MODULE- 2: Electrode System

Electrochemistry:
It is the branch of chemistry, which deals with the study of inter
conversion of electrical energy into chemical energy that takes place
through electrochemical redox reactions.
Electrochemical cell:
The device which converts chemical energy into electrical energy
and electrical energy into chemical energy are called electrochemical
cells.
Types of Electrochemical cell:
➢Galvanic cell
➢Electrolytic cell
➢Concentration cell
➢Fuel cell
Galvanic Cell:
➢A cell which converts chemical energy into electrical energy
➢Cell reaction is spontaneous
➢ΔG is –ve, Ecell is +ve
➢Requires salt bridge to separate two half cells
➢Anode: -ve electrode at which oxidation takes place
➢Cathode: +ve electrode at which reduction takes place
➢Example: Daniell Cell
Single Electrode Potential (E):
It is defined as the potential developed at the interphase between
the metal and the solution, when a metal is dipped in a solution containing
its own ions. The potential of an electrode depends on metal ion
concentration and temperature.
Metal electrode with low electrode potential (low reduction
potential) acts as anode and undergoes oxidation whereas metal electrode
with higher electrode potential (high reduction potential) acts as cathode at
which reduction occurs.
Standard Electrode Potential (E0):
It is defined as the potential developed under standard conditions
where the temperature is 298K, the pressure is 1 atm, and the concentration
of the electrolytes is 1M.
It is measured with the help of a reference electrode known as the
standard hydrogen electrode and are reported in electrochemical series.
Cell Potential or EMF of the cell (Ecell):
The difference between the electrode potential of two
electrodes constituting electro-chemical cell is called EMF or cell
potential. The potential difference is caused by the ability of electrons
to flow from one half cell to the other.
Ecell = EC- EA Ecell is + ve when Ec > EA

Standard Cell Potential or Standard EMF of the cell (E0cell):

The standard cell potential is the potential difference between
the cathode and anode when measured at 298 K, 1 atm, and with 1 M
solutions.
E0cell = E0C- E0A E0cell is + ve when E0c > E0A
CONCENTRATION CELL
A concentration cell is a limited form of electrochemical cell that has two
equivalent half-cells of the same composition differing only in concentrations.
Types:
➢Electrode concentration cell
It consists of two similar electrode at different conc. (different activity) and
are dipped in same electrolyte solution.
Example: Pt; H2(p1) | H+ ions solution | H2(p2); Pt

➢Electrolyte concentration cell

It consist of electrodes made up of same material that are immersed in
solutions of the same two electrolyte but of different concentrations. The source of
electrical energy in the cell is the tendency of the electrolyte to diffuse from a
solution of higher concentration to that of lower concentration.
Example:M|Mn+(C1)||Mn+(C2)|M,
Zn|Zn2+ (C1)) || (Zn2+ (C2 )|Zn
Construction:
A cell in which both the electrodes are made up of zinc metal
dipped in zinc sulphate solution of different concentrations.
e-

V Cathode
Anode

Zn|Zn2+ (C1)) || (Zn2+ (C2 )|Zn

where C1 and C2 are the molar concentrations of Zn2+ ions in the two
half cells.
Cell Reactions:
Anode: Zn Zn2+(C1) + 2e- (Oxidation)
Cathode: Zn2+(C2) + 2e- Zn (Reduction)
Net cell reaction: Zn2+(C2) Zn2+(C1)
There is a transfer of ions from a solution of higher concentration to a solution of
lower concentration.
Nernst’s Equation: Wkt. Emf of the cell is given as
Ecell = EC − EA
Ecell = [E0 + 2.303 RT log C2] – [E0 + 2.303 RT log C1]
nF nF
Ecell = [2.303RT log C2 – 2.303RT log C1] [E0cell = 0]
nF nF
At 250C, Ecell = 0.0591 log C2
n C1
The following conclusions are drawn from the equation.
1) When the two solutions are of the same concentration, log C2/C1=0 and hence
no current flows through the cell.

2) When C2>C1 then log C2/C1 = +ve & hence E is positive, thus the direction of the
spontaneous reaction is from the more concentrated solution (C2) to less
concentrated solution (C1).

3) Higher the ratio of C2/C1 higher the value of cell potential.

4) When C1>C2 then log C2/C1 = -ve , E is negative, non-spontaneous reaction.

5) E0cell is zero, because both metal electrodes are made up of same materials.

