6 - General Principles and Processes of Isolation of Elements

Objectives
The students will be able to
Define the important terms involved like mineral, ore, concentration of ore, calcinations etc

Outline different methods of concentrating ores

Explain reduction of metal oxides to get metals

Explain the thermodynamic principles involved in reduction of meta oxides

Describe extraction of iron from haematite in a blast furnace

Apply principle of electrochemistry in extraction

Explain extraction of aluminium

Describe different methods of refining metals
Introduction
Metals occur in nature sometimes in free or native state, but most of these occur in nature in the form of chemical combination. The earthy impurities such as
sand, clay, rocks etc. associated with ore are collectively known as gangue or matix. Large number of metal in nature occur in the combined form along with
other elements, but some metals, such as Ag, Au, Pt etc. Occur in the native form (metallic state) in some regions. The natural material in which the metal or
their compounds occur in the earth is known as mineral. The natural material in which the metal or their compounds occur in the earth is known as mineral. A
mineral may be a single compound or a complex mixture of varois compounds. Thus all ores are minerals, but all mineral are not ores. A mineral from which a
metal can be profitably extracted is called an ore. Hence bauxuite is an ore of aluminium. while clay is a mineral. The extraction and isolation of metals from
ores involve the following major steps
Concentration of the ore

Isolation of the metal its concentrated ore, and

Purificataion of the metal
The entire scientific and technological process used for isolation of the metal from its ores is known as metallurgy




Occurrence of Metals
We know that "elements are the building units of the universe". It is believed to have over 92
different kinds of elements exist in nature. A number of new elements have been prepared in
the laboratory by artificial means during the course of nuclear research and the total number
of elements known at the present time is 104. The importance of an element does not depend,
however, on its abundance. For example, carbon, which occurs to the extent of only 0.2% of
the total is extremely important for life on earth.
Minerals are the various compounds of metals, which occur in nature and are obtained by
mining are called minerals. Ores are minerals from which metals can be conveniently and
economically extracted. Haematite is the ore of iron because it is used in the extraction of
iron. The unwanted impurities such as mud, stones, sand etc. which are present in the ore are
called matrix or gangue.
Metallurgy is the process of extracting metals from their ores. The following steps are usually
involved in metallurgy.

(i) preliminary treatment (concentration of ore),

(ii) reduction (extraction of the metal from the concentrated ore), and

(iii) refining of the extracted metal
The principal ores of aluminium, iron, copper and zinc are listed in the
table 6.1 below.
Table 6.1 Metals, ores and their Composition
Metal Ores Composition
Aluminium Bauxite
Kaolinite
AlO
x
(OH)
3-2x

(where 0<x<1]
Al
2
(OH)
4
Si
2
O
3

Iron Haematite

Magnetite
Siderite
Iron pyrites
Fe
2
O
3
Fe
3
O
4
FeCO
3
FeS
2

Copper Copper pyrites
Malachite
Cuprite
Copper glance
CuFeS
2
CuCO
3
.Cu(OH)
2
Cu
2
O
Cu
2
S
Zinc Zinc blende
Calamine
Zincite
ZnS
ZnCO
3
ZnO

Hydraulic Washing
In hydraulic washing, the powdered ore is added to a stream of flowing water. The lighter
particles are carried away with the flowing water, while the heavier particles of the ore are left
behind. The method makes use of the difference in densities of the ore and the impurities. It is
also called the gravity separation method

Magnetic Separation
Magnetic ores like magnetite, chromite, etc. are concentrated by the magnetic separation
method. The powdered ore is allowed to fall on the moving belt of a magnetic separator. The
magnetic ore is attracted by the magnetic roller of the separator and falls nearer, while the
non-magnetic impurities are thrown away and form a separate heap. In this way, magnetic
ores are separated from nonmagnetic gangue and become concentrated.
Liquation Method
In the liquation method, the ore is heated on the sloping floor of a furnace. The impurities,
which have a higher melting point, do not melt. The metal, in the concentrated form, flows
down because it has a lower melting point. Metal ores of tin, lead and bismuth (which have
low melting points) can be concentrated by this method.
Froth Floatation Process
The froth floatation process is generally used for concentration of sulphide ores like
ZnS (zinc blende), PbS (galena), CuFeS
2
(copper pyrites), etc. The principle of this method
is that ore particles are more readily wetted by pine oil while the gangue particles are
wetted by water.
The crushed ore is treated with pine oil (or eucalyptus oil) and water in a tank. It is then
agitated with air. A froth is formed at the top of the tank. This froth takes the ore particles
away with it. The gangue is left behind at the bottom. The froth is then collected which is
the concentrated form of the ore.
Leaching
In the leaching method, the ore is treated with a suitable reagent, an acid or alkali. The
metal ore dissolves while the impurities separate out. For example, bauxite (Al
2
O
3
.2H
2
O), an
ore of aluminium, is concentrated by treating with a hot solution of sodium hydroxide. The
amphoteric Al
2
O
3
dissolves, while the impurities remain unaffected. The filtrate is the
concentrated form of the metal (present as sodium aluminate).
Al
2
O
3
+ 2 NaOH 2 NaAlO
2
+ H
2
O
(present in impure bauxite) Sodium aluminate
(soluble)
Impurities in bauxite + NaOH No action

