Unit 6: General Principles and Processes Of Isolation Of Elements

Common terms
Minerals: Naturally occurring materials containing metals or metallic compounds in the
earth’s crust obtained by mining are termed as minerals.
Eg: The minerals of Iron haematite (Fe2O3)

Ores: The minerals from which metals can be extracted conveniently and economically
are called as ores.
Eg: Haematite (Fe2O3) is the ore of iron because it is used in the extraction of iron.

Matrix/Gangue: The unwanted impurities which are present in the ore are called
matrix/gangue.
Eg: Silica is the gangue in haematite (Fe2O3) ore.

Metallurgy: The scientific and technological process used for the isolation of the metal
from its ore is termed as metallurgy.

Occurrence of Metals
 Among metals, aluminium is the most abundant. (Third most abundant element in
earth’s crust 8.3% approx. by weight). It is a major component of many igneous
minerals including mica and clays.
 Many gemstones are impure forms of Al 2O3 and the impurities range from Cr (in
‘ruby’) to Co (in ‘sapphire’).
 Iron is the second most abundant metal in the earth’s crust. It forms a variety of
compounds and their various uses make it a very important element. It is one of the
essential elements in biological systems as well.

Some important ores are listed below

Aluminium Iron Copper Zinc
1. Bauxite AlOx(OH)3-2x 1. Haematite Fe2O3 1. Copper Pyrites Cu FeS2 1. Zinc Blende ZnS

2. Kaolinite [Al2(OH)4 Si2O5] 2. Magnetite Fe3O4 2. Melachite 2. Calamine ZnCO3

CuCO3.Cu(OH)2
3. Siderite FeCO3 3. Zincite ZnO
3. Cuprite Cu2O
4. Iron Pyrites FeS2
4. Copper Glance Cu2S

Principles and Methods of Extraction

Broad classification is as follows:
1. Concentration of Ores
2. Conversion of ores into oxides or other desired compounds
3. Reduction of ores to form crude metals
4. Refining of metals

Concentration of Ores (Dressing or Benefaction)

Removal of the unwanted materials (gangue) from the ores is known as Concentration of
ores or Dressing or Benefaction. The purified ore is called as ore concentrate.

Common methods of ore concentration are explained below.

1. Hydraulic washing or Gravity separation : This is based on the differences in
gravities of the ore and the gangue particles. The powdered ore is washed with stream of
water. The lighter gangue particles are washed away with water leaving behind heavier
ore particles.
Eg: Haematite is concentrated by this method.

2. Magnetic separation: This is based on differences in magnetic properties of the ore

components. If either the ore or the gangue (one of these two) is capable of being
attracted by a magnetic field, then such separations are carried out (e.g., in case of iron
ores). The ground ore containing magnetic particles and non magnetic particles are
passed over a magnet. The magnetic particles are attracted by the magnet and the non
magnetic particles move away from the magnet.

3. Froth Floatation method: The powdered ore is mixed with water. To it, collectors
and froth stabilizers are added. Collectors (e. g., pine oils, fatty acids, xanthates, etc.)
enhance non-wettability of the mineral particles and froth stabilizers (e. g., cresols,
aniline) stabilize the froth. Air is passed into the mixture. The ore particles are adsorbed
on oil to form froth and gangue is wetted by water. Froth carrying the mineral is skimmed
off and dried to recover the ore.
This method is used to separate gangue from sulphide ores.

Sometimes, it is possible to separate two sulphide ores by adjusting proportion of oil to

water or by using ‘depressants’. For example, in case of an ore containing ZnS and PbS,
the depressant used is NaCN. It selectively prevents ZnS from coming to the froth but
allows PbS to come with the froth.

4. Leaching: When the ore is treated with suitable solvent or chemical reagent, the ore is
soluble in the solvent and the gangue is insoluble.
a) Example 1: Leaching of Alumina from bauxite
Step 1: Digestion of powdered bauxite ore with concentrated NaOH at 473- 523K
temperature and 35-36 bar pressure. Here, alumina is leached out as sodium aluminate.
Al2O3 + 2NaOH + 3H2O → 2Na[Al(OH) 4]

Step 2: Neutralization of aluminate in solution by passing CO2 gas and precipitation of

hydrated alumina by seeding it with freshly prepared samples of hydrated Al2O3.
2Na[Al(OH)4] + CO2 → Al2O3.xH2O(s) + 2NaHCO3

