Introduction to Refining

1. Chemical methods: (i) Fire refining, (ii) Steel making, (iii) Refining via volatile compound

2. Electro-chemical methods: Electro-refining (electrolysis)

3. Physical methods: (i) Liquation, (ii) Fractional/Selective distillation of impurities, (iii) Zone

refining
Fire refining: Fire refining is based on the difference in affinity for oxygen for
the different elements.
1. The crude metal must be melted before it can be refined
2. The chemical reactions involved are usually oxidation reactions

To remove impurities by fire refining, impurities must oxidized readily than

the metal to be refined
Steel making: Impure iron or hot metal is produced in blast furnace by
reduction of iron oxides in presence of carbon as reducer. Generally, hot
metal contain 3-4% C, 0.5-1.25% Si, 0.25-0.75% Mn, 0.4% P and 0.04% S.
Impurities can be removed by oxidation from the impure iron to get steel.
This refining process is known as steel making. Hot metal is takin in a
container where it is converted to steel by lancing oxygen.
In Ellingham diagram, SiO2 is at lower position than FeO line; means Si has
good affinity of oxygen than Fe, hence Si will first react with oxygen than Fe.
Oxides of impurities are mixed with addition of flux (lime) to form liquid slag.
Refining via volatile compounds: This process is applied for high melting point
and boiling points metals, where distillation is impossible for Zr and Ti. Impure
metals react with gaseous reagents to produce volatile compounds are
relatively low temperature. These compounds are subsequently decomposed
by heating or cooling to yield pure metal and the original reagent can be
recycled.
1. Purification of nickel by carbonyl process:
Ni (impure) + 4CO (g) = Ni(CO)4 (g) [at 450C]
Ni(CO)4 (g) = Ni (pure) + 4CO(g) [at 1800C]
2. Iodide process:
Zr (impure) + 4I (g) = ZrI4 (g) [at 2000C]
ZrI4 (g) = Zr (pure) + 4I(g) [at 14000C]
Electrochemical Methods (Electrorefining): In the electrochemical methods of
refining, the impure metal is made the anode and the pure metal is deposited
on a cathode.
The starting cathode sheet may be a pure strip of the metal itself or some
other inert metal

The electrolyte contains an ionizable salt of the metal

At anode: Cu Cu2+ + 2e
At cathode: Cu2+ + 2e Cu

Reactive metals such as Al, Mg, Ti, Zr, or Mo must be electro-refined using a
suitable molten salt as electrolyte.
Liquation or Liquid Phase Separation: In liquation, the impurity separates out
from the parent metal due to immiscibility. The efficiency of separation being
depends upon the nature of the metal impurity phase diagram. Liquation carried
out by slowly cooling a liquid metal to permit a second phase, either by liquid or
solid, to separate out.
The purification of Pb through Zn removal, on cooling impure Pb and solid Zn
separates out leaving a liquid poorer in Zn and richer in Pb. This method
depends on differences in melting points and densities of immiscible phases (MP
of Pb is 327oC and Zn is 420oC).
Selective distillation: The component A has a boiling point (TA) lower than that
of component B (TB). On heating, A vaporizes more easily. When the liquid of
composition X is heated, the first vapour has a composition Y (at temperature T)
which has content of A.
The composition of the vapour and the liquid depends on the temperature are
which they are at equilibrium. At any temperature, the vapour has higher
fraction of component A compare to that in the liquid. Therefore, A can be
preferably removed from component B by distillation.

Fig: Liquid vapour equilibrium diagram

Zone refining: In zone refining, a small molten zone moves through a long
charge of alloy or impure material. The differences in impurity concentration
between liquid and crystallizing solid lead to segregation of impurities into the
moving liquid zone and a corresponding purification of the solidifying material.
When the liquid is cooled slowly, then the solidification
begins at a particular temperature. The initial solid is
purer. As the temperature is slowly down, more and
more solid separates, the final solid having less purer.