ELECTROLYSIS OF ALUMINA

ELECTROLYSIS OF
ALUMINA

The electrolysis of alumina is carried out in a steel tank lined inside with graphite. The
graphite lining serves as cathode. Anode is also made of graphite rods hanging in the
molten mass.
The electrolyte consists of alumina dissolved in fused Cryolite(Na 3AlF6) and
Fluorspar(CaF2).
Cryolite lowers the melting point of alumina to 9500C and fluorspar increases the
fluidity of the mass so that the liberated aluminum metal may sink at the bottom of the
cell.
When electric current is passed through this mixture, the aluminum is collected at the
cathode in molten state
and sinks at the bottom and is tapped off.

Ionization of Alumina:
2Al2O3 → 6O-2 + 4Al+3
Reaction at Cathode:
4Al+3 + 12e- → 4Al
Reaction at Anode:
6O-2 → 3O2 + 12e-
C + O2 → CO2

REFINING OF
ALUMINIUM

Aluminum metal produced by the electrolysis of alumina is 99% pure but contains
impurities of Fe, Si and Al2O3. Aluminum is further refined by hoope’s method.
 HOOPE’S METHOD

This is an electrolytic process. Electrolytic cell is made of iron, which is lined with carbon
at the bottom. It contains three layers of fused mass. The lower layer consists of an alloy of
impure aluminum with copper. This layer serves as anode. The middle layer consists of a
solution of cryolite (Na3AlF6) and barium fluoride. The upper layer consists of pure aluminum
and serves as cathode. These three layers are separated from each other due to difference
in specific gravity.
During electrolysis Al+3 ions from the middle layer migrate to the upper layer where they
are reduced to aluminum by gaining three electrons. Equal numbers of Al+3 ions are
produced in the lower layer. These ions migrate to the middle layer. Pure aluminum is
tapped off from time to time. Hoope’s method gives 99.99% pure aluminum.
Electro-Chemical Changes:
Na3AlF6 →3NaF + AlF3

AlF3 → Al+3 + 3F-

At the cathode:

Al+3 + 3e- → Al

At the anode:

Al → Al+3 + 3e-

Overall reaction:

Al+3 + Al → Al + Al+3