Introduction :

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. Ores may be classified mainly into following four classes.

(a) Native ores: They contain the metal in free state . Silver, gold, platinum etc, occur as native ores.
(b) Oxidised ores : These ores consist of oxides or oxysalts of metals.
(c) Sulphurised ores :These ores consist of sulphides of metals like iron, lead, zinc, mercury etc.
(d) Halide ores :These ores consist of halides of metals

Some Important ores of metals

Metal Ores Composition

AlOX(OH)3–2X
Aluminium Bauxite
[where 0 < X < 1] Al2O3
Kaolinite (a form of clay) [Al2 (OH)4 Si2O5]
Iron Haematite Fe2O3
Magnetite Fe3O4
Siderite FeCO3
Iron pyrite FeS2
Copper Copper pyrite CuFeS2
Copper glance Cu2S
Cuprite Cu2O
Malachite CuCO3.Cu(OH)2
Zinc Zinc blende or Sphalerite ZnS
Calamine ZnCO3
Zincite ZnO

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 of the ore. (B) Dressing or concentration of the ore.
(C) Isolation of the crude metal from its ore (D) Purification or refining of the metal.
(A) Crushing and Grinding : The ore is first crushed by jaw crushers and ground to a powder (pulverisation of
the ore) in equipments like ball mills and stamp mills.
(B) Concentration :The removal of unwanted impurities from the ore is called dressing, concentration or
benefaction of ore. Some of the important procedures are described below.
(i) Hydraulic washing or Gravity separation or Levigation method
(ii) Electromagnetic separation :
(iii) Froth floatation process
(iv) Leaching

(C) Extraction of crude metal from concentrated ore :The concentrated ore must be converted into a form
which is suitable for reduction.Usually the sulphide ore is converted to oxide before reduction.Oxides are
easier to reduce. Thus isolation of metals fromconcentrated ore involves two major steps as given below.
(i) Conversion to oxide (ii) Reduction of the oxide to metal.
(i) Conversion to oxide :
Conversion of ore into oxide is carried out in two ways depending upon the nature of ore.
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 :
(a) The carbonate ore gets decomposed to form the oxide of the metal, e.g.,

CaCO3 (calcite ore / lime stone)  CaO + CO2

ZnCO3 (calamine)  ZnO + CO2
(b) Water of crystallisation present in the hydrated oxide ore gets lost as moisture, e.g.,

2Fe2O3.3H2O (limonite)  2Fe2O3(s) + 3H2O(g) 

Al2O3. 2H2O (bauxite)  Al2O3 (s) + 2H2O(g) 
(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.
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.
Properties of a slag :
(i) Slag is a fusible mass & has low melting point.
(ii) It is lighter than and immiscible with the molten metal. It is due to these impurities that the slag floats as
a separate layer on the molten metal and can thus be easily separated from the metal. The layer of the slag
on the molten metal prevents the metal from being oxidised.
Type of flux : Fluxes are of two types viz., acidic flux and basic flux.
(a) Acidic flux : It is an acidic oxide like SiO2, P2O5. It is used to remove the basic impurity like CaO, FeO,
MgO etc in the form of slag
CaO + SiO2  CaSiO3
(flux) (slag)
(b) Basic flux : It is a basic oxide like CaO, MgO. It is used to remove the acidic impurity like SiO2, P2O5 etc.
in the form of slag.
SiO2 + CaO  CaSiO3
(flux) (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 :
A large number of commercial processes come under this category. Carbon can be used to reduce a number
of oxides and other compounds, and because of the low cost and availability of coke this method is widely
used. The disadvantages are that a high temperature is needed, which is expensive and necessitates the
use of blast furnace.
Reduction with carbon :
PbO + C  Pb + CO (extraction of lead)
2Fe2O3 + 3C  4Fe (spongy iron) + 3CO2
1200 º C
ZnO + C   Zn + CO (extraction of zinc)
1800 º C
SnO2 + 2C (anthracite)   Sn + 2CO (extraction of tin)
1200 ºC
  Mg + CO
MgO + C electric furnace
Reduction with CO : In some cases CO produced in the furnace itself is used as a reducing agent.
Fe2O3 + 3CO  2Fe + 3CO2
Fe3O4 + 4CO  3Fe + CO2
PbO + CO  Pb + CO2
CuO + CO  Cu + CO2
2
Carbon or carbon monoxide reduction process is usually carried out in blast furnace. There are some disadvantage
of using carbon as reducing agents e.g.,
(a) Some metallic oxides like CaO give metallic carbides instead of metals.

CaO + 3C  CaC2 + CO
(b) During the cooling of the products, in many cases, reformation of the oxide and carbon may take place.
MgO + C Mg + CO

Reduction by other metals :

If the temperature needed for carbon to reduce an oxide is too high, for economical or practical purposes,
reduction by other metals is done. Also, certain metallic oxides cannot be reduced by carbon because the
affinity of oxygen for the metal is greater than its affinity for carbon. Such 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 is mixed with requisite amount of Al-powder (this mixture is called thermite mixture) and is placed in a
large fire-clay crucible. An intimate mixture of Na2O2 or BaO2 and Mg powder (called ignition mixture or igniter)
is placed in a small depression made in the thermite mixture. The crucible is surrounded by sand which
prevents the loss of heat by radiation. A piece of Mg ribbon is struck into the ignition mixture and the charge is
covered by a layer of fluorspar (CaF2) which acts as a heat insulator. Now Mg-ribbon is ignited so that ignition
mixture catches fire and flame is produced, leading to a violent reaction between Mg and BaO2 with the evolution
of large amount of heat.
Mg + BaO2  BaO + MgO + Heat
Heat produced in the above reaction makes Cr2O3 and AI-powder react together.
Cr2O3 + AI  2Cr () + AI2O3
Molten Cr-metal formed settles down at the bottom of the crucible.

An application of aluminothermic process has been used for joining the broken pieces of iron (welding). In this
process thermite mixture consisting of Fe2O3 and Al-powder in 3 : 1 ratio is placed in a funnel shaped crucible
lined internally with magnesite and having a plug hole at its bottom. The thermite mixture is covered with a
mixture of BaO2 plus Mg-powder (ignition mixture) in which a piece of Mg ribbon is inserted. The ends of the iron
pieces to be welded are thoroughly cleaned and surrounded by a fire-clay mould. When Mg ribbon is ignited,
ignition mixture catches fire and Fe2O3 gets reduced to Fe by Al-powder.
2Al + Fe2O3  AI2O3 + 2Fe (molten) ; H = – 3230 kJ (The reaction is used for thermite welding)
3 Mn3O4 + 8 AI  4 AI2O3 + 9 Mn
B2O3 + 2Al  2B + Al2O3 (extraction of boron)

