Electrochemistry

1.1

CHAPTER-1
ELECTROCHEMISTRY

1.1 Important Terminologies

Current:
Flow of electrons through any conducting material is known
as the current.
Oxidation:
The tendency to lose electrons
Reduction:
The tendency to gain electrons
Electrode:
When a metal rod is dipped in its salt solution, it develops a
positive or negative potential. This assembly is called as an
electrode.
Anode:
The electrode at which oxidation occurs is called as anode.
Cathode:
The electrode at which reduction occurs is known as cathode.
Electrolytes:
Electrolytes are the conductors which are in the form of
solution or fused state in which conductance takes place due
to the movement of ions present in it.

1.2
Chemistry

Engineering

Electrochemical cell:
The electrochemical cell consists of two conductors called
electrodes that are immersed in an electrolyte and are
connected externally by means of a metal conductor.
Electrolysis:
The process that occurs in the electrochemical cell is called as
electrolysis. It is the breakdown of electrolyte into ions by
electricity.
Half cell:
A part of a cell containing electrode dipped in an electrolytic
solution is called as a half cell.
Oxidation half cell :
The electrode where oxidation takes place i.e. where electrons
are lost
Reduction half cell :
The electrode where reduction takes place i.e. where electrons
are gained
Conductors:
Material that permits electric current to pass through.
Example: Copper, aluminium, silver, fused salts, bases, aqueous
solutions of acids etc.,
Insulators or non-conductors:
Materials which do not allow the electric current to pass
through it.
Example: Wood, plastics etc.,

Electrochemistry
1.3
Standard electrode potential:
It is the potential of the electrode which is in contact with
its solution of 1M concentration which is measured at 298K and
1atm pressure.
Single electrode potential:
The measure of tendency of a metallic electrode to lose or
gain electrons, when it is in contact with a solution of its own
salt.

Representation Notation and sign conventions:

1.

Molecules, elements, gases and electrode material are

represented by the usual chemical symbols. Concentration
of ions and molecules and partial pressures of gases are
given in brackets.

2.

Interface between an electrode and electrolyte or between

two electrolytic solutions is represented by a semicolon (;)
or by a single vertical line (l).
Example
Zn ; Zn2+ or Zn l Zn2+

3.

Example:
Ag, AgCl l ClIn the example the (,) indicates that the Ag and AgCl
should be taken together always to constitute an electrode.

4.

The electrode on the left is written in the order the

electrode and then the ion (Zn l Zn2+)

5.

The electrode on the right is written in the order, ion and

then electrode (Zn2+l Zn)

6.

A double vertical line (ll) represents a salt bridge which

has zero potential difference.

Engineering

1.4
Chemistry
7.

Example:
Zn l Zn2+ ll Cu2+ l Cu
The combination of two single electrodes or two half cell
constitute an cell
The left hand electrode is anode
The right hand electrode is cathode
The left hand half cell is cathode half cell
The right hand half cell is anode half cell
Zn l Zn2+ ll Cu2+ l Cu
(anode)
(Cathode)
At anode oxidation takes place Zn Zn2+ + 2e
At cathode reduction takes place Cu2+ + 2e Cu
Example:

8.
9.

If E0cell of the reaction is positive, the cell reaction takes

place and is said to be spontaneous.
If E0cell of the reaction is negative, the cell reaction is not
feasible and is said to be non-spontaneous.

1.2 Role of Salt bridge

The salt bridges are U-shaped and contain agar-agar gel
containing KCl or MNO3. Some times NH4NO3 is also used. The
reason for using these salts, is that the cations and anions have
almost same speed and same transport number.
The salt bridge provides a passage for the flow of charges
in the internal circuit and thus prevents the accumulation of
charges. In the presence of salt bridge, the charges present flow
towards the oppositely charged electrodes. The negative ions
move from the copper electrode passes through the CuSO 4
solution, salt bridge and zinc sulphate solution to zinc rod. The
positive ions move in the reverse direction i.e., zinc rod to copper

Electrochemistry
1.5
rod. Hence flow of electricity is maintained when the salt
bridge is used.
But when the salt bridge is not used the electrons
released by the anode flow to the cathode through the external
circuit. During this there occurs an accumulation of charges near
the two electrodes, which prevents further flow of current. Hence
the electrochemical change stops and current drops to zero.

Introduction
. Electrochemistry is branch of chemistry. This is based on
properties of a solution when it is made part of an
electrochemical cell. The principle of electrochemical cell deals
with the conversion of energy from electrical to chemical and
vice versa. This principle is used in the construction of cells and
batteries which is a source of electrical energy. Refining of
copper involving electrolysis is done to obtain high quality
electric cables. The electroplated materials are now used in large
scale in automobile industries, in jewelry, etc.. These provide
both protection of metals from corrosion and aesthetic appeal.
The extraction of the metals from its ores like sodium from
common salt also involves electrolysis.
Not only the electrochemical concept is used for
protecting the material but also used in explaining the cause of
destruction of metal. For example, corrosion of steel beams used
in the construction works like bridges, houses etc., occur through
this principle. But methods like cathodic protection has been
developed involving the same principle, so as to counteract and
protect metals from corrosion.
Galvanic cell
These cells convert chemical energy into electrical
energy.

Engineering

1.6
Chemistry

These cells generate an electric current due to chemical

reaction occurring within them. The redox reaction occurring in a
galvanic cell is spontaneous and involves a decrease in the free
energy system.
Example:

Dry cell, Lechlanche cell, Daniel cell.

Electrolytic cell
These cells convert electrical energy into chemical
energy.
In these cells chemical change is brought about when
from outer source the current is passed into the electrolyte. This
reaction is non-spontaneous but is feasible.
Example:
Used in electroplating, electrotyping, electro-refining of metals.

Differences between Electrolytic cells and electrochemical

cells.
S.No

Electrolytic cell

Electrochemical cell

1.

In
electrolytic
cell
electrical energy is
converted into chemical
energy

In electrochemical cell
Chemical
energy
is
converted into electrical
energy

2.

The negative charge is Here the negative charge is

carried by cathode
carried by anode.

3.

The positive charge is Here the positive charge is

carried by anode
carried by cathode

4.

The chemical reaction The e.m.f produced in the

takes
place
during cell depends on the type of
electrolysis is governed the electrode used and on

Electrochemistry
1.7
by the Faradays law of the concentration of the
electrolysis
electrolytes
5.

Calumniator is used for Potentiometer is used for

the measurement of the measurement of e.m.f
electricity passed during produced in the cell
the electrolysis process

6.

Here the external energy Here electrons are drawn

is used for the supply of from the cell.
electrons to the cell

1.3 Reversible cell

A cell is said to be reversible when
1. there is infinitesimally small difference in the driving and
opposing force.
2. it is possible to reverse any change taking place by
applying a force infinitesimally greater than one acting on
it.
Therefore, in a reversible cell the reaction occurs only
when the current is drawn from connector.
A reversible cell satisfies the following conditions:
1. If an external EMF equal to that of the cell is applied in
opposite direction, no reaction should take place on
either of the two electrodes.
2. If the external EMF is slightly greater than the EMF of
the cell, the overall cell reaction gets reversed. In this
case the current flows in the opposite direction.

1.8
Chemistry

Engineering

Example
The Daniel cell is a reversible cell. It maybe represented by
Zn(s) Zn2+(1M) Cu2+(1M) Cu(s)

At standard conditions, in the Daniel cell with emf 1.1. volts, the
cell reaction is
Zn(s) + Cu2+(1M)

Zn2+(1M) + Cu(s)

When an external emf is slightly greater than 1.1 volts the cell
reactions gets reversed as follows
Cu(s) + Zn2+(1M)

Zn(s) + Cu2+(1M)

The current will now flow in opposite direction.

1.4 Irreversible cell

Cells which do not obey the conditions of thermodynamic
reversibility are called as irreversible cells.
An irreversible cell satisfies the following conditions.
1.
2.

Even if external EMF applied is equal to emf of the cell

the reaction does not stop.
Even when the external EMF applied is slightly greater
than that of the cell, the reaction occurs in the same
direction and does not get reversed.

Electrochemistry
1.9

Example:
Zn(S)

H2SO4(soln) Cu(s)

The following cell reaction occurs

ZnSO4 + H2

Zn + H2SO2

Liberation of hydrogen occurs which results in irreversibility.

1.5 Electrode Potential

When a metal is in contact with a solution of its own ions
at 25C, it may either undergo oxidation reaction or reduction
reaction.

Fig 1.1
If it is a oxidation reaction
M(s)

Mn+ (aq) + ne

1.10
Chemistry

Engineering

The Mn+ leaves the metal electrode and enters into

solution. This leaves the free electrons on metal electrode
resulting in a negative charge on the electrode. This negative
charge attracts the positively charged ions in the solution leading
to the formation of a layer of positive ions around the metal
electrode.
Similarly, if it is a reduction reaction
Mn+(aq) + ne
M(s)
The Mn+ ion from solution enter into the metal electrode
resulting in positive charge on the electrode. This attracts the
negative charged ions in the solution leading to the formation of a
layer of negatively charged ions around the electrode.
The formation of a layer of negative or positive ions
around the metal electrode is called Helmholtz electrical double
layer. Because of this layer a potential difference is set up
between the metal and the solution. At equilibrium, this potential
difference will become constant and this is known as standard
electrode potential of metal.

Single Electrode Potential

Definition:
Single electrode potential is the measure of tendency of
a metallic electrode to lose or gain electrons, when it is in contact
with a solution of its own salt.
The tendency of a metallic electrode to lose electrons is
known as oxidation potential and the tendency of an electrode
to gain electrons is known as reduction potential.

Electrochemistry
1.11
It is impossible to measure absolute value of single
electrode potential because neither oxidation nor reduction takes
place independently. It is possible to measure the potential
difference between two electrodes with the help of the
potentiometer. In other words, we can only measure electrode
potential with reference to a reference electrode.

Standard Electrode Potential

Definition
Standard electrode potential is the tendency of a
metallic electrode to lose or gain electrons when in contact with
1M concentration of its own salt solution at 250C.

Electromotive Force and its Measurements

Definition
Electromotive force or EMF of a galvanic cell is defined
as the difference of electrode potential which causes the flow of
current from one electrode to another when virtually no current is
drawn from the cell.
(NOTE: the difference between cell potential and EMF is, cell
potential is positive while EMF can have positive as well as
negative value.)
Measurement
It is necessary that no current should be drawn from the
cell while measuring its EMF. This is possible only when the
EMF of the cell under study is balanced by EMF of some other
cell. This is done in Poggendorfs compensation method
Poggendorfs compensation method
In this method the EMF of the given cell is compensated
by the EMF of a known standard cell so that no current could
flow in the circuit.

