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Basic Principles of Metallurgy

 A few elements like carbon, sulphur, gold, platinum, copper, silver, mercury and noble gases, occur
in the free state while others in combined forms like oxides, sulphides, carbonates, sulphates, silicates etc.
in the earth’s crust.
 Among metals, aluminium is the most abundant. It is the third most abundant element in earth’s crust
(8.3% approx. by weight). It is a major component of many igneous minerals including mica and clays.
Many gemstones are impure forms of Al2O3 and the impurities range from Cr (in ‘ruby’) to Co (in
‘sapphire’). Iron is the second most abundant metal in the earth’s crust. It forms a variety of compounds
and their various uses make it a very important element.

Terminology:

Metallurgy:

 The scientific and technological process used for isolation of the pure metal from its ores is known
as metallurgy.
 Depending upon the nature of metal and the nature of ore, different methods are used in the
extraction process. The different metals used are a) Pyrometallurgy, b) Hydrometallurgy and c)
Electrometallurgy
 Pyrometallurgy: A process in which the ore is reduced to metal at high temperature using a
suitable reducing agent like carbon, hydrogen, aluminium etc. is called pyrometallurgy.
 Hydrometallurgy: A process of extraction of metals from aqueous solutions of their salts
using suitable reducing agents is called hydrometallurgy.
 Electrometallurgy: A process of extraction of metals by electrolytic reduction of molten
(fused) metallic compounds is called electrometallurgy.
Minerals:

 A naturally occurring chemical substance obtained in mining which contains the metal in a free state
or combined state is called mineral.
Ores:

 A mineral containing a high percentage of metal from which the metal can be profitably extracted is
called an ore. Ex: Copper glance (Cu2S), Haematite ( Fe2O3)
 Types of Ores: Ores may be divided into four groups
 Native Ores: These ores contain the metal in free state eg. Silver gold etc.
 Oxidized Ores: These ores consist of oxides or oxy-salts (eg. carbonates, phosphate) and
silicate of metal. e.g. Haematite, the ore of iron Fe2O3, Bauxite the ore of aluminium
Al2O3.2H2O, Cassiterite SnO2, Cuprite Cu2O, Zincite ZnO, Ilmenite FeTiO3, Rutile, TiO2 etc.
 Important carbonate ores are limestone (CaCO3), Calamine (ZnCO3), Siferite,
(FeCO3), Cerrusite, (PbCO3) etc.
 Important sulphate ore is Anglesite (PbSO4).
 Sulphurised Ores: These ores consist of sulphides of metals like iron, lead, mercury etc. e.g.
iron pyrites (FeS2). galena (PbS), Cinnabar (HgS). They are also called pyrites
 Halide ores: Metallic halides are very few in nature. Chlorides are most common examples
include horn silver (AgCl) carnallite KCl. MgCl2.6H2O and fluorspar (CaF2), Cryolite, (Na3AlF6).
 Silicate Ores: Hemimorphite, (2ZnO.SiO2.H2O)
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Gangue:

 ores are usually contaminated with unwanted earthly(sandy) or undersides materials known as
gangue. For example in the extraction of iron, silica is gangue present in haematite (Fe2O3).

Mineral Wealth in India:

Metal Reserves States

Goa, Madhya Pradesh,

Iron Approx. 1750 crore tonnes Bihar, Karnataka, Orissa and
Maharashtra.

Bihar, Goa, Madhya Pradesh,

Maharashtra, Tamil Nadu, Gujarat,
Aluminium 2 million tonnes. Karnataka, Orissa, Uttar Pradesh,
Andhra Pradesh, Jammu &
Kashmir and Rajasthan.

Singhbum district (Bihar), Balaghat

Copper 60 crore tonnes district (Madhya Pradesh) and
Jhunjhunu district (Rajasthan)

Zawar mines near Udaipur (Rajasthan)

and at
Hazaribagh (Jharkhand), Sargipalli
Zinc and Lead Not significant
mines in Orissa and
Bandalamottu lead project in Andhra
Pradesh, Gujarat and Sikkim

Hazaribagh (Jharkhand)
Tin –
and Orissa

Gold from Kolar fields

and Hutti gold fields (Karnataka).
Gold and Silver –
lead-zinc ores of Zawar
mines (Rajasthan) contain some silver
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Titanium 100 to 150 million tonnes beach sands of Kerala and Tamil Nadu

Sodium Ladakh and Kashmir and sea water

Steps Involved in Extraction of Metals:

 The extraction and isolation of metals from ores involve the following major steps:
 Concentration of the ore (or) Purification of the Ore
 Conversion of ores into oxides or other desired compounds.
 Reduction of ores to form crude metals
 Refining of metals
Step – 1: The concentration of the ore:

 The removal of earthy and siliceous impurities (i.e. gangue or matrix) from the ores is called
concentration, dressing or benefaction. of ores. This process increases the percentage of the desired metal
or metal compound in the ore.
 It involves several steps and selection of these steps depends upon the differences in physical
properties of the compound of the metal present and that of the gangue. The type of the metal, the
available facilities and the environmental factors are also taken into consideration.
Hand picking:

 In this process the earthy impurities (heavy impurities) which are present in the ore like rocky
materials, pellets are picked by hand.
Pulverizing:

 Ore obtained from mines is in a lump form. It is finely ground to form powdered ore, the process is
called pulverizing.
 For pulverizing the ore, jaw crushers or grinders are used. The big lumps of the ore are brought in
between the plates of a crusher forming a jaw. One of the plates of the crusher is stationary while the other
moves to and fro and the crushed pieces are collected below.
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 The crushed pieces of the ore are then pulverized (powdered) in a stamp mill. The heavy stamp rises
and falls on a hard die to powder the ore.