As it is a strongly exothermic reaction, it proceeds with explosive violence and only initial heating is needed.
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
 Advantages of using Na and Mg as reducing agents are the higher reducing power of the metals and solubility
of their halides in water so that the reduced metals can be washed free from impurities.
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.
Examples :
2HgS + 3 O2  2HgO + 2SO2
2HgO + HgS  2Hg + SO2
Cu2S + 3O2  3Cu2O + 2 SO2
2Cu2O + Cu2S  6Cu + SO2
2PbS + 3O2  2PbO + 2 SO2
2PbO + PbS  3Pb + SO2
The extraction of Pb by heating its sulphide ore (PbS) in air can also be represented as
PbS + 2 O2  PbSO4
PbSO4 + PbS  2 Pb + 2 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. Electrolytic reduction of copper has the additional advantage of allowing
the recover of valuable minor contaminants such as silver.
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 other solvents : Electrolysis can be carried out in solvents other than water. Fluorine reacts violently with
water and it is produced by electrolysis of KHF2 dissolved in anhydrous HF.
3. In fused melts : Elements that react with water are often extracted from fused melts of their ionic salts.
Aluminum is obtained by electrolysis of a fused mixture of AI2O3 and cryolite Na3[AIF6]. Both sodium and
chlorine are obtained from the electrolysis of fused NaCI. In this case upto two-third by weight of CaCI2 is added
as an impurity to lower the melting point from 803 to 505ºC.
Electrochemical principles of metallurgy :
Electrolytic reduction can be regarded as a technique for driving a reduction by coupling it through electrodes
and external circuit to a reactive or a physical process with a more negative G. The free energy available from
the external source can be assessed from the potential it produces across the electrodes using the thermodynamic
relation :
G = –nFE ..........(i)
where n is the number of electrons transferred, F is Faraday’s constant (F = 96.5 kJ/mol) and Eº is electrode
potential of the redox coupled formed in the system.
Hence, the total Gibb’s energy of the coupled internal and external process is
G + G (external) = G – nFEext
If the potential difference of the external source exceeds
G
Eext = –
nF
the reduction is thermodynamically feasible; thus, the overall process occurs with a decrease in free energy.
More reactive metals have large negative values of the electrode potential. So their reduction is difficult. If the
difference of two E0 values corresponds to a positive E0 and consequently negative G0 in equation (i), then the
less reactive metal will come out of the solution and the more reactive metal will go to the solution, e.g.,
Cu2+ (aq) + Fe(s)  Cu(s) + Fe2+(aq)
In simple electrolysis, the Mn+ ions are discharged at negative electrodes (cathodes )and deposited there.
Precautions are taken considering the reactivity of the metal produced and suitable materials are used as
electrodes. Sometimes a flux is added for making the molten mass more conducting.
Hydrometallurgy : The processing of ores and minerals as well as metals and their compounds at relatively
low, often ambient temperatures employing aqueous solution is known as hydrometallurgy. Occasionally, organic
reagents are also used. This method of extraction is generally used for low grade ores. Copper is extracted by
hydrometallurgy from low grade ore it is leached out using acid and bacteria. The solution containing Cu2+ is
treated with scrap iron or H2.
CuSO4 + Fe  Cu(s) + FeSO4
A hydrometallurgical process for the extraction of metals from ores, concentrates, or secondary materials
essentially contains three basic steps—dissolution of the valuable metal in the aqueous solution (leaching)
purification of leach solution and subsequent recovery of metal from the purified solutions either by electrolysis
or by adding some electropositive metal to it.

Some of the metals obtained by hydrometallurgy are as follows :

Extraction of Ag and Au : Metals like Au and Ag can be precipitated for their salt solution by electropositive
metals for example, Zn.
Metallic Ag is dissolved from its ore in dilute NaCN solution, and the solute so obtained is treated with scrap Zn
when Ag is precipitated. Air is blown into the solution oxidize Na2S. Leaching the metals like silver, gold with
CN– is an oxidation reaction (Ag  Ag+ or Au  Au+)
Ag2S (s) + 4CN– (aq)  2 [Ag(CN)2]– (aq) + S2– (aq)

2[Ag(CN)2]– (aq) + Zn (s)  [Zn (CN)4]2– (aq) + 2Ag (s)

4Au (s) + 8 CN– (aq) + O2 (g) + 2H2O (l)  4 [Au(CN)2]– (aq) + 4OH– (aq)

2[Au(CN)2]– (aq) + Zn (s)  [Zn(CN)4]2– (aq) + 2 Au (s)

Here Zn acts as reducing agent.

Leaching pitch blends with H2SO4 or sodium carbonate to dissolve uranium:

1
U3O8 + 3 Na2CO3 + O  3 Na2UO4 + 3 CO2
2 2

1
U3O8 + 3 H2SO4 + O  3 UO2SO4 + 3 H2O
2 2
Precipitation of Mg (OH)2 from sea water using lime solution:
MgCI2 + Ca(OH)2  Mg(OH)2 + CaCI2.

Extraction of Aluminium : It involves the following processes

(a) Purification of bauxite :

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

The purified Al2O3 is mixed with Na3AlF6 (cryolite) or CaF2 (fluorspar) ) which lowers the melting point of the
mixture 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
The electolysis 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–

Extraction of Na : The fused mixture of NaCl and CaCl2 is taken in Down’s cell which consists of circular
iron cathode and carbon anode. On passing the electric current the following reactions take place :
Ionisation of NaCl : NaCl Na+ + Cl–
+
Collection of Na at cathode : Na + e  Na(Reduction).
–

Collection of Cl2 at anode : Cl– + e–  Cl (Oxidation), Cl + Cl  Cl2 .

Na can also be obtained by electrolysing molten NaOH in Castner’s cell.

Oxidation Reduction :
Besides reductions, some extractions are based on oxidation particularly for non-metals.
(a) 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).
2Cl– (aq) + 2H2O(l)  2OH–(aq) + H2(g) + Cl2(g)
The G0 for this reaction is + 422 kJ. When it is converted to E0 (using G0 = –nE0F), we get E0 = –2.2 V.
Naturally, it will require an external e.m.f. that is greater than 2.2 V. But the electrolysis requires an excess
potential to overcome some other hindering reactions. Thus, Cl2 is obtained by electrolysis giving out H2 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.
THERMODYNAMICS OF EXTRACTION : ELLINGHAM DIAGRAM OF A METAL
Some basic concepts of thermodynamics help us in understanding the theory of metallurgical transformations.
Gibbs energy is the most significant term here.The change in Gibbs energy, G for any process at any
specified temperature, is described by the equation: G = H – TS .............(1)
where, H is the enthalpy change and S is the entropy change for the process. For any reaction, this
change could also be explained through the equation: G° = – RTlnK .............(2)
where, K is the equilibrium constant of the ‘reactant-product’ system at the temperature,T. A negative G
implies a +ve K in equation (2) And this can happen only when reaction proceeds towards products. From
these facts we can make the following conclusions:
1. When the value of G is negative in equation (1) only then the reaction will proceed. If S is positive, on
increasing the temperature (T), the value of TS would increase (H < TS) and then G will become –
ve.
2. If reactants and products of two reactions are put together in a system and the net G of the two
possible reactions is –ve, the overall reaction will occur. So the process of interpretation involves coupling
of the two reactions, getting the sum of their G and looking for its magnitude and sign. Such coupling
is easily understood through Gibbs energy (G–) vs T plots for formation of the oxides

#6
Ellingham Diagram :
The graphical representation of Gibbs energy was first used by H.J.T.Ellingham. This provides a sound basis
for considering the choice of reducing agent in the reduction of oxides. This is known as Ellingham Diagram.
Such diagrams help us in predicting the feasibility of thermal reduction of an ore. The criterion of feasibility is
that at a given temperature, Gibbs energy of the reaction must be negative.
(a) Ellingham diagram normally consists of plots of fG vs T for formation of oxides of elements i.e., for the
reaction, 2xM(s) + O2(g)  2Mx O(s)
In this reaction, the gaseous amount (hence molecular randomness) is decreasing from left to right due to
the consumption of gases leading to a –ve value of S which changes the sign of the second term in equation
(1) Subsequently G shifts towards higher side despite rising T (normally, G decreases i.e., goes to lower
side with increasing temperature). The result is +ve slope in the curve for most of the reactions shown above
for formation of Mx O(s).

(b) Each plot is a straight line except when some change in phase (s liq or liq  g) takes place. The
temperature at which such change occurs, is indicated by an increase in the slope on +ve side (e.g., in the
Zn, ZnO plot, the melting is indicated by an abrupt change in the curve).

(c) There is a point in a curve below which

G is negative (So Mx O is stable). Above
this point, Mx O will decompose on its own.

(d) In an Ellingham diagram, the plots of G

for oxidation (and therefore reduction of the
corresponding species) of common metals
and some reducing agents are given. The
values of fG, etc.(for formation of oxides) at
different temperatures are depicted which
make the interpretation easy.

(e) Similar diagrams are also constructed for

sulfides and halides and it becomes clear why
reductions of Mx S is difficult. There, the fG°
of Mx S is not compensated.

