METALLURGY

The compound of a metal found in nature is called a

mineral. The minerals from which metal can be
economically and conveniently extracted are called ores.
Hence all minerals are not ores but all ores are minerals.
Ores may be classified mainly into following four classes.
(a) Native ores
Which contain the metal in Free State and are
found in the association of rock or alluvial
impurities like clay, sand etc. Silver, gold,
platinum etc, occur as native ores.
(b) Oxidised ores:
These ores consist of oxides or oxysalts (e.g.
carbonates, phosphates, sulphates and silicates) of
metals.
Oxidised ores: Haematite (Fe 2 O 3 ), Bauxite
(Al 2 O 3 .2H 2 O), Cassiterite (SnO 2 ) etc.
Sulphate ores: Epsom salt (MgSO 4. 7H 2 O),
Anhydride (CaSO 4 ) Anglesite (PbSO 4 ) etc.
Phosphate ores; Hydroxy apatite
[3Ca 3 (PO 4 ) 2 Ca(OH) 2 ], Chlorapatite
[3Ca 3 (PO 4 ) 2 .CaCI 2 ] etc.
Silicate ores: Asbestos or Calcium magnesium
silicate (CaSiO 3 , 3MgSiO 3 ), Talc[Mg 3 (Si 4 O10)
(OH) 2 ],
(c) Sulphurised ores:
These ores consist of sulphides of metals like
iron, lead, zinc, mercury etc.
Examples: Iron pyrites (FeS 2 ), Galena (PbS).
Zinc blende (ZnS), Cinnabar (HgS)
(d) Halide ores:
These ores consist of halides of metals
Example: Horn silver (AgCI), Carnallite
(KCI.MgCI 2 .6H 2 O), Fluorspar (CaF 2 ) etc.
Process of extraction of a metal from its ore is called
metallurgy. The following processes are employed for the
extraction of metal in the pure form.
(i) Crushing of the ore.
(ii) Dressing or concentration of the ore.
(iii) Reduction of metal oxide to free metal
(iv) Purification or refining of the metal.
removal of these unwanted useless impurities from the ore
is called dressing, concentration or benefaction of ore.
The concentration is carried out by using various physical
and chemical processes.
(A) Physical process:
(a) Gravity separation or Levigation method:
It is based on the difference in the densities of the
gangue and ore particles. In this, the powdered
ore is agitated with water or washed with a
upward stream of running water, the lighter
particles of sand, clay etc are washed away
leaving behind heavier ore particles. For this
either hydraulic classifier or Wilfley table is used.
It is used for the concentration of oxide and
native ores.
Crushed
ore
Water Riffles
Gangue with
Ore particle with water
(b) Electromagnetic separator:
It is used when either the ore or the impurities
associated with t are magnetic in nature. A
magnetic separator consists of a belt (of leather or
brass) moving over two rollers, one of which is
magnetic. When the powdered ore is dropped on
the belt at the other end, magnetic component of
the ore is attracted by the magnetic rollers and
falls near to the rollers while the non-magnetic
impurities fall farther away.
For Examples: Chromite ore (FeO.Cr 2 O 3 ) is
separated from non-magnetic silicious impurities
and cassiterite ore(SnO 2 ) is separated from
magnetic Wolframite (FeWO 4 + MnWO 4 ).

Powdered ore
(i) Crushing and Grinding: The ore is first
Electromagnets
crushed by jaw crushers and ground to a powder
by reduction equipments like ball mills and stamp
mills.

Gangue
(ii) Concentration: The ores usually contain Moving Belt

unwanted impurities like sand, clay, stones and Magnetic ore

other useless silicates. These unwanted useless
impurities are called gangue or matrix. The

Page 1
(c) Froth floatation process:
This is a very useful technique for separating
sulphide ores of zinc, copper and lead from the
gangue. A suspension of the finely powdered ore
is made with water and frothing agent called
collectors are added to it (e.g pine oils xanthates,
and fatty acids) which enhance the non-wet
ability of the mineral particles and the froth
stabilizers (e.g cresols and aniline) which
stabilize the froth.
The principle of the process is that the mineral
particles are wetted by oils and the gangue
particles by water.
A rotating paddle agitates the liquid mixture and
draws in air and causes the formation of a froth
which carries with it the mineral particles.
The light froth floats to the surface and is
skimmed off. It is allowed to collapse and dry for
recovery of ore particles.
Reagents used in froth floatation are of four type:
1. Frothers: Which create froth e.g. pine oil
2. Collectors: Which help on attachment of ore
particles to an air bubble in froth. E.g, Sodium
Xanthates
3. Activators: Simple inorganic compounds
which enhance the floating property of metal
sulphide. E.g CuSO 4
4. Depressents: Which suppress the floatation of
a particular particle selectively.
e.g; NaCN can be used as a depressant in the
separation of ZnS ore and PbS ore. NaCN acts as
a depressant for ZnS and does not prevent PbS
from the formation of the froth. Hence, the two
ores can be separated from one another.
4NaCN + ZnS  Na 2 [Zn(CN) 4 ] + Na 2 S
CN- is then destroyed by any oxidizing agent and
ZnS is floated again.
(B) Chemical Process:
(a) Calcination:
It is used for carbonate or hydrated oxide ores.
Ore is strongly heated in absence of air or a
limited supply of air below its melting point,
generally in reverberatory furnance The moisture
is removed, the volatile matter is burnt away and
the oxide of metal is obtained from carbonate ore.
ZnCO 3  ZnO + CO 2 ;
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2Fe 2 O 3 .3H 2 O  2Fe 2 O 3 + 3H 2 O;
CaCO3 → CaO + CO2
(b) Roasting:
In roasting the ore (usually the sulphide) is heated
in a regular supply of air at a temperature below
the melting point of the metal. All the
combustible organic matter burns away and the
ore becomes more porus. The metal is converted
to the oxide or sulphate.
Some times during roasting process a part of the
sulphide may act as a reducing agent in the
subsequent process/step.
2ZnS + 3O 2  2ZnO + 2SO 2
2PbS + 3O 2  2PbO + 2SO 2
PbS + 2O 2  PbSO 4
2Cu 2 S + 3O 2  2 Cu 2 O + 2SO 2
The process of roasting is generally carried out in
a reverberatory furnace.
(c) Sintering
Ore is heated till its fusion just begins. It helps in
converting small pieces of ore into bigger mass.
Most of the features are common with roasting.
(d) Leaching
The process consists in treating the powdered ore
with a suitable reagent (such as acids bases or
other chemical reagents) which can selectively
dissolve the ore but not the impurities. The ore is
recovered from the solution by a suitable
chemical method. Red bauxite an ore of
aluminium containing iron oxide and silicates as
impurities is purified by adding concentrated
solution of sodium hydroxide.
Al 2 O 3 . 2H 2 O + 2NaOH  2NaAlO 2 (soluble) +
3H 2 O
Fe 2 O 3 insoluble as red mud and, therefore
separated by filtration.
NaAlO 2 + 2H 2 O  Al(OH) 3 ↓ (white) + NaOH
Δ
2Al(OH) 3 → Al 2 O 3 + 3H 2 O
 Leaching is also used for the extraction of precious
metals like silver, gold etc by converting these metals
or there are into their soluble complexes.
4Ag + 8NaCN + O 2 + 2H 2 O  4Na[Ag(CN) 2 ] + 4NaOH
2Ag 2 S + 8NaCN  4Na[Ag(CN) 2 ] + 2Na 2 S
4Na 2 S + 5O 2 + 2H 2 O  2Na 2 SO 4 + 4NaOH + 2S
(iii) Reduction of metal oxide to free metal:
Various processes are used for the reduction of
Roasted/calcined ore to the metallic form.
(a) Chemical reduction:
(c) Displacement method / Hydrometallurgy:
(i) Carbon as a reducing agent: It is based on dissolving the metal sought in
Carbon in the form coal, coke, charcoal and aqueous solutions of acids or alkalis and
carbon monoxide acts as reducing agent and subsequent precipitation. Some metals are
reduces many metal oxides into the respective reduced by displacement by a more
metals. electropositive (i.e. reactive) metal from their
SnO 2 + 2C  
1473-1573 K
→ Sn + 2CO soluble complexes/salts.
Silver and gold are obtained from their soluble
ZnO + CO  → Zn+CO 2
1600K
cyanide complexes by displacement with more
Fe 2 O 3 + CO →
823 k
2FeO + CO 2 reactive zinc metal.
FeO + CO   
→ Fe+CO 2
1123 K
2[M(CN) 2 ]- + Zn → [Zn(CN) 4 ]2- + 2M ;
where M = Ag or Au.
(ii) Hydrogen as a reducing agent:

MoO 3 + 3H 2 → Mo + 3H 2 O; (d) Electrolytic reduction:

Highly electropositive elements of groups 1 and 2
WO 3 + 3H 2 → W + 3H 2 O
are obtained by electrolytic reduction of their
 Its use is restricted because of its inflammable nature. fused chlorides (or oxo salts are first converted in
to their chloride and then subjected to electrolytic
(iii) Aluminium as a redcing agent. (Alumino
reduction).
reduction thermic process/or Goldschmidt
This method is also used for the extraction of
thermic process).
aluminium. The fused alumina containing
Cr 2 O 3 + 2AI → AI 2 O 3 + 2Cr Na 3 AIF 6 is electrolyzed when aluminium is
3Mn 3 O 4 + 8AI → 4AI 2 O 3 + 9Mn obtained at cathode and oxygen is liberated at
anode.
(iv) Other electro positive metals as reducing agents:
 Smelting:
TiO 2 + 2Mg → Ti + 2MgO Process of extracting the metal by fusion of its oxide
TiO 2 + 4Na → Ti + 2Na 2 O with carbon or aluminium or other reducing agents.

(b) Auto-reduction  Flux:

If the roasted ore or clacined ore still contains non-
In this process the metal is obtained either by
fusible impurities of earthy matter an additional
simple roasting or by the reduction of its partly
substance called as flux is usually added during the
oxidized form.
reduction process to convert them into easily fusible
(a) From cinnabar → Mercury matter called slag.
HgS + O 2 → Hg + SO 2 Flux + Gangue → Δ
Easily fusible matter (slag)
2HgS + 3O 2 → 2HgO + 2SO 2 Slag melts at the temperature of furnace, insoluble in
molten metal, and being lighter floats over the surface
2HgO → Hg + O 2
of the molten metal, from where it can be skimmed off.
2HgO + HgS → 3Hg + SO 2
FLUX

(b) From copper glance → copper

2Cu 2 S + 3O 2 → 2Cu 2 O + 2SO 2
2Cu 2 I + Cu 2 S → 6Cu +SO 2 Acidic flux Basic flux
Silica (SiO)2 and Calcined lime stone(CaO),
(c) From Galena → lead borax(Na2B4O7) magnesite(MgO)
2PbS + 3O 2 → 2PbO + 2SO 2 Remove basic impurities such dolomite(MgO,CaO) and
as lime, basic oxides, etc haematite ore (Fe2O3) .
2PbO + PbS → 3Pb + SO 2
Remove acidic impurities
CaO + SiO2 CaSiO3
PbS + 2O 2 → PbSO 4 like SiO2, P4 O10 etc
MnO + SiO2 MnSiO3
PbS + PbSO 4 → 2Pb + 2SO 2 P2O5 + 3CaO
FeO + SiO2 FeSiO3 Ca3(PO4)2 (Thomas slag)
 A part of the sulphide ore acts as a reducing agent.
SiO2 + CaO CaSiO3

