B.SC.

2nd year(Inorganic Chemistry)

Extraction of Aluminium
Aluminium is the third most abundant element (8.3% by weight) in the earth's crust after oxygen
(45.5%) and silicon (25.7%). The important minerals of aluminium are:
a) Bauxite, AlOx(OH)3-2x (0 < x <1) or Al2O3.2H2O
b) Cryolite, Na3AlF6
c) Orthoclase, KAlSi3O8
d) Mica (muscovite), KAl2(Si3AlOl0)(OH)2
e) Beryl, Be3Al2Si6O18
f) Corundum, Al2O3
Aluminium is extracted from bauxite. Bauxite consists of mainly 50-60% of aluminium oxide.Crude
bauxite is contaminated with impurities like ferric oxide(Fe 2O3),silica(SiO2) and small amount of
titanium dioxide(TiO2) etc. Aluminium is commonly extracted from its ore by electrolysis process.
The bauxite which contains much ferric oxide and little silica,is known as red bauxite. Bauxite which
contains much silica and less ferric oxide is called white bauxite
Pure Aluminium metal is extracted from bauxite in a three-stage process.
a) Purification of Bauxite (Bayers Process or modern wet process) to obtain pure Alumina.
b) Electrolysis of pure Alumina in molten cryolite (Na3AlF6) (Halls process).
c) Refining of Aluminium (Hoopes process).

Purification of bauxite
(a)Baeyer's process or modern wet process---for--red bauxite
(b)Serpeck's process---for---white bauxite
(c)Hall's process----for---low grade bauxite
(a) Bauxite contains silicon dioxide (SiO2), iron oxides and titanium(IV) oxide as impurities. The
bauxite ore is digested with a concentrated solution of sodium hydroxide at 473-523 K and 35-36 bar
pressure. Aluminium oxide and silica dissolve to form sodium aluminate (NaAlO 2) and sodium silicate
respectively leaving behind iron oxide and TiO2, which are filtered off.

The filtrate containing sodium aluminate and sodium silicate is diluted and seeded with freshly
precipitated aluminium hydroxide, which induces the precipitation of aluminium hydroxide leaving
behind sodium silicate in solution.

The aluminium hydroxide is filtered dried and calcined at 1473 K to yield pure alumina.
Al(OH)3 Al2O3 + 3H2O

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 B.SC. 2nd year(Inorganic Chemistry)

Electrolysis of pure alumina (Hall-Heroult process)

fig - Hall's cell

Pure alumina is dissolved in molten cryolite (Na 3AlF6) and is electrolyzed in an iron tank lined inside
with carbon. Carbon lining serves as cathode while a number of carbon rods dipping in the fused
electrolyte serve as anode. Cryolite improves the electrical conductivity of the cell, as alumina is a
poor conductor. Moreover, cryolite lowers the melting point of the mixture to about 1250 K. Other
impurities such as CaF2, NaF and AlF3 may also be added. The temperature of the electrolyte is
maintained between 1200-1300 K.
On passing electric current, aluminium is liberated at the cathode and gets collected at the bottom of
the tank from where it is removed. Oxygen liberated at the anode combines with the carbon of the
anode to produce carbon monoxide, which either burns or escapes out. The reactions taking place
during the electrolysis are:

At anode
F- ions are oxidized and nascent fluorine so produced reacts with Al2O3 to form AlF3 and dioxygen gas.

4C + 3O2 2CO + 2CO2

At cathode
Aluminium ions get reduced to give aluminium metal.

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 B.SC. 2nd year(Inorganic Chemistry)

The dioxygen gas liberated at carbon anode reacts with carbon to form CO gas which either escapes
out or is burnt to produce CO2.
Since during electrolysis the carbon electrodes get consumed they have to be replaced periodically.

Refining of aluminium (Hoopes process)

The metal obtained in the above step is about 99% pure and for most purposes it is taken as pure
metal. However, further purification of aluminium can be carried out by Hoopes process. The cell
consists of an iron tank lined with carbon at the bottom. A molten alloy of copper, crude aluminium and
silicon is used as the anode. It forms the lower most layer in the cell. The middle layer consists of
molten mixture of fluorides, of sodium aluminium and barium (cryolite + BaF 2). The upper most layer
consists of molten aluminium. A set of graphite rods dipping in molten aluminium serve as cathode.

fig - Purification of aluminium by Hoop's cell

On passing current aluminium ions from the fused electrolyte are discharged at cathode and pure
aluminium collects as the top layer. Meanwhile, an equivalent quantity of aluminium from crude alloy
at the bottom goes into electrolyte in the middle layer. Crude aluminium is added from time to time
and pure aluminium tapped off from the top.
Uses of Al
Aluminium is a lightweight metal with a density of 2.7 g cm -3. Al can be easily extruded through dies to
form various shapes. It is used for making angles used in windows. Aluminium cables are used to
transmit electric current. Al alloys are used in aircraft and other transportation vehicles. Finely
powdered Al is used as anti rust in paints. Al foil is used as wrapper and utensils are used for
household purposes. Al is used as a reducing agent in Alumino-thermite process.
ALUMS