Materials Chemistry for Energy and Data Processing - 24CHECS12

Module-3
Introduction to Electrochemistry, Smart Sensor Systems and Devices

Introduction to Electrochemistry

Electrochemical cell:
It is the device used to transform chemical energy (spontaneous reaction) into
electrical energy (non-spontaneous reaction) using electrical energy from an external source.
These are two types such as
(1) Galvanic/ voltaic cell: It converts chemical energy into electrical energy e.g.: Daniel
cell
(2) Electrolytic cell: It converts electrical energy into chemical energy

An important aspect of electrochemistry is the inter conversion of electrical energy

and chemical energy that takes place through oxidation–reduction (redox) reactions. Redox
reactions form the basis of electrochemical cells.
In oxidation, a species loses one or more electrons resulting in an increase in the
oxidation number.
M ↔ Mn+ + ne (oxi) {oxidation is loss OIL}
In reduction, the species gains one or more electrons resulting in the decrease in
oxidation number.
Mn+ + ne ↔ M (red) {Reduction is gain RIG}
An electrochemical cell consists of two electrodes which when connected by a metallic
wire, an electric current flows as a result of a spontaneous red-ox reaction. Each electrode
usually consists of a metal in contact with a solution of its own ions. Since a cell is a

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combination of two electrodes, each electrode is referred to as a single electrode or half cell.
A potential called the electrode potential arises at the electrode in contact with its ionic
solution. The difference between the potentials of the two half cells constitutes the
electromotive force (emf) of the cell.
The devices which are used to convert chemical energy into electrical energy or electrical
energy into chemical energy are called electrochemical cells.

Single Electrode Potential (E): is defined as the potential developed at the interface between
the metal and the solution, when it is in contact with a solution of its ions.
Or It is the potential developed at the surface of an electrode when an metal is in contact with
its own ions.

Standard electrode potential (E0):

It is the potential developed when the electrode is in contact with a solution of unit
concentration at 298K, if the electrode involves a gas, then the gas is at 1 atm pressure.

Nernst equation for Single electrode

In 1889, Nernst derived a quantitative relationship between electrode potential
and concentration of electrolyte species. Consider the following reversible electrode
reaction
Mn+ + ne-  M
In case of metal – metal ion electrode, as M is solid metal, [M] = 1, ⸫ ln(1) = 0
RT ln[ M n ]
 E = E° + ----------- (7)
nF
Substituting the values for R (8.314 JK-1mol-1), F (96500Cmol-1), T (298K) and converting
natural log to base 10 in eqn. (7) we get,
° 0.0591 log[ Mn ]
E=E +
n
This is the mathematical representation of Nernst equation.
Nernst equation for cell potential
Then, Nernst equation for emf of cell is given by

0.0591  Species.at.Cathode 
Ecell  E 0 cell  . log  
n  Species.at. Anode 

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Types of Electrodes:
The classification of electrodes not only depends on electrode material but the full
electrode system comparing of electrode and electrolytes as well as additional substances that
may be involved in the reaction. Electrodes can be classified as,

1. Metal-metal ion electrode: Metal in contact with a solution containing its own ions.
Ex: Zinc road in contact with ZnSO4 solution (Zn/Zn2+).
2. Metal-metal salt ion electrode: Metal in contact with insoluble or sparingly soluble
salt as a sold phase next to the electrode immersed in a solution containing common
anion.
Ex: Calomel electrode consisting of mercury in consisting with insoluble mercurous
chloride in contact with KCl solution is an example for this type (Hg/Hg2Cl2/KC1).
3. Gas electrodes: It consists of gas bubbling about an inert metal wire or foil,
immersed in a solution containing ions to which the gas is reversible. Metal provides
the electrical contact between gas and its ions.
Ex: Hydrogen electrode (Pt/H2/HCl).
4. Ion selective electrodes: Electrodes which have the ability to respond to specific
ions.
Ex: Glass electrode which responds to hydrogen ions (Ag/AgCl/HCl/Glass).

