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METALMETALLURGY
Metallurgy: The science and technology of extraction of metals economically from the respective ores and
preparation of alloys.
Mineral: The compounds of metals which are naturally occurring in the earth’s crust. A mineral often has a
fixed composition.
Ore: The mineral from which a metal can be extracted economically and conveniently. For example,
FeS2 is a mineral of iron but not its ore. It is due to high cost of production and high sulphur
content.
Gangue: The impurities present in the ore, e.g. SiO2.
Pyrometallurgy: It involves the use of elevated temperature and changes in the chemical composition of
the entire body of ore. Basic processes of pyrometallurgy are
(a) Calcination (b) Roasting (c) Smelting (d) Distillation

Types of ores
Ores

Native/Elemental ores Combined ores

Ex: Ag, Au, Pt etc

Oxygen containing Sulphide Halide ores

ores ores

Oxosalts Oxides

Carbonates Phosphates Nitrates Sulphates

Principal steps in the metallurgical operations:
Step I Concentration of the ore
1. Physical methods:
(a) Gravity separation
(b) Magnetic separation
(c) Froth floatation
2. Chemical methods:
(a) Leaching
Step II Conversion of ore into suitable form (mostly oxide) for reduction
(a) Calcination
(b) Roasting
Step III Reduction
(a) Smelting
(b) Reduction by more electropositive metal, e.g. Al, Zn etc.
(c) self-reduction
(d) electrolytic reduction
Step IV Refining
(a) Distillation
(b) Liquation
(c) Poling
(d) Fractional distillation
(e) Electrolytic refining
(f) Zone refining
(g) Thermal decomposition
(i) Van Arkel method
(ii) Mond’s process

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Step-I Concentration of the ore:
The unwanted impurities, e.g. earth particles, rocky matter, sand, limestone etc. present in an ore are
called gangue or matrix. The process of removal of gangue from the ore is technically known as concentration
or ore dressing and the purified ore is known as concentrate.
There are various physical and chemical process involved in this step.
1.1 GRAVITY SEPARATION OR HYDRAULIC WASHING (LEVIGATION)
This method of concentration of the ore is based on the difference in specific gravities of the metallic ore
and gangue particles. Generally metal ores are heavier than the gangue associated with them. By flowing
the powdered ore in a current of water, the lighter rocky impurities can be washed away and the ore
particles are left behind. For this, either wilfley table or Hydraulic classifier is used. Generally oxide and
carbonate ores are concentrated by this method. i.e. haematite and cerussite. There are two gravity
concentration methods.

1.2 MAGNETIC SEPARATION

This method of separation is used when either the ore particles or the gangue associated with it possess magnetic
properties. For example, chromite Fe(CrO2)2 being magnetic can be separated from the nonmagnetic
silicious gangue by magnetic separation. This method is widely used for the separation of two minerals,
when one of them happens to be magnetic. The magnetic mineral can be separated from the nonmagnetic
one by this method.
For example, wolframite (FeWO4 + MnWO4) which is magnetic is separated from cassiterite SnO2 which is
nonmagnetic by this method. Similarly, rutile TiO2 (magnetic) can be separated from chlorapatite,
3Ca3(PO4)2. CaCl2 by magnetic separation.
1.3 FROTH FLOATATION PROCESS
This method is extensively employed for the preliminary treatment of the minerals especially sulphides.
The process is based on the difference in wetting characteristics of the gangue and the ore with water
and oil. The former surface being preferentially wetted by water and of the latter by oil. The crushed ore
along with water (slurry) is taken in a floatation cell. Various substances (additives) are added depending
on the nature of the ore and a current of air is blown under pressure. The air is broken into tiny bubbles
which are distributed throughout the volume of the pulp, attaching themselves to those solid particles
which have become water repellent after reagent treatment. The bubbleparticle aggregates float to the
surface of the suspension where a mineralladen froth forms. The additives added are usually of three
types.
(i) Frothers: Frothers increase froth stability within desired limit. For example, pine oil, soaps, resins etc.
(ii) Collectors: These attach themselves by polar groups to grains of some mineral and form water repelling
films on those minerals. Hence, these minerals attach with bubbles and go to froth. Collectors will attach
with themselves only to minerals with definite chemical composition and lattice structure. They are high
molecular weight organic compounds. The most common among them are xanthates, carboxylic acids
and their salts.
S

