Electrochemistry

(Types of Electrodes, Applications of EMF,

Determination of pH)
(Faradays law of Electrolysis, Electrolysis of NaCl,
Ionic Strength)

Dr.S.SURESH
Assistant Professor
Email:avitsureshindia@gmail.c
om

Types of Electrodes

Different Types of
Electrodes
An electrochemical cell consists of two
electrodes,
positive
and
negative.
Each
electrode along with the electrolyte constitutes
a half cell. The commonly used electrodes in
different electrochemical cells are

Metal-Metal ion electrodes

Metal-Amalgam electrodes
Metal insoluble metal salt electrodes
Gas electrodes
Oxidation-reduction electrodes

Metal-Metal ion
electrodes
An electrode of this type consists of a
metal rod (M) dipping into a solution of
its metal ions(Mn+). This is represented as
M/Mn+
Example:
Cu rod dipping in Copper sulphate
solution (Cu/Cu2+)

Metal-Metal ion
electrodes
The electrode reaction may be represented as
Mn+ + ne M
If the metal rod behaves as negative
electrode (i.e the reaction involves oxidation)
the equilibrium will shift to the left and hence
the concentration of the Metal ions in the
solution will increase.
On the other hand, if the metal rod behaves
as positive electrode (i.e the reaction involves
reduction), and the equilibrium will shift to
the right and hence the concentration of the
metal ions will decrease.

Metal-Amalgam
Electrodes
The
activities
and
the
electrode
potentials of highly reactive metals such
as sodium, potassium, etc. are difficult to
measure in aqueous solution. Hence, the
activity of the metal is lowered by
dilution with mercury.
M(Hg)/Mn+
Example
Na, Hg (C1)/Na+(C2)

Metal-Insoluble metal salt

electrodes
This type of electrode consists of a metal
(M) covered by a layer of sparingly soluble
salt (MX) dipping into a solution containing
a common anion (X). These electrodes are
represented as
M/MX // X (a)

Example:
(a)Calomel
Electode:
It
consists
of
Mercury-Mercurous chloride in contact
with a solution of potassium chloride
(Hg/Hg2Cl2, KCl)

Gas Electrodes
In a gas electrode hydrogen gas is
continuously
bubbled
through
a
1M
solution of the acid. A inert metal like
platinum is used, since it is not attacked
by acid. The inert metal in electrode does
not participate in the electrode reaction
but helps in making electrical contact. Let
the gas bubbled be X2, then the electrode is
denoted as
Pt, X2 (1atm) /X+(a)

Example:
Standard hydrogen electrode: Pt, H 2
(1atm)/H+(1M)

Oxidation-Reduction electrodes
(or) Red-Ox electrodes
In this type of electrode the potential is
developed due to the presence of ions of the
same substance in two different valence(i.e.
oxidation) states.
This electrode is set up by inserting an inert
metal like platinum in an appropriate solution
containing a mixture of ferrous (Fe2+) and Ferric
(Fe3+) ions.
In this electrode the potential is due to the
tendency of the ions to change from one
oxidation state to the other more stable
oxidation state.
These electrodes are represented as
Pt/Mn1+ (a1), M n2+ (a2)

Applications of EMF
measurements

Applications of EMF
measurements
(i) Determination of valency of ion in doubtful cases
The valency of mercurous ion can be determined by
determining the EMF of a concentration cell of the type given
below.

Hg/ Hg2(NO3)2 (C1) // Hg2(NO3)2(C2) / Mercury

The EMF of the cell, E, is given by the expression

E=

C
0.059
log 2
n
C1

It was found that when C2/C1 was 10, (i.e. C2 = 1M and

C1 =
0.1M) the EMF was 0.0295V. Therefore, the valency of
mercurous ion is 2, and it should be represented as
.
Hg 22

Applications of EMF
measurements
(ii) Determination of solubility product of
sparingly soluble salt:
The solubility product constant of a sparingly
soluble salt is a kind of equilibrium constant.
Consider the salt MX in equilibrium with its ions
in a saturated solution.

X (aq
M (aq )
)
MX(s)
+
The solubility product of the salt is given by
Ksp = [M+] [X]

The cell is represented as M,

R.H.E

MX(s)

+ e

M + X

M M (aq )

L.H.E

MX(s)M
(aq )

Overall reaction
E

M+ X(sat.sol.) // MX(s), M

+ e

+
X (aq
)

E R - E L
We know that G = nFE
And
G = 2.303 RT log K sp
log Ksp =

nFE
2.303 RT
2.303 RT
E
= log K sp
nF

0.059
=log K sp
n

(iii)Free energy, enthalpy and entropy changes in electrochemical reactions:

The standard free energy can be calculated as follows
G = nFE
n= number of electrons, F = 96500 C, E = EMF of the
cell.
By knowing the standard EMF of a cell we can calculate the entropy change
using the equation
S = n F
Then the enthalpy change
can be calculated using the
E

equation
T p
G = H TS

Determination of
pH

Determination of
pH
By using a glass electrode:
It consists of thin walled glass bulb
(made of special type of glass having
low melting point and high electrical
conductivity) containing a Pt wire in
0.1M HCl. The thin walled glass bulb
functions as an ion-exchange resin,
and an equilibrium is set up between
the sodium ions of glass and
hydrogen ions in solution. The
potential difference varies with the
hydrogen ion concentration, and it
0
[E
given by
G 0.0592 pH]

Determination of pH by using a
glass electrode
The cell may be represented as
Pt, 0.1M HCl/ Glass// KCl(Satd. Soln.)/ Hg2Cl2(s). Hg
The EMF of the cell is measured by
ECell =
E R - E L
E Calomel - E Glass
ECell =
= 0.2422 V
= 0.2422 V
pH =

[E 0G 0.0592 pH]
E 0G 0.0592 pH
0.2422 V - E 0G - E Cell
0.0592 V

Faradays Law of
Electrolysis

Faradays Law of
Electrolysis
First Law: According to it during
electrolysis,
the
amount
of
any
substance deposited or evolved at any
electrode is proportional to the quantity
of electricity passed
The quantity of electricity (Q) is equal to
the product of the current strength and
the time for which it is passed.
Q = current strength time

Faradays Law of
Electrolysis
If W is the weight of a substance
liberated/deposited at an electrode
during electrolysis, then from first law,
we get:
WQ
But Q = it
W it
W = Zit

Faradays Law of
Electrolysis
Second Law: According to it the weights of
different substance evolved/deposited by
the passage of same quantity of electricity
are
proportional
to
their
chemical
equivalent weights
WE
Where
W = Weight of the substance liberated or
deposited.
E = Chemical equivalent weight of the
substance liberated/deposited.

Electrolysis of aqueous
sodium chloride
When sodium chloride is
water, it ionises as
NaCl Na+
+ Cl
Water also dissociates as
H2 O H +
+ OH

dissolved in

When electric current is passed through

aqueous sodium chloride solution using
platinum electrodes

Electrolysis of aqueous
sodium chloride
H+ ions move towards the cathode. The H +
ions gain electrons and change into neutral
atoms. Hydrogen atom is unstable and
combines with another atom to form stable
hydrogen molecule.
Hydrogen atom is unstable and combines
with another atom to form stable hydrogen

molecule
H+
+ e
H (atom unstable)

H
+ H
H2 (stable)

Electrolysis of aqueous
sodium chloride
Cl ions move towards anode. These Cl ions
lose electrons and change into neutral atoms,
chlorine atom is unstable and combines with
another atom to form stable chlorine molecule.
At Anode:
Cl e
Cl atom (unstable)

Cl
+ Cl
Cl2 (stable)

Hence in the electrolysis of aqueous solution
of sodium chloride, hydrogen is liberated at
cathode while chlorine is liberated at anode.

Electrolysis of aqueous
copper sulphate solution
(using pt electrode)
When copper sulphate is dissolved in water, it
ionizes as
CuSO4 Cu2+ + SO42
H2O

H+

OH (slightly ionized)

When electric current is passed through copper

sulphate solution using platinum (Pt) electrodes:
(a) Cu2+ ions move towards cathode. These Cu 2+
ions gain electrons and change into neutral
atoms and get deposited at cathode.
Cu2+
+ 2e
Cu
(deposited)

At Cathode
OH ions move towards anode. These OH ions lose
electrons and change into neutral hydroxyl groups.
At Anode:
2OH e
2OH (neutral)

The neutral hydroxyl groups being unstable react with
other neutral OH groups to form water and oxygen.
2OH
H2O
+ O
O + O

O2

Hence during electrolysis of copper sulphate solution

using platinum electrodes, copper and oxygen are
liberated.

Ionic Strength

Ionic strength of
solutions
Ionic strength is a measure of
the concentration of ions in that
solution. Ionic strength may be
1
expressed as
C Z2
2

Ionic
strength
Calculate the ionic strength of 0.1M
solution of NaCl
1
C i Zi2
2
For Na+ C = 0.1 and Z = 1
For Cl C =1 0.1 and Z = 1

(0.1 12 0.1 12 ) 0.1

2

Ionic
strength
Calculate the ionic strength of 0.1M
solution of Na2SO4, MgCl2 and MgSO4
respectively.
Na2SO4

MgCl2
MgSO4

1
(0.2 12 0.1 2 2 ) 0.3
2

1
(0.1 2 2 0.2 12 ) 0.3
2
1
2
2
(0.1 2 0.1 2 ) 0.4
2

Ionic strength
The ionic strength of a solution containing
more than one electrolyte is the sum of the
ionic strength of the individual salts
comprising the solution.
Hence, the ionic strength of a solution
containing Na2SO4, MgCl2 and MgSO4 each at
a concentration of 0.1M is 1.0.