Limitations of Ellingham Diagram :

1. The graph simply indicates whether a reaction is possible or not i.e., the tendency of reduction with a
reducing agent is indicated. This is so because it is based only on the thermodynamic concepts. It does not
say about the kinetics of the reduction process (Cannot answer questions like how fast it could be ?).
2. The interpretation of G is based on K (G° = – RT lnK). Thus it is presumed that the reactants and
products are in equilibrium: MxO + Ared xM + AOox
This is not always true because the reactant/product may be solid. [However it explains how the reactions
are sluggish when every species is in solid state and smooth when the ore melts down.It is interestng to note
here that H (enthalpy change) and the S (entropy change) values for any chemical reaction remain nearly
constant even on varying temperature. So the only dominant variable in equation (1) becomes T. However,
S depends much on the physical state of the compound. Since entropy depends on disorder or randomness
in the system, it will increase if a compound melts (s  l) or vapourises (l  g) since molecular randomness
increases on changing the phase from solid to liquid or from liquid to gas].
The reducing agent forms its oxide when the metal oxide is reduced. The role of reducing agent is to provide
G negative and large enough to make the sum of G of the two reactions (oxidation of the reducing agent
and reduction of the metal oxide) negative.

llurgy # 7
 As we know, during reduction, the oxide of a metal decomposes:

1
MxO(s)  xM (solid or liq) + O (g) .............(3)
2 2
The reducing agent takes away the oxygen. Equation (3) can be visualised as reverse of the oxidation of the
metal. And then, the fG– value is written in the usual way:

1
xM(s or l) + O (g)  MxO(s) [G (M,MxO)] .............(4 )
2 2
If reduction is being carried out through equation (3), the oxidation of the reducing agent (e.g., C or CO) will
be there :

1
C(s) + O (g)  CO(g) [G(C.CO)]
2 2

1
CO(g) + O (g)  CO2(g) [G(CO.CO )]
2 2 2

If carbon is taken, there may also be complete oxidation of the element to CO2:

1 1 1 1
C(s) + O2(s)  CO2(g) [ G(C.CO )]
2 2 2 2 2

On subtracting equation (4) [it means adding its negative or the reverse form as in equation (3) from one of the
three equations, we get:
MxO(s) + C(s)  xM(s or 1) + CO(g)
MxO(s) + CO(g)  xM(s or 1) + CO2(g)
1 1
MxO(s) + C(s)  xM(s or 1) + CO2(g)
2 2
These reactions describe the actual reduction of the metal oxide, MxO that we want to accomplish. The rG
values for these reactions in general, can be obtained by similar subtraction of the corresponding f G values.
As we have seen, heating (i.e., increasing T) favours a negative value of rG. Therefore, the temperature is
chosen such that the sum of rG in the two combined redox process is negative. In rG 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 rG value becomes more negative for the combined process including the reduction of
MxO. The difference in the two rG values after that point determines whether reductions of the oxide of the
upper line is feasible by the element represented by the lower line. If the difference is large, the reduction is
easier

Metallurgy of some important metals

1. Extraction of iron from ore haematite :
Oxide ores of iron, after concentration through calcination / roasting in reverberatory furnace are mixed with
lime stone and coke and fed into a Blast furnace from its top with the help of a cup and cone arrangement.
Here, the oxide is reduced to the metal.
FeO(s) + C(s)  Fe(s/l) + CO (g)

Reactions involved in blast furnace :

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
 The iron obtained from blast furnace contains about 4% carbon and many impurities in smaller amount (e.g.,
S, P, Si, Mn). This is known as pig iron. Cast iron is different from pig iron and is made by melting pig iron with
scrap iron and coke using hot air blast. It has slightly lower carbon content (about 3%) and is extremely hard
and brittle.
Further Reductions : 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
2. Extraction of copper :
(a) From cuprous oxide [copper() oxide] : 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
(b) From copper glance / copper pyrite (self reduction) : In actual process the ore is heated in a
reverberatory furnace after mixing with silica. Reactions that take place in the furnace are.
2CuFeS2 + 4O2  Cu2S + 2FeO + 3SO2
Cu2S + FeO + SiO2  FeSiO3 (fusible slag) + Cu2S (matte)
Copper matte is then charged into silica lined convertor (Bessemer 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.
2FeS + 3O2  2FeO + 2SO2 ; FeO + SiO2  FeSiO3
2Cu2S + 3O2  2Cu2O + 2SO2 ; 2Cu2O + Cu2S  6Cu + SO2 (self reduction)
The solidified copper obtained has blistered appearance due to the evolution of SO2 and so it is called blister
copper.
(c) From low grade ores and scraps :
Leaching of cuprite (Cu2O) or copper glance (Cu2S) with dil. H2SO4 in presence of air, gives a solution of
CuSO4 and the impurities present in the ores remain undissolved in the acid. Leaching of malachite green,
Cu(OH)2. CuCO3 with dil. H2SO4 also gives a solution of CuSO4 .
2Cu2O + 4H2SO4 + O2  4CuSO4 + 4H2O
cuprite solution
Cu2S + 4H2SO4 + 4O2  4CuSO4 + 4H2O + 2SO2 
copper glance solution
Cu(OH)2.CuCO3 + 2H2SO4  2CuSO4 + 3H2O + CO2 
malachite green solution
Copper metal can be recovered from CuSO4 solution (obtained as above) either by electrolysing it (cathode
is of Cu-metal and anode is of lead) Cu-metal is collected at cathode or by treating it with scrap iron which,
being more reactive than Cu, displaces Cu from CuSO4 solution and Cu gets precipitated (Metal displacement
method).
CuSO4 (aq) + Fe(s)  FeSO4 (aq) + Cu(s)  .
Cu2+ (aq) + H2(g)  Cu(s) + 2H+ (aq)
3. Extraction of lead :
(i) Roast in air to give PbO, and then reduce with coke or CO in a blast furnace.
 C
2PbS(s) + 3O2 (g)  2PbO (s) 
 2Pb() + CO2 (g)

(ii) PbS is partially oxidized by heating and blowing air through it. After some time the air is turned off
and heating is continued. The mixture undergoes self reduction as given below.
heat in Heat in
  3Pb() + SO (g)
3PbS(s)   PbS (s) + 2PbO (s) absence
air of air 2

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 : It involves following steps.
(A) Purification :
(i) Crushing and concentration :The ore is crushed and washed with a stream of running water
(ii) Electromagnetic separation : It is used to remove magnetic impurity of Wolframite.
(iii) Roasting : CuS + 2O2  CuSO4 ; FeS + 2O2  FeSO4
(iv) Leaching : Sulphates of copper and iron are dissolved in water.
(v) Washing : The ore is washed with running water to remove the finer iron oxide produced in
roasting. The ore thus obtained contains 60 – 70% SnO2 and is called as black tin.
(B) Smelting :
SnO2 + 2C  Sn + 2CO
2Fe + O2  2FeO
6. Extraction of Magnesium :
(i) From Carnallite :
The ore is dehydrated in a current of hydrogen chloride and the mixture of fused chlorides is
electrolysed.
(ii) From Magnesite :
The concentrated ore is calcined at higher temperature
Heated
MgCO3 Strongly
  MgO + CO2

The calcined ore is heated with coke in a current of dry chlorine gas.

