• Class 12 Chemistry Isolation of Elements

• Understanding the Terms Minerals & Ores

• Mineral word is derived from the word ‘Mine’.
• The naturally occurring substances in the form of which the metals occur in the earth crust are
called minerals.
• Every mineral is not suitable for the extraction of the metal.
• The mineral from which the metal is economically and conveniently extracted is called an ore.
• Thus, all ores are minerals but all minerals are not ores.
• Impurities associated with ores are called gangue or matrix.

• The extraction and isolation of metals from ores involve the following major steps:
• Concentration of the ore,
• Isolation of the metal from its concentrated ore, and
• Purification 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
• Earth crust is the source of many elements. Out of these elements, 70% are metals. Aluminium
is the most abundant metal of earth crust and iron comes second.
• The percentage of different elements in earth crust is:-
• O-49%, Si-26%, Al-7.5%, Fe-4.2%, Ca-3.2%, Na-2.4%, K-2.3%, Mg-2.3%, H-l%
• Metals occur in two forms in nature:-
• In native state
• In combined state, depending upon their chemical reactivities.
Native State
Elements which have low chemical reactivity or noble metals having least electropositive character are
not attacked by oxygen, moisture and CO2 of the air. These elements, therefore, occur in the Free State
or in the native state, e.g., Au, Ag, Pt, S, O, N, noble gases, etc.
Combined State
Highly reactive elements such as F, CI, Na, K, etc., occur in nature combined form as their compounds
such as oxides, carbonates sulphides, halides, etc.
Hydrogen is the only non-metal which exists in oxidised form only.

Extraction & Isolation of Metals

Following are the steps involved in extracting the metal, then isolating the impure metal from the ore
and finally purify the metal.
 
• Concentration of the Ore: - The first step is to remove the impurities from the ore and it does
not involve any chemical process. It is based on the difference between the physical properties
of the metal and the unwanted particles.
 
Following are the physical processes involved:-
1. Hydraulic Washing
2. Magnetic separation
3. Froth Flotation Method
4. Leaching
 
• Isolation of the metal from its concentrated ore: - This process involves of getting impure
metal from its concentrated ore. It is a chemical process.
Following are the processes involved:-
1. Conversion of oxide (Calcination & Roasting) & Reduction to form metal.
2. Electrochemical Process
3. Oxidation reduction
 
• Purification of the metal: - It involves the purification of the metal.
Following are the processes involved:-
1. Distillation
2. Liquation
3. Electrolysis
4. Zone refining
5. Vapour phase refining
6. Chromatographic methods
 
Concentration of ores: -
1. Benefaction: - Removal of the unwanted materials (e.g., sand, clays, etc.) from the ore is known
as concentration, dressing or benefaction. It involves several steps and selection of these steps
depends upon the differences in physical properties of the compound of the metal present and
that of the gangue.
2. Hydraulic Washing: - This method is based on the differences in gravities of the ore and the
gangue particles. The process by which lighter earthy impurities are removed from the heavier
ore particles by washing with water is called levigation. The lighter impurities are washed away.
 This method is commonly used for oxide ores such as haematite, tin stone and native ores of
Au, Ag, etc.

1. Magnetic Separation: - This method 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
is carried on a conveyer belt which passes over a magnetic roller.

1. Froth Flotation Method: - In this method is use to remove gangue from sulphide ores. In this
process, a suspension of the powdered ore is made with water. This method is based on the
preferential wetting of ore particles by oil and that of gangue by water .As a result the ore
particles become light and rise to the top in the form of froth while the gangue particles become
heavy and settle down. Thus adsorption is involved in this method.
Working of Froth Flotation Method
1. It contains Collectors (e. g., pine oils, fatty acids, xanthates, etc.) which will enhance the non-
wettability of the mineral particles and froth stabilisers (e. g., cresols, aniline) as a result it
stabilises the froth.
2. The mineral particles become wet by oils while the gangue particles by water. A rotating paddle
agitates the mixture and draws air in it. As a result, froth is formed which carries the mineral
particles. The froth is light and is skimmed off. It is then dried for recovery of the ore particles.
3. 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.
 1. Leaching: - Leaching is often used if the ore is soluble in some suitable solvent.
Following are the examples to explain the process of leaching.
(a) Leaching of alumina from bauxite :-
The principal ore of aluminium, bauxite, usually contains SiO2, iron oxides and titanium oxide (TiO2)
as impurities.
Concentration is carried out by digesting the powdered ore with a concentrated solution of NaOH at
(473 – 523) K and (35 – 36) bar pressure.
This way, Al2O3 is leached out as sodium aluminate (and SiO2 too as sodium silicate) leaving the
impurities behind:
Al2O3(s) + 2NaOH (aq) + 3H2O (l) → 2Na [Al (OH) 4]( aq)