Page 3
(IV) Refining of Crude Metal (iii) Poling
U

The crude metal obtained is impure. The impure
metal is subjected to some purifying processes
known as refining in order to remove the
impurities. The processes used for refining
depend upon the nature of the metal and the
nature of impurities.
(a) Distillation
U
This process is used for those metals which are
The impure metal containing oxide as impurities
can be purified by this method. The molten
impure metal is stirred with green poles of wood.
The green poles of wood release the hydrocarbon
gases, which reduce the oxide impurities. This
method is used in purifying copper in olden
times.
(d) Electrolytic Refining
U U

easily volatile such as: Zn, Hg, Cd. The impure
meal is heated in a furnace and its vapors are
condensed in a receiver. The non-volatile
impurities are left behind in the furnace.
(b) Liquation
U
This process is based on the difference in
fusibility of metal and impurities. When the
impurities are less fusible than the metal, this
process is employed. The impure metal is placed
It is different form electrolytic reduction. The
impure metal is made anode and a thin sheet of
pure metal is made cathode. As electrolysis
proceeds, pure metal from anode is transferred to
the cathode, whereas the impurities settle down
as anodic mud or anodic sludge. For example Cu,
Ag, Au, Pb, Zu, etc. are refined by this method.
(e) Special methods for Refining
U U

on the sloping hearth of the furnace and gently

heated. The metal melts and flows down leaving (i) Mond’s Process
U U

behind the impurities on the hearth. This method It is used mainly for refining of nickel. Impure Ni
is used to purify Bi, Sn, Pb and Hg. is treated with carbon monoxide at 330K – 350K,
(c) Pyrometallurgical Oxidation
U U
when volatile compounds Ni(CO) 4 is formed. R R

This method is used when the impurities have a The impurities are left behind and the volatile
great affinity for oxygen than the metal itself. Ni(CO) 4 is transferred into another container,
R R

This method is usually employed for refining the where it is heated more strongly at 450 K to give
metals like Fe, Cu, Ag. The oxidation can be pure Ni. The CO gas produced is used again.
330 −350 K 450 K − 470 K
done by various ways. Ni + 4CO   
→ Ni(CO) 4 R R   → Ni +
(i) Cupellation
U
4CO
Impure Volatile (Pure)
Cupellation is a process used to separate noble
metals such as gold or silver from base metals
(ii) Van Arkel Method
U U

such as lead. In this process, an alloy consisting

In this method, zirconium (or titanium) is heated
of both noble and base metals is placed in a
in iodine vapor at about 870K to form volatile
crucible. This mixture is then melted and allowed
Zrl 4 . The vapors of volatile ZrI 4 are then
R R R R

to freeze. When solidified, a button consisting of

decomposed electrically over tungsten filament to
precious metals and lead can be removed from
get pure metal.
the slag of metal oxides and other materials. After
Zr + 2I 2 → ZrI 4  
→ Zr 870 K 2075 K
cooling, the metals are placed in a special pot R R R R + 2I 2
R

(Impure) (Vapors) (Pure)

made of bone ash or clay called a cupel. Under
high heat, lead turns to litharge, a lead oxide, (iii) Zone Refining
U U

which is absorbed by the cupel or lost to the This method is used for
atmosphere. At the end of the cupellation process, extracting ultra-pure
a button of pure gold and silver remains in the metals. This method is
bottom of the cupel. based upon the principle
(ii) Bessemerisation
U

that when a molten

The impure metal is heated in a furnace and a solution of impure
blast of compressed air is blown through the metal is allowed to cool,
molten mass. The impurities get oxidized. For the pure metal
example, the molten pig iron is taken in a crystallizes out, while
Bessemer converter and compressed air is passed the impurities remain in
which oxidized the impurities. the melt. A movable
2Mn + O 2 → 2MnO ; Si + O 2 → SiO 2
heater is fitted around
R R R R R

2C + O 2 → 2CO ; MnO + SiO 2 → MnSiO 3 (slag)

the rod of impure metal.
R R R R R R

The heater is slowly

moved across the rod. The metal melts at

Page 4
 movable heater is fitted around the rod of impure
metal. The heater is slowly moved across the (iii) Serpeck’s Method
rod. The impurities melts at the point of heating (used for white bauxite containing silica as
and as the heater moves on from one end of the impurities)
rod to the other end, the pure metal crystallizes Al 2 O 3 .2H 2 O + 3C +N 2 Electric furnace
while the impurities pass into the adjacent melted 2AlN + 3CO + 2H 2 O
zone. This process is repeated number of times 2AlN+3H 2 O → Al(OH) 3 ↓ + NH 3
unless metal of desired purity is obtained. The SiO 2 + 2CO → 2CO + Si
process is carried out in an inert atmosphere to
2Al(OH) 3  → Al 2 O 3 + 3H 2 O
1473K
prevent the oxidation of metal. For example,
Silicon and Gallium for being used in
semiconductors are purified by this method. (b) Electrolysis of pure fused Al 2 O 3 (Hall – Heroult
method):

Cathode: Iron tank lined in molten electrolyte.

1. Aluminium: Anode: Carbon rods dipped in molten electrolyte.
Ores:
(i) Oxides: Bauxite: Al 2 O 3 . 2H 2 O (main); Diaspore: Electrolyte: Mixture of fused alumina (2-8%),
Al 2 O 3 .H 2 O; Corundum: AI 2 O 3 cryolite (80-85%) and fluorspar (5-7%)
(ii) Silicates: Felspar : KAISi 3 O 8 ; Kaolin: Al 2 O 3 . Temperature ≈ 1000oC
Na 3 AIF 6 ⇔ 3NaF + AIF 3 → AI+3 + 3F
-
2SiO 2 .2H 2 O; Beryl: Be 3 AI 2 Si 6 O 18
(iii) Fluorides: Cryolite: Na 3 AIF 6 At cathode: AI+3 + 3e- → AI
(iv) Sulphates: Alunite or alum stone: K 2 SO 4 . At anode : 3F- → 3F + 3e-
Al 2 (SO 4 ) 3 . 4Al(OH) 3 2AI 2 O 3 + 12F → 4AIF 3 + 2O 2

O 2 → CO
(v) Phosphate: Turquaoise: AIPO 4 .AI(OH) 3 .H 2 O 1
C+
2

CO+ O 2 → CO 2
Extraction of Aluminium from Bauxite – It involves 1
following three steps 2
(a) Purification of Bauxite:

(i) Baeyer’s method

(used for red bauxite containing Fe 2 O 3
and silicates as impurities )
o
Al 2 O 3 .2H 2 O+2NaOH   →
190 C,8atm

2NaAlO 2 +3H 2 O
(Soluble)

