acts as the self indicator. The visible end point is achieved when the
last trace of reductant is oxidised and the first lasting linage of pink colour appears.
ii. Dichrometric titrations
In this, the oxidising agent is potassium dichromate (K2Cr2O7) in acidic medium.

Eg : Cr2 O 72  6Fe 2   14H  

 2Cr 3  6Fe3  7H 2 O

Here Cr2 O 72  is not a self indicator. In dichrometric titrations, diphenylamine is used as indicator,,

which is oxidised to blue colour at the end point by Cr2 O 72  ions.

iii. Iodimetric and Iodometric titrations

Iodimetric titrations
Iodimetry is concerned with the titrations using a standard solution of iodine while iodometry deals
with the titration of iodine liberated in chemical reactions. Starch is used as indicator. Starch reacts

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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)
with iodine in presence of iodide to form a blue complex. This is a very sensitive colour reaction.
Iodimetric titrations involve the direct used of iodine as oxidising agent and thiosulphates, , sulphates,
aresenates etc as reducing agents.

I 2  2S2 O32  
 2I   S4 O 62
Iodometric titrations
These titrations involve the indirect use of iodine for estimation of oxidising agents like KMnO4, K2Cr2O7,
CuSO4, etc. Which oxidises I– ions to I2.

2Cu 2   4I  
 Cu 2 I 2  I 2
Iodine thus obtained is titrated against sodium thiosulphate solution.

I 2  2S2 O32  
 2I   S4 O 62
On addition of starch after the liberation of iodine from the reaction of Cu2+ ions on iodide ions, an
intesnse blue colour appears. This colour disappears when iodine is consumed by the thiosulphate
ions. Thus, the end point can easily be determined.
REDOX REACTIONS AND ELECTROCHEMICAL CELLS
In aqueous solutions, the spontaneous redox reactions can be carried out directly as well as indirectly.
The energy liberated during the direct and indirect redox reactions appear in different forms. Let us
discuss briefly, the direct and indirect redox reactions.
1. DIRECT REDOX REACTIONS : A redox reaction in which oxidation and reduction takes place
int he same vessel is called direct redox reaction. In such reactions, the transference of electrons
from reducing agent to oxidising agent occurs over a very short distance (generally within the molecular
diameters). For example, if a zinc rod is immersed in copper sulphate solution taken in a beaker, a
spontaneous reaction takes plae and the following observations are made:

i. Zinc rod starts dissolving and loses its mass gradually.

ii. The blue colour of CuSO4 solution slowly fades
iii. A reddish brown precipitate of copper settles down at the bottom of the beaker
iv. The reaction is exothermic, i.e., it takes place with the evolution of heat
v. The solution remains electrically neutral

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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)
vi. The reaction does not continue indefinitely but stops after some time.
The overall reaction taking place in the beaker may be represented as:

Zn  s   Cu 2 (aq)  SO24 (aq) 

 Zn 2  aq   SO 24  aq   Cu  s 

from copper sulphate

Discarding the common SO 24  ions. Zn  s   Cu  aq  

 Zn 2 (aq)  Cu  s 
2

INDIRECT REDOX REACTIONS AND ELECTROCHEMICAL CELLS

The redox reactions in which oxidation and reduction take place in different vessels are
called indirect redox reactions. In such reactions, the transference of electrons between reducing
agent and oxidising agent takes place indirectly through the conducting wires. The arrangement for
carrying out the indirect redox reaction is referred to as electrochemical cells.
Electrochemical cell or Galvanic cell : An electrochemical cell is a device in which chemical energy
is converted into electrical energy. These are also called galvanic cells or voltaic cells after the names
of Luigi Galvani and Alessandro Volta respectively who were among the first few to conduct experiments
on conversion of chemical energy into electrical energy.
In order to understand as to how the indirect redox reaction is used to produce electfical energy let us
consider one of the simplest electrochemical cells involving reaction between zinc and copper
sulphate(Daniell cell).
Daniell cell is a simplest form of galvanic cell, a zinc rod is placed in ZnSO4 solution and a copper rod
is placed in CuSO4 solution in two separate beakers. The two metallic rods which act as electrodes
are connected by a conducting wire through a voltmeter. The two solution are joined by the inverted U-
tube known as salt bridge. The tube is filled with squeous solution os some electrolyte such as KCl,
KNO3 or NH4Cl to which gelatin or agar-agar has been added to convert it into semi-solid paste. A
schematic diagram of this cell has been shown in figure.

