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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. An ore is usually contaminated with earthy or undesired
materials known as gangue.
(a) Native ores contain the metal in free state. Silver, gold, platinum etc,
occur as native ores.
(b) Oxidised ores consist of oxides or oxysalts (e.g. carbonates, phosphates,
sulphates and silicates ) of metals.
(c) Sulphurised ores consist of sulphides of metals like iron, lead, zinc,
mercury etc.
(d) Halide ores consist of halides of metals.

Metal Ores Composition

Aluminium Bauxite AlOX(OH)3–2X [where 0 < X < 1] Al2O3
Diaspore Al2O3.H2O
Corundam Al2O3
Kaolinite (a form of clay) [Al2 (OH)4 Si2O5]
Iron Haematite Fe2O3
Magnetite Fe3O4
Siderite FeCO3
Iron pyrite FeS2
Limonite Fe2O3.3H2O
Copper Copper pyrite CuFeS2
Copper glance Cu2S
Cuprite Cu2O
Malachite CuCO3.Cu(OH)2
Azurite 2CuCO3.Cu(OH)2
Zinc Zinc blende or Sphalerite ZnS
Calamine ZnCO3
Zincite ZnO
Lead Galena PbS
Anglesite PbSO4
Cerrusite PbCO3
Magnesium Carnallite KCl.MgCl2 6H2O (K2MgCl4 .6H2O)
Magnesite MgCO3
Dolomite MgCO3 CaCO3
Epsomsalt (Epsomite) MgSO4 7H2O
Langbeinite K2Mg2(SO4)3
Tin Cassiterite (Tin stone) SnO2
Silver Silver glance (Argentite) Ag2S
Chlorargyrite (Horn silver) AgCl.

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Metallurgy :
The scientific and technological process used for the extraction/isolation
of the metal from its ore is called as metallurgy.
The isolation and extraction of metals from their ores involve the following
major steps:

(A) Crushing and Grinding : The ore is first crushed by jaw crushers and
ground to a powder.
(B) Concentration :
The removal of unwanted useless impurities from the ore is called dressing,
concentration or benefaction of ore.
(i) Hydraulic washing or Gravity separation or Levigation method :
It is based on the difference in the densities of the gangue and ore particles.
This method is generally used for the concentration of oxide and native
ores.
(ii) Electromagnetic separation :
It is based on differences in magnetic properties of the ore components.
Chromite ore(FeO.Cr2O3) is separated from non–magnetic silicious
impurities and cassiterite ore(SnO2) is separated from magnetic Wolframite
(FeWO4 + MnWO4).
(iii) Froth floatation process. This method is commonly used for the
concentration of the low grade sulphide ores like galena, PbS (ore of Pb)
; copper pyrites Cu2S.Fe2S3 or CuFeS2 (ore of copper) ; zinc blende, ZnS
(ore of zinc) etc., and is based on the fact that gangue and ore particles
have different degree of wettability with water and pine oil; the gangue
particles are preferentially wetted by water while the ore particles are wetted
by oil. In this process one or more chemical frothing agents are added.
(iv) Leaching : Leaching is often used if the ore is soluble in some suitable
solvent, e.g, acids, bases and suitable chemical reagents.
(C) Extraction of crude metal from concentrated ore :
The isolation of metals from concentrated ore involves two major steps as
given below.
(i) Conversion to oxide :
Calcination. It is a process of heating the concentrated ore strongly in a
limited supply of air or in the absence of air. The process of calcination
brings about the following changes :

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(a) The carbonate ore gets decomposed to form the oxide of the metal.
(b) Water of crystallisation present in the hydrated oxide ore gets lost as
moisture.
(c) Organic matter, if present in the ore, gets expelled and the ore becomes
porous. Volatile impurities are removed.
Roasting. It is a process of heating the concentrated ore (generally sulphide
ore) strongly in the excess of air or O2 below its melting point. Roasting is
an exothermic process once started it does not require additional heating.
Smelting :
Slag formation : In many extraction processes, an oxide is added
deliberately to combine with other impurities and form a stable molten
phase immiscible with molten metal called a slag. The process is termed
smelting.
The principle of slag formation is essentially the following :
Nonmetal oxide (acidic oxide) + Metal oxide (basic oxide)  Fusible
(easily melted) slag
Removal of unwanted basic and acidic oxides: For example, FeO is the
impurity in extraction of Cu from copper pyrite.
2CuFeS2 + 4O2  Cu2S + 2FeO + 3SO2
Cu2S + FeO + SiO2  FeSiO3 (Fusible slag) + Cu2S (matte)


 (upper layer) (lower layer)
(roasted pyrite )

Matte also contains a very small amount of iron(II) sulphide.

