UNIT - IV

ELECTROLYTIC PROCESS AND

STORAGE OF ELECTRICITY
 SYLLABUS
• Electrolysis
• Polarization factor
• Preparation of work for electroplating
• Tanks and other equipment
• Method of charging and maintenance
• Nickel – iron and Nickel – cadmium batteries
• Components and materials
• Capacity rating of batteries
• Battery chargers.
 Electrolyte
The substances which decompose when
an electric current is passed through them
are called electrolyte
Or
A compound which when molten or
dissolved in aqueous solution conducts an
electric current and is decomposed in the
process.
 ELECTROLYSIS
1. The process of decomposition of electrolyte
by the passage of electric current through
them is called electrolytic process or
electrolysis.
2. The chemical change that takes place when
an electric current passes through a molten
or aqueous electrolyte.
3. The processes based on the fact that
electrical energy can produce chemical
changes are called electrolytic processes.
 Used for...
• Extraction of pure metals from their ores
(e.g.,Copper, Zinc, aluminium, Magnesium etc.)
• Refining of metals (e.g., gold, silver, copper, nickel
etc.)
• Manufacturing of various chemicals (e.g., Caustic
soda, potassium permanganate, chlorine etc.)
• Electro-deposition of metals including electro-
plating, eletro typing, electro forming;
• Building up of worn parts in metallurgical,
chemical and other industries.
 Electrolysis-The basic principle
• If two electrodes are dipped in an electrolyte
and potential is applied across them,the
electrodes are named as +ve or anode and –ve
or cathode.
• The molecules of the substance dissolved are
“dissociated”.
• They are broken up in to two types of ions
i.e.,+ve and –ve ions.
• Consider the case of copper
sulphate dissolved in water.
• It dissolved into positively
charged copper ions and
negatively charged sulphate
ions.
• If two electrodes are placed
in the solution and one of
them is connected to the
+ve terminal of d.c. and the
other to –ve terminal,then
the positively charged ions
travel towards the cathode
and negatively charged ions
towards anode as shown in
fig.
• Copper is deposited at the cathode as metal.
• The sulphate ions are collected at the anode and react
with water giving out oxygen as shown in the following
reaction,
2So4 + 2 H2o =2H2So4 +o2
• Oxygen is liberated as gas at the anode and H2So4 is
formed in the electrolyte.
• If the anode is made of copper the sulphuric acid reacts
with it forming copper sulphate and libertaing hydrogen.
H2So4 +Cu = CuSo4 + H2
• Thus the copper of the anode goes into solution and
copper from copper sulphate is deposited on the cathode.
• The whole process described above is called electrolysis.
Electrolysis of molten lead (II)
bromide
Electrolyte: PbBr2 (l)
Ions present: Pb 2+ , Br -

Using graphite electrodes:

At the cathode: Pb 2+ + 2e Pb

At the anode: 2Br - Br2 + 2e

Electrolysis of concentrated hydrochloric acid
Electrolyte: HCl (aq)
Ions present: H + , Cl - from HCl
H + , OH - from H2O
Using graphite electrodes:

At the cathode: H + ions migrate to it.

2H + + 2e H2

At the anode: Cl - and OH - ions migrate to it.

Cl - ions preferentially discharged due to higher concentration.

2Cl - - 2e Cl2
 Definitions of various terms used in
Electrolysis
1. Electrode:
A metal or graphite rod by which the current
enters or leaves an electrolyte.

2. Anode:
The positive electrode from which electrons enters the
electrolyte.

3.Cathode
The negative electrode from which electrons leaves the
electrolyte.
4. Ion:
An atom when looses or gains an electron is known
as ion.

5. Cation:
The atom which has lost one electron is termed as
cation.The cation is a positively charged ion that is
attracted to the negatively charged electrode, the
cathode.

6. Anion:
the atom which has gained one electrode is termed
as Anion.The anion is a negatively charged ion
which is attracted to the positively charged
electrode, the anode.
7. Atomic Weight:
It is the ratio of the weight of an atom of an element
to the weight of an atom of hydrogen.
8.Valency:
The valency of an element is given by the No.of
atoms of hydrogen which can combine or can be
replaced by one atom of element in a chemical reaction.
9.Chemical equivalent or equivalent weight:
It is defined as ratio of atomic weight to valency.
10.Electro-chemical Equivalent:
The mass of element liberated per unit quantity of
electricity during electrolysis is known as electro
chemical equivalent.
 Faraday’s Laws of Electrolysis
• Michael Faraday (an English Scientist)
formulated the laws governing the electrolytic
processes.
Faraday’s First Law:
It states that “The mass of a substance
liberated from an electrolyte in a given time is
proportional to the quantity of electricity
passing through the electrolyte”.
That is, m α Q α I×t
m=ZIt
Where,
Z = A constant called the electromechanical
equivalent
I = The steady current in amperes, and
t = Time (second) for which current I flows through
the electrolyte.
If I=1A, t=1s and Z=m
Thus electromechanical equivalent, Z, of a
substance is defined as the amount of the
substance deposited on passing a steady electric
current of 1A for one second through its solution.
The S.I unit of Z is Kilogram per Coulomb (Kg/C).
Faraday’s Second Law:
This law states that “when the same
quantity of electricity is passed through
several electrolytes,the masses of the
substances deposited are proportional to their
respective chemical equivalents or equivalent
weights”.
ie., Z αal to the chemical equivalent.
Terms Connected with Electrolytic
processes
• Following terms are used in electrolytic
processes,
1. Current efficiency
2. Voltage
3. Energy feeiciency.