Hydraulic washing or Gravity Separation:

 It is done by two ways a) Wilfley table method and b) Hydraulic classifier method
 Wilfley Table Method: The pulverized ore is made to fall through the hopper on slanting floor of
Wilfley’s table. The floor of Wilfley’s table is made up of fixed wooden triangular strips called cleats or
riffles. This floor is continuously vibrating. A running stream of water is passed across the table. The
lighter gangue particles are washed away and the heavier ore particles settle between wooden cleats of the
table.
 Hydraulic Classifier Method: Hydraulic classifier consists of a tank having hopper at the top and a
pipe for carrying pressurized water. The ore is fed into the tank from the top, and the water is allowed
with high pressure from the bottom of the tank. During this process the lighter impurities which are
adhered to the ore float over the water which is removed by flowing water. The ore particles will settle
down at the bottom of the tank. In this process, the lighter impurities are removed.

Magnetic separation:

 In this method, electromagnetic separators are used. This method of concentration is used when
either the ore or impurities associated with it are magnetic in nature.
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 This process is used for the Iron ore only. → The ore is passed through a belt which is connected by
two rotating wheels, one among is made up of magnetic material. Once the ore is passed through the belt,
the ore or impurity particles having magnetic properties are attracted to the magnetic wheel and fall near
to it. While the impurities or ore particles which are nonmagnetic are not attracted by the magnetic wheel
and fall away from the magnetic wheel as shown in the figure. Thus two separate heaps are formed.

 Example: Cassiterite is ore of tin (Sn) contains non-magnetic stannic oxide SnO2, the magnetic
impurity tungstate or wolframite FeWO4. They can be separated by this method.

Froth floatation:

 Principle: The surface of sulphide ores is preferentially wetted by oils while that of gangue is
preferentially wetted by water. Hence this method is used for concentration of sulphide ores.
 Process: In this process, a suspension of the powdered ore is made with water. Certain oils like pine
oil, eucalyptus oil, xanthates or fatty acids are added as collectors along with froth stabilisers. Collectors
are the chemical substances which enhance non-wettability of the mineral particles. Froth stabilizers are
the chemical substances stabilise the froth. e.g.: cresols, aniline.
 A rotating paddle agitates the mixture and draws air in it. As a result, a froth is formed which carries
the mineral particles. The froth is light and is skimmed off. It is then dried for recovery of the ore particles

 Depressants are the chemical substances which help to separate two sulphide ores by adjusting the
proportion of oil to water. For e.g., in case of an ore containing ZnS and PbS, the depressant used is
NaCN. It selectively prevents ZnS from coming to the froth but allows PbS to come with the froth.
Leaching:

 Leaching is a process in which powdered ore is treated with a suitable reagent which is selectively
dissolved the ore but not the impurities. This process is often used if the ore is soluble in some suitable
solvent. It is a chemical method used for purification of ore.
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 Leaching of Alumina from Bauxite:

 The principal ore of aluminium bauxite consists of three chemical impurities ferric oxide (Fe2O3),
silica (SiO2) and titanium oxide (TiO2).
Bayer’s Process:

This method is used when major impurity is ferric oxide (Fe2O3)

The ore is treated with Sodium hydroxide solution (NaOH), at about 423 K. The impurity ferric oxide
(Fe2O3) does not react with NaOH and can be removed by filtration.

Al2O3.2 H2O(s) + 2NaOH(aq) → 2NaAlO2 (aq) + 3 H2O(l)

 The solution is filtered to remove insoluble impurities and is agitated with freshly prepared Al(OH)3,
so that the aluminium in NaAlO2 get precipitated to Al(OH) 3.
2NaAlO2 + 2 H2O → NaOH + Al(OH) 3

 The precipitate obtained in the process is washed, dried and heated to get Al2O3.
Al(OH3 →Heat Al2O3 + 3 H2O

Hall’s Process:

 In this process, the ore and sodium carbonate are fused together to convert aluminium oxide into
soluble sodium meta aluminate.
Al2O3.2 H2O(s) + Na2CO3(aq) → 2NaAlO2 (aq) + CO2(g) + 2H2O(l)

 The insoluble residue contains the impurities of silica and iron oxide. The filtrate is warmed and
neutralized by passing carbon dioxide through the solution to produce aluminium hydroxide.
2NaAlO2 + 3 H2O + CO2(g) → 2Al(OH) 3 + Al(OH)3 + Na2CO3(aq)

 The precipitate obtained in the process is washed, dried and heated to get Al2O3.
Al(OH3 →Heat Al2O3 + 3 H2O

Step – 2: 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
from concentrated ore involves two major steps viz., (a) conversion to oxide, and (b) reduction of the
oxide to metal.
Step – 2A: Conversion to Oxide:

Roasting:

 Roasting is a process in which ores are heated to a high temperature below their melting point in the
presence of an excess of air.
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 Calcination is generally used for ores containing carbonates and hydrated oxides.
 Roasting is carried out in a reverberatory furnace This process is usually used for sulphide ores.
During this process the moisture is removed, organic matter is destroyed and non-metallic impurities like
that of S, P and As are oxidized and removed as volatile gases.
S8 + 2 → 8SO2↑ (Sulphur dioxide)

