MODULE 1 ELECTRODE SYSTEM AND GREEN ENERGY.

Electrode system: Introduction, types of electrodes, Reference electrode: Introduction,

calomel electrode – construction, working and applications of calomel electrode.
Concentration cell – Definition, construction and Numerical problems. Ion selective
electrode – definition, construction, working and applications of glass electrode.
Determination of pH using glass electrode.
Batteries: characteristics and classification, Construction, working and applications of
lithium-ion battery
Green energy: Introduction, construction and working of solar photovoltaic cell,
advantages, and disadvantages. Generation of energy (green hydrogen) from water
electrolysis, advantages, and storage of hydrogen

ELECTRODE SYSTEM
Electrochemistry is a branch of physical chemistry which deals with (a)
properties and behaviors of electrolytes (b) interconversion of electrical and chemical
energy.
A device which converts chemical energy into electrical energy or vice versa is
known as electrochemical cell. An electrochemical cell is an arrangement consisting of
two electrodes, and an electrolyte connected externally by means of electric wire.
There can be two types of electrochemical cells.
(i) Cell which converts chemical energy into electrical energy is known as
galvanic cell or voltaic cell
(ii) Electrochemical cell which converts electrical energy into chemical energy is
known as electrolytic cell
Galvanic Cells: Galvanic cell consists of two electrodes dipped in two electrolyte
solutions which are separated by a diaphragm. eg : Daniel Cell. Here zinc is anode where
oxidation reaction take place and copper is cathode where reduction takes place.
By convention electrode where oxidation reaction occurs is known as anode
(Zn) and electrode where reduction reaction takes place is known as cathode (Cu). In a
galvanic cell anode is negative terminal where as cathode is positive terminal. Flow of
electrons is from anode to cathode. The direction of flow of positive electricity is from
cathode to anode.

1
Reactions:
At the anode: Zn → Zn2+ + 2e-
At the cathode: Cu2+ + 2e- → Cu
Net reaction: Zn(s)+ Cu2+(aq) → Zn2+(aq)+ Cu(s)

A potential difference exists between anode and cathode. This is known as EMF
of the cell. It is given by
Ecell = Ecathode − Eanode (reduction potentials of both anode and cathode)

Single electrode and single electrode potential

One half of a galvanic cell where either oxidation half- reaction or the reduction-
reaction of the cell occurs is called a single electrode. A single electrode is an
arrangement where a metal electrode is immersed in a solution containing its own ions.
A single electrode develops a definite electric potential due to the spontaneous
oxidation or reduction half-reaction occurring at it. It is called single electrode potential
Potential developed at the interface of an electrode and electrolyte, when metal
is immersed in a solution containing its own ions (ions reversible to itself) is known as
single electrode potential. If measurements are done under standard condition of
temperature (298 K) pressure ( 1atm) and unit concentration of electrolyte is known as
standard electrode potential.

2
Evaluation of single electrode potential:
Single electrode potential can be calculated using Nernst equation. Nernst
equation is an expression of a quantitative relationship between electrode potential/cell
potential and concentration of the electrolyte species in an electro-chemical reaction.

Mn+(aq) + ne- M(s) [ Reduction reaction]

2.303 𝑅 𝑇
E = Eo + log [Mn+]
𝑛𝐹

E= Electrode potential
E0= Standard electrode potential
R= Universal gas constant (8.314 joules / mol/ K)
T= Temperature in Kelvin scale
F= Faraday constant (96,500 Coulombs / mol)
n = Number of electrons transferred in the half reaction.
[Mn+] = Concentration of metal ion at given time
At 298 K, by substituting the values of R and F equation reduces to,

