CHAPTER- 02

Electrochemistry

Branch of chemistry that deals with the production of electricity and the energy
released during the spontaneous reaction and is used to carry out non
spontaneous reaction transformations.

Electrochemical cell:
It is a device that converts chemical energy into electrical energy. These cells
are energy efficient and pollution free.
Galvanic or Voltaic cell:
The cell that converts chemical energy into electrical energy and has an
electrical potential equal to 1.1 V and the conc. Of the ions are unity.
Zn + Cu+2 → Zn+2 + Cu
Electrolytic cell:
A device that uses electrical energy to carry non spontaneous reaction chemical
reaction.
Application of external voltage in the Galvanic cell:
• Eext < 1.1 V
(i) Electrons flow from zinc to copper and current flows from copper
to zinc.
(ii) Zinc dissolves at anode and copper gets deposited at cathode.

• Eext = 1.1 V
(i) No flow of current and electrons hence no chemical reaction takes
place.

• Eext > 1.1 V

(i) It functions as an electrolytic cell hence, the electrons will flow in
the opposite direction i.e. from copper to zinc and current from
zinc to copper
(ii) Zinc gets deposited at cathode and copper dissolves at anode.
 Half Cells or Redox Couple:
The two portions of the cell at which oxidation and reduction reactions takes place.

Electrode Potential:
Potential difference between the electrode and the electrolyte.

Standard Electrode Potential:

When the conc. of all the species involved in the half cell is unity then the
electrode potential is called standard electrode potential.
Cell Potential:
The potential difference between the two electrodes and is measured in volts.
E◦cell = E◦cathode - E◦anode
Electromotive Force (emf):
It is the cell potential difference between the electrode potential of the cathode
and anode.
Cell Representation:
A cell is represented by putting a vertical line between metal and electrolyte
solution and a double vertical line between the two electrolytes connected by
the salt bridge.
Eg. Cu + 2 Ag+ → Cu+2 + 2 Ag
For the above reaction the cell is represented as
Cu/Cu+2 Ag+ /Ag

Measurement of Electrode Potential:

Potential of an individual half cell cannot be measured. Thus acc.to convention,
a half cell called standard hydrogen potential (SHE)is set against the individual
half cell that has a zero potential at all temperatures and represented by
Pt(s) / H2 (g) / H+(aq)
SHE consist of platinum electrode coated with platinum black dipped in acid
solution and hydrogen gas is bubbled through it.
The conc. of both the reduced and oxidised form of hydrogen is unity, thus the
pressure of the gas is 1 bar and conc. of hydrogen ion is 1 molar.
SHE is taken as anode that has a electrode potential zero.
** Cu does not dissolve HCl as Cu has a positive value of standard electrode
potential thus Copper itself gets reduced than hydrogen.
** Metals like platinum, gold etc are used as inert electrode as they don’t
participate in the reaction but only provides its surface for the reaction to take
place.
** Electrochemical cells are extensively used for determining the pH of
solutions, solubility product, equilibrium constant and thermodynamic
properties and for potentiometric titration.

NERNST EQUATION:
This equation gave a relationship between the electrode potential , temperature
and the conc. of the metal ion.
M+(aq) + ne- → M(s)
E(M+/ M) = E◦(M+/ M) - RT ln [M] (i)
nF [M+]
where, R = 8.314 J/K/mol (gas constant)
T = 298 K (temperature)
F = 96500 C (faraday’s constt)
Substituting the values in eqn (i) we get,

Ecell = E◦cell - 0.0591 log [oxidation]

n [Reduction]