P4 + 5O2 → 2P2O5 ↑ (Phosphorus pentaoxide)

4As + 3O2 → 2As2O3↑ (Arsenious oxide)

Ores are generally converted into metallic oxides

2ZnS (Zinc sulphide) + 3O2 → 2ZnO (Zinc oxide) + 2SO2↑

2PbS (Lead oxide) + 3O2 → 2PbO (Lead oxide) + 2SO2↑

2Cu2S (Cuprous sulphide) + 3O2 → 2Cu2O (Cuprous oxide) + 2SO2↑

Calcination:

 Calcination is a process in which the ore is heated to a high temperature below its melting point in
the absence of air or in a limited supply of air.
 It is carried out in a reverberatory furnace In this process moisture, volatile impurities like carbon
dioxide, sulphur dioxide are expelled from the ore. The ore is made porous. Carbonate ores decompose to
form a metal oxide and carbon dioxide.
ZnCO3 + Heat →ZnO(s) + CO2(g) ↑

CaCO3 + Heat →CaO(s) + CO2(g) ↑

CaCO3.MgCO3 + Heat →CaO(s) + MgO(s) + 2CO2(g) ↑

2Fe2O3 . 3H2O + Heat →2Fe2O3 + 3H2O(g) ↑

Reduction of Free Metal:

Smelting:
Reduction of a metal from its ore by a process involving melting
Several reducing agents such as sodium, magnesium and aluminium are used for reduction.
The calcinated or roasted ore is mixed with carbon (coal or coke) and heated in a reverberatory or a blast
furnace.
Carbon and carbon monoxide produced by incomplete combustion of carbon reduce the oxide to the metal.
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Flux:

The ores even after concentration contain some earthy matter called gangue which is heated combine with
this earthy matter to form an easily fusible material. Such a substance is known as flux and the fusible
material formed during reduction process is called slag.


Acidic fluxes like silica, borax etc are used when the gangue is basic such as lime or other metallic oxides
like MnO, FeO, etc
Basic fluxes like CaO, lime stone (CaCO3), magnesite (MgCO3), hematite (Fe2O3) etc are used when the
gangue is acidic like silica, P4O10 etc.

Refining of Metals:

The metals obtained by the application of above reduction methods from the concentration ores are usually
impure. The impure metal is thus subjected to some purifying process known as refining in order to remove
undesired impurities. Various process for this are

i.e., Liquation process, Distillation process,Cupellation,Poling,Electrolytic refining, Bessemerisation.

Zone refining (Fractional crystallization): This method is employed for preparing extremely pure metals.
This method is based upon the principle that when a molten solution of the impure metal is allowed to cool,
the pure metal crystalises out while the impurities remain in the melt.
Electro-refining: In this method, the impure metal is converted into a block which forms the anode while
cathode is a rod or plate of pure metal. These electrodes are suspended in an electrolyte which is the solution
of a soluble salt of the metal usually a double salt of the metal. When electric current is passed, metal ions
from the electrolyte are deposited at the cathode in the form of pure metal while an equivalent amount of
metal dissolves from the anode and goes into the electrolyte solution as metal ion. The soluble impurities
present in the crude metal anode go into the solution while the insoluble impurities settle down below the
anode as anode mud.
Van-Arkel Method: In this method, the metal is converted into it volatile unstable compound such as
iodide leaving behind the impurities. The unstable compound thus formed is decomposed to get the pure
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metal.

Cupellation and Poling are used for refining of metals, cupellation is contain impurities of other metals
with traces of lead are removed from silver by heating impure silver with a blast of air in a cupel (an oval
shaped pan made up of bone ash) in which lead is oxidised to lead oxide (PbO) which being volatile escapes
leaving behind pure silver.Poling is used for refining of such metals which contain impurities of its own
oxide. In this process, the molten impure metal is stored with green wooden poles. At the high temperature
of the molten metal, wood liberates methane which reduces the oxide of the metal to free metal.

Thermodynamic Principles of Metallurgy:

ΔG =ΔH-TS
or ΔG0 =-RT ln K
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An element A can reduce element B if ΔG value for oxidation of A to AO is lower than the ΔG value
for oxidation of B to BO.
i.e. ΔG(A→AO) < ΔG(B→BO)

Extraction of Aluminium
Aluminium is the most abundant metal in the earth’s crust. Aluminium does not occur free in nature, but its
compounds are numerous and widely distributed.
The chief and important ore from which aluminium is exclusively and profitably obtained is Bauxite,
AI2O3.2H2O. The extraction of the metal from bauxite involves the three main steps.
 Purification of Bauxite
 Electrolytic reduction of Alumina, (AI2O3)
 Purification of AI.
1. Ores of Aluminium
Name of Ore Formula of Ore

Cryolite Na3AlF6

Feldspar K2Oal2O3×6SiO2 or KalSi3O8

Mica K2O×3Al2O3×6SiO2×2H2O

Corundum Al2O3

Aluminium is mainly extracted from bauxite ore.