0.0592
E = Eo + log [Mn+]
𝑛

3
 This expression is known as the Nernst equation for electrode potential at 298 K.
From these equations, it is clear that,
i) If the concentration of the solution (Mn+) is increased, the electrode
potential increases and vice versa.
ii) If the temperature is increased, the electrode potential increases and vice
versa.
Types of electrodes:
For electrochemical work, different types of electrodes are used. Some examples are:
(i) Metal-metal ion electrode: Eg : Zn/ Zn2+
(ii) Metal-metal insoluble salt electrode: Eg calomel electrode(Hg (l) /Hg2Cl2/ Cl- )
(iii) Gas electrode: Hydrogen electrode ( Pt/ H2/H+)
(iv) Amalgam electrode: Eg : Lead amalgam electrode ( Pb-Hg/ Pb2+)
Measurement of single electrode potential:
It is not possible to determine the potential of a single electrode using voltmeter.
We can measure EMF of the cell by clubbing the electrode under consideration with an
electrode whose potential is known. EMF of the cell can be measured either using
voltmeter or by any other methods.
Ecell = Ecathode − Eanode
With the knowledge of EMF of cell, and electrode potential of one electrode, electrode
potential of unknown electrode can be determined.
Electrode, whose potential is either arbitrarily fixed as zero, or whose potential
is exactly known is termed as reference electrode.
Reference electrodes
In order to measure the potential of any single electrode it should be combined
with another electrode of known potential to form a galvanic cell. In other words,
reference electrodes are the electrode with reference to which, the electrode potential
of any electrode can be measured
The criteria for an electrode to act as a reference electrode are;
1. The potential of that electrode should be known, under the condition of utility.
2. It must be reliable, stable, and reproducible.
3. The potential of the electrode should be of minimum variation with temperature.
In other words, potential gradient with respect to temperature must be minimum

4
Types of reference electrodes.
1) Primary reference electrode: Standard hydrogen electrode (SHE) is the only
primary reference electrode. The potential of all other electrodes is measured
with respect to the hydrogen electrode. For all practical purpose, electrode
potential of standard hydrogen electrode is fixed as zero.
2) Secondary reference electrode: Due to the difficulties involved in the use of SHE
as a reference electrode, some other electrodes of constant electrode potential
are referred to as secondary reference electrodes. E.g., calomel electrode.
Calomel electrode: Construction and working
Calomel electrode is an example for metal-metal insoluble salt electrode. It
consists of mercury and mercurous chloride and a solution of KCl. Mercury is placed at
the bottom of a glass tube having a side tube on each side. Mercury is covered with a
paste of mercurous chloride (calomel) with mercury and KCl. A platinum wire sealed
into a glass tube is dipped into mercury and used to provide the external electrical
contact. The concentration of KCl solution used is either decinormal, normal or
saturated. Correspondingly, the electrode is known as decinormal, normal or saturated
calomel electrode respectively.

The electrode can be represented as :

Hg (l) /Hg2Cl2 (sat’d) / Cl-
The calomel electrode can act as anode or cathode depending on the nature of another
electrode with which is in contact with. When coupled with zinc calomel electrode acts
as cathode, where as when coupled with copper it acts as anode.

5
When it acts anode, the electrode reaction is
2Hg (l) → Hg22+ (aq) + 2e-
Hg22+(aq) + 2Cl- (aq)→Hg2Cl2
________________________________
2Hg(l) + 2Cl- (aq) → Hg2Cl2 (s)+ 2e-
_________________________________
When it acts as cathode, the electrode reaction is,
Hg22+(aq) + 2e-→ 2Hg(l)
Hg2Cl2 (s) → Hg22+ (aq) + 2Cl-
__________________________________
Hg2Cl2(s) + 2e- → 2Hg (l) + 2 Cl-(aq)
____________________________________

The net reversible electrode reaction is,

Hg2Cl2(s) + 2e− 2 Hg (l) + 2 Cl-(aq)

After applying Nernst equation, electrode potential is given by

2.303 𝑅𝑇
E = Eo – 𝑙𝑜𝑔 [Cl-]2
2𝐹

By substituting the values of R (8.314 JK-1 mol-1) and F (96,5000 C mol-1) at T = 298
K we get:
E = Eo - 0.0591 log [Cl-] at 298 K
Variation of electrode potential of calomel electrode with concentration of KCl
KCl concentration Electrode potential ( Volt)
0.1N 0.3335
1.0 N 0.2810
Saturated 0.2422
As the concentration of KCl increases, electrode potential of calomel electrode
decreases.

