SRI KRISHNA COLLEGE OF ENGINEERING AND

TECHNOLOGY
(AN AUTONOMOUS INSTITUTION, AFFILIATED TO ANNA UNIVERSITY, ACCREDITED BY NAAC WITH
‘A’ GRADE)
ACCREDITED BY NBA (CSE, IT, ECE, EEE, MECH, MCT & CIVIL)

SKCET CLASS LECTURE

SUBJECT : 23AS101 - APPLIED SCIENCE

(Common to B.E. CSD, CSE, CSE (CYBER SECURITY),
ECE, EEE, MCT & [Link]. AI&DS, IT)

MODULE : ELECTROCHEMISTRY

TOPIC : ELECTROCHEMISTRY

FACULTY : Dr. M. JEYARAJ

[Link]
Description
❖ Electrochemical cells-electrolytic cell-reversible and
irreversible cells
❖ Free energy and emf, cell potentials
❖ Nernst equation and applications. Oxidation and
reduction potentials
❖ Standard hydrogen electrode, saturated calomel
electrode,
❖ Glass electrode-pH measurement
Introduction
Electrochemistry is a branch of chemistry, which deals with
the chemical applications of electricity. Electrochemistry deals with
the chemical reactions produced by passing electric current
through an electrolyte or the production of electric current
through chemical reactions.
Conductors
A substance or material that allows electric current to pass
through it is called a conductor. The ability of a material to conduct
electric current is called conductance.
All metals, graphite, fused salts, aqueous solutions of acids,
bases, etc.,
Non-Conductors (or) Insulators
Materials which do not conduct electric current are called
non-conductors or insulators.
Plastics, wood, most of the non metals, etc.,
Types of Conductors
The conductors are broadly classified into two types
1. Metallic conductors (or) Electronic conductors
Metallic conductors are solid substances, which conduct electric current
due to the movement of electrons from one end to another end. The
conduction decreases with increase of temperature.

All metals, graphite.

2. Electrolytic Conductors

Electrolytic conductors conduct electric current due to the movement of

ions in solution or in fused state. The conduction increases with increase
of temperature.

Acids, bases, electrovalent substances.

Oxidation and Reduction potential
The tendency of an electrode to lose electrons is called the
oxidation potential, and the tendency of an electrode to gain
electrons is called the reduction potential.
Factors affecting electrode potential
The rate of the above reactions depend on
[Link] nature of the metal.
[Link] temperature.
[Link] concentration of metal ions in solution.
Single electrode potential (E)
It 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.

Standard electrode potential (E°)

It 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 of 1 molar concentration at 25°C.
Nernst equation for electrode potential
Consider the following redox reaction
Mn+ + ne− −−−−−> M
For such a redox reversible reaction, the free energy change (∆G) and its
equilibrium constant (K) are inter related as
∆G = − RT ln K + RT ln [ Product ]
[ Reactant]
= ∆G° + RT ln [ Product ] ........ (1)
[ Reactant ]
where,
∆G° = Standard free energy change
 The above equation (1) is known as Van’t Hoff isotherm.
The decrease in free energy (− ∆G) in the above reaction involves
transfer of ‘n’ number of electrons, then ‘n’ faraday of electricity will
flow. If E is the emf of the cell, then the total electrical energy (nEF)
produced in the cell is
− ∆G = nEF
(or)
− ∆G° = nE°F ........ (2)
where,
− ∆G = decrease in free energy change.
(or) − ∆G° = decrease in standard free energy change. Comparing
equation 1 and 2, it becomes
− nEF = − nE°F + RT ln [ M ]
[ Mn+] . .......(3)
Dividing the above equation (3) by − nF
[ the activity of solid metal [M] = 1 ]
E = E° − RT ln 1
nF [ Mn+ ]

In general, E = E° − RT ln [Product]
nF [Reactant]
(or)
E = E° + RT ln [ Mn+ ]
nF
 When, R = 8.314 J/K/mole; F = 96500 coulombs ;
T = 298 K (25°C), the above equation becomes

In general,

Similarly for oxidation potential

“Nernst equation for single electrode potential”.

Applications of Nernst equations

1. Nernst equation is used to calculate electrode potential of

unknown metal.