The aluminate in solution is neutralised by passing CO2 gas and hydrated Al2O3 is precipitated. At this
stage, the solution is seeded with freshly prepared samples of hydrated Al2O3 which induces the
precipitation
2Na [Al (OH) 4] (aq) + CO2 (g) → Al2O3.xH2O(s) + 2NaHCO3 (aq)

The sodium silicate remains in the solution and hydrated alumina is filtered, dried and heated to give
back pure Al2O3:

Al2O3.xH2O(s) → Al2O3(s) + xH2O (g) (Temp at 1470K)

(b) Other examples

In the metallurgy of silver and that of gold, the respective metal is leached with a dilute solution of
NaCN or KCN in the presence of air (for O2) from which the metal is obtained later by replacement:

4M(s) + 8CN– (aq) + 2H2O (aq) + O2 (g) → 4[M (CN) 2] – (aq) + 4OH– (aq)

(M= Ag or Au)

2[M (CN) 2] – (aq)] + Zn(s) → [Zn (CN) 4]2-(aq) + 2M(s)

Extraction of Crude Metals from Concentrated Ore
The concentrated ore is usually converted to oxide before reduction, as oxides are easier to reduce.
Thus, isolation of crude metal from concentrated ore involves two major steps:
1. Conversion to oxide.
2. Reduction of the oxides to metal.
 Conversion to oxide
• Calcination: - It is the process of converting an ore into its oxides by heating it strongly, below
its melting point in a limited supply of air or in absence of air.
During calcination, volatile impurities as well as organic matter and moisture are removed.
• Fe2 O3 x H2O (∆) → Fe2 O3 (s) + x H2 O (g)
• ZnCO3 (s) (∆) → ZnO(s) + CO2 (g)
• Roasting: - In roasting, the ore is heated in a regular supply of air in a furnace at a temperature
below the melting point of the metal. This process is commonly used for sulphide ores and is
carried out in blast furnace or reverberatory furnace. Roasting helps to remove the non-metallic
impurities and moisture.
Some of the reactions involving sulphide ores are:
• 2ZnS + 3O2 → 2ZnO + 2SO2
• 2PbS + 3O2 → 2PbO + 2SO2
• 2Cu2S + 3O2 → 2Cu2O + 2SO2

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

• (Slag)
• Meaning of slag: - During metallurgy, ‘flux’ is added which combines with ‘gangue’ to form
‘slag’. Slag separates more easily from the ore than the gangue. This way, removal of gangue
becomes easier.
 Reduction of oxide to the metal
• The roasted or the calcined ore is then converted to the free metal by reduction. Reduction
method depends upon the activity of metal.
• Metals which are low in the activity series (like Cu, Hg, and Au) are obtained by heating their
compounds in air: metals which are in the middle of the activity “cries (like Fe. Zn, Ni, Sn) are
 obtained by heating their oxides with carbon while metals which are very high in the activity
series (e.g., Na, K, Ca, Mg, Al) are obtained by electrolytic reduction method.
• Using the concepts of thermodynamics will help us to know the metallurgical transformations.
• Gibb’s Energy:- The change in Gibbs energy i.e. ∆G = ∆H - T∆S equation(A)
Where, ΔH is the enthalpy change and ΔS is the entropy change for the process.

• This equation can also be written as:- ΔG(-) = – RTlnK equation(1)

Where, K is the equilibrium constant of the ‘reactant – product’ system at the temperature, T. A
negative ΔG implies a +ve K in equation (1).
• Following conclusions can be made:-
• When the value of ΔG is negative in equation (A), only then the reaction will proceed.
• If reactants and products of two reactions are put together in a system and the net ΔG of the two
possible reactions is –ve, the overall reaction will occur.
• During reduction, the oxide of metal decomposes:
MxO(s) à xM (solid or liquid) + (1/2) O2 (g)   Equation (2)

The reducing agent takes away the oxygen. Equation (2) is the reverse of the oxidation of the metal.
And then, the Δf G (-) value is written in the usual way: xM(s or l) + (½) O2 (g) → MxO(s) [ΔG (-) (M,

MxO)] equation (B)

• If reduction is being carried according to equation(2), the oxidation of the reducing agent(e.g. C
or CO) will be:-
• C(s) + (1/2) O2(g) → CO (g) [ΔG(-) (C,CO)]   equation (3)
• CO(s) + (1/2) O2(g) → CO2 (g) [ΔG(-) (C,CO)]  equation(4)
• If carbon is taken, there may also be complete oxidation of the element to CO2:
• (1/2) C(s) + (1/2) O2(g) → (1/2) CO2(g) [(1/2) ΔG(C,CO2)]   equation(5)
• On subtracting equation (B) from one of the three equations (3, 4 or 5).
• MxO(s) + C(s) → xM(s or l) + CO(g)
• MxO(s) + CO(g) → xM(s or l) + CO2(g)
• MxO(s) + (1/2) C(s) → xM(s or l) +( ½) CO2(g) equation(8)
• These reactions describe the actual reduction of the metal oxide, Mx