Engineering

1.12
Chemistry

Construction
It consists of a potentiometer wire AB stretched over a
meter scale. The cell C is a source of direct current. Its positive
electrode is connected to end A while the negative electrode to
the end B of the wire. X is the cell whose EMF is to be measured
while the cell S is standard cell of known EMF. The positive
electrodes of both the cells X and S are connected to the end A of
the wire while their negative electrodes are connected to the two
terminals of a double pole double throw switch P. The third
terminal of the plug is connected to a sliding contact D through a
galvanometer G.
-

C (Storage battery)

Adjustable resistance

Standard cell
S

Sliding contact

P
X
Cell for which emf is to be measured

Fig 1.2

G
Galvanometer

Measurement of emf of a cell

Working
Standard cell S is first brought into the circuit with the
help of the double pole double throw switch and the null point D
is found when no current passes through the circuit and
galvanometer does not record any deflection. At this point, the
EMF of the cell C is balanced by that of the cell S. If Ec is the
EMF of the cell C and Es is the EMF of the cell S, then

Electrochemistry
1.13

(Ec / Es) = AB/AD

Now, the cell S is removed from the circuit and the cell X
is connected in the circuit. The bridge is again balanced and the
null point D is found for no current flowing in the circuit. At this
stage, the EMF of the cell C is balanced by that of the cell X. If
EX is the EMF of the cell X, then
(Ec / Ex) = AB/AD
From the above equations

Ec / E s
Ec / E x
Ex
Es
emf of the test cell
emf of the standard cell

i.e.,

emf of the test cell

AB / AD
AB / AD'

AD'
AD

AD
AD'

Ex

AD'
Es
AD

Length AD'
emf of the standard cell
Length AD

Since the EMF of the standard cell S is known and the

length AD and AD can be directly read with the help of meter
scale, the EMF of cell X under study can be obtained.

Engineering

1.14
Chemistry

Standard cell
Poggendroffs compensation method requires a standard
cell whose EMF is standard and is precisely known. For this a
saturated Weston cadmium cell is used. The standard cell has a
very low temperature coefficient and its EMF does not change
with time. These unique properties make it a standard cell.
Representation
Cd(12.5% in Hg) 3CdSO4.8H2O(Satd soln) Hg2SO4(s), Hg(l)

Electrode reactions
At anode :

Cd(s) + SO42-(aq)

At cathode : Hg2SO4(s) + 2e

CdSO4(s) + 2e
2Hg(l) + SO42- (aq)

Overall cell reaction :

Cd(s) + Hg2SO4(s)

CdSO4(s) + 2Hg(l)

Construction
This type of cell consists of a H-shaped glass vessel. The
bottom of the glass limbs are sealed with platinum wire. The
cathode contains mercury and mercurous sulphate is placed over
it. The anode consists of an amalgam of cadmium (Hg-Cd) over
which some crystals of CdSO4. (8/3)H2O are placed. The rest of
the part of the vessel is filled with saturated solution of CdSO 4.
The upper end of the arms is closed with corks. The purpose of
solid crystals is to keep the electrolyte saturated at all
temperatures. The emf of this cell is 1.01807 V at 20C.

Saturated
CdSO4

Electrochemistry
1.15

CdSO4 8/3 H2O

Cd-Hg
Fig 1.3

The Weston Standard cell

Hg

Applications of EMF measurements

1.
2.
3.
4.
5.
1.

Determination of solubility of sparingly soluble salts and

its solubility products
Determination of the valency of an ion
Determination of pH
Determination of standard free energy change and
equilibrium constant.
In potentiometric titrations.

Determination of solubility of sparingly soluble salts

and its solubility products
There are salts that are sparingly soluble in water, whose
solubility is difficult to be determined by other methods.

Engineering

1.16
Chemistry
Example :

Silver chloride (AgCl)

The solubility of these sparingly soluble salts can be determined

by the EMF measurement by constructing a concentration cell.
Construction of the cell
Ag(s) AgCl(s) KCl (0.01N) AgNO3(0.01 N) Ag(s)
(unknown)
In this, one of the Ag electrodes is placed in contact with
0.01N AgNO3 solution and the other electrode is in contact with
0.01N KCl solution. The two solutions are connected through a
salt bridge containing saturated solution of ammonium nitrate. A
drop of AgNO3 solution is added to the KCl solution. This forms
a small amount of AgCl which is sufficient to give a saturated
solution.
Working
One of the electrodes of this cell thus is in contact with a
solution of silver ions of known concentration (0.01N). The
other electrode is in contact with a solution of unknown
concentration of silver ions furnished by the ionisation of
sparingly soluble silver chloride formed.
The EMF of the above cell is given as
C
RT
E cell 2.303
log 2
nF
C1

i.e.,

E cell 2.303

RT
0.01
log
1 F
C

E cell 0.0591 log

0.01
C

Electrochemistry
1.17

where, the only unknown factor is the C, the concentration of

Ag+ ions furnished by AgCl in KCl solution. The emf of the cell
can be measured and thus the concentration of AgCl C is
calculated.
Multiplying the concentration of AgCl with the equivalent
weight of AgCl (143.5), the solubility of AgCl is calculated in
gm/litre.
(OR)
The solubility product of silver chloride is given by
Ksp(AgCl) = C 0.01
The solubility (S) of the silver chloride is then given by
S=

K sp( Ag Cl )

2 Determination of the valency of an ion

The valency of the ions could be determined from the
EMF of the concentration cells.
Example
The valency of the mercurous ion could be obtained as follows
Construction of the cell
Mercury / Mercurous nitrate (C1) // Mercurous nitrate (C2) / Mercury
solution
solution

The salt bridge contains the saturated solution of ammonium

nitrate.

Engineering

1.18
Chemistry

The EMF of the cell is given by

E cell 2.303

C
RT
log 2
nF
C1

C2 and C1 are known concentration of mercurous nitrate

electrolyte. The emf is obtained experimentally.
Substituting these values in the above equation the n the
valency of the mercurous ion is calculated.
3.

Determination of pH
The pH could be obtained using any one of the indicator
electrodes.
Example :
Using a standard hydrogen electrode:
Construction
A cell with a reference electrode and hydrogen electrode
is constructed using a salt bridge.
Pt, H2(1atm), H+(c= unknown) // KCl(satd), Hg2Cl2(s), Hg
Calculation
The potential of the reference electrode i.e. calomel
electrode is +0.2422 volts is known. The emf of the cell is
obtained experimentally. Substituting the values in the following
equation
Ecell = Eright Eleft
(1)
Thus the potential of hydrogen electrode used is
calculated as follows.

Electrochemistry
1.19
Eleft = Eright Ecell

(2)

To obtain the pH, the potential of the hydrogen electrode

calculated from eqn (2) is substituted in the following Nernst
equation
E H ( aq) / H 2 ( g ) E 0 H ( aq) / H 2 ( g )

RT
ln[ H ]
nF

By convention E0 of hydrogen is zero, therefore

RT
EH ( aq) / H 2 ( g )
ln [ H ]
nF
RT
E H ( aq) / H 2 ( g ) 2.303
log [ H ]
1 F
E H ( aq) / H 2 ( g ) () 0.0591 log[ H ]
E H ( aq) / H 2 ( g ) () 0.0591 pH

Thus, substituting the value of the hydrogen electrode

calculated from equation(2), the pH could be determined from the
above equation.
E 0.2422
pH cell
0.0591
By using glass electrode
A cell with a reference electrode and glass electrode is
constructed using a salt bridge as follows.
Construction
Pt, HCl(0.1N) / glass / test soln // KCl(satd), Hg2Cl2(s), Hg(l)

Engineering

1.20
Chemistry

The salt bridge consists of KCl solution.

Calculation
The potential of the reference electrode i.e. calomel
electrode is 0.2422volts is known. The emf of the cell is obtained
experimentally. Thus substituting the values in the following
equation
Ecell = Eright Eleft

(1)

The potential of a glass electrode used is calculated as follows.

Eleft = Eright Ecell

(2)

To obtain the pH, the potential of the glass electrode obtained

from eqn (2) is substituted in the equation (3) or (4).
EG = E0G + 0.0591 log[H+]
EG = E0G - 0.0591 pH
pH

(OR)

E 0 G EG
0.0591

E 0 G E cell E calomel
pH
0.0591

. (3)

..(4)

[ Where EG = Ecalomel Ecell and glass electrode is anode].

Thus the pH is calculated using the glass electrode.
4.Determination of standard free energy change and
equilibrium constant

Electrochemistry
1.21
The standard free energy change (G0) of a reaction can
be calculated from the using the standard emf from the following
expression
( )G0 = nFE0
Where,
F = 96,500 coulombs
E0 = Standard emf of the cell
n = number of electrons involved
The equilibrium constant k of a reaction can be calculated from
the following equation:
E cell

0.0591
log K
n

Where,
E0 is the standard EMF of the cell
k is the equilibrium constant
n is the number of electrons involved in the reaction.

1.6 Electrochemical series

The electrochemical series is the arrangement of various
electrode systems in the increasing order of their standard
reduction potentials.

Importance of Electrochemical series

1.

The most active metals are at the top of the series.

2.

The electrode system having negative values of standard

reduction potentials act as anode when connected to a
standard hydrogen electrode, while those having positive
values act as cathode.

Engineering

1.22
Chemistry
3.

On moving from the top to the bottom in the series,

tendency to gain electrons i.e. the tendency for reduction to
occur increases.
Li will act as the strongest reducing agent.
Standard reduction potentials
Electrode reaction
Oxidised
form

Reduced
form

Standard reduction
Potential, E0, V

Potassium

K+ + e-

-2.925

Calcium

Ca2+ + 2e-

Ca

- 2.87

Sodium

Na+ +e-

Na

-2.714

Magnesiu
m

Mg2+ +2e-

Mg

-2.37

Aluminum

Al3+ 3e-

Al

-1.66

Zinc

Zn2+ + 2e-

Zn

-0.763

Chromium

Cr3+ + 3e-

Cr

-0.74

Iron

Fe2+ + 2e-

Fe

-0.440

Lead

Pb2+ +2e-

Pb

-0.126

Hydrogen

2H+ +2e-

H2

0.00

Copper

Cu2+ +2e-

Cu

+0.337

+0.5355

Iodine

I2 + 2e

2I

Mercury

Hg22+ + 2e-

2Hg

+ 0.789

Silver

Ag+ +e-

Ag

+0.7991

Bromine

Br2(l) + 2e-

2Br-

+1.0652

Platinum

Pt2+ + 2e-

Pt

+1.2

Electrochemistry
1.23
Gold
Fluorine

Au+ + e-

Au

+1.68

F + 2e-

2F-

+ 2.87

Increasing ease of reduction of reactant

Increasing ease of
oxidation of reactant

Electrochemistry
4.

On moving from the bottom to the top in the series, the

tendency to lose electrons i.e tendency for oxidation
increases.
F2 will act as the strongest oxidizing agent.
The systems placed above hydrogen are stronger
reducing agents, while the one below the hydrogen are
weaker reducing agents.

5.

APPLICATIONS OF ELECTROCHEMICAL SERIES

1.
To predict the relative oxidizing and reducing power
In general,
Oxidizing agents have positive Eo Values
o Higher the positive value, stronger will be the
oxidizing agent that is placed below the hydrogen.

2.

Reducing gents have negative Eo values

o Higher the negative value stronger will be the
reducing agent that are placed above the hydrogen
To predict the spontaneity of any redox reaction
For any spontaneous reaction
G = -ve
Since
G = -nFEcell
Ecell should be positive for spontaneous reaction.
The Ecell is calculated from the standard redox potentials by
using the relation
Ecell = Ecathode Eanode

3.

Displacement of hydrogen by metals from dil. acids

The displacement of hydrogen from an acid is a reduction
process i.e.
2H+ + 2e

H2(g)

Eo = 0.00 volts

Electrochemistry

This is brought about by a metal whose reducing power is

greater than that of hydrogen. Hence any metal placed
above hydrogen in electrochemical series i.e. with negative
std. reduction potential can displace hydrogen from a dil.
acid.
Example :
Zn, Mg, Ni.
4.