CH3-CH2-O-C-S-Na+
Sodium ethyl xanthate
(iii) Activators and Depressants:
Minerals similar in chemical composition, such as sulphides of copper, lead and zinc exhibit an almost
equal ability to absorb collectors; for this reason, when present in the same suspension, they will tend to
froth together. For the purpose of selective flotation, this tendency may be controlled by supplementary
reagents, known as depressors. Depressors are inorganic compounds, which form films on solid
particles, thereby preventing the absorption by collectors. The film is produced through a chemical
reaction between the depressor and the surface layer of the mineral.
The collector effect, may be enhanced by activators. They are inorganic compounds soluble in water.
Added to the suspension, an activator can destroy or modify the depressor film on the solid particles so
that they are now able to absorb the collector ions or molecules and become floatable. For example,
galena (PbS) is usually associated with zinc sulphide (ZnS), pyrites (FeS2) and quartz (SiO2). Floatation
is carried out by using potassium ethyl xanthate (collector) along with sodium cyanide and zinc vitriol
(depressants). They depress the floatation property of ZnS grains by forming a complex, so mainly PbS
passes into the froth when air is blown in. The froth spills over and is collected. After galena has been
removed with the froth, the process is repeated by adding CuSO4 (activator). This breaks the depressor
film on ZnS grains hence, now these grains are available for collector, which are removed with the froth.
The acidification of remaining slurry leads to the floatation of pyrites.

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1.4 LEACHING
Leaching converts the ore particles (or impurities) into soluble salts while the impurities (or ore particles)
stay in the residue. For example,
(a) Al2O3+Fe2O3+SiO2+TiO2+NaOH Na[Al(OH)4] + impurity as residue
soluble
Impurity

bauxite
Na[Al(OH)4] is converted back into Al2O3 by passing CO2 into the solution.
(b) Ag2S is extracted from silver glance by using NaCN in the presence of air.
Ag 2S+NaCN   Na[Ag(CN)2 ]+Na 2S
soluble
(c) In the extraction of tin, the removal of impurities like FeS2 and Cu2S involves leaching. The two
sulphides are roasted carefully to produce soluble sulphates that are washed away with hot water.
Step-II Conversion of the ore into suitable form for reduction:
In the case of most of the metals, the ore is first converted into its oxide before proceeding for reduction.
The reason can be explained by Ellingham diagram which explains the temperature dependency of G0 of
different oxides.

When we observe the Ellingham diagram for oxides, the following characterstics are found.
1. The line for the formation of CO has negative slope. For the formation of CO2, it is zero
On differentiating ΔG 0 =ΔH0 -TΔS0 w.r.t temperature,
(ΔG 0 )
= -ΔS0
T
As S0 for the formation of CO is positive, the slope is negative.
2. The lines for all other oxides have positive slopes. One more point is that the slopes of some of the lines
are changing midway. The reason is that the respective metals melt at that temperature making S0 of
the reaction more negative.
3. When Ellingham diagram for sulphides and that for oxides are compared, it becomes clear that direct
reduction of sulphides is less favourable than first converting them into oxides and the subsequent
reduction of oxides.

2.1 Calcination
It is a process in which the ore is subjected to the action of heat (below the fusion
temperature of the ore) in the absence or limited supply of air. What happens in calcination?
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(a) Carbonate ores are converted into oxides.
CuCO3.Cu(OH)2  2CuO + H2O + CO2
(Malachite)
MgCO3  MgO + CO2
(Magnesite)
(b) Hydrated ores become anhydrous.
2Fe2O3.3H2O  2Fe2O3 + 3H2O
(Limonite)
(c) Impurites like S, As and Sb are removed in the form of vapours.
2.2 ROASTING
In this process, the ore is heated in the presence of excess of oxygen. What happens during roasting?
(a) sulphides are converted into either oxides (at relatively high temperature) or sulphates (at relatively
low temperature).
2PbS + 3O2  2PbO (or PbSO4) + 2SO2
2ZnS + 3O2  2ZnO (ZnSO4) + 2SO2
2Cu2S + 3O2  2Cu2O (or CuSO4) + 2SO2
Roasting or calcination can be carried out in a reverberatory furnace.
(b) Oxide in the lower oxidation state is converted into the one with higher oxidation state.
1
2FeO+ O2 
 Fe2 O3
2
(c) When tin stone (SnO2) containing impurities, CuS and FeS2, is roasted, CuS and FeS2 are converted
into water soluble sulphates (CuSO4 and FeSO4) which are washed away with hot water.
(d) The impurities like organic matter, S and As are removed in the form of their volatile oxides.
Step-III Reduction:
3.1 SMELTING (Carbon reduction)
What happens in smelting? Carbon or carbon monoxide reduces the oxide into metal. If any
sulphate is formed in roasting, it is reduced to sulphide in smelting.
ZnO + C Zn + CO or ZnO + CO  Zn + CO2 ZnSO4 + C ZnS + CO
PbO + C Pb + CO or PbO + CO Pb + CO2 PbSO4 + C PbS + CO
Fe2O3 + 3C  2Fe + 3CO or Fe2O3 + 3CO  2Fe + 3CO2
1. Reduction does not always happen during smelting. For example, in the extraction of copper,
smelting is done without the reduction of the ore. Carbon is added only to maintain the temperature so
that the slag (FeSiO3) floats.
2. Below 7100C, CO is a better reducing agent than carbon and vice versa is true above 7100C, which
is evident from the Ellingham diagram.