To remove unwanted acidic impurities like sand and P4O10, smelting is
done in the presence of limestone.
CaCO3  CaO + CO2
CaO + SiO2  CaSiO3 (fusible slag)
6CaO + P4O10  2Ca3(PO4)2 (fusible slag - Thomas slag)
(ii) Reduction of a metal oxide :
The free metal is obtained by reduction of a compound, using either a
chemical reducing agent or electrolysis.

Chemical reduction method :

Reduction with carbon :
PbO + C  Pb + CO (extraction of lead)
Reduction with CO : In some cases CO produced in the furnace itself is
used as a reducing agent.

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Fe2O3 + 3CO  2Fe + 3CO2

Reduction by other metals :
Metallic oxides (Cr and Mn) can be reduced by a highly electropositive
metal such as aluminium that liberates a large amount of energy (1675
kJ/mol) on oxidation to AI2O3. The process is known as Goldschmidt or
aluminothermic process and the reaction is known as thermite reaction.
Cr2O3 + AI  2Cr () + AI2O3
Magnesium reduction method : Magnesium is used in similar way to
reduce oxides. In certain cases where the oxide is too stable to reduce,
electropositive metals are used to reduce halides.
Kroll p rocess
TiCI4 + 2 Mg   Ti + 2 MgCI2
1000 –1150º C

M p rocess
TiCI4 + 4Na     Ti + 4 NaCI

Self-reduction method :
This method is also called auto-reduction method or air reduction method.
If the sulphide ore of some of the less electropositive metals like Hg, Cu,
Pb, Sb, etc. are heated in air, a part of these is changed into oxide or
sulphate then that reacts with the remaining part of the sulphide ore to
give its metal and SO2.
Cu2S + 3O2  3Cu2O + 2 SO2
2Cu2O + Cu2S  6Cu + SO2
Electrolytic reduction :
It presents the most powerful method of reduction and gives a very pure
product. As it is an expensive method compared to chemical methods, it
is used either for very reactive metals such as magnesium or aluminum or
for production of samples of high purity.
1. In aqueous solution : Electrolysis can be carried out conveniently and
cheaply in aqueous solution that the products do not react with water.
Copper and zinc are obtained by electrolysis of aqueous solution of their
sulphates.
2. In fused melts : Aluminum is obtained by electrolysis of a fused mixture
of AI2O3 and cryolite Na3[AIF6].

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Extraction of Aluminium : It involves the following processes

(a) Purification of bauxite :

(b) Electrolytic reduction (Hall-Heroult process) :

2Al2O3 + 3C  4Al + 3CO2

Cathode : Al3+ (melt) + 3e–  Al(l)

Anode : C(s) + O2– (melt)  CO(g) + 2e–
C(s) + 2O2– (melt)  CO2 (g) + 4e–

Metallurgy of some important metals

1. Extraction of iron from ore haematite :
Reactions involved :
At 500 – 800 K (lower temperature range in the blast furnace)

3 Fe2O3 + CO  2 Fe3O4 + CO2

Fe3O4 + CO  3Fe + 4 CO2

Fe2O3 + CO  2FeO + CO2
At 900 – 1500 K (higher temperature range in the blast furnace):
C + CO2  2 CO ; FeO + CO  Fe + CO2
Limestone is also decomposed tom CaO which removes silicate impurity
of the ore as slag. The slag is in molten state and separates out from iron.
CaCO3  CaO + CO2 ; CaO + SiO2  CaSiO3
2. Extraction of copper :
From copper glance / copper pyrite (self reduction) :
2CuFeS2 + 4O2  Cu2S + 2FeO + 3SO2
Cu2S + FeO + SiO2  FeSiO3 (fusible slag) + Cu2S (matte)

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2FeS + 3O2  2FeO + 2SO2 ; FeO + SiO2  FeSiO3

2Cu2S + 3O2  2Cu2O + 2SO2 ;
2Cu2O + Cu2S  6Cu + SO2 (self reduction)

3. Extraction of lead :
 C
(i) 2PbS(s) + 3O2 (g)  2PbO (s) 
 2Pb() + CO2 (g)


heat in Heat in
(ii) 3PbS(s)   PbS (s) + 2PbO (s)   3Pb() + SO2 (g)
air absence of air