Applications:
(i) To determine the electrode potential of the unknown electrode
The test electrode, Zn(s) /Zn2+(aq) is coupled with a saturated calomel electrode.

6
 Zn(s) / Zn2+ (aq) ││ Cl- /Hg2Cl2(s) / Hg

The EMF of the so formed cell is determined experimentally by potentiometer.

E cell = E cathode – Eanode = 0.2422 – Ezn

Ezn = 0.2422 – E cell

(ii)To determine the pH of a solution cell:

Pt, H2(1atm) H+ (x) // Hg2Cl2(s) / Hg (l)
E cell = E cathode – E anode
= 0.242 – (− 0.0592 pH)
𝑬𝒄𝒆𝒍𝒍 −𝟎.𝟐𝟒𝟐
pH =
𝟎.𝟎𝟓𝟗𝟐
Advantageous of calomel electrode:
(i) Simple in construction, easy to handle
(ii) Electrode potential remains constant over a period of time
(iii) Electrode potential is reproducible
(iv) Electrode potential does not vary much with temperature
Limitations of calomel electrode
(i) Mercury compounds are poisonous in nature
(ii) It can not be operated at higher temperature as the decomposition of Hg2Cl2
take place

Concentration Cell:
Concentration cell is a galvanic cell in which two electrodes of the same metal are
in contact with solutions of its ions with different concentrations. EMF arises due to the
difference in concentrations of electrolytes

7
 The above concentration cell can be represented as:

Zn| ZnSO4 (C1) || ZnSO4 (C2)| Zn

The electrode reactions are

At Anode: 𝑍𝑛 → 𝑍𝑛2+ (𝐶1 ) + 2𝑒

At Cathode:𝑍𝑛2+ (𝐶2 ) + 2𝑒 − → 𝑍𝑛
Overall reaction: 𝑍𝑛2+ (𝐶2 ) → 𝑍𝑛2+ (𝐶1 )

Where C1 and C2 are concentrations of ZnSO4 solution at anode and cathode

respectively & C2> C1
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑅 − 𝐸𝐿
0.0591 0.0591
= [𝐸 0 + 𝑙𝑜𝑔(𝐶2 )] − [𝐸 0 + 𝑙𝑜𝑔(𝐶1 )]
𝑛 𝑛
Where E0 is the standard electrode potential of the species in the concentration cell.
0.0591 𝐶2
𝐸𝑐𝑒𝑙𝑙 = 𝑙𝑜𝑔 ( )
𝑛 𝐶1
Note: Concentration cell will have positive EMF, only when C2 > C1
Cell will stop functioning when C2 = C1

Numerical problems
1. A concentration cell was constructed by immersing two silver electrodes in
0.02M and 2M AgNO3 solutions. Write the cell representation, cell reactions, and
calculate the emf of the cell at 250C.
(i) Cell representation:
Ag|AgNO3 (0.02 M) || AgNO3 (2M)|Ag
(ii) Electrode reactions:
At anode: Ag Ag+ (0.02M) + e¯
At cathode: Ag+ (2M) + e¯ Ag
NCR: Ag+ (2M) Ag+ (0.02M)
(iii)The emf of the concentration cell:
0.0591 𝐶2
𝐸𝑐𝑒𝑙𝑙 = 𝑙𝑜𝑔
𝑛 𝐶1