Displacement of metals from salt solution

A metal with lower value of reduction potential can displace
another metal with higher value of reduction potential.
Example: Zinc displaces copper from its solution
spontaneously, but reverse reaction is not feasible.
Zn + Cu2+

Cu + Zn2+

5.

Electropositive character of metals (tendency to form

positive ions)
The metals at the top of the electrochemical series have the
greater tendency to lose electrons. So, these metals at the
top, possesses the highest electropositive character. The
value of the std. reduction potentials increases in going
down the series, which implies that the electropositive
character of metals decreases.
Example: Alkali metal > Hg, Ag, Au

6.

Thermal stability of the metal oxide

Higher the electro positive character, greater is the stability
of its oxide. Hence the stability of oxides of metals
decreases in going from top to bottom of the series.
Example: Alkali metal oxides like Na2O is more stable than
Ag2O, HgO etc.

7.

Calculation of standard cell potentials (EoCell)

Electrochemistry
The EoCell is calculated using
EoCell = EoCathode - Eoanode
Where EoCathode is the standard reduction potentials of
cathode
Eoanode is the standard reduction potentials of anode.
8.

To calculate equlilbrium constants

Go = - RTlnKeqm
Go = - nFEo
Eo = (RT/nF) ln keqm
ln keqm = nFEo/RT
From E0 equilibrium constant can be calculated.

9.

Prediction of correct metallurgical method

Eo values of Cu, H2O and Al are (+)0.34, (-)0.83and (-)
1.66V.
Cu gets easily reduced when compared to H2O and H2O get
reduced more easily than Al. Thus, copper is produced by
electrolysis of aqueous CuSO4 and aluminium cannot be
produced form aqueous solution of aluminium
This is because when Al3+(aq) is electrolyzed, only H2O will
be electrolysed and not Al3+

1.7 Thermodynamics of a reversible cell

Electrochemistry

NERNST EQUATION FOR ELECTRODE POTENTIAL

Nernst equation is used to calculate the electrode potential
of the electrode assembly under any given condition. It tells us
the effect of electrolyte concentration on electrode potential.
Nernst equation is given by
E cell E 0 red

0.0591
[product ]
log
n
[reactant]

This is applicable to a general redox reaction.

Consider a equation
aA + bB

cC +dD

For a general reversible chemical system, according to VantHoffs isotherm and Gibbs free energy, the relation between the
free energy change G and its equilibrium constant is expressed
as
[product]
G () RT ln K RT ln
[reactant]
. (1)
But ,
G0 = ( ) RTln K
Substitute equation (2) in (1)

(2)

Electrochemistry
G G 0 RT ln

[product]
[reactant]

. (3)

where, G0 = standard free energy change .

For a reversible reaction, the decrease in free energy (G ) is
given by
G = () nFE
...(4)
G0 = () nFE0
(or)

()G0 = nFE0

(5)

Where ,
G0 is the standard free energy change .
n is the number of electrons
F is Faraday = 96,500 Coulombs of electricity
E0 is the standard potential
Substituting the equation (4) and (5) in equation (3), we get
( ) nFE ()nFE 0 RT ln

[product]
[reactant]

Rearranging the above equation

E red E 0 red RT ln

[product]
[reactant]

(6)

Electrochemistry

Consider a reduction reaction

Mn+ + ne

Applying eqn. (6) to an electrode reduction equation

RT
[M ]
E red E 0 red
ln
nF [M n ]
Since [M] = 1 for the solid metal
E red E 0 red

RT
1
ln
nF [M n ]

The above equation may be written as,

E E0

RT
ln [M n ]
nF

Where, R = 8.314 J/K/mole;

T = 298C;
F = 96500 coulombs.
Substituting the value of R, T and F
E red E 0 red

0.0591
ln [M n ]
n

The above equation is known as Nernst equation.

Nernst equation for a reduction reaction
0.0591
E red E 0 red
ln [M n ]
n

Electrochemistry

Consider an oxidation reaction

M

Mn+ + ne

Similarly for an oxidation reaction Nernst equation is

Nernst equation for an oxidation reaction
0.0591
E ox E 0 ox
ln [M n ]
n

Applications of Nernst equation

1.
2.
3.
4.
5.

To study the effect of electrolyte concentration on

electrode potential
For calculation of the potential of a cell under nonstandard conditions
Determination of unknown concentration of one of the
ionic species in a cell when a concentration of other ionic
species is known.
The pH of a solution can be calculated.
To find the valency of an ion or the number of electrons
involved in the electrode reaction.

1.8 Types of Electrodes

Electrodes are of two types namely:
Reference electrode
Indicator electrode
We know that absolute value of a single electrode
potential cannot be measured, because the oxidation or reduction
does not take place independently. The potential difference
between two electrodes can be measured only by combining two

Electrochemistry
electrodes to form a complete cell and by using the
potentiometer.
Thus electrode potential can be measured with reference
to a reference electrode.

Reference electrodes:
Reference electrode is an electrode which has a constant
emf or constant potential, with which we can compare the
potentials of other electrodes.
There are two types of reference electrode
1) Primary reference electrode
Example : Standard hydrogen electrode (SHE)
2)

Secondary reference electrode

Example : Calomel electrode, Ag-AgCl electrode,
Glass electrode, Quinhydrone electrode etc.

PRIMARY REFERENCE ELECTRODE

Standard Hydrogen Electrode (SHE)

Electrochemistry

Fig 1.4
Standard hydrogen electrode is an example of primary
reference electrode. It consists of platinum foil or wire coated
with platinum black dipped into a molar (1M) solution of H + ions.
The platinum wire is surrounded by an outer tube into which the
hydrogen enters through a side inlet and escapes at the bottom
through the test solution. Hydrogen gas at 1 atmosphere pressure
is passed through it continuously at 2980K. Although an open
vessel as shown in diagram, in practice the electrode will be used
in a stoppered flask with a suitable exit for hydrogen.
Its potential is arbitrarily taken as zero at all
temperatures. SHE is a reversible electrode i.e, depending on the
nature of another electrode to which it is connected, i.e., this
electrode may act as anode or cathode.
Representation
: Pt, H2(g), (1atm) /H+(1M)
Reaction
As Anode

: H2(g)

2H+(aq) + 2e

Electrochemistry
As cathode

: 2H+(aq) + 2e

H2(g)

Electrode Potential of SHE : arbitrarily considered as zero

SECONDARY REFERENCE ELECTRODE
Due to the difficulties encountered with SHE, secondary
reference electrode is developed
Definition:
The electrodes whose electrode potentials are found using
the primary reference electrode and are always constant at given
conditions are used instead of primary reference electrode.
As at first the potential is obtained from the primary
reference electrode which is then being used as a reference to
another (to a third) electrode in order to obtain its (third
electrodes) electrode potential this is called as secondary
reference electrode.
Example:

Calomel electrode, Ag-AgCl electrode, quinhydrone

electrode etc.

Calomel electrode
It is a secondary reference electrode
Construction
It consists of a glass tube provided with a bent side tube A and
another side tube B containing a rubber tubing that could be
closed with a screw clip. The glass tube consists of layer of pure
mercury in the bottom. The surface of the mercury is covered
with a paste of mercurous chloride and mercury in potassium
chloride.

Electrochemistry

B
A

Fig 1.5 Calomel Electrode

A saturated solution of KCl is filled in the tube. A
platinum wire sealed through a glass tube C, is dipped in the
mercury layer for electrical contact. The glass tube C contains a
little mercury into which an amalgamated copper wire dips. The
side tube is used to make electrical contact with other electrode
through a salt bridge.
Representation: Hg(l), Hg2Cl2(S) / KCl(satd)
Reaction
Anode
2Hg(l)
Hg22+(aq) + e
2+
Hg2 (aq)+ Cl
Hg2Cl2(S)
-----------------------------------2Hg(l) + Cl-(aq)
Hg2Cl2(S) + e
Cathode
Hg2Cl2(S) + e
Hg 22(aq) e

Hg 22(aq) Cl
2Hg(l)

Electrode potential :
E = E0Cl-/Hg2Cl2/Hg - (RT/nF) ln [Cl-]

Electrochemistry
Working
Electrode As anode
Hg liberates electrons and sends Hg22+ ions into solution.
The Hg22+ would combine with Cl- ions furnished by the KCl
forming sparingly soluble Hg2Cl2. The result is a fall in
concentration of the chloride ions in the solution with electrons
transferred to metal.
Electrode As cathode
If the electrode involves reduction reaction, the Hg22+ ions
furnished by the sparingly soluble Hg2Cl2 would be discharged at
the cathode. Hence more and more of calomel would pass into
solution. This results in an increase in concentration of the
chloride ions.
Thus the potential of the calomel electrode depends on the
activity of the chloride ions and increases as the activity of the
chloride ions decreases. The electrode is reversible with respect
to chloride ions.
Potential of saturated calomel electrode (SCE) is
(+)0.2422 volts, Normal calomel electrode (NCE) i.e. 1N KCl is
(+)0.28 volt and Decinormal calomel electrode (DNCE ) i.e. 0.1N
KCl is (+)0.3338 Volts
Advantages of calomel electrode
1.
It is simple to construct
2. Results of cell potential measurements are reproducible and
stable over a long period and do not vary with temperature.

Silver Silver chloride electrode

Electrochemistry
Construction
It consists of a silver wire or a silver plated platinum wire
coated electronically with a thin layer of silver chloride, dipping
into a potassium chloride solution of known concentration. The
potentials of the 0.1M and saturated Ag-AgCl electrode at 25C
with respect to the normal hydrogen electrode are 0.29. and 0.199
volt respectively.
Representation :
Ag(S), AgCl(s) / KCl(satd)
Reactions :
At anode
Ag(s)
Ag+ + eAg+ + Cl-(aq)
AgCl(s)
Ag(s) + Cl-(aq)
AgCl(s) + eRT
ln[ Cl ]
0
nF
Electrode potential = E = E +

At cathode
AgCl(s)
Ag+ + eAgCl(s) + e-

Ag+ + Cl-(aq)
Ag(s)
Ag(s) + Cl-(aq)

This result in the removal of chloride ions from the

solution with electrons transferred to the metal. The overall
reaction involves only the concentration of Cl- ions as the
variable. Thus the electrode is reversible with respect Cl- ion.

Electrode potential:
E = E0Cl + (RT/nF) ln [Cl-]
Working

Electrochemistry

Electrode as anode
Since the sparingly soluble salt AgCl is in contact wit Cl ion solution, the solution is saturated. Some Ag passes from the
electrode into the solution
Ag

Ag+ + e

The Ag+ ions produced combine with Cl- of KCl to form AgCl(s).
This result in the removal of chloride ions from solutions with
electrons transferred to metal.
Electrode as Cathode
If the electrode involves reduction reaction, the Hg22+
ions furnished by the sparingly soluble Hg2Cl2 would be
discharged at the cathode. Hence more and more of calomel
would pass into solution. This results in an increase in
concentration of the chloride ions.
Thus the potential of the calomel electrode depends on the
activity of the chloride ions and increases as the activity of the
chloride ions decreases. The electrode is reversible with respect
to chloride ions.
Uses
This electrode is used to measure the concentration of the
chloride ions.

