Redox Reactions and

Electrochemistry
JEE Syllabus
Electronic concepts of oxidation and reduction, redox reactions, oxidation
number, rules for assigning oxidation number, balancing of redox
8
CHAPTER
reactions. Eectrolytic and metallic conduction, conductance in electrolytic
solutions, specific and molar conductivities and their variation with
concentration: Kohlrausch’s law and its applications. Electrochemical cells
- Electrolytic and Galvanic cells, different types of electrodes, electrode
potentials including standard electrode potential, half - cell and cell
reactions, emf of a Galvanic cell and its measurement; Nernst equation
and its applications; Relationship between cell potential and Gibbs’
energy change; Dry cell and lead accumulator; Fuel cells; Corrosion and
its prevention.

CONCEPT OF OXIDATION & REDUCTION THIS CHAPTER

Oxidation Reduction INCLUDES
(i) Loss of electron (i) Gain of electron  Concept of
Oxidation-Reduction
(ii) Loss of hydrogen (ii) Gain of hydrogen
 Oxidation Number
(iii) Gain of oxygen (iii) Loss of oxygen
 Oxidising and
(iv) Increase in oxidation number (iv) Reducing agent
Decrease in oxidation number
 Balancing Redox
Reactions
OXIDATION NUMBER  Electrolytic cells &
Oxidation number is defined as the change (real or imaginary) which an atom Galvanic cells
appears to have undergone when it is present in combination. There are certain  Standard electrode
rules laid down in order to determine the oxidation number. potential

(a) O.N. of an atom in free elements is zero.  Electrochemical

series
(b) O.N. of oxygen is -2 while in peroxides it is -1, in OF2 it is +2.
 emf of Galvanic cell
(c) O.N. of hydrogen is +1 while in metal hydrides it is -1.
 Gibb's energy change
(d) O.N. of an ion is equal to the electrical charge present on it. and cell potential

(e) O.N. of group IA elements is +1 and that of group IIA elements is +2  Electrolysis

(f) For complex ions, the algebraic sum of oxidation numbers of all the
 Electrolytic conduction
atoms is equal to the net charge on the ion.  Molar conductivity

(g) In case of neutral molecules the algebraic sum of the oxidation number  Kohlrausch's law and
of all the atoms present in the molecules is zero. its application

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Increase in oxidation number of an element in a reaction is known as oxidation while decrease in oxidation
number of an element in a reaction is known as reduction.
Besides +ve and -ve values, fractional values of oxidation number are also possible
Ex. Na2S4O6
2×1 + 4x + 6(-2) = 0
x = 2.5
Ex. Fe3O4
3×x +4(-2) =0

8 2
x 2
3 3
Ex. N3H
3x +1 =0

1
x
3

OXIDISING AND REDUCING AGENT

Oxidising agent or oxidant
The substance which oxidises others and itself get reduced.
Reducing agent or reductant
The substance which reduces others and itself get oxidised.
Reduction

Zn(s) + Cu+2 (aq) Zn+2(aq) + Cu

e.g.,
Oxidation
In the above redox reaction Zn is acting as reducing agent and Cu+2 as oxdising agent.

BALANCING REDOX REACTIONS

It occurs by two methods, i.e.
A. Oxidation number method
B. Ion electron method

Oxidation Number Method Ion Electron Method

1. Write the skeleton equation representing 1. Write down the redox reaction in ionic form.
chemical change.
2. Assign oxidation numbers to find out which 2. Split the redox reaction into two half
atoms are undergoing oxidation and reduction reactions, one for oxidation and other for
write separate equation for the atoms reduction
undergoing oxidation and reduction
3. Find the change in oxidation number in each 3. Balance the number of atoms ions
equation. undergoing reduction and oxidation.
Make the change equal in both the
equation by multiplying with suitable
integers. Add both the equations.

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4. Now balance those elements which are not 4. Now add electrons on that side of reaction
undergoing oxidation or reduction except H where they are deficient to equalise the
and O. Then balancing H and O with the help charge on both sides. Multiply if required by
of H2O. suitable number to balance electron on both
side of reaction.

5. Now add both the half reaction and now

balance atoms not undergoing reduction
and oxidation (except H and O). Now
balance H and O with help of water.
Balancing of H2O can also be done as per the medium given
(1) Acidic Medium : Add H2O on that side of reaction where oxygen are deficient and double number of H+
on opposite side of reaction.
(2) Basic Medium : Add H2O on that side of reaction where oxygen are excess and double number of OH–
on opposite side of reaction.

