Unit 5.

3: Industrial Applications of Electrolysis – Electrometallurgy, Electroplating,

Electrolytic Refining.
Electrometallurgy
Chemically active and highly electropositive elements such as alkali metals and alkaline earth
metals and metals with high negative oxidation potentials cannot be obtained by different
metallurgical processes (extraction processes of metals from its ore/minerals) such as
amalgamation process, reduction by complex salt, water gas, silicon and calcium carbide, coke,
aluminium, hydrogen etc. These metals can also not be obtained by reducing their oxides, with
carbon, because oxides of these metals are very stable and have to be heated very strongly with
carbon to reduce to metal. Further, these metals are expected to form metal carbides with carbon
at higher temperature. Hence, these metals are extracted by electrolytic reduction method and
this is also known as Electrometallurgy.

Electrometallurgy is a method in metallurgy that uses electrical energy to produce metals by

electrolysis. It is usually the last stage in metal production.

Alkali metals, usually occurs in nature as chlorides, e.g., Sodium Chloride (NaCl), Carnallite
(MgCl2.KCl.6H2O) etc. Alkaline earth metals such as Ca, Ba, Sr etc. occur as carbonates, which can
readily be converted into halides. Metals such as Li, Na, K, Rb, Cs, Sr, Ca, Ba etc. are best obtained
by the electrolysis of their fused chlorides salts. Electrolytic reduction or Electrometallurgy is
carried out by the electrolysis of fused chlorides salts under the inert atmospheric condition using
an anode and cathode separated by a membrane diaphragm to avoid the further reaction of
products formed at anode and cathode.
For example, electrolysis of fused sodium chloride, NaCl using Iron (Fe) cathode and graphite
anode gives sodium metal.
NaCl ↔ Na+ + Cl-

At cathode: 2Na+ + 2e → 2Na At anode: 2Cl- → Cl2 + 2e

Fig. 01

Similarly, Magnesium is prepared by the electrolysis of fused Carnallite.

MgCl2 ↔ Mg2+ + 2Cl-

At cathode: Mg+2 + 2e → Mg At anode: 2Cl- → Cl2 + 2e

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Unit 5.3: Industrial Applications of Electrolysis – Electrometallurgy, Electroplating,
Electrolytic Refining.
Electroplating
Electroplating is elecrtodeposition of metals on metals, non-metals and alloys. It is the process by
which a coating metal is deposited on the base metal or alloy by passing a direct current through
the electrolytic solution containing the soluble salt of coating metal. The base metal to coated or
electroplated is usually made the cathode of the electrolytic cell and coating metal is made the
anode.
A metal salt in aqueous solution undergoes ionisation to form metal ions. When the electric
current is passed through the salt solution by dipping the two electrodes in the solution, the metal
ions migrate to the cathode and get deposited. If anode is the same metal of which the salt is in
the solution, the salt is reformed by the anode metal passing into the solution in the form of ions.
If anode is made of coating metal, then the concentration of the electrolytic solution will remain
unaltered, because metal ions deposited on cathode from solution are continuously replaced by
the reaction of ions with the anode metal. For example, when copper sulphate is used as an
electrolyte and copper is used as anode or coating metal, the copper sulphate will ionise as
follows:
CuSO4 ↔ Cu2+ + SO42-

On passing electricity, Cu2+ ions will go to the cathode and get deposited there,

Cu2+ + 2e → Cu (at cathode)

The free sulphate ions will migrate to the anode and dissolved an equivalent amount of copper to
form CuSO4.
Cu + SO42- → CuSO4 + 2e (at anode)

Fig. 02
[Fig. 02, A simplified diagram for electroplating of copper (orange colour) on a conductive object (the
cathode, "Me", gray colour). The electrolyte is a solution of copper sulfate, CuSO4. A copper anode is used
to replenish the electrolyte with copper cations Cu2+ as they are plated out at the cathode.]

The copper sulphate formed is dissolved in the electrolyte. In this way, there is a continuous
deposition of metal on the cathode.

If the anode is made of inert material graphite, then electrolytic salt is added to the cell to
maintain proper coating metal ion concentration in the cell. The process of electroplating is

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Unit 5.3: Industrial Applications of Electrolysis – Electrometallurgy, Electroplating,
Electrolytic Refining.
continuous because there is no consumption of anode and so replacement of anode is not
required.

Applications: Electroplating is widely used in industry and decorative arts to improve the surface
qualities of objects—such as resistance to abrasion and corrosion, reflectivity, electrical
conductivity, or appearance. It may also be used to build up thickness on undersized or worn-out
parts, or to manufacture metal plates with complex shape, a process called electroforming. It is
also used to purify metals such as copper. Some applications are -
1. Electroplating is used for decoration- To increase the commercial as well as decorative
value, the base metals such as iron , brass, copper, aluminium etc. are electroplated with
gold, silver, nickel, chromium copper, platinum etc.
2. Plating for protection- Electroplating has widely been used for depositing protective
coating of zinc, cadmium, tin, copper etc. on iron and steel to protect from corrosion,
rusting and chemical attack.
3. Electroplating on non-metallics- Non-metallics such as glass, porcelain, leather wood etc.
are electroplated for decoration, preservation and also for increasing their strength.

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Electrolytic Refining
In the Electrolysis refining method, the crude metal to be refined act as anode and pure metal is
deposited at the cathode. During the electrolytic refining of crude metal noble metals such as
gold, silver and platinum metals are recovered as by-products. Almost the whole amount of
copper and nickel produced is subjected to electrolytic refining and noble metals are recovered
from them.
It is the process of refining of metal in which impure metal is made the anode and a thin strip of
pure metal is made the cathode. A solution of metal salt is used as an electrolyte. The apparatus is
shown in the figure given below. When electric current is passed through the electrolyte, the
impure metal from the anode is dissolved in the electrolyte and an equal amount of pure metal
from the electrolyte is deposited on the cathode. The soluble impurities go into the solution
whereas the insoluble impurities settle down at the bottom of the anode which is known as anode
mud. Following diagram shows the electrolytic refining of copper in which anode is impure copper
and cathode is thin strip of pure copper while the electrolyte used is the copper sulphate solution.

Fig. 03

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