Fe 2 O 3 is insoluble & separated as red mud by

 Cryolite and CaF 2 lower the melting point of mixture
filtration. Solution is diluted with water. and make the molten mass conducting.
It induces the precipitation of AI(OH) 3 .  Anodes are periodically changed as they are consumed
Al(OH) 3 is filtered leaving behind silicates in by oxygen liberated at anode (0.5 kg of carbon anode is
solution. burnt for 1 kg of aluminium).
NaAlO 2 +2H 2 O → NaOH + AI(OH) 3 ↓
(c) Electrolytic refining (Hoop’s process) :
2Al(OH) 3  → Al 2 O 3 +3H 2 O
1473K
lron box lined with carbon contains the three
different layers of molten liquids having different
(ii) Hall’s Method densities.
(used for red bauxite containing Fe 2 O 3 and Bottom layer: impure alumina along with carbon
silicates as impurities) lining acts as anode
Al 2 O 3 .2H 2 O+Na 2 CO 3  →
Fuse
Middle layer: mixture of fluorides of Na+,Ba2+
2NaAlO 2 + CO 2 + 2H 2 O and AI3+ acting as electrolyte.
(soluble) Top layer: pure aluminium acts as cathode.
0
2NaAlO 2 +3H 2 O+ CO 2 →
60 On passing the current aluminium ions are
2Al(OH) 3 ↓ + Na 2 CO 3 discharged at cathode from the middle layer and
an equivalent amount is taken from bottom layer
2Al(OH) 3  → Al 2 O 3 +3H 2 O
1473K
leaving behind the impurities.
Aluminium obtained is 99.98% pure.

Page 5
2. Magnesium: • It is not made anhydrous by simple heating because
Ores: it gets hydrolysed
Δ
Carnallite: MgCI 2 .KCI6H 2 O (K 2 MgCI 4 .6H 2 O)(main) ; MgCI 2 . 6H 2 O → MgO + 5H 2 O + 2HCI
Epsom salt (Epsomite) MgSO 4. 7H 2 O: (d) Electrolysis of fused anhydrous MgCI 2 :
Magnesite: MgCO 3 ;
Kiesserite MgSO 4 . H 2 O ;
Dolomite MgCO 3 . CaCO 3 [CaMg(CO 3 ) 2 ] ;
Kainite K 2 SO 4 . MgSO 4 . MgCI 2 ;
Langbeinite: K 2 Mg 2 (SO 4 ) 3
Mg is also found in talc, asbestos and chlorophyll.

(i) From Carnallite :

The ore is dehydrated in a current of hydrogen
chloride and the mixture of fused chlorides is
Magnesium chloride obtained by any of the above
electrolysed.
methods is fused and mixed with sodium chloride
and calcium chloride in the temperature range of
(ii) From Magnesite:
973 – 1023 K. The molten mixture is electrolysed.
(a) Calcination:
Magnesium is liberated at the cathode (iron pot) and
MgCO 3     → MgO + CO
Heated Strongly
2 chlorine is evolved at graphite anode.
(b) Reduction and chlorination: MgCI 2 ⇔ Mg2+ + 2CI-
Δ
MgO + C + CI 2 → MgCI 2 + CO At cathode: Mg2+ + 2e- → Mg (99% pure)
MgO + C (Other reducing agnets like Si, AI can At anode: 2CI- → Cl 2 + 2e-
o
be used)     → Mg + CO
2000 C, Vacuum

(c) Electrolyis of fused chlorides to get magnesium; A stream of coal gas is passed through the pot to prevent
Oxidation of magnesium metal. The magnesium obtained
(iii) From Dolomite: in liquid state is purified by distillation under reduced
(a) Calcination: pressure.
Δ
CaCO 3 . MgCO 3 →
3. Iron
CaO.MgO + 2CO 2
Ores:
(b) Reduction by ferrosilicon at 1273 K
Hematite Fe 2 O 3 (Main);
under reduced pressure:
Limonite Fe 2 O 3 . 3H 2 O;
2CaO.MgO + FeSi → Magnetite Fe 3 O 4 ;
2Mg + Fe + Ca 2 SiO 4 Siderite FeCO 3 ;
Iron Pyrites FeS 2
(iv) From Sea water (Dow’s process): Commercial forms of iron
Sea water contains 0.13% magnesium as chloride (a) Pig Iron: Fe ≈ 93%, C ≈ 5%, rest are impurities of
and sulphate Mn, P, Si etc. It is the impurest form and is hard
(a) Precipitation of magnesium as and brittle. It is obtained from blast furnace. It is
magnesium hydroxide by slaked lime remelted and poured into mould heir it becomes
MgCl 2 + Ca(OH) 2 → cast iron.
Mg(OH) 2 ↓ + CaCI 2 (b) Wrought Iron: C ≈ 0.15 - 0.28%. It is the purest
(b) Preparation of hex hydrated form and is malleable and fibrous.
magnesium chloride: (c) Steel : C ≈ 0.15 - 1.5% ; Alloy of Fe with other
metals like Mn, Ni, Cr.
Mg(OH) 2 + 2HCI(aq) →
Stainless steel contains 11.5% Cr and 2% Ni
MgCl 2 + 2H 2 O
The solution on concentration and crystallization
Extraction of Pig Iron from ore haematite : (Carbon
gives the crystals of MgCI 2 .6H 2 O
reduction method) It involves following steps :
(c) Preparation of anhydrous magnesium (a) Concentration: By gravity separation and
chloride:
electromagnetic separator to remove earthy and
MgCl 2 .6H 2 O   →
Dry HCI (g) silicious impurities.
MgCl 2 + 6H 2 O (b) Calcination/Roasting (in limited supply of air):
Impurities of S, P and As are removed as their