Step 3: The hydrated Al2O3 is filtered, dried and heated to 1470K to get pure Al2O3.
Al2O3.xH2O Al2O3 + xH2O

b) Example 2: Metallurgy of gold/silver

Step 1: Gold or silver metal is leached with a dilute solution of NaCN or KCN in the
presence of air.
4M + 8CN– + 2H2O+ O2 → 4[M(CN)2] – + 4OH– (M= Ag or Au)
Step 2: The metal is obtained from the solution by adding zinc.
Conversion of ores into oxides or other desired compounds
The concentrated ore must be converted into a form which is suitable for reduction.
There are important methods to achieve this.
1. Roasting: Roasting is a process in which the ores are heated to a high temperature in
the presence of air.
2ZnS + 3O2 → 2ZnO + 2SO2
2PbS + 3O2 → 2PbO + 2SO2
2Cu2S + 3O2 → 2Cu2O + 2SO2

The sulphide ores of copper are heated in reverberatory furnace. If the ore contains iron,
it is mixed with silica before heating. Iron oxide ‘slags of ’ as iron silicate and copper is
produced in the form of copper matte which contains Cu2S and FeS.
FeO + SiO2 → FeSiO3

2. Calcination: Calcination is a process in which the ores are heated in the absence of air.
Fe2O3.xH2O Fe2O3 + xH2O
ZnCO3 ZnO+ CO2
CaCO3.MgCO3 CaO+ MgO+ 2CO2

Reduction of ores to form crude metals

 Reduction of the metal oxide usually involves heating it with some other substance
acting as a reducing agent (C or CO or even another metal).
 The reducing agent (e.g., carbon) combines with the oxygen of the metal oxide.
MxOy + yC → xM + y CO
 Some metal oxides get reduced easily while others are very difficult to be reduced.
In any case, heating is required.
 To understand the variation in the temperature requirement for thermal reductions
(pyrometallurgy) and to predict which element will suit as the reducing agent for a
given metal oxide, Gibbs energy interpretations are made.

Thermodynamic Principles of Metallurgy

Ellingham Diagrams: Set of curves got by drawing graphs of values versus the
temperature for the oxidation of metals by one mole of oxygen.
Characteristics of Ellingham diagram:
1. The graph for the formation of metal oxides always slopes upwards.
2. There is a sudden change in the slope at temperatures like Melting point and boiling
point.
3. For metals like silver and mercury, the variation of for the formation of their oxide
is greater than zero.
4. Any metal oxide with lower value is more stable than any other metal oxide with
higher .

Application of Ellingham diagram

1. Extraction of Iron by reduction of haematite.
 Oxide ores of iron, after concentration through calcination/roasting are mixed with
limestone and coke and fed into a Blast furnace from its top. Here, the oxide is
reduced to the metal.
 Zone of combustion: here coke burns with oxygen to form carbon dioxide with
heat liberation. This increases the temperature upto 2200K.

As CO2 goes up, it reacts with remaining coke to form CO. As this is endothermic
reaction, the temperature goes on decreasing as it goes up.

 Zone of reduction: At 500 - 800K, CO reduces iron oxide to iron.

At 900 – 1000K,
  Zone of slag formation: At 1123K, silica present in the ore combine with the lime
to form a slag.

 The iron obtained from Blast furnace contains about 4% carbon and many
impurities in smaller amount (e.g., S, P, Si, Mn). This is known as pig iron.
 Cast iron is different from pig iron and is made by melting pig iron with scrap iron
and coke using hot air blast. It has slightly lower carbon content (about 3%) and is
extremely hard and brittle.
 Wrought iron or malleable iron is the purest form of commercial iron and is
prepared from cast iron by oxidising impurities in a furnace lined with haematite.

Behavior of carbon in the extraction of iron on the basis of Ellingham diagram

 Above 1073K, . Therefore coke is better reducing agent to

reduce iron oxide to iron at higher temperature.
 Below 773K, . Therefore CO better reducing agent to
reduce iron oxide to iron at lower temperature.

2. Extraction of copper from cuprous oxide

 According to the Ellingham diagram, the free change for copper oxide is almost at
the top suggesting both carbon and carbon monoxide can be used for reduction.
 The sulphide ores are roasted/smelted to give oxides.
2Cu2S + 3O2 → 2Cu2O + 2SO2
  The oxide can then be easily reduced to metallic copper using coke:

Cu2O + C → 2 Cu + CO

 The iron impurities present in the sulphide ore is removed by sand.

FeO + SiO2 → FeSiO3 (Slag)
 Thus we obtain copper matte which is a molten mixture of Cu2S and FeS.
 Copper matte is transferred to a silica lined converter. Some silica is also added
and hot air is blown to convert Cu2S CuO to the metallic copper.

 Traces of FeS are removed as slag.

 The solidified copper obtained has blistered appearance due to the evolution of SO 2
and so it is called blister copper.

3. Extraction of zinc from zinc oxide

 The reduction of zinc oxide is done using coke.
 The temperature in this case is higher than that in case of copper. For the purpose
of heating, the oxide is made into brickettes with coke and clay.

 The metal is distilled off and collected by rapid chilling.