2. Extraction of Aluminium
Purification of Bauxite
By Bayer’s process comercially it is being carried out (for red bauxite not for the white bauxite).
Flow sheet of Bayer’s process for the preparation of pure Al2O3
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Hall’s process
Crude bauxite at 1100°C reacts with Na2CO3, little CaCO3 when CaSiO3, NaSiO2, NaFeO2 etc. form
Al2O3 + Na2CO3 → 2NaAlO2 + CO2
Fe2O3 + Na2CO3 → 2NaFeO2 + CO2
SiO2 + Na2CO3 → Na2SiO3 + CO2
CaO + SiO2 → CaSiO3
Then at 50° – 60°C CO2is passed through NaAlO2 solution and produces thereby Al(OH)3
2NaAlO2 + CO2 + 3H2O ¾® 2Al(OH)3¯ + Na2CO3

2Al(OH)3 Al2O3 + 3H2O

Serpeck’s Process
Bauxite containing high percentage of silica can be purified by Serpeck’s process. In this process finely
powdered bauxite is mixedf with coke and the mixture is heated to 1800°C in a current of nitrogen. The AlN
thus obtained is reacted with hot and dilute NaOH, produced NaAlO2 and excess AlN is hydrolysed and
Al(OH)3 is formed.
Al2O3 + 3C + N2 → 3AlN + 3CO
SiO2 + 2C → Si + 2CO
AlN +NaOH → NaAlO2 + NH2+
NaAlO2 + 2H2O → Al(OH)3¯ + NaOH
AlN + 3H2O → Al(OH)3¯ + NH3

2Al(OH)3 Al2O3 + 3H2O

Electrolytic Reduction of Al2O3

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Pure alumina melts at about 2000°C and is a bad conductor of electricity. If fused cryolite AlF3.3NaF and
CaF2 (Fluorspar) is added the mixture melts at 900°C and Al2O3 becomes a good conductor of electricity.
Metallic Al is liberated at the cathode

Alumina is mixed with cryolite (Na3AIF3), fluorspar (CaF2) in the ratio 20 : 60 whereby, it not only
becomes good conductor but also fuses at about 900oC which is much below the b.p. of aluminium.
The electrolysis of the fused mass is carried out in an iron box, which lined with gas carbon. The lining
serves as the cathode, the anode consists of carbon rods dipped in the fused mass. The fused electrolyte is
kept covered with a layer of powdered coke to prevent any action of air. The voltage employed in the
electrolysis is 5.3 volts. The current passed (about 50,000 amperes) serves to purposes: (i) heating and (ii)
electrolysis. Thus the fused mass is automatically kept at 900oC during electrolysis.
Aluminium is obtained at the cathode and being heavier than the electrolyte sinks to the bottom and is
tapped off periodically from the tap hole. Oxygen liberated at the anode attacks carbon rods and forms CO
and CO2. During electrolysis the concentration of the electrolyte goes on falling thereby increasing the
resistance of the cell which is indicated by the glowing of a lamp placed parallel. Much of the alumina is
then added and the process is made continuous.
Electrolysis of molten mixture
Cathode: Carbon
Anode: Graphite rods
Electrolyte: 60 parts cryolite + 20 parts fluorspar + 20 parts pure Al2O3
Temperature: 900°C
Reactions
According to the 1st theory the following reaction occurs
Al2O3 2Al+3 + 3O–2
At cathode : 2Al+3 + 6e → 2Al
At anode : 3O–2 – 6e → 3O2
As cryolite has greater electrochemical stability it does not dissociate. It only increases the dissociation of
Al2O3
But the second theory states that, cryolite undergoes electrolytic dissociation first then Al+3 goes to the
cathode, produced F2 at anode then reacts with Al2O3 produces AlF3.
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AlF3.3NaF Al+3 + 3Na+ + 6F–

At cathode : Al+3 + 3e → Al
At anode : 6F– – 6e → 3F2
Overall Reaction : Al2O3 + 6F2 → 4AlF3 + 3O2
Solved Problem
Question 1:
Aluminium is not extracted directly from bauxite, instead, bauxite is first purified to produce pure alumina
from which aluminium is extracted by electrolytic reduction – Explain why?
Solution
Aluminium is not directly extracted from bauxite. This is because of the fact that, bauxite is always
associated with impurities like ferric oxide and silica. If bauxite is used directly for the extraction of
aluminium, the iron and silica present in if would deposit at the cathode during its electrolytic reduction.
The aluminium thus obtained at the cathode, becomes contaminated with iron and silica. As a result, the
produced aluminium becomes brittle and is readily attacked by air and water.
___________________________________________
Question 2:
In moist air copper corrodes to produce a green layer on the surface. Explain
Solution:
In presence of moist air a thin film of green basic copper carbonate is formed on its surface and hence
copper corrodes
2Cu + O2 + H2O + CO2 → CuCO3.Cu(OH)2
3. 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
Aluminium as produced by the electrolysis of AI2O3 is 90% pure. It can be refined further up to 99.9%
purity by Hoope’s process.
The electrolytic cell consists of an iron tank lined with carbon. It is filled with three liquids differing in
specific gravity. The upper layer is of pure fused aluminium and serves as cathode.
The bottom layer is that of impure metal in the fused state and serves as anode. The central layer is that of
molten mixture of the fluorides of AI, Ba and Na and serves as an electrolyte
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On passing electric current, pure aluminium goes to the top layer from the central layer and an equivalent
amount of the metal from the bottom layer passes into the central layer. There is thus gradual transference of
aluminium from bottom layer to the top and the impurities are left behind. Crude aluminium is added from
time to time.
4. Uses of Aluminium
 Aluminium, being very light, is used in householf utensils, aeroplane parts, precision and surgical
instruments etc.
 Since it is unattached by nitric acid, is used in chemical plants and also for transporting nitric acid.
 Aluminium foil is used for packing chocolates, cigarettes etc.
 Alums are used as mordents in dyeing and points.
 Mixed with oil, it is used in steam piped and other metal objects.
 It is used as a reducing agent for the production of certain metals such as chromium, iron, manganese
etc.
 Alumina is used for making refractory bricks and ultramarine.
5. Alloys of Aluminium
Aluminium forms a number of useful alloys, which are given as follow;