 Extraction of Iron from oxide

• Oxide ores of iron, after concentration through calcination/roasting (to remove water, to
decompose carbonates and to oxidise sulphides) are mixed with limestone and coke and fed into
a Blast furnace from its top. In this case, the oxide is reduced to the metal.
• One of the main reduction steps in this process is:
• FeO(s) + C(s) → Fe(s/l) + CO (g)
 • Consider the above reaction as 2 simpler reactions, in One reduction of FeO takes place and in
another C is being oxidised to CO:
• FeO(s) → Fe(s) +( ½) O2(g) [ΔG(FeO, Fe)] equation (C)
• C(s) + (1/2) O2 (g) → CO (g) [ΔG (C, CO)]
• When both the reactions take place to yield the equation (8),
The net Gibbs energy change becomes:
ΔG (C, CO) + ΔG (FeO, Fe) = ΔrG equation (9)

• The resultant reaction will take place if RHS of the equation (9) is negative.
• In ΔG (-) vs T plot representing reaction by equation (C), the plot goes upward and that
representing the change C→CO (C, CO) goes downward.
• At temperatures above 1073K (approx.),
• The (C, CO) line comes below the Fe, FeO line [ΔG (C, CO) < ΔG (Fe, FeO)].
• So in this range, coke will be reducing the FeO and will itself be oxidised to CO.
• In a similar way the reduction of Fe3O4 and Fe2O3 at relatively lower temperatures by CO can
be explained on the basis of lower lying points of intersection of their curves with the CO, CO2

 
(Graph 1)  Gibbs energy (ΔGV) vs T plots (schematic) for formation of some oxides (Ellingham
diagram)
Blast Furnace
 
• In the Blast furnace, reduction of iron oxides takes place in different temperature ranges.
• Hot air is blown from the bottom of the furnace and coke is burnt to give temperature upto
about 2200K in the lower portion itself.
• The burning of coke therefore supplies most of the heat required in the process. The CO and
heat moves to upper part of the furnace.
• In upper part, the temperature is lower and the iron oxides (Fe2O3 and Fe3O4) coming from the
top are reduced in steps to FeO.
• Thus, the reduction reactions taking place in the lower temperature range and in the higher
temperature range, depend on the points of corresponding intersections in the ΔrG(-) vs T plots.
• Following are the reactions which are taking place:-
• At 500 – 800 K (lower temperature range in the blast furnace)–
• 3Fe2O3 + CO → 2 Fe3O4
• Fe3O4 + 4 CO → 3Fe + 4CO2
• Fe2O3 + CO → 2 FeO + CO2

 
 • At 900 – 1500 K (higher temperature range in the blast furnace):
• C + CO2 à 2 CO
• FeO + CO à Fe + CO2

Products formed in Blast Furnace

• Limestone is also decomposed to CaO which removes silicate impurity of the ore as slag. The
slag is in molten state and separates out from iron.
• The iron obtained from Blast furnace contains about 4% carbon and some other impurities. This
iron 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 reverberatory furnace lined with haematite.
• This haematite oxidises carbon to carbon monoxide:
• Fe2O3 + 3 C → 2 Fe + 3 CO
• Limestone is added as a flux and sulphur, silicon and phosphorus are oxidised and
passed into the slag. The metal is removed and freed from the slag by passing through
rollers.

Extraction of copper from cuprous oxide [copper [I] oxide]

• Considering the Graph (1) the Cu2O line is at the top.
• So to reduce oxide ores of copper directly to the metal by heating with coke (both the lines of C,
CO and C, CO2 are at much lower positions in the graph particularly after 500 – 600K).
• Most of the ores are sulphide and some may also contain iron. 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
• In actual process, the ore is heated in a reverberatory furnace after mixing with silica. In the
furnace, iron oxide ‘slags of’ as iron silicate and copper is produced in the form of copper
matte. This contains Cu2S and FeS.
• FeO + SiO2 → FeSiO3 (Slag)
• Copper matte is then charged into silica lined convertor.
• Some silica is also added and hot air blast is blown to convert the remaining
• FeS2, FeO and Cu2S/Cu2O to the metallic copper.
• Following reactions take place:
• 2FeS + 3O2 → 2FeO + 2SO2
 • FeO + SiO2 → FeSiO3 (6.38)
• 2Cu2S + 3O2 → 2Cu2O + 2SO2
• 2Cu2O + Cu2S → 6Cu + SO2
• The solidified copper obtained has blistered appearance due to the evolution of
SO2 and so it is called blister copper.