Page 6
 volatile oxides. Any FeO if present is oxidised to
Fe 2 0 3 so that it may not form slag with SiO 2 .
FeCO 3 → ∆ FeO + CO 2 ; 4FeO + O 2 → 2Fe 2 O 3
(c) Smelting: Charge consisting of calcined/roasted
ore (8 parts), lime stone (1part) and coke (4 parts)
is strongly heated with a blast of pre heated air
which is introduced in blast furnace from the
bottom through water – jacketed pipes called
tuyeres. There is a temperature gradient as we
move from the bottom (about 2000K) to the top
(about 500K) in the blast furnace. The following
changes takes place in different zones.
Zone of Combustion or Fusion
The lower portion where coke burns and produce
a lot of heat. Here temperature range is 1775 K
and following reaction occur
C+ O 2 → CO 2 + 406 KJ/mol
A little above this where temperature is about 1475 –
1575 K, iron coming from above melts.
Zone of Heat absorption
The middle portion where temperature is about 1075 K –
1275 K, CO 2 rising up is reduced to CO with the
absorption of heat.
CO 2 + C → CO
CaCO 3 → CaO + CO 2
SiO 2 + CaO → CaSiO 3
In this portion limestone coming from above is
decomposed and the resultant lime (CaO), which acts as
flux, combines with silica which is present as impurity to
form a fusible slag of calcium silicate.
Zone of Reduction
The upper portion (675 K – 975 K) where iron
oxide reduced to spongy iron by the ascending
carbon monoxide
Fe 2 O 3 + 3CO → 2Fe + 3CO 2
This occurs 3 steps
3Fe 2 O 3 + CO → 2 Fe 3 O 4 + CO 2
Fe 3 O 4 + CO → 3 FeO + CO 2
Page 7
FeO + CO → Fe + CO 2
In the top part of the furnace, the reducing agent is carbon
monoxide but at the bottom it is carbon it self. In the lower
hotter part, the main reaction is
FeO + C → Fe+ CO
This iron move down the furnace and absorbs carbon,
Silica, Sulphur etc & Settees down at the bottom of the
furnace the slag floats above iron preventing its oxidation.
These two can be removed from different holes.
Waste gases escaping at the top consist of about 30% CO,
10% CO 2 and remaining N 2 .
(d) Purification of Iron
Iron obtained from the blast furnace is known as
pig iron. Pig Iron consist about 2% - 5% carbon
and other impurities of Si, Mn, S and P.
Pig Iron is converted to cast iron by remelting it in
a vertical furnace heated by coke. Cast iron
expands on solidification and is used for casting
various articles.
Wrought iron is the purest form of iron. It is
obtained by heating cast iron is a reverberatory
furnace lined with iron oxide. Wrought iron
contains about 0.2% carbon.
Iron is purified by Hammering or Poling. In
Hammering casts iron balls are hammered when
impurities are thrown out and white shining sheets
of pure iron is obtained which is called Wrought
iron.
In Poling, molten cast iron is stirred with green
wooden logs when carbon & sulphur impurities
burn out in the form of CO 2 & SO 2
 →
Annealing-Red hot steel CoolSlow
it becomes soft
Hardening - Red hot steel cool
   →
suddenlyby H O 2
brittle and hard
Quenching –
Red hot (bright) steel Coolsudden
  →
lyby H2O or oil
extremely hard and brittle
Tempering - Heating the quenched steel to a
temperature below redness and then cool slowly,
during this a thin film of oxide is formed on the
surface of steel - neither so hard nor so brittle.
4. Tin:
Ores :
Cassiterite or Tin stone: SnO 2 (main); It contains 10% SnO 2
and rest impurities of pyrites of copper and iron and
wolframite which is a mixture of FeWO 4 + MnWO 4 . This
mineral is also called black tin to distinguish it from the
metal Sn which is also called white tin.
Stannite; CuS.FeS.SnS 2
Extraction of tin from Cassiterite: (Carbon Reduction 5. Copper:
Method) It involves following steps. Ores:
Copper pyrites or Chalcopyrites: CuFeS 2 (main); R R

(a) Purification:
U

Cuprite or Ruby copper: Cu 2 O; R R

(i) Crushing and concentration: Malachite: CuCO 3 Cu(OH) 2 ; R R R R

The ore (cassiterite contains 10% of the metal as Azurite: 2CuCO 3 .Cu(OH) 2 ; R R R R

SnO 2 ) is crushed and washed with a stream of

R R

Copper glance: Cu 2 S ; R R

running water to remove the lighter earthy and Bornite or Peacock ore: Cu 5 FeS 4 . R R R R

silicious impurities.
(ii) Electromagnetic separation: Extraction of copper from copper pyrites: It involves
To remove the magnetic impurity of Wolframite. following steps
(iii) Roasting: (a) Crushing and concentration: Ore is crushed and
U U

Concentrated ore is heated in presence of air, when then powdered finely powdered ore is
volatile impurities (S as SO 2 , As as As 2 O 3 and Sb R R R R R R

concentrated by froth floatation process.

as Sb 2 O 3 ) are removed. The impurities of pyrites
R R R R

of copper and iron are converted into their (b) Roasting: Concentrated ore is heated in excess of
U U

respective oxides and sulphates air in a reverberatory furnace.

CuS + 2O 2 → CuSO 4 ; R R R R

2CuFeS + O → Cu S + 2FeS + SO ↑ ; R
2 R R
2 R R
2 R R
2
R

FeS + 2O 2 → FeSO 4
2FeS + 3O 2 → 2FeO + 2SO 2 ↑
P P

R R R

R R P P R R

(iv) Leaching:
2Cu S + 3O → 2Cu O + 2SO ↑
2 2 2 2
Sulphates of copper and iron are dissolved in water.
R R R R R R R R

P P

Impurities are removed as their volatile oxides.

(v) Washing:
The ore is washed with running water to remove S + O → SO ↑ ; R
2
R R
2 R

4P + 5O 2 → 2P 2 O 5 ↑
P P

the finer iron oxide produced in roasting. R R R R R R

4As + S O 2 → 2As 2 O 3 ↑ ;
P P

The ore thus obtained contains 60 - 70% SnO 2 R R

R R R R R R

4Sb + 3O → 2Sb O ↑
P P

and is called as black till. R

2 R R
2 R R
3 R

P P

(b) Smelting :
U U

(c) Smelting:
U U

The black tin is mixed with anthracite coal and Roasted ore mixed with coke and sand is strongly
heated to about 1500K in a reverberatory furnace. heated in a blast furnace.
If SiO 2 is present as impurity then CaO is added
R R

FeO + SiO 2 (flux) → FeSiO 3 (slag)