Alloy Approximate composition Uses

1) Aluminium bronze AI 10%, Cu 90% For hard, non-corrodible vessels

2) Duralumin AI 95%, Cu3% Mn1% Mg1% Aeroplanes and automobile parts

3) Magnalium AI 90%, Mg10% Balance beams

4) Y-alloy AI 92.5%, Cu 4%, Ni 2%, Mg Aeroplan

1.5%

Refining of Aluminium:
The graphite rods dipped in pure aluminium and Cu–Al alloy rod at the bottom in the impure aluminium
work as conductors. On electrolysis, aluminium is deposited at cathode from the middle layer and equivalent
amount of aluminium is taken up by the middle layer from the bottom layer (impure aluminium). Therefore,
aluminium is transferred from bottom to the top layer through middle layer while the impurities are left
behind. Aluminium thus obtained is 99.98% pure.

Hydrometallurgy (solvent extraction)

Solvent extraction is the latest separation technique and has become popular because of its elegance,
simplicity and speed. The method is based on preferential solubility principles.
Solvent or liquid-liquid extraction is based on the principle that a solute can distribute itself in a certain ratio
between two immiscible solvents, one of which is usually water and the other an organic solvent such as
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benzene, carbon tetrachloride or chloroform. In certain cases, the solute can be more or less completely
transferred into the organic phase.

Extraction of Iron

Ores of Iron
Magnetite (Fe3O4)
Red haematite (Fe2O3)
Brown haematic Limonite (Fe2O3.3H2O)
Spathic iron or sidenite (FeCO3)
Iron pyrites (FeS2), Copper pyrites (CuFeS2)

Concentration of the ore

Dressing of the ores: The iron ores are first broken into small pieces 3-5 cm in size.
Roasting or Calcination: During roasting S, As, P are oxidized to the respective oxides.
S + O2 → SO2↑
4As + 3O2 → 2As2O3↑
FeCO3 decomposes as,
FeCO3 → FeO + CO2↑
Fe2O3.3H2O loses water
Fe3O4 is decomposed to ferrous oxide and ferric oxides.
Fe3O4 → FeO + Fe2O3
Ferrous oxide reacts with silica to forms ferrous silicate at high temperature.
FeO + SiO2 → FeSiO3
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But the conversion of FeO into Fe2O3 will prevent the formation of FeSiO3. Thus the mass of the ore
becomes porous causing the increase in the effective surface area.
Smelting in the Blast furnace: Blast furnace is a shaft furnace made of steel plate of 20-30 in with 4-4.6
diameter.

Extraction of Cast Iron

Iron is usually extracted from the haematite. Concentrated ore after calcinations is reduced with carbon i.e.
smelted in the blast furnace.
Reactions taking place in the blast furnace are
Zone of combustion:
C + O2 → CO2
(Coke)
CO2 + C → 2CO; ΔH = +ve (Newmann’s inversion reaction)
Zone of reduction:
The following reduction reactions are called indirect reduction, which is done by CO, which is unstable at
higher temperature (See Ellingham diagram).
Fe2O3 + 3CO → 2Fe + 3CO2
FeO + CO → Fe + CO2
Zone of slag formation:
CaCO3 → CaO + CO2

Zone of fusion (lower part of furnace):

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Molten iron is heavier than from molten slag. The two liquids are periodically tapped off. The molten iron
tapped off from the furnace is solidified into blocks called ‘plags’.
Refer to the following video for blast furnace

Preparation of Wrought Iron

This is done by heating cast iron with haematite (Fe2O3) which oxidizes C to CO, S to SO2, Si to SiO2, P to
P4O10 and Mn to MnO
Fe2O3 + 3C → 2Fe + 3CO
Where CO and SO2 escape, manganous oxides (MnO) and Silica (SiO2) combine to form slag.
MnO + SiO2 → MnSiO3
Similarly phosphorous pentoxide combines with haematite to form ferric phosphate slag.
2Fe2O3 + P4O10 → 4FePO4
Bosh :
The diameter of the furnace gradually increases from the top down wards. Widest part of the furnace is
called Bosh. At above 2m tuyers are there through which hot air blast is blown into the furnace.
Hearth:
Below the bosh this region exists. (1) slag notch is at higher height and (2) tap hole for metal passage at
lower position from the bottom.
At the top of the furnace the hopper is there which is cup and cone arrangement.
Through this charge is introduced ill the course bed in the furnace is 4/5th the of the furnace. How air at
700oC is forced into the furnace through the tuyers.
The thermal gradient inside exists from 1800oC (hearth) to 400oC–900oC in the upper region. Near the both
the temperature varies from 1200o-1300o chemical reactions which take place are:
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At 1200oC near the tuyers,

C + O2 → CO2;
CO2 + C → 2CO
Above bosh 600o-900oC, ferric oxide is partially reduced by CO as
Fe2O3 + 3CO ↔ 2Fe + 3CO2↑