4. Extraction of zinc from zinc blende :

The ore is roasted in presence of excess of air at temperature 1200 K.
2 ZnS + 3O2  2 ZnO + 2SO2
The reduction of zinc oxide is done using coke.
Coke,1673 K
ZnO + C     Zn + CO
5. Extraction of tin from cassiterite :
The concentrated ore is subjected to the electromagnetic separation to
remove magnetic impurity of Wolframite.
SnO2 is reduced to metal using carbon at 1200 – 1300°C in an electric
furnace. The product often contains traces of Fe, which is removed by
blowing air through the molten mixture to oxidise FeO which then floats to
the surface.
SnO2 + 2C  Sn + 2CO
2Fe + O2  2FeO
6. Extraction of Magnesium :
From Sea water (Dow’s process) :
Sea water contains 0.13% magnesium as chloride and sulphate.
It involves following steps.
(a) Precipitation of magnesium as magnesium hydroxide by slaked
lime.
(b) Preparation of hexahydrated magnesium chloride.
The solution on concentration and crystallisation gives the crystals
of MgCl2.6H2O.
(c) Preparation of anhydrous magnesium chloride.
(d) Electrolysis of fused anhydrous MgCl2 in presence of NaCl.
MgCl2 Mg2+ + 2Cl–
At cathode : Mg2+ + 2e–  Mg(99% pure) ;
At anode : 2Cl–  Cl2 + 2e–

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7. Extraction of gold and silver (MacArthur-Forrest cyanide process) :

(a) From native ores : Extraction of gold and silver involves leaching the
metal with CN–.
4Au / Ag (s) + 8CN–(aq) + 2H2O(aq) + O2(g)  4[Au / Ag (CN)2]–(aq) +
4OH–(aq)
2[Au / Ag (CN)2]–(aq) + Zn(s)  2Au / Ag (s) + [Zn(CN)4]2– (aq)
(b) From argentite ore :
Ag2S (conc. ore) + 2NaCN 2AgCN + Na2S.
4Na2S + 5O2 + 2H2O  2Na2SO4 + 4NaOH + 2S
AgCN + NaCN  Na[Ag(CN)2] (soluble complex)
2Na[Ag(CN)2] + Zn (dust)  2Ag  + Na2[Zn(CN)4].

(D) Purification or Refining of metals :

Physical methods : These methods include the following processes
:
(I) Liquation process : This process is used for the purification of the
metal, which itself is readily fusible, but the impurities present in it are
not, used for the purification of Sn and Zn, and for removing Pb from Zn-Ag
alloy.
(II) Fractional distillation process : This process is used to purify those
metals which themselves are volatile and the impurities in them are
nonvolatile and vice-versa. Zn, Cd and Hg are purified by this process.
(III) Zone refining method (Fractional crystallisation method) : This
process is used when metals are required in very high purity, for specific
application. For example pure Si and Ge are used in semiconductors
Chemical methods : These methods include the following methods
:
(I) OXIDATIVE REFINING :
This method is usually employed for refining metals like Pb, Ag,
Cu, Fe, etc. In this method the molten impure metal is subjected
to oxidation by various ways.
(II) POLING PROCESS :
This process is used for the purification of copper and tin which
contains the impurities of their own oxides.
Green wood  Hydrocarbons  CH4
4CuO + CH4  4Cu (pure metal) + CO2 + 2H2O
(III) ELECTROLYTIC REFINING :
Some metals such as Cu, Ni, and AI are refined electrolytically.
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(IV) VAPOR PHASE REFINING :

(i) Extraction of Nickel (Mond’s process) :The sequence of reaction is

H2O(g) + C  CO(g) + H2

50 º C
Ni(s) + 4 CO(s)   [Ni(CO4)] (g)
200 º C
[Ni (CO)4](g)   Ni + 4CO(g)

(ii) Van Arkel–De Boer process :

50 – 250 º C 1400 º C
Impure Ti + 2I2    TiI4     Ti + 2I2
Tungsten filament

s-BLOCK ELEMENTS & THEIR COMPOUNDS

Group 1 of the periodic table consists of the elements : lithium, sodium,
potassium, rubidium, caesium and francium .
The elements of Group 2 include beryllium, magnesium, calcium, strontium,
barium and radium.
Hydration Enthalpy :
The hydration enthalpies of alkali metal ions decrease with increase in
ionic sizes.Li+ has maximum degree of hydration and for this reasons
lithium salts are mostly hydrated e.g., LiCl . 2H2O
Physical properties :
All the alkali metal are silvery white, soft and light metals. Because of the
larger size, these element have low density. The melting and boiling point
of the alkali metals are low indicating weak metallic bonding alkali metals
and their salts impart characteristic colour to an oxidizing flame.
Metal Li Na K Rb Cs
Violet/
Colour Crimson Yellow Lilac Red Blue
red violet

Chemical Properties:
The alkali metal are highly reactive due to their larger size and low ionization
enthalpy.
 Reactivity towards air : They burn vigorously in oxygen forming
oxides. Lithium forms monoxide, sodium forms peroxide, the other metals
form superoxide.
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