Cu 2 O+ FeS → Cu 2 S + FeO ;
R R R R

P P

as flux.
SnO + 2C → Sn + 2CO ↑ FeO + SiO → FeSiO
R R R R

P P

R
2 R
R
2
R R
3 R

SnO 2 + C → SnO + CO ↑
P P
P P

Upper layer containing slag is removed from the

SnO + SiO 2 → SnSiO 3
R R

P P

tapping given and lower layer contains mostly

CaO + SiO → CaSiO
R R R

P P

R
2 R R
3 Cu 2 S with little FeS is called matte.
R R

SnSiO 3 + CaO + C → Sn + CaSiO 3 + CO ↑

P P

R R R R
In recent years after roasting in reverberatory
P P

or use scrap iron furnace, the temperature is increased above the

SnSiO 3 + Fe → Sn + FeSiO 3
R R

P P
R
fusion point and lime stone or silica is added. Iron
oxide is separated as iron silicate.
(c) Refining :
U

(i) Liquation and poling: (d) Bessemerisation (Self-reduction):

U

Impure tin is melted on the sloping hearth of a Matte is charged in to a silica-lined converter,
reverberatory furnace where tin (m.pt. 232°C) is through which hot compressed air is blown.
the first to melt and flows out leaving behind the 2FeS+3O 2 → 2FeO + 2SO 2
FeO + SiO2 → FeSiO 3 (slag)
R R R

P P

less fusible impurities of Cu, Fe, W etc. The liquid

2Cu 2 S + 3O 2 → 2Cu 2 O + 2SO 2
R R

P P

tin is then stirred with poles of green wood to

Cu S + 2Cu O → 6Cu (blister copper) + SO
R R R R R R R R

P P

reduce SnO 2 (if any) to tin. R R

R
2 R R
2 R

P P
R
2
(ii) Electrolytic refining The molten copper is taken into moulds and on
Anode: Impure tin cooling, sulphur dioxide, nitrogen and oxygen
Cathode: Pure tin escape from the metal giving the surface blistered
Electrolyte: H 2 SiF 6 + SnSO 4 + H 2 SO 4 R R R R R R R R R
appearance and thus it is called as blister copper.

Page 8
(e) Poling : 7. Silver:
Molten Cu is stirred with poles of green wood to Ores:
reduce any copper oxide into Cu. Silver glance or argentite: Ag 2 S (main),
Ruby Silver or pyrargyrite: Ag 3 SbS 3 ;
(f) Electrolytic refining: Horn silver or chlorargyrite: AgCI,
Anode: Impure Cu Cathode: Pure Cu Stefinite: Ag 5 .SbS 4 ;
Electrolyte: CuSO 4 + H 2 SO 4 . Proustite: Ag 3 AsS 3
The more electropositive impurities like Zn, Fe, Ni
etc. get dissolved in solution and less positive Extraction of silver from silver glance: It involves
impurities like Ag, Au, Pt, Te, Se etc. collect below following steps.
the anode as anode mud. (a) Crushing and concentration: The ore is crushed,
powdered finely and concentrated by froth
6. Lead: floatation process.
Ores: (b) Treatment with 0.4-0.7% sodium cyanide
Galena: PbS (main),
solution in presence of air or oxygen bubbling
Anglesite: PbSO 4,
(cyanide process) :
Cerussite: PbCO 3
Ag 2 S(conc.ore)+2NaCN → 2AgCN+Na 2 S.
Air

4Na 2 S + 5O 2 + 2H 2 O → 2Na 2 SO 4 + 4NaOH + 2S

Extraction of lead from galena: It involves following
steps. Na 2 S is converted in to Na 2 SO 4 . Hence
(a) Crushing and concentration: The ore is crushed, equilibrium shifts towards right side.
AgCN + NaCN → Na[Ag(CN) ] (soluble complex)
2
powdered finely and concentrated by froth
floatation process.
(c) Precipitation of silver by zinc dust (more
(b) Roasting : In reverberatory furnace in a limited
electropositive elements :
supply of air at moderate temperature
2Na[Ag(CN) 2 ]+Zn(dust) → 2Ag ↓ +Na 2 [Zn(CN) 4 ].
PbS + 2O 2 → PbSO 4
PbS + 3O → 2Pb + 2SO • The silver is filtered, washed, melted with a
2 2
flux of KNO 3 to oxidize away any excess of
(c) Smelting (Self reduction): Supply of air is cut off
Zn.
and the temperature is increased to melt the charge
in reverberatory furnace. (e) Electrolytic refining:
PbS + 2PbO → 3Pb + 2SO 2 Anode: Impure Ag
PbS + PbSO 4 → 2Pb + 2SO 2
Cathode: Pure Ag;
SiO 2 + CaO (flux) → CaSiO 3 (slag)
Electrolyte: AgNO 3 (aq) + HNO 3 .
PbSiO + CaO → PbO + CaSiO (slag)
3 3

 To get silver from commercial lead

 CaO prevents the formation of PbSiO 3 . (argentiferous lead) by Prake's process
 Lead can also be obtained by reduction of PbO (Desilverisation of lead)
(obtained after roasting of galena in a limited supply of
air) by heating with coke and lime stone (flux) in a blast Lead extracted from galena (PbS) contains impurities of Cu,
furnace. Ag, Bi, As, Fe, Zn, Sn etc. and is called commercial, lead or
2PbS+3O 2 → 2PbO + 2SO 2 argentiferous lead. This contains Ag up to 2% which is
PbO + C → Pb + CO extracted by Parkes process.
PbO + CO → Pb + CO 2
Commercial lead is mixed with a little quantity of Zn and
(d) Electrolytic refining (Bett’s Method): the mixture is melted, where Zn-Ag alloy is formed and Pb
Anode: Impure Pb; remains in the molten state. Zn-Ag alloy being lighter
Cathode: Pure Pb; comes on the surface and gets crystallized (higher melting
Electrolyte: PbSiF 6 + H 2 SiF 6 + gelatine point). The alloy is strongly heated where Zn is distilled
On passing the current, pure Pb is deposited on off leaving Ag. This silver contains some Pb which is
cathode. removed by cupellation process. Impure Ag is melted in a
cupel (a boat shaped dish made of bone ash) in reverberatory
Parkes Process: furnace in presence of air. Pb is oxidised to PbO (litharge)
Fuse Pb with Zn. Ag is more soluble in molten Zn than in Pb which is either absorbed by cupel or carried away by blast
and forms Zn-Ag alloy which is lighter, therefore, comes on of air leaving Ag.
the surface and gets crystallized (alloy has higher melting
point).