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.
• ZnO + C → Zn + CO (where coke is the catalyst, and temperature is 673 K)
• The metal is distilled off and collected by rapid chilling.

Electrochemical Principles of Metallurgy

• In the reduction of a molten metal salt, electrolysis is done.
• Consider the equation:-
• ΔG(0) = – nE(-)F equation (1)
• n= number of electrons and E(-) = electrode potential of redox couple formed in the
system.
• More reactive metals have large negative values of the electrode potential.
• This implies their reduction is very difficult.
• If the difference of two E(-) values corresponds to a positive E(-)  and consequently negative
ΔG(0)  in equation (1) .
• As a result then the less reactive metal will come out of the solution and the more reactive metal
will go to the solution.
• For example:- Cu2+ (aq) + Fe(s) → Cu(s) + Fe2+ (aq)
• In simple electrolysis, the Mn+ ions are discharged at negative electrodes (cathodes) and
deposited there. Sometimes a flux is added for making the molten mass more
conducting.
Aluminium
• In the metallurgy of aluminium, purified Al2O3 is mixed with Na3AlF6 or CaF2 which lowers
the melting point of the mix and brings conductivity.
• The fused matrix is electrolysed.
• Steel cathode and graphite anode are used. The graphite anode is useful here for reduction to the
metal.
• The overall reaction may be taken as:
• 2Al2O3 + 3C → 4Al + 3CO2
 • This process of electrolysis is widely known as Hall-Heroult process.
• The electrolysis of the molten mass is carried out in an electrolytic cell using carbon electrodes.
The oxygen liberated at anode reacts with the carbon of anode producing CO and CO2.
• This way for each kg of aluminium produced, about 0.5 kg of carbon anode is burnt away.
• The electrolytic reactions are:
• Cathode: Al3+ (melt) + 3e– → Al(l)
• Anode: C(s) + O2– (melt) → CO(g) + 2e–
• C(s) + 2O2– (melt) → CO2 (g) + 4e-

Refining

• 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.
• Following are the methods used to refine the metals:-
• Distillation
• Liquation
• Electrolysis
• Zone refining
• Vapour phase refining
• Chromatographic methods
 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 can be made to flow on a sloping surface. In this
way it is separated from higher melting impurities.
(c) Electrolytic Refining
• In this method 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.
• The more basic metal remains in the solution and the less basic ones go to the anode mud.
• The reactions are:
• Anode: M → Mn+ + ne–
• Cathode: Mn+ + ne– → M
• This method is used to refine Copper, Zinc etc.
• In case of copper refining-
• Anodes are of impure copper and pure copper strips are taken as cathode.
 • The electrolyte is acidified solution of copper sulphate and the net result of electrolysis
is the transfer of copper in pure form from the anode to the cathode:
• Anode: Cu → Cu2+ + 2 e–
• Cathode: Cu2+ + 2e– → Cu
• Impurities from the blister copper deposit as anode mud which contains antimony,
selenium, tellurium, silver, gold and platinum; recovery of these elements may meet the
cost of refining.
(d) Zone refining
• This method is based on the principle that the impurities are more soluble in the molten form as
compared to 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 crystallises 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.

• Vapour Phase Refining

• The metal is converted into its volatile compound and collected elsewhere. It is then
decomposed to give pure metal.
• There are 2 requirements for this method:-
• The metal should form a volatile compound with an available reagent,
• The volatile compound should be easily decomposable, so that the recovery is easy.
• For example: - Mond Process for Refining Nickel and van Arkel Method for Refining
Zirconium or Titanium.
• Chromatographic method
• The principle of this method is 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.
• The adsorbed components are removed or eluted by using suitable solvents (eluant).
• Depending upon the physical state of the moving medium and the adsorbent material and also
on the process of passage of the moving medium, the chromatographic method is given the
name.
 • The Al2O3 is prepared in a glass tube and the moving medium containing a solution of the
components is in liquid form. This is an example of column chromatography.
• There are several chromatographic techniques such as paper chromatography, column
chromatography, gas chromatography, etc.
Uses of Aluminium, Copper, Zinc & Iron
Aluminium
1. Aluminium foils are used as wrappers for chocolates.
2. The fine dust of the metal is used in paints and lacquers.
3. 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.
4. Alloys containing aluminium, being light, are very useful.
Copper
1. Copper is used for making wires used in electrical industry and for water and steam pipes.
2. 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
1. 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%).
2. Zinc dust is used as a reducing agent in the manufacture of dye-stuffs, paints, etc.
 
Iron
1. 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.
2. Wrought iron is used in making anchors, wires, bolts, chains and agricultural implements.
3. Steel finds a number of uses. Alloy steel is obtained when other metals are added to it.
4. 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.