ELECTROLYTIC CELLS & GALVANIC CELLS:

The chemical changes which involve the flow of the electric current are called electrochemical changes. These
are broadly of two types :
A. Electrolytic Cells : The changes in which electrical energy causes chemical reaction to occur. This
phenomenon is called electrolysis and the devices or cells used to carry out electrolysis are called
electrolytic cells. These reactions are non-spontaneous and are forced to occur by the passage of
electricity.
B. Galvanic Cells : “A device employed to convert the chemical energy of a redox reaction into electrical
energy” is called an electrochemical cell or simple chemical cell. The most common example is Daniel
cell.

V
e– flow
(–) current (+)
Zinc Salt bridge
electrode Copper
electrode
Inert Ions
electrolyte
with agar-agar
ZnSO4
CuSO4
solution solution
Half-cell Half-cell
DANIEL CELL

The net reaction is the sum of two half-cell reactions.

At anode : Zn(s)  Zn 2 (aq)  2e 

At cathode : Cu  2 (aq)  2e   Cu(s )

Net reaction : Zn(s )  Cu 2  Zn  2 (aq)  Cu(s)

Schematic Representation : Zn | Zn+2 || Cu+2 | Cu

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STANDARD ELECTRODE POTENTIAL

Standard Electrode Potential : The potential difference developed between metal electrode and the solution
of its ions of unit molarity (1 M) at 298 K is called standard electrode potential.

Note : Standard reduction potential = – (Standard oxidation potential)

or Standard oxidation potential = – (Standard reduction potential)

Standard Hydrogen Electrode – (SHE)

SHE Half Reaction Electrode Potential
H2  2H+ + 2e– 0.0 V (anode)
2H+ + 2e–  H2 0.0 V (cathode)
With the help of SHE - the SRP values of all the electrodes has been determined and are placed in
electrochemical series.

Note : ECell = O.P. of anode + R.P. of cathode.

or ECell = R.P. of cathode – R.P. of anode.

ELECTROCHEMICAL SERIES
Table in which the standard reduction potentials of various electrodes have been arranged in the increasing order
is called electrochemical series or activity series or electromotive series.
Electrode Electrode reaction E°(volts)
Li+/Li Li+ + e– = Li –3.045 (Lowest)
Zn2+/Zn Zn2+ + 2e— = Zn –0.763
H+/H2, Pt 2H+ + 2e— = H2 0.0 Standard
Cu2+/Cu Cu2+ + 2e— = Cu +0.334

F2/F–, Pt F2 + 2e— = 2F— +2.887 (Highest)

Applications of Electrochemical Series :

The important applications of electrochemical series are:

(a) Relative strength of oxidising and reducing agents. In the series, the elements are arranged in the
increasing order of reduction potentials or decreasing order of oxidation potential. Therefore, the elements
at the top are good reducing agents while those at the bottom are good oxidising agents.

(b) Calculating e.m.f. of the cell : The e.m.f. of the cell can be determined by knowing the standard electrode
potentials from the series as:

E ºcell  E (ºright )  E (ºleft ) (If standard reduction potential are given)

(c) Predicting feasibility of a redox reaction. In general, a redox reaction is feasible only if the species which
has higher reduction potential is reduced i.e., accepts the electrons and the species which has lower
reduction potential is oxidised i.e. loses the electrons. Otherwise, a redox reaction is not feasible. In other
words, the species to release electrons must have lesser reduction potential as compared to the species
which is to accept electrons.

(d) To predict whether a metal can liberate hydrogen from acid or not only the metals which have negative
reduction potentials, can liberate hydrogen from the acids.

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EMF OF GALVANIC CELL

In galvanic cells, current is generated as a result of a spontaneous chemical reaction that occur in the cell.
The main characteristics of galvanic cell are given below

Cathode Anode
(i) Sign Positive Negative
(ii) Half reaction Reduction Oxidation
(iii) Direction of electron Into the cell Out of the cell
movement

Note : Flow of currrent from cathode to anode.

E.M.F is potential difference between the two electrodes of the cell when no current is flowing in the circuit
(i.e., in an open circuit). It is the maximum voltage obtainable from the cell.

Eºcell = EºR.P.(R.H.S) – EºR.P. (L.H.S.)

= EºO.P. (L.H.S.) – EºO.P. (R.H.S.)

= EºO.P. (L.H.S.) + EºR.P. (R.H.S.)

Similarly Ecell = ER.P.(R.H.S.) – ER.P. (L.H.S.)

ER.H.S. or EL.H.S. determined by Nernst equation

Nernst equation
It is a relation between electrode potential, emf of cell, temperature and concentration of ions in solution
represented by the equation

RT [P]
E cell  E ocell  ln
nF [R]

where Ecell = EMF of cell at new concentration

Eºcell = Standard emf of cell (1M, 25ºC and 1 atm)

R = Gas constant = 8.314 JK–1 mol–1.