Page 9
 To get silver from a silver coin or silver (ii) Parting process:
ornaments: Au thus obtained is boiled with conc. H 2 SO 4 or
Coin dissolve
  → AgNO 3 + Cu(NO 3 ) 2
in conc.HNO
HNO 3 where impurities go into the solution
3
leaving Au as a brown powder which contains
heat
     → AgCI (ppt)
to remove excessHNO 3 about 0.002% Ag. This is washed with HNO 3 and
andaddHCI
then with H 2 O.
4AgCI + 2Na 2 CO 3  → Cu + 2H 2 SO 4 → CuSO 4 + SO 2 + 2H 2 O
Fuse
(i)
4 Ag + 4NaCl + 2CO 2 + O 2 2Ag + 2H SO → AgSO + SO + 2H O
2 4 4 2 2
(ii) Boils with caustic soda and glucose: If the % of Au in the impure sample is more than
2AgCl + 2NaOH →
30%, the sample is not attacked by the acid, then
Ag 2 O+ 2NaCl + H 2 O it is made 25% by adding more silver.
Ag 2 O + C 6 H 12 O 6 →
(iii) Electrolytic refining:
2Ag + C 6 H 12 O 7
Anode: Impure Au Cathode: Pure Au
The silver thus obtained is purified by fusion with borax
Electrolyte: 4%AuCl 3 solution acidified with 10%
and KNO 3 followed by electrolytic purification.
HCI
 Separation of Silver from gold (Parting with Purple of Cassius: It is only a form of
H2SO 4 or HNO 3 ): colloidal gold.
2AuCl + 3SnCl (Very dil.) → 2Au + 3SnCl
3 2 4
Alloy (Au < 25%) is boiled with conc. H 2 SO 4
The gold thus precipitated is absorbed by
where Ag is dissolved as Ag 2 SO 4 and Au remains
Sn(OH) 4 formed by hydrolysis of SnCI 4 .
as spongy mass.
SnCl 4 + 4H 2 O → Sn(OH) 4 + 4HCI
Ag 2 SO 4 (Solution) + Zn → 2Ag + ZnSO 4 This form of gold is purple or red in color named
after its discoverer, Cassius.
If alloy contains Au > 30%, then some Ag is
added to it so as to reduce the % of Au below
25%. 9. Zinc: (Not in JEE syllabus)
Ores:
Zincite: ZnO; Zinc blende: ZnS(main); Calamine: ZnCO 3 ;
8. Gold: Franklinite: ZnO.Fe 2 O 3 ;
Occurrence:
Willemite (mineral): Zn 2 SiO 4
(i) Found mostly in Free State in quartz veins called
auriferous quartz.
Extraction of zinc blende: It involves following steps.
(ii) In combined state: as telluride in sylvanite (Ag,
(a) Crushing and concentration: The ore is crushed
Au) Te 2 .
and concentrated by froth floatation process.
(b) Roasting:
Extraction of gold from native ore:
The concentrated ore is roasted in presence of
(a) Crushing and concentration: The gold bearing
excess of air at 1200 K .
ore is crushed, powdered finely and concentrated
2ZnS + 3O 2  
→ 2ZnO + 2SO 2
1200 K
by washing with water
(b) Treatment with 0.25-1% sodium cyanide or
ZnS + 2O 2 → ZnSO 4
potassium cyanide solution (Mac- Arthur
ZnSO 4 is decomposed at higher temperature;
Forrest cyanide process)
2ZnSO 4 → 2ZnO + 2SO 2 ↑ +O 2 ↑
The crushed and concentrated ore is treated with
dil. cyanide solution in presence of air. (c) Reduction (Belgian process):
4Au + 8NaCN + 2H O + O (air) → 4Na[Au(CN) ]
2 2 2
Roasted ore is heated with coke at 1673 K in a
(soluble) + 4NaOH vertical fire clay retort.
(c) Precipitation of gold by zinc : ZnO + C → Zn + CO

2Na[Au(CN) 2 ] + Zn → Na 2 [Zn(CN) 4 ] + 2Au ↓

Vapors of zinc are collected and condensed to get
zinc spelter.
(d) Refining:
(d) Electrolytic refining:
(i) Cupellation:
Anode: Impure Zn
The impure metal is melted in a cupel in presence
Cathode: Pure Zn
of borax and silica and air is passed through the
Electrolyte: ZnSO 4 (aq) + H 2 SO 4
fused mass. Zinc and lead are oxidized and are
blown off.