MgO + C + Cl2  MgCl2 + CO
The magnesium chloride is fused and then electrolysed.
2000 º C
MgO + C (Other reducing agents like Si, Al can be used) Vaccume
  Mg + CO

(iii) 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 :
MgCl2 + Ca(OH)2  Mg(OH)2  + CaCl2
(b) Preparation of hexahydrated magnesium chloride :
Mg(OH)2 + 2HCl(aq)  MgCl2 + 2H2O
The solution on concentration and crystallisation gives the crystals of MgCl2.6H2O
(c) Preparation of anhydrous magnesium chloride :
 ( calcinatio n )
MgCl2. 6H2O      MgCl2 + 6H2O
Dry HCl( g)

It is not made anhydrous by simple heating because it gets hydrolysed


MgCl2. 6H2O  MgO + 5H2O + 2HCl

(d) Electrolysis of fused anhydrous MgCl2 :

Magnesium chloride obtained by any of the above
methods is fused and mixed with sodium chloride and
calcium chloride in the temperature range of
973 – 1023 K. The molten mixture is electrolysed.
Magnesium is liberated at the cathode (iron pot) and
chlorine is evolved at graphite anode.
MgCl2 Mg2+ + 2Cl–

At cathode : Mg2+ + 2e–  Mg(99% pure) ;

At anode : 2Cl–  Cl2 + 2e–

A stream of coal gas is passed through the pot to prevent oxidation of magnesium metal. The
magnesium obtained in liquid state is purified by distillation under reduced pressure. (1 mm of Hg at
873 K).
 (iv) From dolomite :
The concentrated ore is calcined at higher temperature

CaCO3 . MgCO3  CaO. MgO + 2CO2
It is then reduced by ferrosilicon at 1273 K under reduced pressure.
2CaO. MgO + FeSi  2Mg + Fe + Ca2SiO4

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–. This is also an
oxidation reaction (Ag  Ag+ or Au  Au+). The metal is later recovered by displacement method.
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)
Note : The leaching is carried out in presence of air or oxygen to oxidise metal, M (Ag / Au) to M+ which then
react with CN– to form soluble complex, [M(CN)2]–.
(b) From argentite ore :
Ag2S (conc. ore) + 2NaCN 2AgCN + Na2S.
Ag2S and AgCN are in equilibrium so Na2S is oxidised by air in to Na2SO4 . Hence equilibrium shifts
towards right side.
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 :

Metals obtained by reduction processes still contain some objectionable impurities and have to be refined.
Numerous techniques are available, including the following :

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 are infusible.
Examples : (a) Purification of impure tin metal :
(b) Purification of crude zinc :
(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 example pure Si and Ge are used in semiconductors and hence are purified
by this method. Zone refining method is based on the principle that an impure molten metal on gradual
cooling will deposit crystals of the pure metal, while the impurities will be left in the remaining part of the
molten metal.
(IV) Chromatographic 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.

Chemical methods : These methods include the following methods :

(I) OXIDATIVE REFINING :
The method is used when the impurities present in the metal have a greater affinity for oxygen and
are more readily oxidized than the metal.
(i) Bessemerisation (Purification of iron) :
The iron obtained from a blast furnace is a brittle material called cast iron or pig iron. Molten iron
from blast furnace is exposed to a jet of pure O2 gas for about 20 minutes in a furnace that is
lined with basic oxide such as CaO. The impurities in the iron are oxidized and the acidic oxides
that form react with basic CaO to yield a molten slag that can be poured off. Phosphorous, for
example, is oxidized to P4O10, which then reacts with CaO to give molten Ca3(PO4)2.
P4(l) + 5 O2(g)  P4O10(l)
6 CaO (g) + P4O10(l)  2 Ca3(PO4)2(l)
Basic oxide acidic oxide slag
 (ii) Cupellation (removal of lead) :
In this process the molten impure metal is heated in a cupel, which is boat-shaped dish
made of bone ash or cement, and a blast of air is passed over the molten metal. The
impurities are oxidized and the volatile oxides thus produced escape with the blast of air.
The pure metal remains behind in the cupel. Pb present in silver is removed by cupellation
process.
2 Pb(g) + O2  2 PbO(g)
(II) PARTING PROCESS :
Crude gold obtained by MacArthur-Forrest cyanide and chlorination process contains Ag, Cu, Zn,
and sometimes Pb as impurity. Zn and Pb are removed by cupellation process. Cu and Ag are
removed by parting process.
(i) Parting with sulfuric acid or nitric acid: Gold is not attacked by these acids while Cu
and Ag dissolve. If, however, the Au content in an impure sample is more than 30%, the Cu
and Ag are also not attacked by the acid of any strength. Hence, before the acid treatment,
the impure sample is melted with necessary amount of Ag to reduce its gold content to
about 25% (quartation). The resulting alloy, after being granulated in water, is boiled with
H2SO4 or nitric acid when Cu and Ag pass into solution, leaving Au undissolved. Au is
separated and fused again with borax and nitre when 100% Au is obtained.
(ii) Parting with CI2 : Sometimes chlorine is used for the purification of Au. The impure
sample of Au is fused with borax and CI2 gas is forced through it. The base metals are
converted into chlorides that pass out as fumes at this high temperature, and AgCI forms a
separate layer between the fused layer of Au and borax, which is skimmed off and the Au
left behind cast into ingots.
(III) POLING PROCESS :
This process is used for the purification of copper and tin.
(i) Purification of impure copper : Impure copper is remelted in a reverberatory furnace lined
with SiO2 and a blast of O2 is blows into the furnace. O2 oxidises S, Sb and As to their
respective oxides which, being, volatile, get volatilised and are thus removed. Fe is oxidised
to FeO which forms a slag of FeSiO3 with SiO2 lining of the furnace. Molten copper left
behind contains CuO as impurity. This molten copper is treated with powdered anthracite
and then stirred with a pole of green wood. Green wood, at high temperature, liberates
hydrocarbon gases, which are converted into methane (CH4). Methane thus obtained reduces
CuO to free Cu–metal, which is about 99.5% pure and is called tough pitch copper.
Green wood  Hydrocarbons  CH4
4CuO + CH4  4Cu (pure metal) + CO2 + 2H2O
(ii) Purification of impure tin : Impure tin metal contains the impurities of Cu, Fe, W and
SnO2. The impurity of SnO2 is due to the incomplete reduction of tin stone ore (SnO2) during
smelting. In order to remove these impurities, the impure molten tin metal is taken in a big
pot and stirred with a pole of green wood. Green wood, at high temperature liberates
hydrocarbon gases, which are converted into methane CH4. Methane thus obtained reduces
SnO2 to pure metal while the impurities of Cu, Fe, W etc. come up to the surface, where
they come in contact with air and are oxidised to their respective oxides. The oxides form a
scum on the surface of pure tin metal. This scum is removed from the surface. Tin metal
obtained by this method is 99% pure.
Green wood  Hydrocarbon  CH4
2SnO2 + CH4  2Sn + CO2 + 2H2O
(IV) ELECTROLYTIC REFINING :
Some metals such as Cu, Ni, and AI are refined electrolytically. The Hooper process is a process for
the electrolytic refining of aluminum. Impure AI forms the anode and pure AI forms the cathode of the
Hooper’s cell which contains three liquid layers. The bottom layer is molten impure AI, the middle is
a fused salt layer containing aluminum fluoride, and the top layer is pure AI. At the anode (bottom
layer), AI passes with solution as aluminum ion (AI3+), and at the cathode (top layer), these ions are
reduced to the pure metal. In operation, molten metal is added to the bottom of the cell and pure
aluminum is drawn off the top.
At anode : AI  AI3+ + 3e–
At cathode : AI3+ + 3e–  AI
 Copper obtained from the reduction of ores must be purified for use in making electrical wiring
because impurities increase its electrical resistance. The method used is electro-refining.
Impure Cu obtained from ores is converted to pure Cu in an electrolyte cell that the impure copper as
the anode an pure copper as the cathode. The electrolyte is an aqueous solution of CuSO4. At the
impure Cu anode, Cu is oxidized along with the more easily oxidized metallic impurities such as Zn
and Fe. The less easily oxidized impurities such as Ag, Au, and Pt fall to the bottom of the cell as
anode mud, which is reprocessed to recover the precious metals. At the pure Cu cathode, Cu2+ ions
get reduced to pure copper metal, but the less easily reduced metal ions (Zn2+, Fe2+ and so forth)
remain in the solution.
Anode (oxidation) : M (s)  M2+ (aq) + 2e– (M = Cu, Zn, Fe)
Cathode (reduction) : Cu2+ (aq) + 2e–  Cu(s)
Thus, the net cell reaction simply involves transfer of Cu metal from the impure anode to the pure
cathode, Cu obtained by this process is 99.95% pure.
(V) KROLL’S PROCESS :
TiCI4 + 2 Mg  1000 –150 º C
   Ti + 2 MgCI2 (Kroll’s process)