T = Absolute temperature

n = Number of electrons

F = Faraday constant = 96500 C

ln = 2.303 log10

[P] = Concentration of product in mol L–1

[R] = Concentration of reactants in mol L–1

Putting the values of R, F, ln, at 25ºC.

0.059 [P]
Ecell  Eocell  log10
n [R]

Nernst equation is valid for cell as well as half cell.

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GIBB'S ENERGY CHANGE AND CELL POTENTIAL

The electrical work done from the cell = nFE
 – G = nFE
G = –nFE
or Gº = – nFEº
where G = Gibb's energy change
Gº = standard Gibb's energy change
E = emf of cell/electrode potential
Eº = standard emf of cell/standard electrode potential.

ELECTROLYSIS
(a) The decomposition of the electrolyte due to the passage of electricity is known as electrolysis
(b) During electrolysis electrical energy changes into chemical energy.
(c) To have electrolysis we must use D/C.
(d) Electrolysis is a redox phenomenon.
A. Faraday’s laws of electrolysis
(a) First Law : The weight of substance deposited at the electrode is directly proportional to the
quantity of electric charge passed through the electrolytic solution
WQ W = wt in g
Q = quantity of charge
W = ZQ Z = constant known as electrochemical equivalent
W = ZIt I = Current in ampere
t = time in sec
(b) Second law : If the same quantity of current is passed through different electrolytic solutions then
the weights of different substances deposited at the respective electrodes is directly proportional to
their chemical equivalents.
wt. of electrolyte (A) wt. of electrolyte (B)

Eq. wt. of (A) Eq. wt. of (B)

ELECTROLYTIC CONDUCTION
Molten electrolyte and the aquous solution of electrolytes contain free ions and conduct electricity due to the
movement of ions
According to Ohm's law

l
R
a

l
or R  
a
a
   R
l

1 1 l
 
 R a

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where R = Resistance of solution

l = Length
a = Area of cross section of the solution
 = Resistivity of solution
If l = 1 unit of length and a = 1 unit of area

then R

1
Conductance (G) =
R

Unit of conductance = ohm–1 or siemens (s)

1 1 l cell constant l
Specific conductance (K) =    ( is called cell constant)
 R a Resistance a

K = Conductance if l = 1 unit (length) and a = 1 unit (area)

S.I. Unit of K = Sm–1

Note : Specific conductance is now-a-days called conductivity.

MOLAR CONDUCTIVITY ( m )
The conducting power of all the ions furnished by one mole of an electrolyte in any solution is termed as its
molar conductivity

Conductivi ty (K )
m 
Concentrat ion of solution in moles per unit volume (cm 3 )

Unit of m = ohm–1 cm2 mol–1

Molar conductivity increases with increase in dilution or decrease in concentration due to increase in ionisation
but specific conductivity decreases with increase in dilution because number of ions per cm3 of solution
decreases.

KOHLRAUSCH'S LAW
It states that at infinite dilution the molar conductivity of an electrolyte can be expressed as the sum of the
contribution from its individual ions.

m  V   V  (where V+ and V– are the number of cations and anions per formula unit of electrolyte
respectively and  and  are molar conductivities of the cation and anion at infinite dilution respectively).

Application
Some typical applications of Kohlrausch's law are

(i) Determination of m for weak electrolyte

 
Example : m of CH3COOH (weak acid) can be determined by knowing m of three strong electrolytes
NaCl, HCl and CH3COONa

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  CH3COOH =  CH3COO   H

  
NaCl =  Na   
Cl


HCl = H  Cl

 CH3COONa = CH   Na 

3 COO

  CH3 COOH = 
 HCl   CH3COONa   NaCl


= CH COO  H

3

(ii) Determination of degree of dissociation () of a weak electrolyte

c
m
 
m

(iii) Determination of ionisation constant of weak electrolyte of (AB) type

C(  cm )2 C 2
K =

m (  m   cm ) C(1   )

(iv) Determination of solubility of a sparingly soluble salt

1000 .K salt
Concentration of sparingly soluble salt (Cm ) 
( V   V  )

IMPORTANT POINTS

m
(1) Degree of dissociation () can be related with conductance. i.e.,  
m

(2) G° = –nF Ecell n = number of electrons

F = Faraday
(3) Concentration cells are made up of same electrode but deeped in different concentration of its own ion.

e.g., Cu | Cu(02.01M) || Cu(02.2M) | Cu

(4) For spontaneity of reaction, E cell > 0 i.e., G < 0.

(5) Primary Batteries : The reaction occurs only once and battery becomes dead. e.g., Mercury cell.
(6) Secondary Batteries : The cells that can be recharged by passing current through it. e.g., Lead storage
batteries.
Fuel Cell : Energy obtained by combustion of fuels.
(7) Rusting of iron is the example of corrosion which is a electrochemical process.

  

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