Quinhydrone electrode :

Electrochemistry
Quinhydrone is a compound of quinine and hydroquinone
and in solution is decomposed into equimolar quantities of these
substances.
C6H4O2.C6H4(OH)2 = C6H4O2 + C6H4(OH)2
Quinhydrone

quinine

hydroquinone

This consists of platinum wire dipped in an equimolar

solution of hydroquinone and quinone. The electrode is
represented as
Pt(s) QH2(aq), Q(aq)_, H+(aq)
Where QH2 and Q represent hydroquinone C6H4(OH)2
Quinone C6H4O2 respectively .

and

The electrode reaction involved is

C6H4O2(aq) + 2H+(aq)+ 2e
Q(aq) + 2H+(aq) + 2e-

C6H4(OH)2(aq)
QH2(aq)

The potential developed on platinum electrode is given by Nernst

equation as

E red E 0 red

RT [product ]
ln
nF [reactant]

E red E 0 red

RT [product ]
ln
2 F [reactant]

Electrochemistry

E red E 0 red

[QH 2 ]
RT
ln
2 F [Q] [H ] 2

E red E 0 red

RT [Q] [H ] 2
ln
2F
[QH 2 ]

E red E 0 red

RT
[Q]
RT
ln

ln [H ] 2
2 F [QH 2 ] 2 F

In practice the [Q] / [QH 2] is maintained constant at unity

by saturating the solution with the substance quinhydrone, which
is equimolar mixture of quinone and hydroquinone. The middle
term reduces to zero.
E red E 0 red

RT
ln[ H ]
F

(since ln[H+]2 = 2ln[H+] )

E = E0 + 0.0591 log [H+] at 250 C
(or)

E = E0 0.0591 pH

Where E0 is the standard electrode potential of quinhydrone

electrode = 0.6998V.
(or) E = 0.6998 0.0591 pH

Electrochemistry
Determination of pH of a solution using quinhydrone
electrode
To find the pH of a solution, quinhydrone electrode is connected
to a saturated calomel electrode.
This can be represented as
SCE // H+ (unknown) / Q(aq) , QH2(aq) / Pt(s)
Ecell = Eright - Eleft
Ecell = 0.6998 - 0.0591pH 0.2422

pH

0.6998 0.2422 E cell

0.0591

Merits of quinhydrone :
1. It attains equilibrium rapidly
2. It is not so readily incapacitated as the hydrogen electrode
3. It has low internal resistance
4. It is free of salt errors and non-reducing errors.
5. It can be used for pH measurements in non-aqueous
media.
Demerits of quinhydrone
1. It cannot be used in solution of pH greater than 8.
2. It is not stable for long time at high temperatures.
Indicator electrode or Ion selective electrode
The electrode in which the potential changes with change
in concentration is known as indicator electrode. i.e. the indicator
electrode of a cell is one whose potential is dependent upon the
activity of a particular ionic species whose concentration is to be
determined.

Electrochemistry
Example : glass electrode

Glass electrode
The glass electrode is the most widely used hydrogen ion
responsive electrode
Principle :
When a glass membrane is immersed in a solution, a
potential is developed between the two surfaces of the membrane
which is a linear function of the hydrogen ion concentration of
the solution i.e. pH value
Construction
The glass tube of the glass electrode is made of Lithium
based glasses of composition SiO2 63%, Li2O 28%, Cs2O 2%,
BaO 4%, La2O3 3%. Its melting point should be low and
electrical conductivity is high.

Fig 1.6 Glass electrode

The electrode consists of a glass bulb. This is filled with a
solution of hydrochloric acid (usually 0.1M). A silver- silver
chloride electrode is inserted into it. The upper end of the

Electrochemistry
electrode must be sealed. This is done in order to ensure a
constant concentration of the inner hydrochloric acid solution.
The internal hydrochloric acid is maintained at constant
concentration, so that
1.
the potential of the silver silver chloride electrode is
constant
2.
the potential between the hydrochloric acid and the
inner surface of the glass bulb is also constant.
Hence the only potential which can vary is that existing between
the outer surface of the glass bulb and the test solution into which
it is immersed.
So the overall potential of the electrode is governed by
the hydrogen ion concentration of the test solution.
Representation : Ag(s) , AgCl(s) /HCl (0.1M) /Glass
Working
To measure the hydrogen ion concentration of a solution
the glass electrode is immersed in the test solution and is
combined with a reference electrode a calomel electrode. Thus
the cell representation is
Ref. electrode1 / test soln
External reference electrode

Internal std soln/ ref. electrode

2
Ion selective electrode

Ag(s),AgCl(s) /HCl(0.1M) /Glass/ Test soln // KCl(satd) /Hg2Cl2(S), Hg(l)

Electrochemistry
Measurement of pH using glass electrode

Fig 1.7

For pH measurements, E0G is first measured by dipping glass

electrode in buffer solutions of known pH values. Once E0G for a
particular arrangement is determined, the electrode is then placed
in the solution of unknown pH, the emf of the cell is measured
and using the equation, its pH can be calculated.
Ecell = Eright Eleft
= 0.2422 (E0G - 0.0591 pH)
= 0.2422 E0G +0.0591 pH
(or)
pH

E cell 0.2422 E 0 G
0.0591

Electrochemistry

The emf of the cell is expressed as

E = K + (RT/F) ln[H+]
E = K + 0.0591pH
In these equations K is constant and partly dependent on
the nature of the glass used, individual character of each
electrode and its value may vary with time. This variation of K
with time is related to the existence of an asymmetry potential.
The asymmetric potential is due to the differing responses i.e. the
strain due to changes of hydrogen ion activity that is developed at
the inner and outer surfaces of the glass bulb. So glass electrode
has to be standardized frequently placing in a buffer solution of
known hydrogen in activity.
Advantages of Glass Electrode
1. It can be used in any solutions
Example:
in alkaline, oxidizing, turbid, coloured
solutions etc
2. It is most convenient and simple to use
3. It is not easily poisoned
4. Equilibrium is easily achieved
5. A small quantity of solution is sufficient for the
determination of pH.
Disadvantages
1. It gives erroneous results when used in poorly buffered
solutions which are nearly neutral.
2. It is found to be too sensitive to Na+ ions at very high pH
values greater than pH =9 resulting in alkaline error

Electrochemistry

Types of electrode
Type (I) electrode
Metal - Metal ion electrode
Metal amalgam electrode
Gas ion electrode
Type (II) electrode
Metal Metal insoluble salt electrode reversible to anion
Type (III) electrode
Metal Metal insoluble salt electrode reversible to cation
Type (IV) electrode
Redox electrode
Type (I) electrode

1.

Metal - Metal ion electrode

Pure metal (M) is in contact with a solution of its cation

(Mn+)
Representation :

Mn+(aq) / M (s)

Reaction :

Mn+(aq) + ne

M (s)

Electrode potential :
E mn( aq ) / M ( s ) E 0 mn ( aq) / M ( s )

RT
[M ]
ln
nF [ M n ]

Example
Zinc electrode
:
Copper electrode :

Zn(s) /ZnSO4(aq)
Cu(s) /CuSO4(aq)

Electrochemistry

2.

Metal amalgam electrode

Metal amalgam is in contact with a solution of metal ion

Representation :

Mn+(aq) / M(Hg)(s)

Reaction

Mn+(aq) + ne

M(Hg)(s)

Electrode potential :

E mn ( aq) / M ( Hg )( s ) E 0 mn ( aq) / M ( Hg )( s )

RT
[M ]
ln
nF [ M n ]

The active metals which cannot form electrodes when

dipped in their salt solution are converted into metal amalgam
and used. This is because the activity of the metal is lowered
when mixed with mercury.
Example :

Sodium electrode :

Na(Hg)(s) /Na+(aq)

3.

Gas Ion electrode

Inert metal is dipped in a solution containing ions to
which the gas is reversible. The gas is continuously bubbled
through the solution.
Pt(s) , X2 (p = y atm) / X-(aq)
X2 (p) + ne
X-(aq)

Representation :
Reaction :
Electrode potential :

E pt , x

2 ( p) /

X ( aq )

E 0 pt , x2 ( p ) / X ( aq)

RT [ X ( aq) ]
ln
nF
[ PX 2 ]

Electrochemistry
Example
Std. hydrogen electrode :
Chloride electrode :

Pt(s) , H2(g) /H+(aq)

Pt(s) , Cl2(g) /Cl-(aq)

Metal Metal insoluble salt electrode reversible to anion

(type II)
Metal (M) is covered by layer of sparingly soluble salt
(MX) immersed in a solution containing a common anion.
X-(satd) // MX(S)/ M(s)
MX(S) + e
M(s) + X-(aq)

Representation:
Reaction
Electrode potential :
E X ( satd ) // MX

Example :

(s) / M (s)

E 0 X ( satd ) // MX ( s ) / M ( s )

RT
ln[ X ( aq) ]
nF

Calomel electrode : Hg(l) /Hg2Cl2(S), KCl(satd)

Silver electrode : Ag(s) /AgCl(S), KCl(satd)

Metal Metal insoluble salt electrode reversible to

cation (type III)
Metal is in contact with one of its sparingly soluble salt together
with another insoluble salt having the same anion, in the solution
of a salt having a common cation as that of the latter salt.
Representation:

M2X2 (soln), M2X1(S), M1X1(S)/ M1(s)

Reaction
M1X1(S)+ M2n+(aq) + ne

M1(s)+ M2X1(S)

Electrochemistry
Electrode potential :
E = E0 M2X2 (soln), M2X1(S), M1X1(S)/ M1(s) + RT ln [M2n+(aq)]
nF

Example
Pb(s) PbSO4(s), SrSO4(s), SrCl2(soln)
Redox electrode (type IV)
An inert material is (eg. Pt) is dipped in a solution containing
ions in two oxidation states of the substances.
Representation
Reaction :
Mn1+(C1)

Pt/Mn1+(C1), Mn2+(c2)
Mn2+(c2)+ e

Electrode potential :
E Pt/Mn1+(C1), Mn2+(c2) = E0 Pt/Mn1+(C1), Mn2+(c2) - RT ln [Mn2+]
nF [Mn1+]

Example :

Iron electrode : Pt/Fe2+(C1), Fe3+(C2)

GALVANIC CELL (or) VOLTAIC CELL

These cells convert chemical energy into electrical energy
on account of some chemical or physical change taking place
within the cell. The driving force to cause the physical or
chemical change is the decrease in free energy.
Example :
Daniel cell can be obtained by joining an oxidation electrode
Zn/Zn2+ to a reduction electrode Cu2+/Cu as shown in Fig .

Electrochemistry
1.1V
Zn strip (Anode)

Cu strip (Cathode)
+

Zn SO4 solution

Porous plate

Cu SO4 solution

Daniel cell
Fig 1.8 ZnSO4 and CuSO4 solution in
direct contact through porous plate

1.1V

KCl solution
Zn strip (Anode)

Salt bridge

Zn SO4 solution

Cu strip (Cathode)
+

Cu SO4 solution
Galvanic cell

Fig 1.9 ZnSO4 and CuSO4 solution are in

Electrical communication through a salt bridge

Electrochemistry

The solutions in which two electrodes are immersed are

made in communication with each other by a direct contact
through a porous diaphragm or through a salt bridge .The two
electrodes are connected at the outer circuit to a device which
utilize the electrical energy produced .
The cell is represented as
Zn(s)

ZnSO4(aq)

CuSO4(aq)

Anodic reaction : Zn
Cathodic reaction: Cu2+ + 2eCell reaction: Zn + Cu2+

Cu(s)

Zn2+ + 2e- (Oxidation )

Cu

(Reduction )

Zn2++Cu (redox reaction )

The zinc metal acts as anode because it has greater potential

(0.76 V ) than copper (+0.34 V ) . The emf of the cell is
1.1 volts .