6) Ecell is positive, when electrode in contact with electrolyte of higher

concentration (C2) acts as cathode and that in contact with electrolyte of lower
concentration (C1) acts as anode.
Types of Electrodes
➢Metal-Metal ion electrode
Ex: Zn/Zn2+(aq)
➢Metal-Metal salt electrode
Ex: Ag/AgCl(s), Hg/Hg2Cl2(s)
➢Gas Electrode
Ex: SHE (Standard Hydrogen Electrode)
➢Redox electrode
Electrode whose potential is dependent on the concentration of ions of
same substance but are of different oxidation state
Ex: Pt/Fe2+, Fe3+(aq)
➢Reference electrodes
These are the electrodes whose electrode potential values are known
and are used for the determination of electrode potential values of other
electrodes. The potential of the reference electrode remains constant and is
independent of the concentration of the ions in the solution.
Types of reference electrodes
➢ Primary reference electrode
This is the electrode whose electrode potential is arbitrarily taken as zero and used to
measure the electrode potential of another electrode.
Example: Standard hydrogen electrode (SHE)
➢ Secondary reference electrodes
These are the electrodes whose potential with respect to SHE are known and are
commonly used for determination of the electrode potentials of the other electrodes.
Example: Calomel electrode and Ag/AgCl electrode.

➢Ion-selective electrodes
Ex: Glass electrode
Construction and working of calomel electrode
Construction:

➢The calomel electrode consists of narrow inner and outer glass tubes.
➢The bottom of inner glass tube has a layer of mercury followed by a paste of
Hg2Cl2.
➢A platinum wire is dipped into the mercury layer for electrical contact.
➢The outer glass tube is filled with KCl solution.
➢KCl solution of different concentration can be used (Molar, Deci molar or
saturated)
➢A porous plug (salt bridge) is fitted at the bottom of outer glass tube.
➢The calomel electrode is represented as , Hg|Hg2Cl2(s)|KCl(aq)
Working:
The calomel electrode can act as anode or cathode depending on
the nature of the other electrode of the cell
When it acts as anode the electrode reaction is,
2Hg Hg22+ + 2e-
Hg22+ + 2Cl- Hg2Cl2
2Hg + 2Cl- Hg2Cl2 + 2e-

When it acts as cathode the electrode reaction is,

Hg22+ + 2e- 2Hg
Hg2Cl2 Hg22+ + 2Cl-
Hg2Cl2 + 2e- 2Hg + 2Cl-

The reversible reaction is represented as,

Hg2Cl2 + 2e- 2Hg + 2Cl-
The electrode potential is given by,
ECalomel = E0 – 2.303RT log [Hg]2[Cl-]2
nF [Hg2Cl2]
ECalomel = E0 – 0.0591 log [Cl-]2 [Hg] = [Hg2Cl2] = 1
2
ECalomel = E0 - 0.0591 log [Cl-]
It is evident from the above equation that the potential of the calomel electrode depends
on the concentration of the KCl solution.

Concentration of KCl E0 Calomel

0.1M 0.33V
1M 0.281V
Saturated 0.242V
Applications:
➢It is used as secondary reference electrode in the determination of electrode
potential of any other electrode.
Example: Determination of Electrode potential of zinc electrode
To determine the electrode potential of Zn electrode, a zinc rod is dipped in 1 M
solution of ZnSO4. It is combined with calomel electrode through a voltmeter. The
deflection of the voltmeter indicates that current is flowing from calomel electrode
towards zinc electrode, i.e., the electrons are moving from zinc to calomel
electrode. The zinc electrode acts as an anode and the calomel electrode as
cathode.
The cell can be represented as: Zn|ZnSO4(1M)||KCl(sat)|Hg2Cl2|Hg
Ecell = Ec-Ea E0cal > E0Zn [E0cal = 0.242V, E0Zn = -0.76V]

Ecell = Ecal-EZn

EZn = Ecal-Ecell

EZn = 0.242-Ecell (Ecell is measured potentiometrically using voltmeter)

➢Used as reference electrode(SCE) in potentiometric determination .
➢Used as reference electrode in PH determination.

Advantages:
➢It is very handy, compact and easy to transport.
➢Its potential can remain constant and it can easily be reproduced.
➢It is easy to construct and maintain.
➢The cell potential does not vary with temperature.
Ion selective electrode:
Ion selective electrodes are the electrodes that are highly
selective to certain specific ions present in solution containing mixture
of ions. The potential developed by such electrode is dependent on the
concentration of that specific ions present in the solution. It is also
known as membrane electrode as they are made up of certain
membrane materials which are sensitive to specific ions.
Uses:
➢Determination of concentration of number of cations such as K+ , Ca2+, Mg2+, Ag+,
Cd2+ , Pb2+,Cu2+ .
➢Concentration of anions such as NO3 - , CN- , S2- & halide ions.
➢Determination of pH of a solution.
➢Concentration of gas using gas sensing electrodes.
Glass electrode
➢It is a type of ion selective electrode

➢It is made up of glass membrane (silicate glass- Na2O:22%, CaO:6% &

SiO2:72%. It has low melting point, high electrical conductance & can
sense hydrogen ions up to pH 9)