CaCO3 CaO + CO2

2CO CO2 + C

Fe2O3 + 3C → 2Fe + 3CO

CaO + SiO2 → CaSiO3 (slag)
The reaction at 1500oC, MnO2 is reduced to Mn
MnO2 + 2C → Mn + 2CO
Ca3(OH)2 → CaO + P2O5
2P2O5 + 10C → P4 + 10CO
Collection of Cast iron: Metal is cast into ingots or in the ladle for further refining like steel making.
Wrought Iron: Minimum % of carbon is 0.1 – 0.1% and other impurities like S, P, Mn, Si less than 0.3%
Manufacturing Process: Cast iron is taken in pudding furnace and melted by hot blast of air. The chemical
reactions, which occur, are
S + O2 → SO2↑
3S + 2Fe2O3 → 4Fe + 3SO2↑
3Si + 2Fe2O3 → 4Fe + 3SiO2
Mn + Fe2O3 → 2Fe + 3MnO
MnO + Fe2O3 → MnSiO3 (slag)
3C + Fe2O3 → 2Fe + 3CO
4P + 5O2 → 2P2O5; Fe2O3 + P2O5 → 2FePO4 (slag)
The impurities are removed from ion, the melting point of the metal rises and it becomes as semi solid mass.
Metal taken out from the furnace in the form of balls with the help of rubbles. The balls are then beaten
under hammer to separate out the slag. The product thus formed is thus called wrought iron.

Some Important Alloy

Name Composition

Stainless steel Fe, Cr, Ni

Invar Fe, Ni
 19

Alnico Fe, AI, Ni, Co

Brass Cu, Zn

Bronze Cu, Zn, Sn

Gun Metal Cu, Sn

Bell Metal Cu, Sn

German Silver Cu, Zn, Ni

Solder, pewter Pb, Sn

Babbitt metal Sn, Sb, Cu

Steel
Manufacture From CI (Cast Iron)
Acid Bessemer Process
This process is carried out when percentage of P is very low. The lining of the furnace is made of SiO2. The
following reactions take place to lessen the impurities.
2Mn + O2 → 2MnO
Si + O2 → SiO2
MnO + SiO2 → MnSiO3
S + O2 → SO2
4Fe + 3O2 →2Fe2O3
Fe2O3 + 3C → 2Fe + 3CO
2C + O2 → 2CO
When the blue flame of CO drops out it complete oxidation of carbon.
All the reactions are exothermic. After the complete of the reaction calculated amount of spiegeleisen (an
alloy of Fe, Mn, C) is added to the molten mass. After that again air blast is continued for two minutes to
engage the thorough mixing of the speigel. The function of speigcleisen is to supply requisite amount of
carbon to iron to produce steel of desired quality.
FeO + Mn → MnO + Fe
FeO + C → Fe + CO
Carbon and mangenese of the spiegel act as deoxidisers to remove any dissolved O2 and reduce any
ferrous oxide which may be formed during the reactions. Manganese serves to make the steel harder and to
increase its tensile strength. The converter is then tilted and molten steel cast into moulds, or taken in laddle
for further processing.
Basic Bessemer Process
 20

The lining of the converter is of basic materials like CaO, MgO etc. The converter is charged with molten
cast iron and some lime is added to it and hot blast of air under pressure is continued. Mn, Si of CI is first
oxidised. S from SO2, C, P are then oxidised to form CO and P2O5. The P2O5 thus formed combines with
lime to form a basic slag [Ca3(PO4)2.CaO] which is known as Thomas slag.
2Mn + O2 → 2MnO; MnO + SiO2 → MnSiO3 (slag)
Si + O2 → SiO2
S + O2 → SO2
2C + O2 → 2CO
4P + 5O2 → 2P2O5
After the completion of the reactions the air blast is stopped and the converter is tilted and the basic slag is
removed. Spiegeleisen is added to the molten Fe when it is converted and steel.
Open Hearth Process
Open hearth process is the modern process for the manufacture of the high grade steel.
The impurities present in the cast iron are mainly oxidised by the addition of haematite ores and the rest are
oxidised by O2 of air.
The percentage of C, Si is lowered down by the addition of scrap Fe.
Heat generated by burning the mixture of producer gas and air is used to preheat the fuel gas and air.
This regenerative system causes an economic fuel consumption and maintains high temperature (1800°C) in
the furnace.
Reactions taking place in the hearth:
Mn, Si, P, S and carbon are oxiidsed by haematite (Fe2O3) to form their respective oxides. The reactions
occuring are as follows.
2Fe2O3 + 3Si → 4Fe + 3SiO2
Fe2O3 + 3Mn →2Fe + 3MnO
2Fe2O3 + 3S → 4Fe + 3SO2
Fe2O3 + 3C → 2Fe + 3CO
5Fe2O3 + 6P → 10 Fe + 3P2O5
MnO + SiO2 → MnSiO3
CaO + SiO2 → CaSiO3
3CaO + P2O5 → Ca3(PO4)2
3MgO + P2O5 → Mg3(PO4)2 (Slag mixture)
C, P are also oxidised by air to forms carbon monoxide and phosphorus pentoxide.
2C + O2 → 2CO
4P + 5O2 → 2P2O5
 21

After the removal of impurities slag is separated, requisite amount of spiegeleisen is added to the molten
mass to obtain desired quality of steel by deoxidation and recarburisation. While molten ferrosilicon or Al
are also sometiems added for removal of any dissolved gas in it.
Duplex process:
This is actually a combination of acid besemer process and open hearth process. Si, Mn, S, C (partially) are
oxidised and removed or slag or volatite oxides. This process is applied in TISCO.
Varieties of Steel
Carbon steel can be divided into the following groups.
Low carbon (mild steel) 0.15 - 0.3%.
Medium carbon steel 0.3 - 0.6%.
High carbon steel 0.6 - 0.8%.
Tool steel 0.8 - 1.4%.
Alloy Steels

Nickel Steel (2 - 5%) Ni Very hard, tough, resistant to For making shafts, gears,
corrosion etc.