Galvanic cells are of the following two types

1. Chemical cell
2. Concentration cell
CHEMICAL CELL OR FORMATION CELL
In this type, the electrical energy is produced on account
of a chemical change within the cell.
Ex.

Daniel cell, Lechlanche cell, dry cell

Classification
1. Chemical cells with transference

Electrochemistry
2. Chemical cell without transference.
CHEMICAL CELL WITH TRANSFERENCE
The two electrodes are dipped in the electrolyte
containing their ions. These electrolytes are in direct contact but
are separated by a porous diaphragm. This creates a liquid
Junction. Since the ions on the two sides of the liquid junction are
of equal velocities, their moving across the junction sets up
potential called liquid junction potential. It is represented by Ej.
This type of cells involve three types of potential oxidation
potential at the anode, reduction potential at the cathode and
liquid junction potential. However the Ej could be minimized or
even eliminated through the use of a KCl salt bridge.
Representation : M1/M1n+(aq) M2n+(aq) /M2
Reaction
Anode

Cathode

M1(s)

M1n+ (aq) + 2e

M2n+ (aq) + 2e

Cell reaction : M1(s) + M2n+ (aq)

M2(s)
M1n+ (aq) + M2(s)

Cell potential
Ecell = Eanode + Ecathode+ Eliquid junction
Example :

Zn(s) /Zn2+(aq) Cd2+(aq) / Cd(s)

CHEMICAL CELLS WITHOUT TRANSFERENCE

This type of cell consists of two electrodes which are
dipped in same solution. One of the electrode is reversible to
cation of the electrolyte and the other electrode is reversible to
the anion of the electrolyte. Since both electrodes are dipped in

Electrochemistry
same solution the liquid potential is absent. There is no transport
of ions so it is called as chemical cell without transference.
Representation :
Pt(s) , X2(g) / MX(aq) / M(s)
Example : Pt(s) , H2(g) / HCl(aq), AgCl(s) /Ag(s)
H2 is reversible to the H+ ions and Ag/AgCl electrode is
reversible to the Cl- ions.
Reactions
Anode
Cathode

:
:

H+(a1) + e
Ag(s) + Cl-(aq)

(1/2)H2(g)
AgCl(s) + e

Cell reaction :
(1/2)H2(g) + AgCl(s)

H+(aq) + Ag(s) + Cl-(aq)

Cell Potential
ECell = E0Ag / Agcl(s) / Cl- nF
(pH2)1/2

RT ln

aH+ . a Cl-

1.9 Concentration cell

The electrical energy is produced due to the differences in
the concentration of either the electrolyte or the electrode.
The physical transfer of matter involves a decrease in the free
energy of the system. Thus the process is spontaneous. The
electrical energy arises due to the transfer of matter from the
solution / electrode of the higher activity to that of lower activity
Types of concentration cell
1. Electrode Concentration cell

Electrochemistry
2. Electrolyte concentration cell
ELECTRODE CONCENTRATION CELL
Immerse two electrodes of the same material but of different
activities (concentrations) in the same electrolyte. The electrical
energy is produced due to the transfer of matter from one
electrode to other. (i.e. higher activity to that of lower activity
electrode)
In these cells there is no liquid junction potential as these
cells use only one electrolyte.
Types of electrode concentration cell
1. Amalgam electrode concentration cell
2. Gas electrode concentration cell
i.e in electrode concentration cells the electrodes used are either
amalgam electrodes or gas electrodes.
Amalgam electrode concentration cell
Two amalgam electrodes of different activities of the same metal
is immersed in a single common electrolyte thus forming this
cell.
Representation
M(Hg)(a1) Mn+(aq) M(Hg)(a2)
Cell reaction
Anode
:

M(Hg) (a1)

Mn+(aq) + e

Cathode

Mn+(aq) + e

M(Hg) (a2)

Cell reaction :

M(Hg) (a1)

M(Hg) (a2)

Electrochemistry
Thus a transfer of metal occurs from the anode to cathode giving
rise to emf .
Cell potential
Ecell = Eright Eleft

RT
a
RT aMn
Ecell E 0 Mn ( aq) / M ( s )
ln 2 E 0 M ( s ) / Mn ( aq )
ln

nF aMn
nF
a1

E cell ( )

a
RT
ln 2
nF
a1

Thus the emf of the amalgam electrode concentration cell

depends on the ratio of the activities of the metal amalgam taken
in two electrodes. It does not depend on the concentration of H+
ions in the solution. Thus, the electrode with higher gas pressure
should be made anode.
Example :
Ag(Hg) (a1) / AgNO3(aq) / Ag(Hg) (a2)
GAS ELECTRODE CONCENTRATION CELL
Two gas electrodes of different activities of the same gas
are immersed in a single common electrolyte thus forming this
cell.
Representation
Pt(s) , H2 (g) (p1) / HCl(aq)/ H2(g) (p2), Pt(s)
Cell reaction
Anode
: (1/2)H2(g) (p1)
Cathode

: H+(aq) + e

H+(aq) + e
(1/2)H2(g) (p2)

Cell reaction : (1/2)H2(g) (p1) (1/2)H2(g) (p2)

Cell potential

Electrochemistry
Ecell = Eright Eleft

a
RT ( p 2 )1 / 2 0
RT
ln
E H /(1 / 2 ) H 2
ln H 1 / 2
nF
aH
nF ( p1 )

p
RT

ln 2
nF
p1

E cell E 0 (1 / 2 ) H 2 / H
E cell

E cell ()

( p )1 / 2
RT
ln 2 1 / 2
nF
( p1 )

Thus the emf of the gas electrode concentration cell

depends on the ratio of the partial pressure of the gas taken in two
electrodes. It does not depend on the concentration of H + ions in
the solution. Thus, the electrode with higher gas pressure should
be made anode.

Electrolyte concentration cells

It consists of two identical electrodes immersed in into
two solutions of same electrolyte at different concentrations. The
electrodes of such cells are reversible to one of these ions of the
electrolyte. In this there is transfer of matter from electrolyte of
higher activity to electrolyte of lower activity. Due to this transfer
emf is generated.
Example :
Electrolysis of HCl is carried out by passing electricity in
an aqueous solution of HCl through two platinum electrodes.
During this electrolysis process, chlorine is evolved at the anode
and hydrogen is evolved at the cathode. ( Fig ).

Electrochemistry

Platinum electrodes

1 N HCl

Fig 1.10 Electrolysis

When electric current is passed in HCl solution

following reactions take place at the electrodes.

the

At cathode :
The electrode at which reaction occurs is called cathode.
H+ions will move towards the cathode, where H+ ions gets
reduced to hydrogen.
2H+ + 2e

H2

At anode :
The electrode at which oxidation takes place is called the anode.
2Cl

Cl2 + 2e

Types of Electrolyte concentration cells

Electrochemistry
1. Electrolyte concentration cells without transference
2. Electrolyte concentration cells with transference
Electrolyte concentration cells without transference
Two chemical cells with no liquid junction potential are
combined together in such a way that they oppose each other. The
two electrolytes are thus not in direct contact with one another.
Example:
Pt, H2(g)(1atm) HCl(a1), AgCl(s) Ag(s)
Pt, H2(g)(1atm) HCl(a2), AgCl(s) Ag(s)
These two cells are combined together so that they oppose one
another.
Representation
Pt,H2(g)(1atm) HCl(a1),AgCl(s) Ag(s) - Ag(s) AgCl(s),HCl(a2) H2(g)(1atm),Pt

Half cell reactions

Left half cell reaction (1/2) H2 + AgCl(s) Ag(s) + HCl(a1)
Right half cell reaction Ag(s) + HCl(a2) (1/2) H2 + AgCl(s)
________________________________
Overall reaction
HCl(a2) HCl(a1)
This indicates there is transfer of HCl from one concentration to
other. Since the two half cells oppose each other, the net EMF of
the cell is given by
Ecell = Eright Eleft

E cell E 0

RT
1 0 RT

ln
E
ln a1
nF a 2
nF

Electrochemistry

E cell 2.303

a
RT
log 2
nF
a1

Thus the emf of the cells depends on the ratios of the

concentrations/ activities of the two electrolyte solutions used in
the cell.
Electrolyte concentration cells with transference
It consists of two identical electrodes immersed in into
two solutions of same electrolyte at different concentrations. The
electrodes of such cells are reversible to one of these ions of the
electrolyte. The two electrolytes are kept in direct contact with
one another. Thus a liquid junction potential develops at the
interface of two electrolytes.
Electrolyte concentration cells with transference and having
cation as the reversible ion.
Representation
M(s) MX(a1) MX(a2) M(s)
Reactions
Mn+(a1) + ne

Left half cell reaction

M(s)

Right half cell reaction

Mn+ (a2) + ne
M(s)
___________________
Mn+ (a2) Mn+ (a1)

Overall cell reaction

The overall reaction indicates that only the Mn+ from the
electrolyte of concentration C2 is transferred from the electrolyte
of concentration C1.

Electrochemistry
But in actual as the two electrolytes are in direct contact,
both the ions present in the electrolyte also migrate. Since the
transport numbers of cation and anions are not equal, the relative
migration of the both the ions across the liquid junction
contribute significantly to emf.
EMF of the electrolyte concentration cells with transference and
having cation as the reversible ion
Pt, H2(g)(1atm) HCl(a1) HCl(a2) H2(g)(1atm), Pt

E cell 2.303

a
RTt
- log 2
nF
a1

EMF of the electrolyte concentration cells with transference and

having anion as the reversible ion
Ag (s), AgCl(s), HCl(a1) HCl(a2) AgCl(s), Ag

E cell 2.303

a
RTt
log 2
nF
a1

Hence in both the cases, when the electrodes are

reversible to cation or anion, the emf of the cell depends on the
transport number of the ion other than to which the electrode is
reversible. Therefore, such cells are used in the determination of
transport number of the ions.

Electrochemistry

1.10 Conductometric Titrations

Conductance measurements are frequently employed to
find the endpoints of acid-alkali and other titrations.
(NOTE: The titrating solution in the burette is usually five times
stronger than the solution taken in the conductivity vessel. This is
done inorder to minimize the change in the volume in the
conductivity cell due to addition of burette solution)
Experimental methods
The measurement of electrical conductance of a solution
amounts to determination of electrical resistance of the solution
because conductance is just the reciprocal of resistance. The
wheatstone bridge is generally employed for this purpose. This is
shown in figure.
If the ratio of the arms is equal i.e., R 3 = R4 , then the
resistance of the cell is equal to that taken from the resistance box
R2, when the bridge is balanced. It is then possible to read
directly the resistance of the cell.
The reciprocal of this reading is proportional to the
specific conductance. This conductance is then plotted against the
volume added and by titration curves, the end point may be
calculated.
Apparatus
The solution whose conductivity is to be determined, is
placed in the conductivity cell. The cell is connected to the
resistance box R on one side and to a long wire AB on the other
side. I is the induction coil from which the current is led. On
moving the sliding contact along the wire AB, a point is reached
at which the galvanometer reading is zero.