During reduction, additional substance called flux is also added to the ore. It combines with impurities to
form easily fusible product known as slag.
Gangue + Flux  Fusible product (slag)
Flux is a substance that is added to the ore during smelting (a) to decrease the melting point (b) to make
the ore conducting and (c) to remove all the impurities (basic and acidic).
The nature of the flux depends upon the nature of impurity to be removed. An acidic flux (e.g. sand) is
used to remove basic impurities (e.g. metallic oxides like FeO) while basic flux (e.g. CaO) is used to
remove acidic impurities (e.g. sand).
FeO + SiO2  FeSiO3 (fusible slag)
Impurity acidic flux
SiO2 + CaO  CaSiO3 (fusible slag)
Impurity basic flux
Alumina is a bad conductor of electricity but when cryolite (flux) is added, it becomes a good conductor
and the melting point is decreased. Hence, CaF2, KF, cryolite etc are neutral flux.
3.2 Reduction by another metal (aluminium or zinc)
If the temperature needed for carbon to reduce an oxide is too high for economic or practical purposes,
the reduction may be effected by another highly electropositive metal such as aluminium, which liberates
a large amount of energy (1675 kJ mol–1) on oxidation to Al2O3. The process of reduction of a metal oxide
to metal with the help of aluminium powder is called aluminothermy or Goldschmidt Aluminothermic
Process or Thermite process.
This process is employed in the case of those metals, which have very high melting points and are to be
extracted from their oxides. A mixture of concentrated oxide ore and aluminium powder, commonly called
as thermite is taken in a steel crucible placed in a bed of sand. The reaction is initiated by the use of an
ignition mixture containing magnesium powder and barium peroxide. During the reaction, aluminium gets
oxidised to Al2O3 while metal oxides releases metals.
3Mn3O4 + 8Al  9Mn + 4Al2O3 3MnO2 + 4Al  3Mn + 2Al2O3
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B2O3 + 2Al  2B + Al2O3 Cr2O3 + 2Al  2Cr + Al2O3
Sr and Ba are obtained by the reduction of their oxides by aluminium in vacuum.
Magnesium is used in a similar way to reduce oxides. In certain cases where the oxide is too stable to
reduce, electropositive metals are used to reduce metal halides. Titanium (for supersonic aircrafts) and
zirconium (used in atomic reactors) are obtained by the reduction of their tetrachlorides with metallic
sodium or magnesium.
Kroll process
1000 – 1150°C
TiCl4 + 2Mg Ti + 2MgCl2
TiCl4 + 4Na Ti + 4NaCl
Zinc is also used for the reduction process, especially in the case of metallurgy of Au and Ag.
2[Ag(CN) 2 ]- +Zn  2Ag+[Zn(CN) 4 ]-2
2[Au(CN) 2 ]- +Zn 
 2Au+[Zn(CN) 4 ]-2
3.3 Selfreduction process
The cations of the less electropositive metals like Pb, Hg, Sb and Cu may be reduced without the use of
any additional reducing agent. Elevated temperatures and anion or anions associated with the metal may
bring about this change.
For example, in the extraction of mercury, the sulphide ore (cinnabar) is heated in a current of air when
the following reactions take place.
2HgS + 3O2  2HgO + 2SO2
2HgO + HgS  3Hg + SO2 (self reduction reaction)
Similarly, in the extraction of copper, the sulphide and the oxide interact at an elevated temperature to
give the metal.
Cu2S + 2Cu2O  SO2 + 6Cu Cu2SO4 + Cu2O  Cu + SO2 (self reduction reactions)
Similar reactions take place in the selfreduction process for the extraction of lead.
2PbS + 3O2  2PbO + 2SO2
PbS + 2PbO  3Pb + SO2 PbSO4 + PbO  2Pb + 2SO2 (self reduction reactions)
3.4 ELECTROLYTIC REDUCTION
This process is mainly used in the extraction of alkali and alkaline earth metals. In the case of
highly electropositive metals, isolation by chemical reducing agents is extremely difficult. In such cases,
the metal is obtained by electrolysis of fused salts. Some other salts may have to be added to lower the
melting point of the compound taken.
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. (The reaction has many technical difficulties
(i) HF is corrosive (ii) hydrogen produced at the cathode must be kept separate from the fluorine
produced at the anode otherwise explosion may occur (iii) water must be rigorously excluded (iv) fluorine
produced attacks the anode and the reaction vessel).
In fused melts:
Elements that react with water are often extracted from fused melts of their ionic salts. These melts are
frequently corrosive and involve large fuel bills to maintain the high temperature required. Aluminium is
obtained by electrolysis of a fused mixture of Al2O3 and cryolite, Na3[AlF6]. Both sodium and chlorine are
obtained from the electrolysis of fused NaCl: in this case up to twothirds by weight of CaCl2 is added as
an impurity to lower
the melting point from 803°C to 505°C.
An example of this is the manufacture of sodium by electrolysis of a fused mixture of sodium and calcium
chlorides (Down’s process). The cell and electrodes used should not be effected by the electrolyte or the
products. Hence a steel cell, a graphite anode and an iron cathode are employed. The various reactions
that take place are,
On fusion, NaCI Na+ + Cl (ions become mobile)
On electrolysis, (i) At the cathode (negative electrode): Na+ + e  Na (reduction)
(ii) At the anode (positive electrode): Cl  Cl + e (oxidation) ; Cl + Cl  Cl2
The products obtained react readily, hence a suitable arrangement has to be made to keep them
separate.
3.5 THERMAL DECOMPOSITION
Some of the metal oxides are thermally unstable and they can be decomposed to metals.
HgO 4000C  Hg+ 1 O
2
2
300 C 2Ag+ 1 O
Ag 2 O 
0
2
2