Chrome steel (13 - 14%) Cr, 0.7% Resistant to corrosion For making house hold
Ni, 0.3% C materials.

Manganese 9 - 14%Mn Very hard, resistant to ware For making helmets

steel

Inver 30 - 36% Ni 0.3% C Coefficient of expansion is Measuring instruments

very low

Alnico 20% Ni, 12% Al, High magnetic property For making strong
5% Co magnets.

Durairon 16% Si Resistant to acids Vessels for keeping HCl, H2SO-

4 etc.

Extraction of Copper
The chief and important ore of copper from which the metal is most isolated is copper pyrites
(CuFeS2). Froth floatation process is used for concentrating the ore. The powdered ore is suspended in water
and after adding little pine oil is stirred by means of air. The sulphide ore particles come to the surface &
gangue remains at the bottom is rejected.
1. Ores of Copper
 22

Name of Ore Formula of Ore

Copper glance or Chalcocite: Cu2S

Chalcopyrites(copper pyrites): Cu2S×Fe2S3

Cuprite Cu2O

Malachite [CuCO3.Cu(OH)2]

Azurite [2CuCO3.Cu(OH)2]

2. Extraction of Metallic Copper

Concentration of the ore by froth floatation process:
Copper pyrites contains only (2-3)% of copper. The rest of the ore contains iron or sulphide, silica, silicious
materials, sulphur, arsenic etc. as impurities. Froth flotation by Xanthate and pine oil. The froth is collected
and dried when concentrated ore is obtained which contains 25-30% of Cu.
Roasting
Cu2S.Fe2S3 + O2 → Cu2S + 2FeS + SO2
Cu2S.Fe2S3 + 4O2 → Cu2S + 2FeO + 3SO2
2Cu2S + 3O2 → 2Cu2O + 2SO2
Cu2O + FeS → Cu2S + FeO
Smelting of the roasted ore in blast furnace: material required
Roasted ore
Lime stone
Coke (used as fuel)
Silica (used as flux)
Lime stone (used to remove excess silica)
Reactions occurring given as follows
2FeS + 3O2 → 2FeO + 2SO2
Cu2O + FeS → Cu2S + FeO
FeO + SiO2 → FeSiO3 (removed as slag)
CaO + SiO2 → CaSiO3 (removal as slag)

Self reduction in Bessemer Converter

 Reactions involved are,
2FeS + 3O2 → 2FeO + 2SO2
FeO + SiO2 → FeSiO3 (slag)
 23

2Cu2S + 3O2 → 2Cu2O + 2SO2

Cu2S + 2O2 → Cu2SO4
When 2/3 of the cuprous sulphide is oxiidsed, the balst is stopped. The produced Cu2O and Cu2SO4 are
reduced by the rest of cuprous sulphide to produce metallic copper with the evolution of SO2.
Cu2S + 2Cu2O → 6Cu + SO2
Cu2SO4 + Cu2S → 4Cu + 2SO2
As the molten copper cools, it gives off the dissolved of SO2. The SO2 gas escaping in the form of
bubbles, leaves the surface of the metal with full of cavities which gives the metal a blistered appearnace.
This is why the metal thus obtained is by blister copper.
4. Refining of Copper
Copper is refined using electrorefining method.

Anode: Impure copper obtained above

Cathode: Pure copper
Electrolyte: 15% CuSO4 solution + 5% H2SO4

When electric current is passed through the electrolyte, the anodes gradually dissolve and pure copper is
deposited on the cathodes which gradually grow in size. The impurities like Fe, Zn, Ni etc., dissolved in the
solution as sulphates while gold, silver, platinum settle down below the anode as anode mud.
Reactions coming are as follows
CuSO4 Cu+2 + SO4–2
At anode: Cu – 2e Cu+2
At cathode: Cu+2 + 2e Cu
 24

Metallurgy of Lead: Ores, Properties, Extraction, Purification, Uses

 25

Extraction: Lead is mainly extracted from the sulphide ore galena. Galena contains lead sulphide and small
quantities of silver.

Metallurgy of Lead
Ores
1. Galena PbS
2. Cerrusite PbCO3
3. Anglesite PbSO4
4. Lead ochre PbO
Extraction: Lead is mainly extracted from the sulphide ore galena. Galena contains lead sulphide and small
quantities of silver.

1. Concentration: The ore is concentrated by froth floatation process.

2. Smelting in a Reverberatory furnace: The concentrated ore is roasted in a reverberatory furnace at a moderate
temperature. The temperature of furnace is controlled by regulating the air supply. During roasting, galena is partly
oxidized to lead monoxide and partly to lead sulphate.
2PbS + 3O2 → 2 PbO + 2SO2
PbS + 2O2 → PbSO4
More of galena is then added. The temperature is raised and simultaneously the air supply is reduced. Lead
sulphide reacts with the two oxidised products giving lead.