Reference electrodes:
Reference electrodes are the electrode whose potential is known and are used for the
determination potential of other electrode.
Definition: A reversible electrode of known electrode potential, which is used to determine
the electrode potential of other electrode, is called as reference electrode
Reference electrode is classified into two types
1. Primary reference electrode :
2. Secondary reference electrode

 Primary reference electrode

The standard hydrogen electrode is called a primary reference electrode. The potential
of all other electrodes measure with respect to the hydrogen electrode.
Ex: Standard Hydrogen Electrode (SHE)

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Disadvantages of primary reference standard hydrogen electrode:

1. Construction and working is difficult because maintaining concentration at unity and
keeping the pressure of the gas at 1 atmosphere.
2. Platinum is highly susceptible for poisoning by the impurities in the gas
3. It cannot be used in presence of oxidizing and reducing agents.

Secondary reference electrodes:

Due to the disadvantages of primary reference electrode like standard hydrogen
electrode, secondary reference electrodes are introduced.
Definition: “these are the electrodes the potential with respect to SHE are known and are
used to find out the potential of other electrodes.”
Two such secondary reference electrodes are:
1. Calomel electrode (Hg/Hg2Cl2/Cl-)
2. Silver-Silver chloride electrode (Ag/AgCl/Cl-)

Calomel electrode

Construction, working and application of calomel electrode to determine electrode

potential

Calomel electrode consists of glass tube at the bottom of which mercury is placed. Above
Mercury a layer of mercury and Mercurous chloride (called calomel) is placed. 3/4th of
container is filled with saturated KCl solution. Electrode potential of the cell depends on the
concentration of KCl used.
Calomel electrode can be represented as Hg(l) | Hg2Cl2(s) | KCl(aq)

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Working:
Calomel electrode can acts 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  2Cl  
 Hg 2 Cl 2  2e 
When it acts as cathode, the electrode reaction is
Hg 2 Cl2  2e  
 2Hg  2Cl -
The reversible electrode reaction is:
Hg 2 Cl 2 (s)  2e -  2Hg (l)  2Cl 

The electrode potential of the Ecalomel electrode depends on concentration of KCl

solution. It is used as secondary reference electrode in the measurement of single electrode
potential.
Advantages:
1. It is simple to construct.
2. Used as a reference electrode in potentiometer.
3. The cell potential is reproducible, constant and stable over a long period.
4. Cell potential does not vary with temperature.
The potential values are reliable and measurements can be made with great accuracy.
Applications:
1. Used as a reference electrode to determine the potential of any given electrode.
2. Used as reference electrode in potentiometric and pH determinations.

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Concentration cells:
“A concentration cell is an electrochemical cell in which electrode materials and
electrolytes of two half cells are composed of same material but the concentration of the
electrolytes are different”
Ex: Zn/Zn2+(M1) || Zn2+(M2)/Zn
Construction:

 A concentration cell consists of two same metal electrode dipped into their own ionic
solutions of two different concentration.

 Thus in a concentration cell, the electrode with lower electrolyte concentration acts as
anode and the one with higher electrolyte concentration acts as cathode.

 The concentration of ions at anode increases and at cathode decreases, when the cell
is in operation.

Consider two copper rods are dipped into their own ionic solutions of C1 and C2 and it is
represented as Zn/Zn2+(C1) || Zn2+(C2)/Zn
By electrochemical conventions, if C2 > C1 then, we have the following reactions.
At anode; Zn → Zn2+(C1) + 2eˉ
At cathode; Zn2+(C2) + 2eˉ → Zn
The emf of the concentration will be

The emf of the cell is +ve only if C2 > C1

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The following characteristics of concentration cell can be noted:

 When C2 = C1, the concentration cell does not generate electrical energy.
 When C2 > C1, the Ecell is + ve.
 When C2 < C1, Ecell is – ve.
 Higher the ratio of C2/C1, greater is the cell potential.

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