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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)
Observations
i. There is a deflection in the voltmeter which indicates the flow of electrons through the connecting
wires.
ii. The direction of deflection indicates the flow of conventional current from copper to zinc indicating
that copper is +ve terminal and zinc is -ve terminal.
iii. The zinc rod loses mass whereas the copper rod gains mass.
iv. The concentration of zinc sulphate solution increases and that of copper sulphate solution
decreases.
v. The solutions in the two beakers remain electrically neutral throughout.
vi. the reaction as well as the flow of electrons stops after some time.
Now let us explain the above observations in terms of working of cell. Zinc atoms undergo oxidation
and are oxidised to Zn2+ ions, by losing electrons. Zn  s    aq   2e
2
 Zn
The electrons liberated during oxidation are pushed through the connecting wire to copper rod where
these are picked up by Cu2+ ions, which get reduced to copper atoms. The copper atoms as formed
get deposited on the copper rod. That is why copper rod gains weight.

 Cu  s 
Cu 2 (aq)  2e 

The overall reaction taking place in the cell is : Zn  s   Cu (aq) 

 Zn 2 (aq)  Cu  s 
2

The electrode at which oxidation takes place is called anode and that at which reduction takes place
is called cathode. In the above electro-chemical cell oxidation occurs at the zinc rod, therefore, zinc is
anode and reduction occurs at the copper rod, hence, copper is cathode. It may be noted that anode
electrode constitutes –ve terminal and the cathode electrode constitutes +ve terminal of the cell.
By convention, the direction of flow of current is from +ve terminal to -ve terminal which is opposite to
the flow of electrons.
Function of salts bridge : In the electrochemical cell a salt bridge serves two very important functions:
i. It allows the flow of current by completing the circuit
ii. It maintains electrical neutrality
It may be explained as follows:
The transference of electrons from zinc anode to copper cathode leads to development of a net
positive charge around the anode due to formation of Zn2+ ions and net negative charge around the
cathode due to deposition of Cu2+ ions as Cu(s) on the `cathode. The positive charge accumulated
around the anode will prevent electrons to flow from it and the negative charge (due to excess of SO 24 
ions) collected around the cathode will prevent the acceptance of electrons from the anode. As the
transference of electrons stops, no current will flow. The salt bridge come to the aid and restores
electrical neutrality of the solutions in the two compartments. It contains a concentrated solution of an
inert electrolyte, the ions of which are not involved in electrochemical reactions. The anions (Cl–) of
the electrolyte migrate to the anode compartment and cations. (i.e. K+ ions) migrate to the cathode
compartment so that the solutions in these compartments become neutral and the flow of electron
continues. Thus, the salt bridge helps to prevent the accumulation of charges and maintains the flow
of current.

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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)
HALF CELL AND HALF CELL REACTIONS
It has been pointed out that oxidation and reduction in the electrochemical cell take place in different
vessels. These two parts of the electrochemical cell are called half cells and reactions taking place in
them are called half cell reactions. The half cell in which oxidation takes place is called oxidation half
cell and the reaction taking place in it is oxidation half cell reaction. Similarly, the half cell in which
reduction takes place is called reduction half cell and the reaction taking place in it is called reduction
half cell reaction. For example, the half cell reactions in zinc-copper sulphate cell are:

Zn  s  
 Zn 2 (aq)  2e (Oxidation half cell reaction)
Similarly, copper electrode and copper sulphate solution constitute reduciton half cell.

Cu 2  aq   2e 
 Cu  s  (Reduction half cell reaction)
Representation of Galvanic cell
The electrochemical cell can be represented briefly according to certain universally accepted
conventions as described below:
1. The half cell is usually represented as M/Mn+ or Mn+/M where M represent the symbol of the element
and Mn+ represents its cation in electrolyte. The line(/) represents the interface between the two phases
(may be solid/liquid or liquid/solid/gas). The concentration of electrolyte may also be mentioned in
brackets.
Therefore Galvanic cell is representd as

Electrode potential (E)

Electrode potential is a measure of the tendency of an electrode to gain or lose electrons. When it is
dipped in its own solution. The tendency of an electrode to loss electrons is called oxidation potential
(Eoxi). The tendency of an electrode to gain electrons is called reduction potential (Ered). Oxidation
potential is numerically equal to reduction potential but opposite sign. According to IUPAC convension,
the reduction potential alone is called electrode potential.
EMF of the cell (Ecell)
The difference in the electrode potentials of the two electrodes of the cell is termed as electromotive
force. (Ecell or Cell voltage). Mathematically, it can be expressed as