8
 0.0591 2
𝐸𝑐𝑒𝑙𝑙 = 𝑙𝑜𝑔
1 0.02
𝐸𝑐𝑒𝑙𝑙 = 0.0591 𝑙𝑜𝑔100
𝐸𝑐𝑒𝑙𝑙 = 0.0591 × 2
𝐸𝑐𝑒𝑙𝑙 = 0.1182𝑉
2.Represent the cell formed by the coupling of two Cu electrodes immersed in CuSO4
solutions. The concentration of cupric ions in one electrode system is 100 times more
concentrated than other. Write the cell reaction and calculate the potential at 300K.
(i)Cell representation:
Cu|CuSO4 (1M )|| CuSO4 (100M)|Cu
(ii) Electrode reactions:
At anode: Cu Cu2+ (1M) + 2e¯
At cathode: Cu2+ (100M) + e¯ Cu
NCR: Cu2+ (100M) Cu2+ (1M)
(iii)The emf of the concentration cell:
2.303𝑅𝑇 𝐶2
𝐸𝑐𝑒𝑙𝑙 = 𝑙𝑜𝑔
𝑛𝐹 𝐶1
2.303 × 8.314 × 300 100
𝐸𝑐𝑒𝑙𝑙 = 𝑙𝑜𝑔
2 × 96500 1
𝐸𝑐𝑒𝑙𝑙 = 0.0297 𝑙𝑜𝑔100
𝐸𝑐𝑒𝑙𝑙 = 0.0297 × 2
𝐸𝑐𝑒𝑙𝑙 = 0.0595𝑉

Numerical for Practice:

1. A concentration cell is contracted by dipping copper rods in 0.001M and 0.1M
CuSO4 solutions. Give cell construction, write cell reaction, and calculate EMF of
the cell at 298 K.
2. Calculate valency of metal M from the following cell at 294 K, if EMF of the cell is
0.02571 V
M/MCl2 (0.00162M// MCl2 (0.123M/ M
3. Construct a concentration cell formed by the combination of two copper
electrodes dipped in copper sulphate solutions of different concentrations. If
concentration of catholyte is 5.5 times higher than that of anolyte, calculate EMF
of the cell at 298K

9
Ion Selective Electrode:
The electrode which is sensitive to a specific ion present in an electrolyte whose
potential depends upon the activity of a specific ion in the electrolyte is called an ion
selective electrode. The magnitude of the potential of this electrode is an indicator of the
activity of the specific ion in the electrolyte. Example for this type of electrode is glass
electrode.

Glass electrode: Construction

Schematic diagram of the Glass Line sketch of a glass membrane

electrode showing outer analyte solution
and internal reference solution.

Glass electrode consists of a thin glass membrane, typically about 0.03 to 0.1 mm
thick, sealed onto one end of a heavy–walled glass tube. A special variety of glass
(corning 0l5 glass with approximate composition 20 % Na2O, 6 % CaO & 72 % SiO2) is
used which has a low melting point and high electrical conductance.
The glass bulb is filled with a solution of constant pH (0.1 M HCl).. A silver- silver
chloride electrode ( Ag/AgCl) is inserted in the tube which acts as internal reference
electrode. This also serves to establish contact with external circuit. The internal
reference electrode is a part of the glass electrode and it is not the pH sensing element.
Only the potential that occurs between the outer surface of the glass bulb and the test
solution responds to pH changes.
Glass electrode can be represented as follows:

10
 Ag/AgCl, HCl ( 0.1M) // Glass

Working:
The glass is a partially hydrated aluminosilicate containing sodium or calcium
ions.
The hydration of a pH sensitive glass membrane involves an ion-exchange
reaction between singly charged cations in the glass lattice and protons from the
solution. The process involves univalent cations exclusively because divalent cations
are too strongly held within the silicate structure to exchange with ions in the solution
and hence immobile. The ion-exchange reaction can be written as
H+ + MGl Na+ + HGl
Solution glass solution glass
The Na+ ions on the glass membrane are exchanged for H+ ions in the solution at
the hydrated layer. Exchange of ions at the inner and outer hydrated layer can be
diagrammatically represented as follows:

The potential of the electrode is controlled by the difference between the

hydrogen ion concentration inside and outside the thin glass membrane. Since the H +
ion concentration inside the electrode is constant, the electrode’s potential varies only
with the concentration of H+ in the solution outside. Thus, the potential arises from the
difference in positions of ion-exchange equilibrium on each of the two surfaces.