➢It is highly sensitive to H+ ions

➢The most common application of ion-selective glass electrode is for

the measurement of pH
Construction of Glass electrode

Platinum wire

Ordinary glass

0.1M HCl (pH=1) Ag/AgCl

Thin glass membrane

The glass electrode consists of a long glass tube with a thin walled bulb at
the bottom of the glass electrode which is made up of glass membrane as
shown in figure. The bulb contains 0.1M HCl (internal reference solution). An
Ag/AgCl electrode (internal reference electrode) is placed in the solution and
connected by a platinum wire for electrical contact.
The electrode is represented as
Ag|AgCl|HCl (0.1M)| Glass
Principle:

Gel lay er of the

glass bulb
glass membrane

External analyte
Internal solution of
solution of H+ H+ H+ H+
concentration (C1), [H+]=0.1M
concentration (C2)
[H+] = ?
E2 E1
Eb= E2-E1

• A thin walled glass bulb containing an acid is immersed in another

solution as shown in the figure. A potential is developed across the glass
membrane. This is called boundary potential (Eb). The potential is due to
the difference in potential (E2-E1) developed across the gel layer of the
glass membrane between two liquids.
 𝐸𝑏 = 𝐸2 − 𝐸1
𝐸𝑏 = 2.303𝑅𝑇 log 𝐶2 − 2.303𝑅𝑇 log 𝐶1 … … … … … (1)

nF nF
where C1 & C2 are the concentration of H+ ions of the acid solution
inside and outside the glass bulb respectively.
The concentration C1 of the solution inside the bulb is constant. Hence
second term on the right hand side of the equation (1) is constant.
Eb = 2.303RT log C2 + Constant (n=1)
F
Eb = 2.303RT log C2 + K where K = -2.303RT log C1
F F
Eb = K + 0.0591 log C2 … … … … … (2)
K is a constant which depends upon the pH of the solution taken in
the bulb and glass electrode assembly.

Since C2 = [H+] of the external analyte solution,

𝐸𝑏 = 𝐾 + 0.0591log [𝐻+]

𝐸𝑏 = 𝐾 − 0.0591p𝐻 wkt (−log[𝐻+] = p𝐻) … … … … … (3)

Working of Glass Electrode
When the glass electrode is dipped in the test solution, the
Na+ ions of the glass membrane are exchanged for H+ ions of the test
solution.

H+ (soln) + Na+Gl- (glass membrane) Na+ (soln) + H+Gl-(glass membrane)

The boundary potential established due to the above reaction is

mainly responsible for the glass electrode potential EG. The potential
of the glass electrode is given by

𝐸𝐺 = 𝐸𝑏 + 𝐸𝐴𝑔/𝐴𝑔𝐶𝑙 … … … … … (4)
When two solutions are of the same concentration then C1=C2, Eb=0.
However it has observed that even when C1=C2 a small potential is
developed this is called asymmetric potential (Easy). Hence equation
(4) can be written as
𝐸𝐺 = 𝐸𝑏 + 𝐸𝐴𝑔/𝐴𝑔𝐶𝑙 + 𝐸𝑎𝑠𝑦 … … … … … (5)

𝐸𝐺 = 𝐾 − 0.0591p𝐻 + 𝐸𝐴𝑔/𝐴𝑔𝐶𝑙 + 𝐸𝑎𝑠𝑦 … … … … … (6)

EG = E0G – 0.0591pH … … … … … (7)

Where E0G = K + 𝐸𝐴𝑔/𝐴𝑔𝐶𝑙 + 𝐸𝑎𝑠𝑦

Advantages:
➢Glass electrode can be used in the presence of strong oxidizing or
reducing agents or metal ions.
➢Not poisoned easily.
➢Simple to operate
➢Can be used in portable instruments.

Disadvantages:
➢ It is fragile
➢It cannot be used above pH 12 (alkaline error) as interference from
sodium ions occurs i.e., sodium ion exchange together with H+ ions
(glass membrane becomes permeable to sodium).
➢It cannot be used in presence of dehydrating agents such as Conc.
H2SO4, ethyl alcohol
Determination of pH of a solution using glass electrode
The glass electrode is immersed in the solution whose pH is to be
determined. It is combined with a reference electrode such as a
calomel electrode through salt bridge.

Hg/Hg2Cl2/ KCl(sat) //External analyte solution (pH=?)/Glass/HCl (0.1M)/AgCl/Ag

Voltmeter

Glass electrode Calomel electrode

Test solution (pH=?)

The emf of a given cell is measured using an electronic voltmeter.

Emf of the cell is given by
Ecell = EG − ESCE (E0G > E0SCE, Glass electrode is cathode and SCE is anode)

Ecell = (E0G − 0.0591pH) - Esce

pH = E0G - Ecell - Esce
0.0591

E0G is measured by using a solution of known pH

ESCE is known (0.242V)

Ecell is measured using voltmeter