E cell  E cathode  E anode

Since in the representation of a cell cathode is written on right hand side and anode on left hand side,
therefore, EMF of a cell is also sometimes written as

EMF = E right  E left  E R  E L

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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)
Standard and Electrode Potential (E ) 0

The electrode potential under standard conditions (298 K temperature, 1 bar pressure, and 1M
concentration) is called Standard Electrode Potential.
Standard Hydrogen Electrode (SHE)
SHE hydrogen electrode consists of a platinum wire sealed into a glass tube and carrying a plantinum
foil at one end. The platinum foil is coated with finely divided platinum. This electrode is placed in
beaker containing an aqueous solution of some acid (HCl) having one molar concentration of H+ ions.
Hydrogen gas at one atmospheric pressure is continuously bubbled through the solution at a
temperature of 298 K. The oxidation or reduction in the SHE takes place at platinum foil.

 2H  (aq)  2e
When SHE acts as anode, oxidation will take place at it as H 2(g) 

1
In such a case it is represented as Pt, H 2 / H  1M 
2
When SHE acts as cathode, reduction will take place at it as

2H  (aq)  2e 
 H 2(g)

1
In this case it is represented as H+ (1M) / H 2 , Pt . Pt here, is an inert electrode.
2
The electrode potentials of other electrodes are determinated by coupling them with SHE. The electrode
potential of an electrode determined relative to the standard hydrogen electrode under standard
conditions is called standard electrode potential. It is represented as E0. The standard conditions are
1M concentration of ions in the solution, 298 K temperature and 1 atmospheric pressure.
MEASUREMENT OF STANDARD ELECTRODE POTENTIALS
In order to determine the standard electrode potential of an electrode, the electrode in standard conditions
is connected to standard hydrogen electrode to constitute a cell. If the electrode forms the negative
terminal of the cell, it is allotted negative electrode potential and if it forms the positive terminal of the
cell, it is allotted a positive value of electrode potential. The potential difference between the electrodes
is determined with the help of voltmeter (or more correctly by potentiometer). At the same time, direction
of flow of current is also observed which gives the idea of direction of flow of electrons. Electron flow
occurs from anode to cathode whereas current flows from cathode to anode.

E 0cell  E cathode
0
 E anode
0

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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)

Knowing the E 0cell and electrode potential of one of the electrodes (SHE), the electrode potential of the
other electrode can be calculated.
For example, in order to findout standard electrode potential of zinc electrode, zinc electrode containing
1M concentration of Zn2+ ions is the connected to SHE as shown in figure.

The voltmeter reading shows the potential difference E 0cell of 0.76 volt and direction of conventional
current is observed to be from SHE to zinc. This implies that zinc electrode acts as anode and SHE
acts as cathode.

E 0cell  E 0cathode  E anode

0
 E 02H  / H  E 0Zn 2 / Zn
2

0.76  0  E 0Zn 2 / Zn

E 0Zn 2 / Zn  0.76 volts

Similarly, when standard copper electrode is coupled with SHE, the voltmeter reading shows as potential
0
 
difference E cell of 0.34 volt. The direction of flow of conventional current is from copper to SHE. This
means that, in this cell copper acts as cathode and SHE acts as anode.

= E Cu 2 /Cu  E 2H  / H 2
0 0
E 0cell  E cathode
0
 E anode
0

0.34  E 0Cu 2 /Cu  0

E 0Cu 2 /Cu  0.34 volts

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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)

ELECTROCHEMICAL SERIES
The arrangement of various elements in order of increasing values of standard reduction potentials is
called electrochemical series or activity series.
Standard Electrode (Reduction) Potentials at 298 K (Electro-chemical Series)

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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)
Applications of the electrochemical series
1. Calculation of the standard EMF of the cell, From the electrochemical series, the standard reduction
potentials of electrodes are found out. The electrode with higher reduction potential is taken as cathode
and other as anode. From this EMF of the cell is calculated as

EMF0  E 0cathode  E anode

0

Qn. Calculate the EMF of the given cell, also write the overall cell reaction.