Reduction
After concentration, a metal ore is worked for the extraction of the metal. Usually the
concentrated ore is subjected to calcination or roasting to convert it into an oxide form,
which is then reduced to metal.
Calcination
Calcination is the process of heating a concentrated ore in a controlled supply of air, whereby
organic matter and volatile impurities are removed. Generally, carbonate, hydroxide and
hydrated oxide ores are calcined in a reverberatory furnace.
For example
calcination
CaCO
3
CaO + CO
2

calcination
CuCO
3
.Cu(OH)
2
2 CuO + CO
2
+ H
2
O
calcination
2 Fe
2
O
3
.3H
2
O 2 Fe
2
O
3
+ 3 H
2
O
Extraction of Crude Metal from Concentrated Ore
After calcination or roasting, the oxide form is reduced to the metal state. The reduction to
the metallic state is carried out depending upon the position of the metal in the reactivity
series . Metals at the bottom of the reactivity series can be obtained by heating their
compounds. For example, when cinnabar (HgS) is heated in a furnace, it is reduced to
metallic mercury.
HgS + O
2
Hg + SO
2

Cinnabar

Metals in the middle of the series like zinc, iron, nickel, tin, lead, etc. are reduced by a
chemical reducing agent like carbon or carbon monoxide.
ZnO + C Zn + CO

PbO + C Pb + CO

SnO
2
+ 2 C Sn + 2 CO
Thus, zinc oxide (ZnO), lead oxide (PbO) and tin stone (SnO
2
) are reduced with coke (C)
Reduction of haematite ore (Fe
2
O
3
) is done in a blast furnace. Near the top of the furnace,
the iron oxide is reduced to spongy iron by carbon monoxide, in the following stages:

3 Fe
2
O
3
+ CO 2 Fe
3
O
4
+ CO
2

Fe
3
O
4
+ CO 3 FeO + CO
2

FeO + CO Fe + CO
2

Some metal oxides cannot be reduced by carbon or carbon monoxide. Therefore more
powerful reducing agents like sodium, magnesium and aluminium are used for their
reduction. Thus metals like chromium (Cr) and manganese (Mn) are obtained by reduction
with aluminium powder.
Cr
2
O
3
+ 2 Al Al
2
O
3
+ 2 Cr

3 MnO
2
+ 4 Al 2 Al
2
O
3
+ 3 Mn
The metals which are high up in the reactivity series, like sodium, potassium, calcium,
magnesium, etc. cannot be obtained by the use of chemical reducing agents. Such highly
reactive metals are obtained by electrolytic reduction of their fused chlorides. For example,
sodium is obtained by the electrolytic reduction of fused sodium chloride in a 'Downs cell'.
Similarly, calcium is obtained by the reduction of fused calcium chloride.
Thermodynamic Principles of Metallurgy
We know from Thermodynamics that for any reaction the change could be explained through
the equation
G
0
= -RTlnK
where K is the equilibrium constant. In metallurgy the Ellingham diagram is used to predict
the equilibrium temperature between a metal, its oxide and oxygen. It normally consists of
plots of G
0
vs T for formation of oxides of elements. In the temperature ranges commonly
used, the metal and the oxide are in a condensed state (liquid or solid) and the oxygen
gaseous, therefore the G of the oxidation becomes smaller with higher temperature, and
thus the reaction slower. At a sufficiently high temperature, the reaction may invert, and the
oxide spontaneously reduces to metal.
If two metals are present, two equilibriums have to be considered, so that the metal
with the smaller reaction G reduces, the other oxidizes.

