ELECTROLYSIS
Introduction
The term electrolysis was
first popularized in the 19th
century by Michael Faraday.
It was a process that helped
in the study of chemical
reactions in obtaining pure
elements. Today, this
process is commercially
important as it is used
widely in separating or
obtaining pure elements
from naturally occurring
sources such as ores.
What is Electrolysis?
Electrolysis is defined as a process of decomposing
ionic compounds into their elements by passing a
direct electric current through the compound in a
fluid form. The cations are reduced at cathode and
anions are oxidized at the anode.
For example, acidified or salt-containing water can
be decomposed by passing electric current to their
original elements hydrogen and oxygen. Molten
sodium chloride can be decomposed to sodium and
chlorine atoms.
Electrolysis is usually done in a vessel named ‘electrolytic cell’
containing two electrodes (cathode and anode) connected to a direct
current source and an electrolyte which is an ionic compound
undergoing decomposition, in either molten form or in a dissolves state
in a suitable solvent.
Electrolytic Process
In the process of electrolysis, there
is an interchange of ions and atoms
due to the addition or removal of
electrons from the external circuit.
Basically, on passing current,
cations move to the cathode, take
electrons from the cathode (given
by the supply source-battery), and
is discharged into the neutral atom.
The neutral atom, if solid, is
deposited on the cathode and if
gas, move upwards. This is a
reduction process and the cation is,
reduced at the cathode.
At the same time anions, give up their extra electrons to the anode and is oxidized to neutral
atoms at the anode. Electrons released by the anions travel across the electrical circuit and reach
the cathode completing the circuit. Electrolysis involves a simultaneous oxidation reaction at anode
and a reduction reaction at the cathode.
For example, when electric current, is, passed through molten sodium chloride, the sodium ion is
attracted by the cathode, from which, it takes an electrode and becomes a sodium atom.
Chloride ion reaches the anode, gives its electron, and become chlorine atom to form chlorine
molecule.
Na+(in electrolyte) + e–(from cathode) → Na …. At
Cathode
Electrolysis process, while useful to+get
Cl (from electrolyte) → e Clelemental
→ Cl2 ….forms
At Anode
– –
from
compounds directly, it can also be used indirectly in the metallurgy of
alkali and alkaline earth metals, purification of metals, deposition of
metals, preparation of compounds etc
Faraday’s Law of Electrolysis
The amount of the redox reaction depends on the
quantity of electricity flowing through the cell. Amount
of reaction or the number of ions discharged is given
by Faraday’s law of electrolysis. There are two laws.
Faraday’s first law can be summarized as; M=EQ/96485=EIT/
96485
Here, m is the mass of the substance that has undergone change, E is the equivalent mass of the
substance, ‘I’ is the current and ”t is the time in seconds of the passing of current.
Faraday’s second law compares the mass of different substances undergoing a change for the
same current.
ACCORDING TO THIS SECOND LAW,
M1/M2=E1/E2 OR M1/M2=M1/E2
Here, M and E are the changed
mass and equivalent mass of the
substances respectively.
Electrolysis Applications
Electrolysis, as stated above, is a process of
converting the ions of a compound in a liquid state
into their reduced or oxidized state by passing an
electric current through the compound. Thus,
electrolysis finds many applications both in
experimental and industrial products. Some of the
important ones are:
Determination of equivalent eight of
substances.
Metallurgy of alkali and alkaline
earth metals.
Purification of metals.
Manufacture of pure gases.
Manufacture of compounds like
sodium hydroxide, sodium
carbonate, potassium chlorate etc.
Cell Potential or Voltage
The minimum potential needed for the electrolysis process depends on their ability of the
individual ions to absorb or release electrons. This ability is, measured as an electrode potential of
the ions present in the electrolytic cell. The cell potential is the sum of the potential required for
the reduction and oxidation reaction. The potential involved in various redox reactions is available
in literature as standard reduction potential.
Reaction with positive redox cell potentials only will be feasible as per thermodynamic
Gibbs free energy (or standard potential). Generally, the electrolysis is
thermodynamically controlled.
In electrolysis, a potential equal to or slightly more than that, is, applied externally. The
ions, which are stable and not reacting, are made to undergo reaction in the presence of
externally applied potential. External potential hence makes an unfavourable reaction to
take place. In electrolysis, chemical bonds connecting atoms are either made or broken
and so, electrolysis involves the conversion of electrical energy into chemical energy.
Thank You
By Mary Angel Prajesh