2. Corrosion tendency of metals can be predicted.

REFERENCE ELECTRODES (STANDARD ELECTRODES)
The electrode potential is found out by coupling the
electrode with another reference electrode, the potential
of which is known or arbitrarily fixed as zero. The
important primary reference electrode used is a
standard hydrogen electrode, standard electrode potential of
which is taken as zero.
It is very difficult to set up a hydrogen electrode. So
other electrodes called secondary reference electrodes
like calomel electrodes are used.
 Primary Reference Electrode (Standard
Hydrogen electrode)
Construction
Hydrogen electrode consists of platinum foil, that is
connected to a platinum wire and sealed in a glass
tube. Hydrogen gas is passed through the side arm of the
glass tube. This electrode, when dipped in a 1M HCl and
hydrogen gas at 1 atmospheric pressure is passed forms a
standard hydrogen electrode. The electrode potential of
SHE is zero at all temperatures. (Fig. 1.2).
It is represented as,

Pt , H2 (1 atm)/H+ (1 M); E° = 0 V

In a cell, when this electrode acts as anode, the electrode

reaction can be written as
H2 (g) −−−−−> 2H+ + 2e−
When this electrode acts as cathode, the
electrode reaction can be written as

2H++2e- −−−−−> H2(g)

Limitations
i. It requires hydrogen
gas and is difficult to
set up and transport.
ii. It requires considerable
volume of test solution.
iii. The solution may
poison the surface of
the platinum electrode.
iv. The potential of the
electrode is altered
by changes in
barometric pressure.
Secondary Reference Electrode (Saturated Calomel
Electrode)
Construction
Calomel electrode consists of a glass tube containing
mercury at the bottom over which mercurous chloride is
placed. The remaining portion of the tube is filled with a
saturated solution of KCl. The bottom of the tube is
sealed with a platinum wire (Fig. 1.3). The side tube is used
for making electrical contact with a salt bridge. The electrode
potential of the calomel electrode is + 0.2422 V.
It is represented as,
Hg , Hg2Cl2 (s) , KCl ([Link]); E° = 0.2422 V
If the electrode acts as anode the reaction is
2Hg(l) −−−−−> Hg22+ + 2e−

Hg22+ + 2Cl−−−−−−>Hg2Cl2 (s)

2Hg(l) + 2Cl− Hg2Cl2 (s) + 2e−

If the electrode acts as cathode the reaction is

Hg2 Cl2 (s) −−−−−>Hg22+ + 2Cl−

Hg22+ + 2e−−−−−−> 2Hg(l)

Hg Cl + 2e− 2Hg + 2Cl−`

The electrode potential is given by (for example cathode)

The electrode potential depends on the activity of

the chloride ions and it decreases as the activity of the
chloride ions increases. The single electrode potential
of the three calomel electrodes on the hydrogen scale at
298 K are given as

0.1 N KCl = + 0.3338 V

1.0 N KCl = + 0.2800 V
Saturated KCl = + 0.2422 V.
 Measurement of single electrode potential of
Zn using saturated calomel electrode
The saturated calomel electrode is coupled with another
Zn electrode, the potential of which is to be determined (Fig.
1.4). Since the reduction potential of the coupled Zn
electrode is less than E° of calomel electrode (+ 0.2422 V),
the calomel electrode will act as cathode and the reaction is
At Anode:
Zn Zn2+ + 2e− (Oxidation)
At Cathode:
Hg2Cl2 (s) + 2e− 2Hg(l) + 2Cl− (Reduction)
Zn + Hg2Cl2 (s) ZnCl2 + 2Hg (l)

Ecell = E°right − E°left

Ecell = E°cal − E°Zn
E°Zn = E°cal − Ecell
= + 0.2422 − 1.0025
E°Zn = − 0.7603 volt .
Ion-Selective Electrodes (ISE)
Ion-selective electrodes are the electrodes having the ability to
respond only to a particular ions, and develop potential, ignoring
the other ions in a mixture totally. The potential developed by an
ion-selective electrode depends only on the concentration of
particular ions.

Glass Electrode
The glass membrane of the glass electrode is only
selective to H+ ions only in a mixture.
Glass Electrode (Internal Reference
Electrode)
Construction
A glass electrode consists of thin-walled glass bulb (the glass
is a special type having low melting point and high electrical
conductivity) containing a Pt wire in 0.1M HCl (Fig.1.5). The glass
electrode is represented as

Pt, 0.1 M HCl / Glass

HCl in the bulb furnishes a constant H+ ion concentration.