TiCI4 + 4 Na   Ti + 4 NaCI (Imperial metal industries (IMI) process)

under atmosphere of Ar

NaCI is leached with H2O. Ti is in the form of small granules. Zr is also produced by Kroll’s process.
(VI) VAPOR PHASE REFINING :
(i) Extraction of Nickel (Mond’s process) :
50 º C
Ni(s) + 4 CO(s)   [Ni(CO4)] (g)
[Ni (CO)4](g) 200 º C
 Ni + 4CO(g)
(ii) Van Arkel–De Boer process :
Small amounts of very pure metals (Ti, Zr, or Bi) can be produced by this method.
50 – 250 º C 1400 º C
Impure Ti + 2I2    TiI4     Ti + 2I2
Tungsten filament

(VII) PARKE’S PROCESS :

The removal of the impurities of Ag from the commercial lead is called desilverisation of lead and is
done by Parke’s process . Thus, Parke’s process is the desilverisation of lead.
In Parke’s process, the commercial lead, which contains Ag as impurities, is melted in iron pots and
1% of Zn is added to it. The molten mass is thoroughly agitated. Since Ag is about 300 times more
soluble in Zn than in Pb, most of the Ag present in the commercial lead as impurity mixes with Zn,
to form Zn–Ag alloy. When the whole is cooled, two layers are obtained. The upper layer contains
Zn–Ag alloy in the solid state, while the lower layer has lead in the molten state. This lead contains
only 0.0004% of Ag and hence is almost pure. Lead obtained after removing most of Ag from it
(desilverisation of lead) by Parke’s process, is called desilverised lead. This lead contains the impurities
of metals like Zn, Au, Sb etc. These metal impurities are removed from desilverised lead by Bett’s
electrolytic process.
Zn–Ag alloy, formed in the upper layer, is skimmed off from the surface of the molten lead by
perforate ladles. This alloy contains lead as impurity. This impurity of Pb is removed from the alloy
by liquation process, in which Zn–Ag alloy is heated in a slopping furnace, when the impurity of Pb
melts and hence drains away from the solid alloy. Thus purified Zn–Ag is obtained. Now Ag can be
obtained from this purified Zn–Ag alloy by distillation process, in which the alloy is heated strongly
in presence of little carbon in a fire–clay retort. Zn, being more volatile, distills off while Ag remains
in the retort, carbon used in the process reuses the oxide of Zn, if formed. Ag obtained from Zn–Ag
alloy is contaminated with a little of Pb as impurity. This impurity of Pb placed in a cupel (cupel is a boat–
shaped) dish made of bone ash which is porous in nature) in a reverberatory furnace and heated in the
presence of air. By doing so, lead (impurity) is oxidised to PbO(litharge) which volatilises and pure Ag is
left behind in the cupel. Last traces of PbO are absorbed by the porous mass of the cupel.
(VIII) Pudding process : This process is used for the manufacture of wrought iron from cast iron. We
know that cast iron contains the impurities of C, S, Si, Mn and P. When these impurities are
removed from cast iron, we get wrought iron. In this process the impurities are oxidised to their
oxides not by blast of air but by the haematite (Fe2O3) lining of the furnace.
 MISCELLANEOUS SOLVED PROBLEMS (MSPs)
1. At a site, low grade copper ores are available and zinc and iron scraps are also available. Which of the two
scraps would be more suitable for reducing the leached copper ore and why?
Sol. Since zinc lies above iron in electrochemical series, it is more reactive than iron. As a result, if zinc scraps
are used the reduction will be faster. However, zinc is a coastiler metal than iron. Therefore, it will be advisable
and advantageous to use iron scraps.

2. A metal is extracted from its sulphide ore and the process of extraction involves the following steps.
(A) (B ) (C) (D)
Metal sulphide   Concentrated ore   Matte   Impure metal   Pure metal
Identify the steps (A), (B), (C) and (D).
Sol. (A) Froth floatation process. Sulphide ores are concentrated by froth-floatation process.
(B) Roasting. Metal sulphides are roasted to convert into metal oxide and to remove impurities.
In roasting ; 2CuFeS2 + O2  Cu2S + 2FeS + SO2.
2FeS + 3O2  2FeO + 2SO2.
2Cu2S + 3O2  2Cu2O + 2SO2.
FeO + SiO2  FeSiO3
(C) Bessemerisation / self reduction. Reduction of metal oxide by its sulphide takes place in Bessemer
converter.
In Bessemerisation ; 2Cu2O + Cu2S  6Cu + SO2 (self - reduction)
(D) Electro-refining. Pure metal is obtained at cathode.
Mn+ + n e–  m

3. Write chemical equations for metallurgical processes to represent :

(i) roasting of galena (PbS) in limited supply of air at moderate temperature.
(ii) reduction of Cu2O using coke as a reducing agent.
(iii) deposition of pure silver from an aqueous solution of Ag+.
Sol. (i) 2PbS + 3O2  2PbO + 2SO2
PbS + 2O2  PbSO4
(ii) Cu2O + C  2Cu + CO
(Electrolysis )
(iii) Ag+ + e–    Ag  (at cathode)

4. Using data given below, predict whether the reduction of MgO with C is spontaneous or not at 1500ºC.
2 C + O2   2 CO Go  – 530 kJ
2 MgO  2 Mg + O2 Go  + 730 kJ
o
Sol. The positive value of G indicates that the reduction of MgO with C dose not occur to a significant extent at
1500ºC .
2 C + O2  2 CO Go  – 530 kJ
2 MgO  2 Mg + O2 Go  + 730 kJ
2 MgO + 2C  2Mg + 2CO
or MgO + C  Mg + CO Go positive value.

(A) (B ) (C) (D)

5. Sea water   Mg(OH)2   Mg CI2. 6H2O   MgCI2   Mg + CI2
Identify the reagents and processes (A) to (D) and give the name of this process.
Sol. MgCI2 (from sea water) + Ca(OH)2 (A)  Mg(OH)2  + CaCl2 ; Mg(OH)2 + 2HCI (B)  MgCI2 (aq.) + 2H2O
Crystallisation of MgCI2(aq) yields MgCI2.6H2O
Calcinatio n ( C )
MgCI2 6H2O  
Dry HCl
 MgCI2 + 6H2O

Electrolysis( D )
MgCI2()     Mg2+ + 2CI–
 +2e  CI2
–

Mg CI2
(cathode) (anode)
Name of the process is Dow’s process.
6. Convert magnesite into anhydrous MgCI2.

Sol. Mg CO3  MgO + CO2.
MgO + C + CI2  MgCI2 + CO

7. Which is not the correct process-mineral matching in metallurgical extraction.

(A) Leaching : silver (B) Zone refining : lead.
(C) Liquation : tin (D) Van Arkel : Zr
Sol. Lead is purified by Electro-refining. Zone refining is used for the purification of Si and Ge.
Therefore, (B) option is correct.

8. Tin stone, an oxide or of tin is amphoteric in nature. Explain.

Sol. Tin stone is cassiterite i.e. SnO2. SnO2 dissolves in acid and alkali both, hence amphoteric oxide.
SnO2 + 4HCI  SnCI4 + 2H2O
SnO2 + 2NaOH  Na2SnO3 + H2O

9. Select the incorrect statement.

(A) In the Bayer’s AI2O3 goes in to solution as soluble [AI(OH)4]– while other basic oxides as TiO2 and Fe2O3
remain insoluble
(B) Extraction of zinc from zinc blende is achieved by roasting followed by reduction with carbon.
(C) The methods chiefly used for the extraction of lead and tin are respectively carbon reduction and electrolytic
reduction.
(D) Extractive metallurgy of magnesium involves fused salt electrolysis.
Sol. Lead  self reduction; 2PbO + PbS  3Pb + SO2
Tin  carbon reduction, SnO2 + 2C  Sn + 2CO
Therefore, (C) option is correct.