Electrochemical Principles of Metallurgy ( )

Illustration
Hall – Heroult process of extraction of Aluminium
 Purified Alumina Al2O3 is mixed with Na3AlF6 (Cryolite) or CaF2 to lower the
melting point of the mixture and to increase the conductivity.
 The mixture is fused and electrolysed using electrolytic cell.
 Steel vessel with lining of carbon acts as cathode and graphite anode is used.
During electrolysis, Alumina decomposes to give Aluminium ion at cathode and
Oxygen at anode.
  Cell reactions are;
Cathode:

Anode:

Overall reaction:

Refining of crude metals

A metal extracted by any method is usually contaminated with some impurity. For
obtaining metals of high purity, several techniques are used depending upon the
differences in properties of the metal and the impurity. Some of them are listed below.
(a) Distillation
(b) Liquation
(c) Electrolysis
(d) Zone refining
(e) Vapour phase refining
(f ) Chromatographic methods

(a) Distillation: This is very useful for low boiling metals like zinc and mercury. The
impure metal is evaporated to obtain the pure metal as distillate.

(b) Liquation: In this method a low melting metal like tin or lead can be made to flow on
a sloping surface. In this way it is separated from higher melting impurities.
(c) Electrolytic refining: The impure metal is made to act as anode. A strip of the same
metal in pure form is used as cathode. They are put in a suitable electrolytic bath
containing soluble salt of the same metal. On passing current electrolytic reactions lead to
refining of the metal.
Illustration: Refining of copper (Zinc can also be refined by this method)
 Impure copper (blister copper) is made as anode
 Pure copper strips are used as cathode
 The electrolyte is acidified solution of copper sulphate
 Cell reaction on electrolysis
Anode:
Cathode:
 Copper is deposited on cathode.
 Anode dissolves in solution
 Impurities from the blister copper deposit as anode mud

(d) Zone refining: This method is based on the principle that the impurities are more
soluble in the melt than in the solid state of the metal.
 A circular mobile heater is fixed at one end of a rod of the impure metal.
 The molten zone moves along with the heater which is moved forward.
 As the heater moves forward, the pure metal crystallizes out of the melt and the
impurities pass on into the adjacent molten zone.
 The process is repeated several times and the heater is moved in the same
direction.
 At one end, impurities get concentrated. This end is cut off.
 This method is very useful for producing semiconductor and other metals of very
high purity, e.g., germanium, silicon, boron, gallium and indium

(e) Vapour Phase reefing: In this method, the metal is converted into its volatile
compound and collected elsewhere. It is then decomposed to give pure metal.

Illustrations
1. Mond process of refining Nickel –
 Nickel is heated in a stream of carbon monoxide forming a volatile complex,
nickel tetracarbonyl:

 The carbonyl is subjected to higher temperature so that it is decomposed giving the

pure metal:
2. van Arkel method of refining Zirconium or Titanium –
 The crude metal is heated in an evacuated vessel with iodine. The metal iodide
being more covalent, volatilises:
Zr + 2I2 → ZrI4
 The metal iodide is decomposed on a tungsten filament, electrically heated to about
1800K. The pure metal is thus deposited on the filament.
ZrI4 → Zr + 2I2

(f) Chromatographic methods: When a mixture of two or more components is allowed

to move through an adsorption column, the different components are adsorbed at
different levels on the column. These adsorbed components are removed using a suitable
eluant. Mixture of lanthanoids are separated using this technique.

Uses of Aluminium, Copper, Zinc and Iron

Aluminium
 Aluminium foils are used as wrappers for chocolates.
 The fine dust of the metal is used in paints and lacquers. Aluminium, being highly
reactive, is also used in the extraction of chromium and manganese from their
oxides.
 Wires of aluminium are used as electricity conductors.
 Alloys containing aluminium, being light, are very useful.

Copper
 Copper is used for making wires used in electrical industry and for water and
steam pipes.
 It is also used in several alloys that are rather tougher than the metal itself, e.g.,
brass (with zinc), bronze (with tin) and coinage alloy (with nickel).

Zinc
 Zinc is used for galvanising iron.
 It is also used in large quantities in batteries, as a constituent of many alloys, e.g.,
brass, (Cu 60%, Zn 40%) and german silver (Cu 25-30%, Zn 25-30%, Ni 40–
50%).
 Zinc dust is used as a reducing agent in the manufacture of dye-stuffs, paints, etc.
Iron
 Cast iron, which is the most important form of iron, is used for casting stoves,
railway sleepers, gutter pipes, toys, etc.
 It is used in the manufacture of wrought iron and steel.
 Wrought iron is used in making anchors, wires, bolts, chains and agricultural
implements.
 Steel finds a number of uses. Alloy steel is obtained when other metals are added
to it.
 Nickel steel is used for making cables, automobiles and aeroplane parts, pendulum,
measuring tapes, chrome steel for cutting tools and crushing machines, and
stainless steel for cycles, automobiles, utensils, pens, etc

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