 Glass electrode is used as the “internal reference
electrode”. The pH of the solutions, especially coloured
solutions containing oxidizing or reducing agents can be
determined. The thin walled glass bulb called glass
membrane functions as an ion-exchange resin, and an
equilibrium is set up between the Na+ ions of glass and
H+ ions in solution. The potential difference varies with
the H+ ion concentration, and its emf is given by the
expression

EG = E°G + 0.0592 pH
Determination of pH of a Solution using Glass Electrode
The glass electrode is placed in the solution under test
and is coupled with saturated calomel electrode as
shown in the figure 1.6.
 The emf of the cell is measured. From the emf, the pH of
the solution is calculated as follows
Ecell = Eright − Eleft
Ecell = Ecal − EG
Ecell = Ecal − (E°G + 0.0592 pH)
Ecell = Ecal − E°G − 0.0592 pH

pH = Ecal − E°G − Ecell ∴ Ecal = 0.2422 V

0.0592
∴ pH = 0.2422 – EoG – Ecell
0.0592
 Advantages of Glass Electrode
i. It can be easily constructed and readily used.
ii. The results are accurate.
iii. It is not easily poisoned.
iv. Equilibrium is rapidly achieved.
Disadvantages (Limitations)
ii) Since the resistance is quite high, special electronic
potentiometers are employed for measurement.
iii) The glass electrode can be used in solutions only with pH
range of 0 to 10. However above the pH 12 (high
alkalinity), cations of the solution affect the glass and
make the electrode useless.
 Applications of ISEs

(i) ISEs are used in determining the concentrations of

cations like H+, Na+, K+, Ag+, Li+.
(ii) ISEs are used for the determination of hardness Ca2+ and
Mg2+ ions).
(iii) Concentrations of anions like NO3−, CN−, S2−, halides
(X−) can be determined.
(iv) ISEs are used in the determination of concentration of a
gas by using gas-sensing electrodes.
(v) pH of the solution can be measured by using glass
electrode.
CELLS
A cell is a device consisting two half cell. Each half cell
consists of an electrode dipped in an electrolytic solution. The
two half cells are connected through one wire.
TYPES OF CELLS
1. Electrolytic cells.
2. Electrochemical cells (or)voltaic cells (or)
galvanic cells.
 ELECTROLYTIC CELLS
Electrolytic cells are cells in which electrical energy is used to
bring about the chemical reaction.
Electrolysis, electroplating, etc.,
ELECTROCHEMICAL CELLS OR GALVANIC CELLS
Electrochemical cells are entirely different from electrolytic
cells. The cells used for electrolysis (where electrical energy is
converted to chemical energy) are called electrolytic cells, whereas
in electrochemical cells, chemical energy is converted to electrical
energy. Galvanic cells are electrochemical cells in which the
electrons, transferred due to redox reaction, are converted to
electrical energy.
Daniel cell
Cell device (Construction)
Daniel cell consists of a zinc electrode dipped in 1 M ZnSO4
solution and a copper electrode dipped in 1 M CuSO 4
solution. Each electrode is known as a half cell. The two solutions
are inter connected by a salt bridge and the two electrodes are
connected by a wire through the voltmeter.
Reactions occurring in the cell
At anode: Oxidation takes place in the zinc electrode by the liberation
of electrons, so this electrode is called negative electrode or
anode.
At cathode: Reduction takes place in the copper electrode by the
acceptance of electrons, so this electrode is called the positive
electrode or cathode.
Zn −−−−−> Zn2+ + 2e− (at anode)
Cu2+ + 2e− −−−−−> Cu (at cathode)
Cu2+ + Zn −−−−−> Zn2+ + Cu (net cell reaction)
The electrons liberated by the oxidation reaction flow through the
external wire and are consumed by the copper ions at the cathode.
 Salt bridge
It consists of a U-tube containing saturated solution of KCl
or NH4NO3 in agar-agar gel. It connects the two half cells of the
galvanic cells.
Functions of salt bridge
•It eliminates liquid junction potential.
•It provides the electrical continuity between the two half cells.
Conditions for a cell to act as standard cell
The conditions for an electrochemical cell to act as a
standard cell are
•The e.m.f of the cell is reproductive.
•The temperature-coefficient of emf should be very low.
 Representation of a galvanic cell (or) Cell diagram

(i) A galvanic cell consists of two electrodes anode and cathode.

(ii) The anode is written on the left hand side while the cathode
is written on the right hand side.

(iii) The anode must be written by writing electrode metal first

and then electrolyte. These two are separated by a vertical line or
a semicolon. The electrolyte may be written by the formula of
the compound (or) by ionic species.