10. Which of the following is not an ore of iron ?

(A) limonite (B) cassiterite (C) magnetite (D) none of these
Sol. SnO2 , cassiterite is an ore of tin.
Therefore, (B) option is correct.

11. In the extraction of copper from sulphide ore the metal is formed by reduction of Cu2O with :
(A) FeS (B) CO (C) Cu2S (D) SO2

Sol. 2Cu2O + Cu2S  6Cu + SO2 .
Therefore, (C) option is correct.

12. Which of the following is a carbonate ore ?

(A) pyrolusite (B) malachite (C) diaspore (D) cassiterite
Sol. CuCO3.Cu(OH)2 Malachite.
Therefore, (B) option is correct.

13. Assertion : In froth floatation process sodium ethyl xanthate is used as collector.
Reason : Sulphide ores are water soluble.
(A) If both Assertion and Reason are true and Reason is a correct explanation of Assertion.
(B) If both Assertion and Reason are true and Reason is not a correct explanation of Assertion.
(C) If Assertion is true but Reason is false.
(D) If Assertion is false but Reason is true.
Sol. Assertion : Potassium or sodium ethyl xanthate is used as a collector. These get attached with the particles
of the sulphide ore and thus make them water-repellant. Consequently the ore particles pass on into the
froth. Collectors are always added in small quantity.
Reason : Sulphide ores are water insoluble.
Therefore, (C) option is correct.
14. Assertion : In the electrolytic reduction of AI2O3, cryolite lowers the melting point of the mixture and brings
conductivity.
Reason : Cryolite is an ore of aluminium.
(A) If both Assertion and Reason are true and Reason is a correct explanation of Assertion.
(B) If both Assertion and Reason are true and Reason is not a correct explanation of Assertion.
(C) If Assertion is true but Reason is false.
(D) If Assertion is false but Reason is true.
Sol. Assertion : Cryolite as impurity reduces the melting point of Al2O3 from 2200 K to approximately 930 K and
being ionic compound dissociates to give ions which bring about the conductivity of the electrolyte.
Reason : Cryolite is Na3AlF6 and is ore of aluminium.
Therefore, (B) option is correct.

15. Assertion : Reduction of ZnO with carbon is done at 1100ºC.

Reason : Gº is negative at this temperature thus, process is spontaneous.
(A) If both Assertion and Reason are true and Reason is a correct explanation of Assertion.
(B) If both Assertion and Reason are true and Reason is not a correct explanation of Assertion.
(C) If Assertion is true but Reason is false.
(D) If Assertion is false but Reason is true.
Ans. All three oxidation curves for the carbon system lie above that for oxidation of zinc, until a temperature of
approximately 1000ºC is reached. At this point C is thermodynamically capable of reducing ZnO to Zn. Since
this temperature is greater than the boiling point of Zn (907ºC), it will be formed as a vapour. The overall
equation for reduction is
ZnO(s) + C (s)  Zn(g) + CO(g)
Therefore, (A) option is correct.

16. Column-I and column-II contains four entries each. Entries of column-I are to be matched with some entries
of column-II. Each entry of column-I may have the matching with one or more than one entries of column-II.
Column-I Column-II
(A) Pb (p) Bessemerisation
(B) Cu (q) Roasting
(C) Zn (r) Pyrometallurgy
(D) Fe (pig iron) (s) Self-reduction method
Ans. (A) q, r, s; (B) p, q, r, s; (C) q, r; (D) r ;
Sol. (A) 2PbS + 3O2  2PbO + 2SO2 (Roasting)

PbS + PbO2  2Pb + SO2 (Self-reduction method)
(B) 2Cu2S + 3O2  2Cu2O + 2SO2 (Roasting)

Cu2S + 2Cu2O  6Cu + SO2 (Self-reduction takes place in Bessemer converter)
(C) 2ZnS + 3O2  2ZnO + 2SO2 (Roasting)

ZnO + C  Zn + CO (Carbon reduction)
(D) Haematite ore is calcined.

3Fe2O3 + CO  2Fe3O4 + CO2

Fe3O4 + CO  3FeO + CO2

FeO + CO  Fe + CO2
 METALLURGY

4. Extraction of Iron
4.1 Important Ores of Iron
i) Haematite Fe2O3 (red oxide of iron)
ii) Limonite Fe2O3×3H2O (hydrated oxide of iron)
iii) Magnetite Fe3O4 (magnetic oxide of iron)

4.2 Roasting
Cast iron is extracted from its oxides by reduction with carbon and carbon monoxide in a blast furnace to give pig iron.
Ferrous oxide convert into ferric oxide.
Fe 2 O 3 . 3 H 2 O ® Fe 2 O 3 + 3 H 2 O ; 2 FeCO 3 ® 2FeO + 2CO 2 ; 4 FeO + O 2 ® 2 Fe 2 O 3

4.3 Smelting
Iron is usually extracted from the haematite. Concentrated ore after calcination is reduced with
carbon i.e. smelted in the blast furnace.

Reactions taking place in the blast furnace

i) Zone of combustion
C + O 2 ¾¾® CO2
( Coke )

ii) Zone of reduction

Fe2O3 + 3CO ¾® Fe + CO2
iii) Zone of reduction
Fe2O3 + 3CO ¾® 2Fe + 3CO2
FeO + CO ¾® Fe + CO2
iv) Zone of slag formation
CaCO3 ¾¾® CaO + CO2
(lim e stone )

CaO + SiO2 ¾¾® CaSiO3 ;

Fusible slag

v) Zone of fusion lower part of furnace

Molten iron is heavier than from
molten slag. The two liquids are
periodically tapped off. The molten
iron tapped off from the furnace is
solidifed into blocks called ‘pigs’.

4.4 Preparation of Wrought Iron

This is done by heating cast iron with haematite (Fe2O3) which oxidises C to CO, S to SO2, Si to
SiO2, P to P4O10 & Mn to MnO
Fe2O3 + 3C ¾® 2Fe + 3CO
Where CO & SO2 escape, manganous oxide (MnO) and Silica (SiO2) combine to form slag.
MnO + SiO2 ¾® MnSiO3
Similarly phosphorus pentoxide combines with haematite to form ferric phosphate slag.
2Fe2O3 + P4O10 ¾® 4FePO4
 METALLURGY
Note : q The gases leaving at the top of the furnace contain up to 28% CO, and are burnt in cowper's
stove to pre-heat the air for blast
Varieties of iron : The three commercial varieties of iron differ in their carbon contents. These are;
(1) Cast iron or Pig-iron: It is most impure form of iron and contains highest proportion of carbon
(2.5–4%).
(2) Wrought iron or Malleable iron : It is the purest form of iron and contains minimum amount of
carbon (0.12–0.25%).
(3) Steel : It is the most important form of iron and finds extensive applications. Its carbons content
(Impurity) is mid-way between cast iron and wrought iron. It contains 0.2–1.5% carbon. Steels
containing 0.2–0.5% of carbon are known as mild steels, while those containing 0.5–1.5% carbon
are known as hard steels.
Steel is generally manufactured from cast iron by three processes, viz, (i) Bessemer Process which
involves the use of a large pear-shaped furnace (vessel) called Bessemer converter, (ii) L.D.
process and (iii) open hearth process, Spiegeleisen (an alloy of Fe, Mn and C) is added during
manufacture of steel.
Heat treatment of steels : Heat treatment of steel may be defined as the process of carefully
heating the steel to high temperature followed by cooling to the room temperature under controlled
conditions. Heat treatment of steel is done for the following two purposes,
(i) To develop certain special properties like hardness, strength, ductility etc. without changing the
chemical composition.
(ii) To remove some undesirable properties or gases like entrapped gases, internal stresses and
strains. The various methods of heat treatment are,
(a) Annealing : It is a process of heating steel to redness followed by slow cooling.
(b) Quenching or hardening : It is a process of heating steel to redness followed by sudden cooling
by plunging the red hot steel into water or oil.
(c) Tempering : It is a process of heating the hardened or quenched steel to a temperature much
below redness (473–623K) followed by slow cooling.
(d) Case-hardening : It is a process of giving a thin coating of hardened steel to wrought iron or to a
strong and flexible mild steel by heating it in contact with charcoal followed by quenching in oil.
(e) Nitriding : It is a process of heating steels at about 700 o C in an atmosphere of ammonia. This
process imparts a hard coating of iron nitride on the surface of steel.
Properties of steel : The properties of steel depend upon its carbon contents. With the increase in
carbon content, the hardness of steel increases while its ductility decreases.
(i) Low carbon or soft steels contain carbon upto 0.25%.
(ii) Medium carbon steels or mild steels contain 0.25–0.5% carbon.
(iii) High carbon or hard steels contains 0.1 – 1.5 percent carbon.
(iv) Alloy steels or special steels are alloys of steel with Ni, Cr , Co, W , Mn, V etc., For example –
stainless steel is an alloy of Fe, Cr and Ni and it is used for making automobile parts and utensils.
Tool steel is an alloy of Fe, W , V etc.
Uses of steel:In general, steels are used for making machinery parts, girders, tools, knives, razors,
household utensils, etc. The specific use of steel depend upon the nature of metal added to iron.