Zn | Zn 2 1M  || Ag  1M  | Ag . Standard reduction potential for Zn 2 / Zn is –0.76 volts and for Ag+/
Ag is 0.80 volts.
Solutions : It is clear from the cell, that silver electrode acts as a cathode and zinc electrode acts as
anode:

a) Ag   e  
 Ag; E 0  0.80 volts

Zn 2  2e  
 Zn ; E0 = –0.76 volts
Multiply the first equation by 2 so as to equalise the number of electrons

b) 2Ag   2e  
 2Ag; E 0  0.08 volts ..............(i)

Zn 2   2e  
 Zn ; E 0  0.76 volts .............. (ii)

EMF = E cathode  E anode = 0.80 – (-0.76) = 1.56 volts.

0 0

The overall cell reaction can be obtained to subtracting equation (ii) from equation (i).

2Ag (aq)  Zn  s  
 2Ag  s   Zn (aq)
2

2. Comparison of the reactivities of metals.: The metal having smaller reduction potential can displace
metals having larger reduction potential from the solutions of their salts. In other words, the metal
occupying higher position in the series can displace the metals lying below it from the solutions of their
salts. For examlpe, zinc lies above copper in the series and hence, it can displace copper from
copper sulphate solution. Copper cannot displace zinc from zinc sulphate solution because it lies
below zinc in the series and hence, it is less reactive.
3. Predicting the feasibility of a redox reactions. With the help of electromotive series we can predict
whether a given redox reaction will take place or not. From the given equation the substances undergoing
oxidation and reduction are identified. The substance undergoing oxidation will act as anode and the
substance undergoing reduction will act as a cathode. The EMF of this hypothetical cell is calculated
as under:

EMF = E 0cathode  E anode

0

If EMF comes out to be positive the given redox reaction will take place and if EMF comes out to be
negative the given redox reaction will not take place.

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Brilliant STUDY CENTRE CHEMISTRY (ONLINE CLASS NOTES)
Qn. Predict whether the following redox reaction is feasible or not under standard conditions:
2 2
Sn (aq)  Cu(s) 
 Sn(s)  Cu (aq)

Given that ESn 2 /Sn  0.136 volts and E Cu 2 /Cu  0.34 volts
0 0

Solution : The above reaction can be split into two half reactions as given below:

Cu  s   2
 Cu (aq)  2e ...................... oxidation
2
Sn (aq)  Sn  s  ....................... reduction
 2e 
Since at copper electrode oxidation takes place so it acts as anode and at tin electrode reduction
takes place so it acts as cathode.

EMF = E cathode  E anode  E Sn 2 /Sn  E Cu2 /Cu = 0.136  0.34  0.476 volts
0 0 0 0

Since the value of EMF comes out to be negative, the given reaction is not feasible.
4. To compare oxidising and reducing powers of elements
Electrochemical series helps to identify a good oxidising agent or reducing agent. All the substance
appearing on the top of the electrochemical series are a good reducing agent. ie, they have negative
value of standard reduction potential. Whereas those appearing on the bottom of the electro chemical
series are a good oxidising agent. That is they have positive value of standard reduction potential. For
example fluorine electrode with a standard reduction potential value of +2.87 V is a strong oxidising
agent and Li+ with standard reduction potential value of –3.05 V is a strong reducing agent.
5. To predict the reaction of a metal with dilute acids to liberate hydrogen gas.
Some metals like Fe, Zn react with dil.acids like HCl, H2SO4 to liberate H2 gas while some metals like
Cu, Ag do not liberate H2 gas with dil.HCl, dil.H2SO4. A prediction about capacity of a given metal to
produce H2 gas by its reaction with dilute acids can be easily made from the knowledge of electromotive
series. Chemical reaction between metal and acid can be represented, in general as

M  nH  
 M n   n / 2H 2
Metal From acid

For the above reaction to occur, the E 0red of metal (Mn+/M) must be lower than that of hydrogen. Hence,
it can be concluded that metals which lie above hydrogen in the electromotive series can reduce H+
ions to hydrogen and hence, liberate hydrogen gas on reaction with dil acids. In other words, metals
having negative reduction potentials can displace hydrogen from acids. For example,

 
zinc E 0Zn2 /Zn  0.76 volt lies above hydrogen in the series and hence, it can displace hydrogen

 
from dilute acids, whereas copper E Cu 2 /Cu   0.34 volts which is lying below hydrogen in the series
0

cannot displace hydrogen from acids.

35