In industrial processes, the reduction of metal oxides is obtained using carbon, which
is available cheaply in reduced form (as coal).
Extraction of Iron from its Oxides
In the Blast furnace, reduction of iron oxides takes place in different temperature ranges.
Haematite is calcined to remove volatile impurities. The calcined ore mixed with coke (C) and
limestone (CaCO
3
) is fed into the top of a blast furnace. A blast of hot air is blown in at the
bottom of the furnace. The falling coke burns and intense heat is generated. Temperatures
around 1900
o
C are reached near the base of the furnace.
C + O
2
CO
2
+ heat

CO
2
+ C 2 CO
Carbon monoxide (CO) thus produced acts as a reducing agent and reduces iron oxides to
iron.
3 Fe
2
O
3
+ CO 2 Fe
3
O
4
+ CO
2

Fe
3
O
4
+ CO 3 FeO + CO
2

FeO + CO Fe + CO
2



Electrochemical Principles of Metallurgy
Bauxite ore (Al
2
O
3
.2H
2
O) is concentrated by treating it with a hot solution of sodium
hydroxide. The amphoteric Al
2
O
3
dissolves while the impurities remain unaffected. The filtrate
contains sodium aluminate.

Al
2
O
3
+ 2 NaOH 2 NaAlO
2
+ H
2
O
(impure) Sodium aluminate (filtrate)
Impurities in bauxite + NaOH No action
The filtrate is 'seeded' with a little freshly precipitated aluminium hydroxide, Al(OH)
3
, so that
the metal present in the solution is precipitated as pure Al(OH)
3
. It is heated to obtain pure
alumina, Al
2
O
3
.
Heat
2 Al(OH)
3
Al
2
O
3
+ H
2
O
(pure)
A mixture of pure alumina (Al
2
O
3
) and cryolite (Na
3
AlF
6
) is subjected to eletrolytic dissociation
in an electrolytic cell. Cryolite lowers the melting point of the mixture. Aluminium is obtained
at the cathode.
Aluminium
Bauxite ore (Al
2
O
3
.2H
2
O) is concentrated by treating it with a hot solution of sodium
hydroxide. The amphoteric Al
2
O
3
dissolves while the impurities remain unaffected. The filtrate
contains sodium aluminate.

Al
2
O
3
+ 2 NaOH 2 NaAlO
2
+ H
2
O
(impure) Sodium aluminate (filtrate)
Impurities in bauxite + NaOH No action
The filtrate is 'seeded' with a little freshly precipitated aluminium hydroxide, Al(OH)
3
, so that
the metal present in the solution is precipitated as pure Al(OH)
3
. It is heated to obtain pure
alumina, Al
2
O
3
.
Heat
2 Al(OH)
3


Al
2
O
3
+ H
2
O
(pure)
A mixture of pure alumina (Al
2
O
3
) and cryolite (Na
3
AlF
6
) is subjected to eletrolytic dissociation
in an electrolytic cell. Cryolite lowers the melting point of the mixture. Aluminium is obtained
at the cathode.

At the Cathode 2 Al
3+
+ 6e
-
2Al
(l)

At the Anode 6 O
2-
3O
2(g)
+ 12e
The oxygen gas, evolved at anode, reacts with carbon anodes and forms carbon dioxide gas.
C
(s)
+ O
2(g)
CO
2(g)

Thus carbon (graphite) anodes burn away and hence they must be replaced from time to time.
Oxidation Reduction

A very common example of extraction based on oxidation is the extraction of chlorine from
brine. (Chlorine is abundant in sea water as common salt).


The G
(0)
for this reaction is + 422kJ. When it is converted to E
(0)
(using G
(0)
= - nE
(0)
F), we
get E
(0)
= - 2.2V. Naturally, it will require an external e.m.f. that is greater than 2.2V. but the
electrolysis requires an excess potential to overcome some other hindering reactions. Thus, Cl
2

is obtained by electrolysis giving out H
2
and aqueous NaOH as by- products. Electrolysis of
molten NaCl is also carried out. But in that case, Na metal is produced and not NaOH.

Extraction of gold and silver involves leaching the metal with CN
-
. This is also oxidation
reaction . The metal is later recovered by displacement method.

(6.50)

(6.51)

In this reaction zinc acts as a reducing agent.
Refining of the Extracted Metal
The impure metal extracted from its ore may be refined (or purified) by one or more of the
following methods:

(i) Liquation

(ii) Electrolytic Refining

(iii) Distillation

(iv) Vapour phase refining

(v) zone Refining and

(vi) Chromotagraphic methods

(i) Liquation
In the liquation method (also used for concentrating the ore), the impure metal is heated on
the sloping floor of a furnace. The pure metal flows down (lower melting) while the impurities
(higher melting) are left behind. Low melting metals like tin, lead and bismuth are purified
are purified by this method. Low boiling metals like zinc and mercury are purified by
distillation. In this method, impure metals are heated to vaporization. The vapours are
condensed to obtain pure metals.