Electrochemistry

Resistance of the solution

Resistance of R

Length BD
Length AD

Conductance = (1/Resistance of the solution)

Fig 1.11
In order to use the titrations for high precision work the
wheat stone bridge is replaced in the form of visual detector or
(telephone earpiece). In this apparatus the alternating current is
used. The apparatus shown in fig. is used.
Here the A.C is reduced to about 3 to 5 volts by means of
transformer T. The galvanometer G and a rectifier (D) is used.
The 800 ohm resistances A and B are used. The rectifier D may
be rectifying crystal, a copper oxide rectifier or suitable vacuum
tube circuit giving rectification and amplification. The solution to
be titrated is placed in the cell. The resistance A and B adjusted

Electrochemistry
and then the current is recorded in G. The titration is now carried
out and the galvanometer readings are plotted against the volume
of the titrant added.

Fig 1.12
The end point is determined by the point of intersection of two
parts of the curves.
ACID - BASE CONDUCTIVITY TITRATIONS
Principle of acid base conductivity titration
Electrical conductance depends upon the number and
mobility of ions.
Procedure
The acid is taken in the conductivity vessel and alkali in
the burette. Alkali is added gradually and the conductance is
noted. The conductance is plotted against the volume of alkali
added. This plot will have two straight lines AB and CD. The

Electrochemistry
point
Conductance

of intersection X of these two lines gives the volume of

alkali required for neutralisation .
A vs Strong base reaction
Theory of Strong acid

Initial co

Decrease in conductanc

Fig 1.13
The initial conductance is of hydrochloric acid which is
due to the presence of hydrogen and chloride ions. As alkali is
added gradually, the hydrogen ions are replaced by slow moving
sodium ions.
H+ + Cl- + Na+ + OH- Na+ + Cl- + H2O
So on continued addition of sodium hydroxide, the conductance
will sharply decrease until the acid has been completely
neutralised.
Subsequent addition of alkali will result in introducing the
fast moving OH- ions. The conductance therefore after reaching a
certain minimum value, will begin to sharply increase.

Titrati

Electrochemistry
NaOH Na+ + OHTheory of Weak acid vs Strong base reaction

Conductance

D
Increase
Increase in conductance due to formation of highly ionized salt
B

En

A conductance is low due to poor dissoci

Initial
Volume of alkali added

Titration of a weak acid vs stro

When a weak acid (acetic acid) is used the initial

conductance is low because the weak acids have poor
dissociation. As alkali is added gradually, the acid combines with
alkali to yield highly ionized salt. (Acetic acid forms sodium
acetate). This contributes to the increase in conductance.
CH3COOH + Na+ + OH- Na+ + CH3COO- + H2O
On continued addition of sodium hydroxide, the
conductance will slightly increase until the acid has been
completely neutralised.
Subsequent addition of alkali will result in introducing the
fast moving OH- ions. So there is sharp increase in conductance.
NaOH Na+ + OH-

Electrochemistry

Theory of Strong acid vs Weak base reaction

Conductance

Initial conductance due to H+

A

Decrease in conductance due to removal

of H+in conductance due to poor dissociation of weak base
No change

D
C
End point

Volume of alkali added

Fig 1.14Titration of a strong acid vs weak base

The initial conductance is of hydrochloric acid which is
due to the presence of hydrogen and chloride ions. As weak alkali
is added gradually, the hydrogen ions are replaced by slow
moving ammonium ions.
H+ + Cl- + NH4OH NH4+ + Cl- + H2O
On continued addition of ammonium hydroxide, the
conductance will sharply decrease until the acid has been
completely neutralised.
Subsequent addition of weak alkali will not have
appreciable change in the conductance as the weak base has
poor dissociation.

Electrochemistry

Theory of Weak acid vs Weak base reaction

C
o
No change in conductance due to poor dissociation of weak base
n
d
u
Increase in conductance due to formation of highly ionized salt
c
End point
C
D
t
B
a
n
c
A conductance is low due to poor dissociation of weak acids
Initial
e
Volume of alkali added

Fig 1.15 Titration of a strong acid vs strong base

When a weak acid (acetic acid) is used the initial
conductance is low because the weak acids have poor
dissociation. As alkali is added gradually, the acid combines with
alkali to yield highly ionized salt. (acetic acid forms ammonium
acetate). This contributes to the increase in conductance.
CH3COOH + NH4OH CH3COO- + NH4+ + H2O
On continued addition of ammonium hydroxide, the
conductance will increase until the acid has been completely
neutralized.
Subsequent addition of weak alkali will not have
appreciable change in the conductance as the weak base has
poor dissociation.

Electrochemistry
NaOH Na+ + OHTheory of Mixture of weak and strong acids vs strong base
reactions

F
E

The plot resembles the combination of the strong acid

against strong base and weak acid against strong base.
The strong acid first gets titrated first. Only after the
strong acid is neutralised, the weak acid will be neutralised.
Hence the initial conductance is due to the presence of
hydrogen and chloride ions of hydrochloric acid. As alkali is
added gradually, the hydrogen ions are replaced by slow moving
sodium ions.
H+ + Cl- + Na+ + OH- Na+ + Cl- + H2O
On continued addition of sodium hydroxide, first there
will be decrease in the conductance due to the removal of fast
moving H+ ions. This is followed by slight increase in

Electrochemistry
conductance due to the highly ionised salt formed from weak acid
and strong base reaction. This increase is noticed until the weak
acid has been completely neutralized.
CH3COOH + Na+ + OH- Na+ + CH3COO- + H2O
Subsequent addition of alkali will result in introducing the
fast moving OH- ions which results in a sharp increase in
conductance.
NaOH Na+ + OHThe plot of conductance against the volume of alkali
added will have three straight lines AB, EF & CD. The point of
intersection of AB and EF gives the volume of alkali required
for neutralization of strong acid. The point of intersection of
lines EF and CD gives the volume of alkali required for
neutralisation of weak acid.
Precipitation reactions
Example :
Consider the precipitation of silver chloride from potassium
chloride (KCl) and silver nitrate (AgNO3)
Principle
Electrical conductance depends upon the number and
mobility of ions.
Procedure
KCl is taken in the conductivity vessel and AgNO 3 in the
burette. AgNO3 is added gradually and the conductance is noted.
The conductance is plotted against the volume of AgNO 3 added.
The point of intersection of two lines is noted which indicates the
complete precipitation of AgCl.

Electrochemistry

Theory behind the reaction

Conductance

Conductance is constant because Mobility of Cl- and N

Volume of AgNO3

Fig 1.17 Titration of a weak

The Ag+ ions are replaced by the K+ ions. The mobility of

K+ ions and Ag+ is more or less same. So the conductance will
remain more or less constant. After complete precipitation the
value increases because of the mobility of K+ ions.
The point of intersection X of these two lines gives the
volume of AgNO3 required for precipitation of AgCl.
Replacement titration
Procedure
A strong acid is added to a salt of weak acid. The
conductance observed is plotted against the volume of strong acid
added.

Electrochemistry

Theory of Replacement titration

conductance
C

A
D

End point

Volume of HCl added

Fig 1.18 Replacement titrations

When a strong acid is added to a salt of weak acid, the

weak acid is replaced first.
The chloride ions have higher conducting power than
acetate ions. So there will be a slight increase in the conductance
upto the end point. But on continued addition of the strong acid,
conductance increases more rapidly due to H+ ions
The plot of conductance against the volume of strong acid
added will have two straight lines AB and CD. The point of
intersection X of these two lines is the end point required for
complete replacement of ions.
Redox Titration : ( Fe2+ Vs Cr2O72- + H+)
Procedure
Iron solution is added to an acidified solution of
dichromate. The conductance observed is plotted against the
volume of Iron added.

Electrochemistry

Theory of Redox titration

conductance
A
B
C

D
End point

Volume of Fe2+ added

Fig 1.19 Redox titrations

With the solution of acidified dichromate, if we add iron

solution, due to decrease in H+ ions concentration, the
conductance will decrease up to end point.
6Fe2+ +Cr2O72- + 14H+ 6Fe3+ +2Cr3+ + 7H2O
After the equivalent point there will not be any change in the
conductance.
The plot of conductance against the volume of iron added
will have two straight lines AB and CD. The point of
intersection X of these two lines is the end point required for
complete oxidation of ions.

Electrochemistry

1.11 Over voltage

The excess potential that is required in order to operate a
cell than the theoretical potential value of the same cell is called
overvoltage.
Example:
The theoretical value required for Zn2+ to deposit on the
cathode as Zn is 0.76 .
The experimental value is just the same. So no
overvoltage is observed.
But in case of evolution of gases say hydrogen or oxygen
at anode, the experimental potential required to achieve the cell
reaction is much greater than the theoretical potential. This
difference in the experimental potential and the theoretical
potential is the overvoltage.
Electrode
Platinised platinum
Smooth platinum
Nickel
Copper
Mercury

Hydrogen overvoltage
(in volts)
0.01
0.26
0.33
0.54
1.04

This overvoltage is sometimes referred to as the bubble

overvoltage, as it is observed just at the point at which the gas
bubbles begin to appear. The value varies largely with nature of
the metal.
Hydrogen overvoltage
The hydrogen overvoltage is the difference of potential of
the electrode at which hydrogen gas is actually evolved and the
potential of the reversible hydrogen electrode. At zero current

Electrochemistry
density and with platinised platinum as electrode, the over
voltage of hydrogen is zero.
Determination of hydrogen overvoltage
Construction
The electrolytic solution is taken in the H shaped vessel.
There are two electrodes one of which is platinum dipped in
electrolyte. The cell is then connected to a reference electrode
generally calomel electrode through a salt bridge containing the
saturated solution of a salt. The whole apparatus is then
connected to a variable resistance D through a galvanometer. The
potential of the electrodes is determined by connecting it with a
potentiometer.

Fig 1.20
Working
The electrolyte used is a dilute Sulphuric acid. The
current density is maintained at a desired level. The potential of
the cathode at a given current density is measured
potentiometrically by combining it with a calomel electrode. The
difference between this potential and the theoretical potential

Electrochemistry
gives the hydrogen overvoltage at the particular metal at the
given current density.
Factors affecting the phenomenon of over voltage:
1.
Current density :
The over voltage increases with increasing current
density (I) according to the following equation
= a + b log I
where a and b are constants.
The value of b may be represented by
b = 2 x 2.303 RT/F
Its value is equal to 0.118 at ordinary temperatures.
2.

3.
4.
5.

Hydrogen ion concentration

In the absence of strongly absorbed ions the over
voltage is independent of hydrogen ion concentration. In
the case of strongly acidic or alkaline solutions some
deviations occur.
Temperature
Over voltage decreases with increase in
temperature.
Impurities
Impurities present in cathode material greatly
influence the over voltage.
Pressure
At lower pressure, the over voltage increases rapidly on
the cathodes like copper, mercury or nickel.
At high pressures, the over voltage is affected very
slightly.

Electrochemistry
Applications of overvoltage
1.
For solutions of equivalent ionic concentration, the higher
the electrode potential involved, the more easily the
cations will be discharged.
2.
Used in the electrolysis of a solution which is molar w.r.t
zinc sulphate as well as sulphuric acid. Where
electroplating of zinc from acidic solution is achieved due
to the overvoltage only.
3.
It is used in electrolysis of neutral solution of cadmium
salts. Since the overvoltage of hydrogen over cadmium is
0.99V more, cadmium deposition could be achieved
before the evolution of hydrogen.
4.
Metal plating is achieved because of the high value of
hydrogen overvoltage.
5.
In lead accumulators due to over voltage the lead is
deposited on the negative plate accumulators while
changing the cell.
6.
In the electrolytic reduction of organic compounds. In the
reduction of nitrobenzene, the electrodes with high over
voltage i.e. lead are used instead of platinum.
7.
It is utilized in the industrial production of chlorine and
NaOH by the electrolysis of NaCl solution.