Zn / Zn2+ (or) Zn / ZnSO4 (or) Zn; Zn2+

 IV) The cathode must be written by writing electrolyte first
and then the electrode metal. These two are separated by
a vertical line or a semicolon.
Cu2+ / Cu (or) CuSO4 / Cu (or) Cu2+; Cu

(v) The two half cells are separated by a salt bridge, which is
indicated by two vertical lines.
Zn / ZnSO4 (1 M) // CuSO4 (1 M) / Cu (or)
Zn / Zn2+ (1 M) // Cu2+ (1 M) / Cu (or)
Zn ; Zn2+ (1 M) // Cu2+ (1 M) ; Cu
EMF OF A CELL:
Definition
Electromotive force is defined as, "the difference of potential
which causes flow of current from one electrode of higher potential
to the other electrode of lower potential.
Thus, the emf of a galvanic cell can be calculated using the
following relationship.
Measurement of emf of a cell:
The potential difference or emf of a cell can be measured
on the basis of poggendorff’s compensation principle. Here
the emf of the cell is just opposed or balanced by an emf of
standard cell (external emf), so that no current flows in the
circuit.
 The potentiometer consists of a uniform wire AB . A storage
battery (K) is connected to the ends A and B of the wire
through a rheostat (R). The cell of unknown emf (x) is
connected in the circuit by connecting its positive pole to A and
the negative pole is connected to a sliding contact (D) through
a galvanometer G. The sliding contact is freely moved along the
wire AB till no current flows through the galvanometer. Then
the distance AD is measured. The emf of unknown cell is
directly proportional to the distance AD.
Ex ∝ AD
Then the unknown cell (x) is replaced by a standard cell (s) in the
circuit. The sliding contact is again moved till there is null
deflection in the galvanometer. Then the distance ADʹ is
measured. The emf of standard cell Es is directly proportional to
the distance ADʹ. Es ∝ ADʹ
The emf of the unknown cell can be calculated from the following
equation.
Factors affecting emf of a cell
1. Nature of the electrolytes and electrodes.
2. Concentration and composition of the electrolytes.
3. pH and temperature of the solution.
Applications of emf measurements
Determination of standard free energy change and equilibrium
constant.
Determination of pH by using a standard hydrogen electrode.
Solubility of a sparingly soluble salt can be determined.
Valence of an ion can be determined
Differences between electrolytic cells and electrochemical cells
 REVERSIBLE AND IRREVERSIBLE CELLS
1. Reversible Cells
Daniel cell, secondary batteries (rechargeable batteries).Daniel cell is
a very good example for a reversible cell Its emf is 1.1 volt. It is
represented as Zn/ZnSO4(1 M)//CuSO4 (1 M)/Cu
A cell which obey the following three conditions of thermodynamic
reversibility is called reversible cell.
(i) If the Daniel cell is connected to an external source of emf equal
to 1.1 volt, no current flows and also no chemical reaction takes
place in the cell.

(ii) If the external emf is made slightly less than 1.1 volt, small
amount of current flows from the cell and small chemical reaction
occurs.
 (iii) If the external emf is made slightly greater than 1.1 volt, the
current will flow in the opposite direction. Copper will pass
into the solution as copper ions and zinc will get deposited
on the zinc electrode.
2. Irreversible Cells
Zinc – silver cell, Dry cell (Primary Cells)
Cells which do not obey the conditions of thermodynamic
reversibility are called irreversible cells. Zinc-Silver cell is an example
for a irreversible cell.
It is represented as
Zn/H2SO4(aq)/Ag
The cell reactions occur at anode and cathode are,
Zn + H2SO4 −−−> ZnSO4 + H2↑ (at anode)
2Ag+ + 2e− −−−> 2Ag (at cathode)
When the two electrodes are connected, zinc dissolves with the
liberation of hydrogen gas.
When the external emf, slightly greater than the actual emf of the
cell, is applied to it, the above reactions are not reversed.
Because one of the product, H2 gas, is already escaped. Such a cell,
which does not obey the conditions of thermodynamic reversibility
is called an irreversible cell.
Gibbs free energy:
The difference between the enthalpy of a system and the
product of its entropy and absolute temperature; a measure of the
useful work obtainable from a thermodynamic system at constant
temperature and pressure.
In a galvanic cell, the Gibbs free energy is related to the potential
by: ΔG°cell = −nFE°cell
If E°cell > 0, then the process is spontaneous (galvanic cell).
If E°cell < 0, then the process is nonspontaneous (electrolytic cell).