5. Extraction of Aluminium
5.1 Important ores of aluminium

1. Bauxite Al 2O3×2H2O
2. Cryolite Na3AlF6
3. Feldspar K2OAl 2O3×6SiO2 or KAlSi3O8
4. Mica K2O×3Al2O3×6SiO2×2H2O
5. Corundum Al 2O3
6. Alumstone or Alunite K2SO4×Al2(SO4)3×4Al(OH)3
 METALLURGY
5.2 Purification of Bauxite
Purification of Bauxite

Ba yer’s process Hall’s P rocess Serpeck’s proc ess

This process is use d for red (For Red Bauxite) This process is em ployed for
b auxite which contains Al 2 O 3 ×2H 2 O + Na 2 CO 3 th e pu rification of white
relatively large r q uan tities of ¯ bauxite which contain s silica
iron o xide as im purities. 2NaAlO 2 + C O 2 + 2H 2 O as the chief im purity. O re is
A l 2 O 3 ×2H 2 O + 2NaO H iron oxid e a nd silica rem ain powdered , m ixed with coke
B auxite as residue. Sodium me ta and heated to 20 73 K in an
¯ aluminate is heated and atmosphe re of n itrogen
2 NaAlO 2 + 3H 2 O stream of CO 2 passed Al 2 O 3 ×2H 2 O + N 2 + 3C®
S odium meta alumina te thro ugh when A l(O H) 3 gets 2AIN + 3CO + 2H 2 O
(soluble) precipitated. Alum inium nitride
Ferric o xide rem ains insolu ble 2NaAlO 2 + 3 H 2 O + CO 2 SiO 2 + 2 C ® Si- + 2 CO-
Na AlO 2 + 2H 2 O ¯ AlN +3H 2 O ® A l(OH ) 3 ¯ + NH 3
¯ 2Al(O H) 3 ¯ + Na 2 CO 3
A l(O H) 3 ¯ + NaO H

1473 K
2Al(OH)3 ¾¾ ¾
¾® Al2O 3 + 3H2O (calcination of aluminium hydroxide)
Alu min a

5.3 Electrolysis of fused pure alumina (Hall & Heroult Method)

The addition of cryolite (Na3AlF6) and fluorspar (CaF2) makes alumina a good conductor of electricity
and lowers its Fusion temperature from 2323 to 1140 K. the reaction taking place during electrolysis.

Na3AlF6 3NaF + AlF3 AlF3 Al3+ + 3F–

At cathode At anode
Al3+ + 3e– ¾® Al F– ¾® F + e–
2Al 2O3 + 12 F ¾® 4AlF3 + 3O2

2C + O2 ¾® 2CO
2CO + O2 ¾® 2CO2

5.4 Refining of Aluminium

The aluminium metal obtained by the electrolysis of fused almina is about 99.5% pure. It can be further
refined by Hoope’s electrolytic process.

6. Extraction of Tin
The chief ore of tin is cassiterite or tin stone, SnO2. It contains about 10% of tin. The crushed ore is
washed with water to remove lighter impurities. The ore is then roasted to remove arsenic and sulphur
as volatile oxides. Tin is obtained by reducing SnO2 with carbon at 1200- 13000C in an electric furnace.

1200-1300 C o
SnO2 + 2C ¾¾ ¾¾¾ ¾® Sn + 2 CO

The product often contains traces of Fe, which make the metal hard. Fe is removed by blowing air
through the molten mixture to oxidise the iron to FeO, which then floats to the surface.

7. Extraction of Lead
The principal ore of lead is Galena, PbS. The ore is first concentrated by froth floatation process. The
concentrated ore is roasted in air to convert it into lead oxide PbO and lead sulphate. Some galena is
also left unchanged. If the air supply is now reduced, the unreacted PbS reacts with PbO and PbSO4 to
produce metal
 METALLURGY
3PbS + 5O2 ¾® 2PbO + PbSO4 + SO2
2PbO + PbS ¾® 3Pb + SO2
PbSO4 + PbS ¾® 2Pb + 2SO2

8. Extraction of Magnesium
Magnesium from sea-water is obtained by the Dow's process. It consists of electrolysis of molten
magnesium chloride using an iron cathode and a graphite anode. Following are the steps that involved
during the process.

a) Mg+2 is precipitated as magnesium hydroxide by the addition of slaked lime, Ca(OH)2 to the sea
water.

Mg2+ + Ca(OH)2 ¾® Mg(OH)2 + Ca2+

b) Magnesium hydroxide on treatment with hydrochloric acid is converted to chloride which is

crystallised as MgCl 2.6H2O

Mg(OH)2 + 2HCl ¾® MgCl2 + 2H2O

c) Molten mixture of MgCl2 , NaCl and CaCl 2 is electrolysed. Magnesium is formed at the cathode and
chlorine is evolved at the anode. The chlorine is used to make HCl acid which in turn is required for
making magnesium chloride.

Cathode : Mg2+ + 2e- ¾® Mg

Anode : 2Cl- ¾® Cl2 + 2e-

9. Extraction of Copper
9.1 Important Ores of Copper
i) Copper glance (chalcocite) Cu2S
ii) Copper pyrites (Chalopyrites) CuFeS2
iii) Malchite Cu(OH)2 ×CuCO3
iv) Cuprite or Ruby copper Cu2O
v) Azurite Cu(OH)2×2CuCO3

9.2 Metallurgy of Copper

Ores: Copper pyrites (chalcopyrite) CuFeS 2 , Cuprite (ruby copper) Cu 2 O, Copper glance (Cu 2 S) ,
Malachite [Cu(OH )2 . CuCO 3 ], Azurite [Cu(OH ) 2 . 2CuCO 3 ]
 METALLURGY

COPPER PYRITES
(CuFeS2)
Crushed and Sieved

Concentration by froth floatation

Powdered ore + water + pine oil + air ¾® sulphide ore in the froth

Rosting in reverberatory furnace in presence of air

S + O2 ¾® SO2; 2As + 3O2 ¾® 2As2O3
2CuFeS2 + O2 ¾® Cu2S + 2FeS + SO2
Sand + Coke

Smelting in blast furnace in presence of air

2FeS + 3O2 ¾® 2FeO + 2SO2; FeO + SiO2 ¾® FeSiO3 (slag)

Cu2O + FeS
S lag
(Matte)