1.12 Polarisation
The phenomenon of back EMF brought about by the
product of electrolysis is termed as polarization.
Explanation of polarization
In a voltaic cell, zinc and copper electrodes are connected
externally by a wire. Hydrogen ions (carrying a positive charge)
will move towards the copper electrode. They give their charges
at the electrode and escape through the solution as bubbles. In
this process, a film of neutral hydrogen is gradually deposited at

Electrochemistry
the copper electrode. This with time increases in thickness. So it
provides a greater resistance to the flow of the current through
the cell. At this stage the current is diminished.
As the process proceeds, the film of neutral hydrogen increases in
thickness. As hydrogen is positive towards zinc, an electric field
from the layer of hydrogen to that of zinc is set up. This is known
as back emf. When the field is sufficiently high, it stops further
traveling of positively charged hydrogen ions towards the copper
electrode, and hence the current stops altogether.
This is the stage at which the cell is said to be completely
polarized.
Causes of polarization
1.
The liberated gases offer resistance to the normal flow
of current through the cell which requires high voltage
to keep the normal flow.
2.
The product of electrolysis may convert the inert
electrode into active electrodes which can exercise a
back emf.
3.
The deposited metals may also form a cell functioning
in the opposite direction similar to the gas electrodes.
MODERN VIEW
1. Polarisation occurs due to the slowness of one or more
processes taking place at the electrodes.
2. Due to slowness of the diffusion of ions in the solution.
Concentration polarization.

Factors which affect electrode polarization :

1.
2.

Concentration of electrolyte
High concentration of electrolyte increases the
polarization effects.
Nature of ions deposited on electrodes :
Extent of polarization increases when there is formation
of the adherent and non-porous film on the electrodes.

Electrochemistry
3.
4.

5.
6

Size of the electrode

Small surface area of the electrode increases the
polarization effects.
Nature of electrode surface
Rough surface of the electrode decreases polarization
effects than smoother of surface.
For example, platinum black electrode exhibits less
polarization effect than the smooth platinum electrode.
Stirring of the electrolytic solution
Polarization effects can be minimized by stirring.
Temperature
The rate of diffusion of ions increases with increase in
temperature, which reduces the polarization effects.

Effects of electrode polarization

1.
Polarized galvanic cells develop smaller potential than
theoretically predicted.
2.
In an polarized electrolytic cell, more than theoretically
required potential has to be used to maintain a given
current strength.
Elimination of polarization
1.
Mechanical method
By brushing off the hydrogen from time to time from the
electrode.
By roughening the surface of the electrode, so the bubbles
may not stick to the surface.
2.

Electro-chemical method
In these electro-chemical methods, the two solutions are
taken such that the hydrogen meets with a second solution, from
which ions of the same metal as that of the positive plate or gas is
liberated.

Electrochemistry
3.
Chemical method
Usage of depolarizers.
The chemicals which are used to eliminate polarization are
known as depolarizers.
The depolarizers are usually strong oxidizing agents (like
nitric acid or chromic acid). They convert evolved hydrogen into
water thus not allowing the hydrogen to get absorbed on the
electrode.

1.13 Decomposition potential

The minimum voltage necessary to produce continuous
electrolysis of an electrolyte is called the decomposition
potential of the electrode.
Example
When two smooth platinum electrodes are placed in dilute
Sulphuric acid and a low voltage is applied, practically no current
flows through the circuit.
C

Current(C)

E
D

Applied Voltage (V)

Fig 1.21 Decomposition Potential

Electrochemistry
But as the applied voltage is gradually increased by
means of the external battery, to electrolyse the solution, the
current increases in the manner as shown in the current density vs
potential plot.
It could be seen that an appreciable voltage is required for
free flow of electricity through the cell. The emf applied at the
point D at which the electrolysis restarts and proceeds
continuously, is called the decomposition voltage

Measurement of Decomposition potential

Principle
The decomposition potential can be measured by plotting
current density against the applied voltage. The point where there
is sudden increase in the current gives the measure of
decomposition potential.
Construction
The apparatus consists of two platinum electrodes A and
A dipped in an electrolyte as shown in fig. S is a stirrer for
stirring the solution constantly. The two electrodes are connected
to a voltmeter V through ammeter C to measure the strength of
current. B is the external source of E.M.F and R is the variable
resistance. The voltage may be measured by voltmeter V.
First of all a resistance is applied from R and the ammeter and
voltmeter readings are noted. Then at another reduced resistance
from R, again the values of V and C are taken. The process is
continued until the electrolysis in the cell is not visible.
A series of current density is taken versus the applied voltage
above and below the decomposition potential.
i.e., The current (C ) is plotted against the applied voltage (V).

Electrochemistry
Importance and significance of decomposition potential
1.
It is of greater importance in the controlled deposition of
metals or other electrolytic products from an solution
containing different electrolytes. The one having the
lowest decomposition potential is electrolysed first.
2.
The knowledge of decomposition potential are of use in
electro refining, electroplating and electrometallurgy of
metals.
3.
Used in separation of copper and zinc electrically.

1.14 Kohlrauschs law

Kohlrauschs law states that at infinite dilution when
dissociation is complete and all interionic effects vanish, each
ion moves independently of its co-ion and contributes to the
total molar conductance of an electrolyte a definite share.
Thus the equivalent conductivity of an electrolyte at infinite
dilution (0) is the sum of two parts one due to the cation + and
other due to the anion
0 = 0+ + 0
In terms of molar conductivities the Kohlrauschs law may be
mathematically stated as
0m = 0+ + 0
where
0+ = contribution of cation towards the molar
conduction at dilution.
0
= contribution of anion towards the molar
conduction at dilution.

Applications of Kohlrauschs law

Electrochemistry

i) Determination of molar conductivity of weak electrolytes

The equivalent conductivity for a weak electrolyte does
not become constant even at very high dilutions, so it is not
possible to determine the value of 0 for these directly.
Kohlrauchs law can be used to determine 0 for weak
electrolytes.
Example :
The equivalent conductance of a weak electrolyte like
acetic acid can be determined by determining the equivalent
conductances of strong electrolytes like HCl , CH 3COONa and
NaCl at infinite dilutions as below :

0CH COO 0H 0H 0C l 0CH COO 0Na (0Na 0C l )

3

i.e.,

0m CH 3COOH 0m HCl 0m CH 3COONa 0m NaCl

Similarly
0m NH 4OH 0m NH4Cl 0m NaOH 0m NaCl
The molar conductance at infinite dilution of a sparingly soluble
substances like silver chloride, can also be obtained from similar
considerations.
m AgCl m NH4Cl m AgNO3 m NH 4 NO3
ii) To find net Ionic product of water
Water dissociates feebly. Dissociation of water may be written as:
H2O

H+ + OH-

Its equilibrium is given by the relation

Electrochemistry

H OH K

H 2O

Since the dissociation of water is very low, concentration of

undissociated molecules [H2O] may be considered to remain
constant . Hence
[H+] [OH] is also a constant.
This constant is called Ionic product of water and is represented
as Kw . Thus ,
Kw = [H+] [OH]
In pure water the product of the concentration of hydrogen and
hydroxide ion is constant. The conductivity of purest distilled
water is first determined experimentally. Let it be k.
The equivalent conductivity of water is given by
0 H OH
Applying the formula
= k V (Volume in cm3 containing 1 eq of electrolyte)
where k = conductivity of water
= 18 k
( V = 18 in case of water)
The degree of dissociation of water ,

18k
0
H OH
From the dissociation of water H2O
H+ + OH
[H+] = c = [OH]
where c is moles of H2O per litre of water = 1000/18 . Knowing
the values of c and , [H+] and [OH] is computed. And from
this

Electrochemistry
Kw = [H+] [OH] = c2 2 is worked out.
iii) Determination of solubility of sparingly soluble salt :
There are number of salts , such as silver chloride, barium
sulphate, lead sulphate etc., which are so sparingly soluble in
water.
The conductance of the solution containing sparingly soluble salt
in water is determined using conductivity meter 1
The conductance of water used in the preparation of the
solution is also determined 2
Specific conductance ( 2 1 ) cell constant
Let the specific conductance be z Sm-1.
Suppose the solubility of silver chloride = x mole /m3
Then concentration of AgCl in aquous solution = x mol/m3
Molar conductance m is given by
m

specific conductanc e
Concentrat ion of AgCl in solution

z
= x
At infinite solution, from Kohlrausch law,
0m AgCl 0 Ag 0 Cl

or

z
Ag 0 Cl
0

z
0

Solubility of AgCl in water is = Ag Cl

0

Electrochemistry

iv) Degree of Dissociation of Weak electrolyte :

The degree of dissociation of weak electrolyte such as
NH4OH , acetic acid can be determined by measuring the
equivalent conductivity , of the solution of the electrolyte at
any given dilution. Since 0 is the equivalent conductance when
electrolyte is fully dissociated , the ratio /0 would give the
degree of dissociation of the weak electrolyte
/0 =
0 could be obtained from Kohlrauschs law.
Similarly, if 0 and the degree of dissociation are known, can
be calculated.
v) Limiting (or absolute )mobilities of ions .
The mobility of an ion u is its speed under potential gradient of
1 volt/cm .
At infinite dilution,
Limiting ionic conductanc e
Limiting ionic mobility
96490
Example 1 : The molar conductance of sodium acetate,
hydrochloric acid and sodium chloride at infinite dilution are
91104, 426.16104 and 126.45 104 S m2 mol1 respectively
at 250C Calculate the molar conductance at infinite dilution for
acetic acid.
Solution :
Om CH 3COONa OCH COO ONa
3
= 91104 S m2 mol1
Om HCl OH OCl
= 426.16104 S m2 mol1
Om NaCl ONa Ocl
= 126.45 104 S m2 mol1
OCH COO OH OCH COO ONa OH OCl ONa OCl
3

(or)

Electrochemistry

Om CH 3COOH Om CH 3COONa Om HCl Om NaCl

= (91 + 426.16 126.45 ) 104
= 390.71 104 S m2 mol1
Example 2: The molar conductance of a 0.01 M solution of
acetic acid was found to be 16.30 104 S m2 mol1 at 250C. The
molar ionic conductances of hydrogen and acetate ions at infinite
dilution are 349.8104 and 40.9104 S m2 mol1 respectively,
at the same temperature. What percentage of acetic acid is
dissociated at this concentration
Solution :
Om CH 3COOH OCH COO OH
3

= ( 40.9 +349.8) 104 = 390.7 104 S m2 mol1

m
16.3 10 4 S m 2 mol 1
o
0.04172
m 390.7 10 4 S m 2 mol 1
0.01 M acetic acid is 4.172 percent dissociated.
Example 3 : The conductivity of a saturated solution of barium
sulphate at infinite dilution is 3.06 10-6 ohm-1 cm-1 The
equivalent conductance of BaSO4 at infinite dilute is 143 ohm-1
cm2 eq-1. What is the solubility of BaSO4 at 250C in gm
equivalent per litre. ( AU Jan 2005)
Solution :
Conductivity of saturated solution of Barium sulphate
K = 3.06 106 ohm1 cm1
Equivalent conductivity of BaSO4 =
0 143 ohm 1 cm 2 equ 1
.
1000 k
0
Concentration of BaSO4 = C = BaSO 4
1000 3.06 10 6
143
=