Page 10
Thermodynamic Principles of Metallurgy
For any process, Gibbs free energy change (∆G) is given
by the equation,
∆G = ∆ - T∆S ---- (i)
where ∆H is the enthalpy change and ∆S is the entropy
change and T is the absolute temperature. The free energy
change is also related to the equilibrium constant K of the
reactant-product system at temperature T by the following
equation.
∆ G = - RT ln K ... (ii)
If ∆G is -ve, then K will be positive. This means that the
reaction will proceed towards products. From these facts,
we can draw the following conclusions:
1. The criterion of feasibility of a reaction at any
temperature is that the ∆G of the reaction must be
negative. Thus, if ∆S is + ve in Eq. (i), on increasing
the temperature (T), the value of T∆S will increase and
when T∆S > ∆H, ∆G will be —ve and the reaction will
proceed in the forward direction.
2. A reaction with ∆G positive can be still made by The Ellingham diagram for oxides shows the following
coupling it with another reaction having large negative important features:
∆G so that the net ∆G of the two reactions is negative. 1. Ellingham diagram normally consist of plots of ∆ G°vs
Such couplings can be easily understood through Gibbs T for the formation of oxides of elements, i.e. for the
energy ∆ f G0 vs T plots for the formation of oxides (Fig) reaction: 2 x M (s) + O 2 (g)  2 M x O(s)
Such coupling reactions can be easily under-stood 2. The graphs for metal oxide all slope upwards because
through Ellingham diagram. the change in Gibbs energy becomes less negative with
increase in temperature.
Ellingham Diagram 3. Each plot follows a straight line unless there is some
Ellingham diagram normally consists of plots ∆ f G0 or ∆G° change in phase. The temperature at which such a
vs T for formation of oxides of elements similar diagrams change occurs, is indicated by an increase in the slope
can also be constructed sulphides and halides. Such on the + ve side. For example, in the Zn—ZnO plot, at
diagrams help us in predicting the feasibility of thermal the melting of zinc (692 K) is indicated by an abrupt
reduction of an ore. increase in the +ve slope of the curve.
Consider the formation of an Oxide: 4. When the temperature is increased, a point will be
reached when the line crosses ∆ G = 0 line. Below this
2 xM (s) + O 2 (g)  2 M x O(s) …(i) temperature the ∆ f G° of oxide is negative and hence
the oxide is stable. Above this temperature ∆ f G° of
In this reaction, dioxygen—a gas has been used up and the oxide is positive and hence the oxide becomes
metal oxide—a solid is formed. unstable and decomposes on its own into metal and
Since gases have higher entropy than liquids and solids, oxygen.
therefore, during this reaction, ∆S becomes negative. 5. In principle, when the plot of one metal lies below that
Thus, if temperature is increased, T∆S becomes more of another, the first metal is capable of reducing the
negative. oxide of the second.
Since T∆S is subtracted in Eq. (i), therefore, ∆G becomes 6. A vertical line drawn on the Ellingham plot of the
less negative. metal oxides at any T gives the sequence of the
Thus, ∆G increases with an increase in temperature. stabilities of the metal oxides.
In other words, ∆G shifts towards higher side despite rising 7. A metal forming a more stable oxide (higher - ∆ G)
T (normally, ∆G decreases, i.e., goes to lower side with will be potential reducing agent for the less stable
increasing temperature). oxide.
The result is a +ve slope in the curve for most of reactions Thus Al metal will reduce CuO and FeO but not MgO.
involving the formation of metal oxides, M x O (s) as shown
in Figure

Page 11
8. If the two lines intersect the free energy change for the
reduction will be zero at that temperature and
equilibrium results.
Note:
The diagram predicts that MgO and ZnO will decompose
if heated strongly enough. But this does not much hope for
extracting pure Mg or pure Zn by straight forward heating
of the oxide, because the temperature above which they
will decompose (extrapolate the line to cross the ∆ G°=0
line) is way above their boiling points.
Limitations of Ellingham Diagram
1. Kinetics of reduction. Ellingham diagrams are based on
thermodynamic concepts, therefore, these diagrams
simply suggest whether the reduction of a given metal
oxide with a particular reducing agent is possible or
not. It, however, does not tell anything about the
kinetics of the reduction process, i.e., how fast will be
the reduction process.
2. Reactant/product equilibrium. The interpretation of
∆G° is based upon K (i.e., ∆G° = - RT In K). Thus, it is
presumed that reactants and products are in
equilibrium.
M x O + A red ⇔ x M + AO ox
But, this is not always true because the
reactant/product may be solid.
Theory of Pyrometallurgy
In the light of the thermodynamic principles and
Ellingham diagram, let us first discuss the reduction of a
metal oxide with carbon.
Now we know that during reduction, the oxide of the
metal decomposes, i.e.,
Reduction: M x O (s)  x M (s or l) + 1/2 O 2 (g) ...(i)
and the reducing agent takes away the oxygen given by the
metal oxide, i.e.,
Oxidation: C (s) + 1/2O 2 (g)  CO (g) ... (ii)
The role of the reducing agent here is to provide a large
negative ∆G° to make the sum of the ∆ r G° of the above
two reactions (i.e., reduction of the metal oxide and
oxidation of the reducing agent) negative. Now Eq. (i) is
actually reverse of Eq. (iii) representing the oxidation of
the metal.
1
x M (s or l) + 2 O 2 (g)  M x O (s) ; ∆G° (M, M x O) ...(iii)
However, if, instead of partial oxidation of C to CO,
complete oxidation of C to CO 2 occurs, the
Page 12
oxidation of the reducing agent maybe represented as
follows :
1 1 1 1
2 C(s) + 2 O 2 (g)  2 CO 2 (g); 2 ∆G° (c, co 2 ) ...(iv)
If, instead of C, CO is used as the reducing agent, the
oxidation of the reducing agent may be represented as
1
follows : CO (g) + 2 O 2 (g) CO 2 (g) ; ∆G° (c, co 2 ) ...(v)
On subtracting Eq. (iii) from one of the three equations,
(ii), (iv) and (v), we have,
M x O (s) + C(s)  x M(s or 1) + CO (g) ...(vi)
1 1
M X O (s) + 2 C (s)  x M (s or l) + 2 CO 2 (g) ...(vii)
M x O (s) + CO (g)  x M (s or 1) + CO 2 (g) ...(viii)
These three equations (vi), (vii) and (viii) describe the
actual reduction of the metal oxide, M x O to the free metal,
M. The ∆ r G° values for these reactions, in general, can be
obtained by subtraction of the corresponding ∆ f G° values
from the Ellingham diagram. If these values are —ve, the
reduction is feasible otherwise not.
Without going into the calculations for ∆ r G°, we can still
predict the feasibility of a reduction process simply by
looking at the Ellingham diagram.
Metals for which free energy of formation (∆ f G°) of their
oxides is more negative can reduce those metals for which
the free energy of formation (∆ f G°) of their respective
oxides is less negative.
As we have seen, heating (i.e., increasing T) favours a
negative value of ∆rG0. Therefore, the temperature is
chosen such that the sum of ∆rG0 in the two combined
redox process is negative.
In ∆rG0 vs T plots, this is indicated by the point of
intersection of the two curves (curve for MxO and that for
the oxidation of the reducing substance).
After that point, the ∆rG0 value becomes more negative
for the combined process including the reduction of MxO.
The difference in the two ∆rG0 values after that point
determines whether reductions of the oxide of the upper
line are feasible by the element represented by the lower
line.
For example, the temperature at the intersection point A of
the Al  Al 2 O 3 and Mg  MgO curves is approx. 1665
K. Therefore, below 1665 K, Mg can reduce Al 2 O 3 to Al
but above 1665 K, Al can reduce MgO to Mg.
Page 13