(ii) Electrolytic Refining
In the electrolytic method, a block of impure metal is made the anode and a thin sheet of pure
metal the cathode. The electrolytic cell contains a soluble salt of the metal as the electrolyte.
On passing electric current, the pure metal gets deposited on the cathode, through the
electrolyte. The less electropositive impurities settle down below as anode mud, while the
more electropositive impurities pass into the solution. Metals like copper, silver, gold, zinc,
nickel, etc. are purified by this method. Electrolytic refining of copper impure copper is the
anode; the pure copper is the cathode; copper sulphate solution is the electrolyte is shown in
figure.
(iii) Distillation
It is very useful for low boiling metals like zinc and mercury. The impure metal is evaporated
to obtain the pure metal as distillate.
(iv) Vapour Phase Refining
The metal is converted into its volatile compound and collected. It is then decomposed to pure
metal. Mond's process for refining nickel and van Arkel method are examples of vapour phase
refining.
Mond Process for Refining Nickel
In this process, nickel is heated in a stream of carbon monoxide forming a volatile complex,
nickel tetracarbonyl:

Ni + 4CO 330 Ni(CO)
4

The carbonyl is subjected to higher temperature so that it is decomposed giving the pure
metal:
In this process, nickel is heated in a stream of carbon monoxide forming a volatile complex,
nickel tetracarbonyl:

Ni + 4CO 330 Ni(CO)
4

The carbonyl is subjected to higher temperature so that it is decomposed giving the pure
metal:

Ni(CO)
4
Ni + 4CO

Van Arkel method
This method is based on the thermal decomposition of a metal compound. The metal like
titanium, thorium or zirconium is converted into an unstable compound, usually an iodide, and
is decomposed on a hot metal filament.

(v) Zone Refining
When an impure metal is solidified, crystals of pure metal are deposited in preference to the
impurities present which remain in molten form. Based on this principle, the zone refining
process is used to obtain metals of very high purity.
A circular heater is fitted around a rod of an impure metal and is slowly moved along the rod.
At the heated zone, the rod melts. As the heater moves along, pure metal crystallizes out of
the melt while the impurities are carried away in the molten zone to the end of the rod.

The process is repeated and after several passes, the impurities are completely swept to the
end which is finally discarded. Silicon, germanium and gallium, which are used for making
semiconductors are purified by this technique.
(vi) Chromotographic Methods
This method is based on the principle that different components of a mixture are differently
adsorbed on an adsorbent. The mixture is put in a liquid or gaseous medium which is moved
through the adsorbent. Different components are adsorbed at different levels on the column.
Later the adsorbed components are removed (eluted) by using suitable solvents (eluant).
Column chromatography is very useful for purification of the elements which are available in
minute quantities. Paper chromatography, column chromatography, gas chromatography, etc
are some of the chromatographic techniques.
Uses of Aluminium, Copper, Zinc and Iron
Many metals find a variety of uses. Copper, being a good conductor of heat and electricity, is
used in the manufacture of electrical appliances, wires, utensils, vacuum pans, calorimeters,
etc. It is also used in electroplating, electrotyping, and in making printed electronic circuits.
Aluminum is a light metal and does not get rusted. It is extensively used as building material,
for making the bodies of aeroplanes, railway coaches, etc. Being a good conductor of heat
and electricity, aluminium is used in transmission cables, household utensils, and laboratory
equipment. Finely divided aluminium powder mixed with linseed oil is used in silvery paints
and lacquiers. Aluminium foils are used as wrapping material in the food industry. The metal
is also used in the extraction of other metals from their oxides. Thus chromium (Cr) and
manganese (Mn) are obtained by the reduction of their oxides with aluminium powder.
Cr
2
O
3
+ 2Al Al
2
O
3
+ 2 Cr

3 MnO
2
+ 4Al 2 Al
2
O
3
+ 3 Mn
Aluminum powder is used in flashlight bulbs.
Zinc is used to galvanize iron for protecting the latter from rusting. It is also used as cathode
in dry cells. It is used as a constituent of many alloys . For example brass and german silver.
It is used as a reducing agent in the manufacture of paints and dye-stuffs.
Pig iron is used for preparing objects like pipes, stoves and hot water radiator. Wrought iron
is used to make electromagnets. It is also used in ornamental works. Cast iron which is the
important form of iron is used for casting stoves, railway sleeper, toys etc. Nichrome an alloy
of iron consists of iron 25%, nickel 60% and chromium 15%. It melts at very high
temperature. So it is used as resistance coils in electric heaters. Alnico another alloy of iron
consists of iron 50%, aluminum 20%, nickel 20% and cobalt 10%. This is strongly magnetic.
It is used to make strong permanent magnets