Electrochemistry
= 2.14105 gm/equ/lit
we know equivalent weight of BaSO4 = 116.5
Solubility of BaSO4 = C equivalent weight of BaSO4
= 2.14105 116.5
= 2.49 103 gm lit1
Example 4 :
A conductivity cell , when filled with an aqueous solution of 0.02
M KCl at 250C, had a resistance of 250 ohm. Its resistance, when
filled with 6105 M NH4OH solution was 105 ohm . The specific
conductance of 0.02 M KCl was 0.277 S m-1 . The molar
conductances at infinite dilution of NH4+ and OH ions are
73.4104 and 198104 S m2 mol-1, respectively. Calculate the
degree of dissociation of 6105 M NH4OH solution.
Solution :
Since specific conductance = k = cell constant/R , hence
Cell constant = kR = 0.277 Sm1 ( 250 ) = 69.2 m1
For NH4OH solution,
c = 6 105 M = 6 105 mol dm3 = 6 102 mol m3
k cell constant
69.2 m 1
m

c
cR
(6 10 2 mol m 3 )(10 5 )

= 115 104 S m2 mol1

According to Kohlrauschs law,

0m = 0+ + 0 = (73.4 +198) 104 S m2 mol1
= 271.4 104 S m2 mol1

115 10 4 S m 2 mol 1
0m
0.424
m 271.4 10 4 S m 2 mol 1
Example 5: At 250C the specific conductance of a saturated
solution of AgCl is 2.68 104 S m-1 and that of water with which
the solution was made is 0.86 104 Sm-1. If molar conductances
at infinite dilution of AgNO3 , HNO3 and HCl are respectively,

Electrochemistry
133 104, 421 104 and
426 104 S m2 mol1, calculate
the solubility of AgCl in grams per dm 3 in water at the given
temperature.
Solution : ksolution = kAgCl + kwater
kAgCl = ksolution kwater
= (2.68 0.86) 104 S m1 = 1.82 104 S m1
Since AgCl is formed according to the reaction
AgNO3 + HCl

AgCl + HNO3

Hence using kohlrauschs law,

0m AgCl 0m AgNO3 0m HCl 0m HNO3
= (133.0 + 426.0 421.0 ) 104 S m2 mol1
= 138.0 104 S m2 mol1

m k

0
c and for the saturated solution of the salt, m m
k
1.82 10 4 S m 1
c 0
1.32 10 2 mol m 3
4
2
1
m 138 10 S m mol
= 1.32 105 S dm3
Mm(AgCl) = 143.5 g mol1
Solubility of AgCl = (1.32 105 mol dm3)(143.5g mol1)
= 1.89 103 g dm3

Example 6 : At 250C the specific conductance of a 0.01M aqueous

solution of acetic acid is 1.63 102 S m1 and the molar conductance at
infinite dilution is 390.7 102 S m2 mol1. Calculate the degree of
dissociation and hence the dissociation constant of the acid.
Solution : k = 1.63 102 S m1,
c = 0.01 mol dm1 = 0.01 103 mol m3

k 1.63 10 2
m
16.3 10 4 S m 2 mol 1
3
c 0.01 10

The degree of dissociation is given by

Electrochemistry
16.3 10 4 S m 2 mol 1
0.0417

390.7 10 4 S m 2 mol 1
The dissociation constant of the acid =
c 2 (0.01 mol dm 3 )(0.0417) 2
K

1.82 10 5 mol dm 3
1
1 0.0417

0
m

Review Questions
1)i) What is single electrode potential
ii) Derive Nernst equation . Explain the various terms
involved ( Anna University May 2003 )
2)How is emf of electrochemical cell determined by
potentiometry . (Anna Univ Campus Nov2002 )
3)Define the term single electrode potential .
Derive the Nernst equation and give its applications .
(Anna Univ. Model Q.P)
4)How is calomel electrode constructed ? . Discuss how this
electrode may be used for the determination of pH of a solution
( Anna University Model Q.P )
5) What is emf series . Explain its significance .
6)What are galvanic cells and concentration cell .
7)The emf of the cell Zn/ZnCl2 // AgCl /Ag is 1.005 V at 25 0C .
Calculate the heat of reaction H at the given temperature.
8)Explain different kinds of single electrodes with examples .
9)What are reversible and irreversible calls . Give examples
10)What is electrochemical series , what are its applications .
11)Define e.m.f , Derive an expression for emf of a cell
12)Explain sacrificial anode cell
13)Determine the emf or Zn-Fe cell at 2980K . The oxidation
potentials of zinc and iron are +0.76V and +0.44V respectively .

Electrochemistry
14)Determine the potential developed when a zinc rod is kept
immersed in zn(NO3)2 solution of strength 0.5M at 250C
E0Zn2+/Zn = -0.76 V
15) Determine the emf of the cell Zn/Zn 2+// Ag+/Ag , when
Zn2+ = 0.1 M and Ag+ = 10M , Ecell at 250C = 1.56 V.
16. What do you understand by a half cell ? What are the half
cells present in a Daniel cell ?
17. What for you understand by a standard hydrogen electrode
and what its significance ?
18.What is a salt bridge and what is its role in a Galvanic cell ?
19. What is electrochemical series and what are its important
features ?
20. Write short notes on the Following :
i) Potential decomposition
ii) Over voltage

Example Problems
Example 1: ( Anna SE , Jan2001)
Determine the emf of a Daniel cell at 250C , when the
concentration of ZnSO4 and CuSO4 are 0.001M and 0.1 M
respectively . The standard emf of the cell is 1.1 volt
Solution:
Given : E0 = 1.1 Volts C2 = 0.1 , C1 = 0.001
The emf of the cell is given by
c
0.0591
E cell E 0
log 2
n
c1
0.0591
0 .1
1 .1
log
2
0.001
= 1.1591 Volts

Electrochemistry
Example 2
Determine the emf of a concentration cell at 25 0 C consists of
two Zn electrodes immersed in a solution of zinc ions of 0.1M
and 0.01M concentration.
Solution :
Given : n = 2 C1 = 0.01 C2 = 0.1
The reaction is
Zn2+ + 2e- Zn
The emf of the cell is given by

c
0.0591
log 2
n
c1
0.0591
0.1

log
2
0.01

E cell
E cell

= 0.0296 Volts
Example 3 ( Anna University Dec2001 )
Determine the reduction potential of Cu/Cu 2+ is 0.5M at 250
C E0Cu/Cu2+ = 0.337 V .
Solution :
E0 = 0.337 Volts , [Cu2+] = 0.5
The reduction potential is given by
E

0.0591 log [Cu2+]

n
0.0591 log 0.5
2
0.328 Volts

Electrochemistry
Example 4
Determine the emf of the concentration cell given below:
Cu Cu2+
Cu2+ Cu
(0.2M)
(2M)
Solution :
Given : n = 2 C1 = 0.2 M C2 = 2 M
The reaction is
Cu2+ + 2e- Cu
The emf of the cell is given by
c
0.0591
E cell
log 2
n
c1
0.0591
2

log
2
0.2
= 0.029 Volts
Example 5
Determine the emf of the following cell
Zn Zn2+
Ag+ Ag ,
[Zn 2+ ] = 0.1 M ,
+
0
0
[Ag ] = 0.1M , E Ag = +0.8Volts , E Zn = 0.76 Volts
Solution :
Given :
[Zn2+ ] = 0.1 M , [Ag+] = 0.1M ,
E0Ag = +0.8Volts , E0Zn = 0.76 Volts
The emf of the cell is given by
Ecell =

Ecathode
Eanode
+
( EAg /Ag)
(EZn2+/Zn )
0.0591
0.0591
0
0
E Ag

log 0.1 E Zn

log 0.1
1
2
= (0.8 (0.76) ) 0.02955
= 1.53045 Volts

Electrochemistry
Example 6
Determine the emf of the cell at 25 0C concentration of ZnSO4
and CuSO4 are 0.01 M and 0.1 M respectively . The standard
e.m.f of the cell is 1.1 volts .
Solution:
Given :
Ecell

[ZnSO4] = 0.01 M , [CuSO4] = 0.1 M ,

= Ecathode Eanode

= ECu2+/Cu EZn2+/Zn
0.0591
0.0591
0
0
E Cu

log 0.1 E Zn

log 0.01
2
2
/ Cu
/ Zn
2
2
0.0591
0 .1
0
0
E Cu
E Zn

log
2
2
/ Cu
/ Zn
2
0.01
( We have E0Cu2+/Cu - E0Zn2+/Zn = 1.1 volts )
0.0591
0 .1
log
2
0.01
= 1.129 Volts

E cell 1.1

Example 7:
Determine the emf of a concentration cell consisting of silver
electrodes immersed in 0.01M and 0.1 M solutions of its ions
at 250 C .
Solution :
For the concentration cell with silver electrode ,
The electrical reaction involved is Ag Ag+ + e
n = 1 , C2 = 0.1 M and C1 = 0.01M
The emf of the cell is given by
c
0.0591
E cell
log 2
n
c1

Electrochemistry
0.0591
0 .1
log
1
0.01
= 0.0591 Volts

Example 8 :
The standard electrode potentials of lead and silver are
0.18V and + 0.8V respectively . Determine the emf .
Solution :
E0Pb2+/pb = 0.18 V
E0Ag+/Ag = + 0.8 V
Ecell = E0cathode E0anode
= +0.8 ( 0.18 )
= 0.98 Volts
Example 9 ( Anna University Nov2001)
Determine the concentration of H+ in the following cell .
Pt, H2 ( P= 1 atm) H+ (C = 10-6 M)
H+ ( C= ? )
H2 ( P = 1atm) Pt
Ecell = 0.118V at 250C
Solution :
The emf of the cell is given by
c
0.0591
E cell
log 2
n
c1
c
0.0591
0.118
log 26
1
10
0.118
log c 2 log 10 6
0.0591
C2 = 1 10-4 M

Electrochemistry

Example 10
Determine the emf of the following cell at 250C .
Pt , H2 HCl solution
HCl solution H2, Pt
pH = 4.05
pH = 2.35
Solution :
We have pH = - log [H+] = - log C
logC1 = 4.05 , logC2 = 2.35
The emf of the cell is given by
c
0.0591
E cell
log 2
n
c1
c
0.0591
E cell
log 2
1
c1
E cell 0.0591(log c 2 log c1 )
or

E cell 0.0591( 2.35 (4.05))

= 0.1004 V

Example 11 (Anna University campus Nov 2002)

Find the potential of the cell in which the following reactions
take place at 250C .
Zn(S) + Cu2+ ( 0.02 M ) Cu(S) + Zn2+
Solution :
(0.4M )
Given : E0 (Zn2+/Zn) = 0.76 V
E0 (Cu2+ /Cu) = 0.34 V
E0cell = E0 (Cu2+ /Cu) E0 (Zn2+/Zn)
= 0.34 ( 0.76 ) = 1.10 Volts
According to Nernst equation
Ecell = E0cell 2.303 RT log
nF

Zn2+(products)
Cu2+(reactants)

= 1.1 2.303 8.314 298 log (0.4/0.02)

[prouct]
[Reactan
t]
Electrochemistry
= 1.06 Volts .