Bessemerisation in bessemer converter in presence of air

2FeS + 3O2 ¾® 2FeO + 2SO2; FeO + SiO2 ¾® FeSiO3
2Cu2S + 3O2 ¾® 2Cu2O + 2SO2
Auto
2Cu2O + Cu2S ¾¾ ¾
¾® 6Cu + SO2
reduction

Blister copper (98% Cu + 2% impurities)

*Electrolytic refining
Anode–impure copper plates
Cathode-pure copper plates
Electrolyte -CuSO4 + H2SO4

Pure copper at cathode (99.9% pure)

Note : q Blister copper : Which contain about 98% pure copper and 2% impurities (Ag, Au, Ni, Zn etc.)
Properties of copper : It has reddish brown colour. It is highly malleable and ductile. It has high
electrical conductivity and high thermal conductivity. In presence of CO 2 and moisture Cu is covered
with a green layer of CuCO 3 . Cu(OH ) 2 . 2Cu + H 2 O + CO 2 + O 2 ® CuCO 3 .Cu(OH ) 2 . It undergoes
displacement reactions with lesser reactive metals e.g. with Ag. It can displace Ag from AgNO 3 . The
finally divided Ag so obtained is black in colour'
 METALLURGY

10. Extraction of Silver

10.1 Important Ores of Silver:
i) Argentite or silver glance, Ag2S
ii) Horn Silver AgCl
iii) Pyragyrite (Ruby Silver), Ag2S, Sb2S3

10.2 Metallurgy of silver:

Silver is mainly extracted from argentite (Ag2S) by Cyanide Process
SILVER ORE (Argentite)

Concentration by froth floatation

Powdered ore + water + pine oil + air ¾® sulphide ore in the froth

CYANIDATION
Concentrated ore + NaCN solution (0.4 – 0.6%) + Air
Ag2S + 4NaCN 2Na[Ag(CN)2] + Na2S
4Na2S + 5O2 + 2H2O ¾® 2Na2SO4 + 4NaOH + 2S

Filtrate

Precipitation of silver with zinc

2Na[Ag(CN)2] + Zn ¾® 2Ag + Na2[Zn(CN)4]
Black ppt.

fuse
Black ppt. of Ag + KNO3 ¾¾ ¾¾® compact mass silver metal

Electrolytic refining
Anode–impure silver plates
Cathode-pure silver plates
Electrolyte -AgNO3 solution + HNO3

Pure silver at cathode

11. Extraction of Gold

Ores :Bismuthaurite ( BiAu 2 ), Syvanite ( AgAuTe 2 ) , Calverite ( AuTe 2 ) .
Extraction : By cyanide or Mac-Arther forest cyanide process,
4 Au + 8 NaCN + 2H 2 O + O 2 ® 4[ NaAu(CN ) 2 + 4 NaOH]
Sodium aurocyanide

2 Na[ Au(CN ) 2 + Zn ® Na 2 [ Zn(CN ) 4 ] + 2 Au

Refining : Anode : Crude gold; Cathode : Pure gold.
Electrolytic Solution : Gold chloride in hydrochloric acid.
Plattner chlorine extraction process,
AuCl 3 + 3 FeSO 4 ® FeCl 3 + Fe 2 (SO 4 ) 3 + Au
AuCl 2 + 3 H 2 S ® 6 HCl + 3S + 2 Au
Quartation process : Refining of gold carried out by this method. It involves separation of gold and Ag by
H 2 SO 4 .
 METALLURGY
Gold is soft and hence for making ornaments it is generally hardened by adding Ag or Cu . The weight of
gold is expressed in terms of Carats. Pure gold is taken as 24 carats.
20 carats means, it contain 20 parts by wt. of gold in 24 parts by wt. of given alloy.
20 250
\percentage of gold in 20 carat gold sample = ´ 100 = = 83.33%
24 3

12. Extraction of Zinc

Ores :Zincite (red zinc ore) ZnO, Franklinite ( ZnOFe 2 O 3 ) , Zinc blende (ZnS), Calamine ( Zinc spar) ZnCO 3 .
Extraction : Concentration: Froth floatation
1200 K D
Roasting: ZnS + 3O2 ¾¾ ¾ ¾® 2 ZnO + 2SO2 ; ZnS + 2O 2 ¾¾® ZnSO 4
D
2 ZnSO 4 ¾¾® 2 ZnO + 2SO 2 + O 2 .
Reduction of ZnO: The oxide ore is mixed with crushed coke and heated to about 1670K in fire clay retorts
(Belgian process). The crude metal obtained called Zinc spelter.
Refining : By distillation and by electrolytic method
Anode : Spelter; Cathode : Pure zinc wire; Electrolyte : Zinc sulphate.

Note : q Zinc is a volatile metal (easily vaporisable)

qAt ordinary temperature zinc metal is brittle but on heating at 120 – 150 o C it is malleable and ductile.

12. Some Other Important Compounds

1. MgCO3 Magnesite 2. MgCO3×CaCO3 Dolomite
3. MgSO4×7H2O Epsomsalt 4. KCl×MgCl 26H2O Carnallite
5. MgAl 2O4 Spinal 6. H2MgSiO3 Talc
7. Ca2Mg5Si 8O22(OH)2 Asbestos 8. KAlSi3O8 Feldspar
9. Cu(OH)2CuCO3 Malachite 10. Cu(OH)22CuCO3 Azurite
11. PbS Galena 12. Fe3O4 Magnetite
13. 3Fe2O33H2O Cimonite 14. AgNO3 Lunar Caustic
15. ZnSO4×7H2O White Vitriol 16. SnCl2×5H2O Butter of Iron
17. CaO Quick lime 18. Na2SO4×10H2O Glauber’s salt
19. Pb3O4 Red lead 20. Pb(OH)22PbCO3 White lead
21. Na2CO3 Soda ash 22. NaOH Caustic Soda
23. KOH Caustic potash 24. Ca(OH)2 Slaked lime
25. CaSO42H2O Gypsum 26. (CaSO4)2H2O Plaster of Paris
27. FeSO4×7H2O Green Vitriol 28. Hg2Cl 2 Calomel
Corrosive
29. HgCl2 30. PbSO4 Anglesite
Sublimate
31. PbO Cittarge 32. ZnO Philosopher’s wool
33. HgS Cinnabar 34. BaSO4 Baryte or heavy spar
35. ZnS Zinc blende
 METALLURGY

12. Some important Alloy

Sl. No. Name Composition
1. Stainless Steel Fe, Cr, Ni
2. Invar Fe, Ni
3. Alnico Fe, Al, Ni, Co
4. Brass Cu, Zn
5. Bronze Cu, Zn, Sn
6. Gun Metal Cu, Sn
7. Bell Metal Cu, Sn
8. German Silver Cu, Zn, Ni

13. Solved Problems

13.1 Objective

Example 1: The actual reducing agent of hematite in blast furnace is

(A) C (B) CO (C) Al (D) CO2
Solution:
C + O2 ¾® CO2 ; C + CO2 ¾® 2CO
CO + Fe2O3 ¾® 2FeO + CO2 ; CO + FeO ¾® CO2 + Fe
\ (B)

Example 2: Calamine is an ore of

(A) Hg (B) Zn (C) Cd (D) Ca
Solution:
Calamine is an ore of Zn containing ZnCO3.
\ (B)

Example 3: Froth floatation process for the concentration of ores is a practical application of
(A) Adsorption (B) Absorption (C) Coagulation (D) Sedimentation
Solution:
Gangue particles are wetted by water and adsorbed.
\ (A)

Example 4: Plumbo-solvency refers to

(A) Oxidation of lead to lead oxide
(B) Oxidation of lead to red lead
(C) Dissolution of lead in water containing air
(D) Making lead wires by forcing heated metal through a die
Solution: Lead dissolves in water containing dissolved air, due to the formation of lead hydroxide. This solvent
action of water on lead is called plumbo-solvency.
\ (c)
Example 5: The metal oxide, which cannot be reduced to metal by carbon is
(A) ZnO (B) Fe2O3 (C) PbO (D) Al2O3