PbS+2PbO → 3Pb+SO2
PbS+PbSO4 → 2Pb+2SO2
Thus in this process roasting and smelting are carried out in the same furnace,
at two different temperatures.
About 90% of lead is obtained as metal, the rest passes into slag. Lead is
recovered from the slag by heating with lime and powdered coke.
 26

Purification of Lead
Lead extracted by the above method contains impurities such as silver, copper, tin, bismuth, gold and iron. It is
refined by the following processes.
a.Liquation
The impure metal is heated on a sloping hearth. Lead melts and flows down the slope. The infusible impurities
remain on the hearth.
b. Desilverisation
Silver is removed by either Pattinson's process or Park's process.
c. Electrolytic refining
Very pure lead is obtained by this process.
Anode - Impure lead
Cathode - Very pure lead
Electrolyte - Lead fluosilicate + Hydrofluosilicic Acid
(PbSiF6) (H2SiF6)

The metallic impurities which are more electropositive than lead, such as iron and tin, go into the solution while
the rest of the impurities are thrown down as anode mud.

Physical properties

1. Lead is a bluish grey metal with a bright luster.

2. It is soft and can be cut with a knife and drawn into a wire and rolled into a sheet.
3. It is not a good conductor of heat and electricity. It marks paper.
Chemical properties
1. Action of air
i. It is unaffected by dry air but in moist air a layer of lead carbonate or lead hydroxide is deposited on its
surface which protects it from further action of air.
ii. When heated in air or oxygen, lead is oxidized to litharge (PbO) and red
lead (Pb3O4)
2Pb + O2 → 2PbO 3Pb + 2O2 → Pb3O4
2. Action of water
Lead is not attacked by pure water in the absence of air, but water containing dissolved air has a solvent action on it due
to the formation of lead hydroxide (a poisonous substance). This phenomenon is called Plumbo solvency.
2Pb + O2 + 2H2O → 2Pb(OH)2
3. Action of acids
i) Dilute H2SO4 and HCl have no action on lead.
ii) Hot Conc. H2SO4 liberates SO2 but the reaction is retarded by the formation
of an insoluble layer of lead sulphate.

Pb + 2H2SO4→ PbSO4 + 2H2O + SO2→

iii) Concentrated HCl evolves hydrogen and also forms Chloroplumbic acid
Pb + 2HCl → PbCl2 +H2→
PbCl2 + 2HCl --- > < --- H2PbCl4 (chloroplumbic acid)

Uses: Lead is used

 27

i. For making lead pipes,

ii.For making telegraph and telephone wires,
iii.In making bullets and lead accumulators,
iv. In lead chambers, for the manufacture of sulphuric acid,
v. For making alloys like solder, pewter and type metal,
vi. For preparing tetraethyl lead (Pb(C2H5)4) which is used as an additive to petrol to prevent knocking

Extraction Of Zinc: Application Of Metallurgy

Zinc Mining
The most commonly available ore used in the extraction of Zinc is called Zinc Blende also known as Zinc
Sulphide (ZnS). Historically extraction of zinc has been more difficult than extraction of other metals
because at temperatures where metals such as iron typically begins to melt, zinc is a gas. Due to its very low
boiling point, at such temperatures, zinc will escape with exhaust gases. Zinc Blende does not contain a very
high percentage of zinc and hence it needs to be concentrated. The best concentration method for zinc ore
is known as froth flotation.

Concentration of Ore: Froth Flotation Process

Froth Flotation process is mainly used to remove gangue from sulphide ores. The ore is powdered and a
suspension is created in water. The main ingredients of the froth flotation are the Collectors and Froth
Stabilizers. Collectors (pine oils, fatty acids etc) increase the wettability of the metal part of the ore and
allows it to form a froth and Froth Stabilizers (cresols, aniline etc) sustain the froth. The oil wets the metal
and the water wets the gangue. Paddles and air constantly stir up the suspension to create the froth. This
frothy metal is skimmed off the top and dried to recover the metal.

Metal from Concentrated Ore

The next step in the extraction of zinc is called Roasting. The concentrated ore is finely ground into small
pieces and then suspended in a rising stream of air. The sulphur content can be reduced hugely with this
process. This also converts the Zinc Blende to ZnO which is way more reactive. The reaction occurring here
is

2ZnS+3O2−>2ZnO+2SO2
Zinc Oxide is then mixed with Coke and ground into fine pieces and heated at 1673 K in fire clay containers
in a process which is also known as the Belgian Process. Here the Zinc Oxide gets reduced to metallic Zinc.
The carbon from coke acts as the reducing agent in this reaction. The reaction of the final step of extraction
of zinc is

2ZnO+C−>2Zn+CO2
Since, the boiling point of Zinc is way back at 1180 K, the zinc formed immediately vaporizes and distills
over leaving behind non-volatile impurities such as Cadmium, Lead and Iron. This gas containing zinc
 28

vapours is collected and cooled to yield solid zinc. This crude metal is called Spelter. It can be further
purified by fractional distillation.

Zinc alloys with many other metals: Nickel silver, bronze, brass and soft electrical solder all contain zinc. A
lot of the zinc manufactured is used to galvanize iron to prevent corrosion.