11
Electrode potential of glass electrode
The overall potential of the glass electrode depends upon three parameters
✓ The boundary potential (Eb)
✓ The potential of the internal Ag/AgCl reference electrode. (E Ag/AgCl.)
✓ A small unpredictable contribution called the asymmetry potential, (E asym.)
(1) The boundary potential Eb: It varies with the pH of the analyte solution. It is
made up of two potentials, E1 & E2 which develop at the two surface of the glass
membrane i.e. the potential developed at the inner glass surface and the potential
developed at the outer glass surface.
Eb = E1−E2 (1)
Where Eb is the boundary potential
E1 = potential developed at the interface between the exterior of the glass and the
analyte solution
E2 = Potential developed at the interface between the internal solution and the interior
of the glass.
Eb = The boundary potential is related to the concentration of hydrogen ion in each of
the solutions by the Nernst-like equation.
Eb = E1 – E2 = 0.0592 log Cl / C2 (2)
Where C1 = HCl solution of unknown pH (external solution)
C2 = HCl solution of known pH ( internal solution)
Eb = K + 0.0592 log C1 (3) (Recall pH= -log [H+]

Eb = K − 0.0592 pH where K= -.0592 log C2

The boundary potential is then a measure of the hydrogen ion concentration of the
external solution.
(2) The potential of the internal Ag/AgCl reference electrode. E Ag/AgCl.
(3) A small unpredictable contribution called the asymmetry potential, E asym.
The sources of the asymmetry potential include the following.
i) Differing conditions of strain in the two glass surfaces during
manufacture
ii) Mechanical abrasion on the on the outer surface during use
iii) Chemical etching of the outer surface during use.

12
 The asymmetry potential changes slowly with time. The glass electrode potential
can be written in the equation form as
EG = Eb + EAg/ AgCl + E asym (4)
Substitution of eqn – (3) for Eb, gives
EG = K + 0.0592 log C1 + EAg/AgCl + E asym
= K – 0.0592 pH + E Ag/AgCl + E asym (5)
EG = EoG – 0.0592 pH (6)
where EoG = K + EAg/AgCl + E asym. a combination of three constant terms = constant.

To measure the hydrogen ion concentration of the test solution, the glass electrode
(indicator electrode) must be combined with an external reference electrode.

Applications: Determination of pH:

The glass electrode has an emf that changes with hydrogen ion concentration, i.e the
glass electrode is the most important indicator electrode for hydrogen ion. It is used for
the measurement of pH under many conditions and normally calomel electrode is used
as reference electrode to complete the cell
Cell: SCE / Test solution / GE
Set up of indicator electrode and reference electrode for the measurement of pH.

E cell = E glass – E calomel where

E glass = Electrode potential of the glass electrode.

13
 E calomel = Electrode potential of the Saturated calomel electrode
E cell = 𝐸𝐺0 – 0.0592 pH – 0.2422
𝐸𝐺0 – 0.2422 – Ecell
pH =
0.0592
The standard glass electrode (𝐸𝐺0 ) potential can be determined by dipping the glass
electrode in a solution of known pH.
Determination of pH is mainly required in clinical & food analysis, environmental
monitoring (industrial waste acidity of rain) and process control (fermentation, boiler
water, galvanization & precipitation)

Advantageous of glass electrode

(i) Simple to use.
(ii) Equilibrium is rapidly achieved
(iii) Results obtained are highly accurate
(iv) It is not easily poisoned
Limitations of glass electrode:
(i) Glass electrode must be immersed in distilled water, when it is not used
(ii) Standard glass electrode potential need to be determined frequently
(iii) Can not used in highly acidic and alkaline solution
(iv) Commercial versions are moderately expensive

Numerical
1. A glass electrode dipped in a soln. of pH = 4 offered an EMF of 0.2066 V with SCE
at 298 K. When dipped in a soln. of unknown pH at the same temperature, the
recorded emf was 0.1076 V. Calculate the pH of the soln. [ESCE = 0.2422 V].
2. The cell SCE / (0.1M) HCl / AgCl(s), Ag gave EMF of 0.24 V and 0.26 V with
buffer having pH value 2.8 and unknown pH value respectively. Calculate the pH
value of unknown buffer solution. Given ESCE= 0.2422 V

14
15