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Step IV Refining
4.1 BY POLING
This method is employed when the metal contains the impurities present in the form of its oxide. To
reduce the impurity level, air is blown through molten metal to which a suitable flux may be added.
Impurities are oxidized and escape as gases (CO2) or pass into slag. Finally the surface of molten metal
is covered with low sulphur coke (to prevent oxidation of the metal) and green logs of wood are
introduced into the molten metal. Hydrocarbon gases reduce any oxide of the metal that might have been
formed. This method is used for the purification of Cu and Sn.
4.2 BY LIQUATION
Readily fusible metals like Sn, Pb and Bi are refined by this method. Impure metal in the form of ingots is
placed in the upper part of a sloping hearth (usually of a reverberatory furnace) maintained at a
temperature slightly above the melting point of the metal. The impurities remain behind as dross while the
pure metal melts and flows down into a well at the bottom of the incline.
4.3 BY CUPELLATION
This is a method employed to purify silver containing lead as an impurity. The impure silver is heated in a
shallow vessel made of boneash under a blast of air. The lead is easily oxidised to powdery lead
monoxide. Most of it is carried away by the blast of air. The rest melts and is absorbed by the bone ash
cupel. Pure silver is left behind. Silver itself is not oxidised under these conditions.
4.4 BY DISTILLATION
Some metals have very low melting point and soon vaporise on heating while the associated impurities
remain in the solid state. Zinc, mercury and arsenic are purified by this method. Vaccum distillation gives
very pure product and is used in the refining of the metals of IA and IIA.
4.5 BY FRACTIONAL DISTILLATION
This process is applied for the separation of cadmium from zinc. In the metallurgy of zinc, the metal is
invariably associated with cadmium. The impure zinc is mixed with powdered coke and heated when the
first portion of the condensate contain cadmium while zinc is obtained in the subsequent portions.
4.6 BY ELECTROLYTIC REFINING
This is a very convenient method for refining many impure metals. Most of the metals such as copper,
silver, gold, zinc and chromium are refined electrolytically. The impure metal is made the anode and a
thin sheet of the pure metal as cathode. A solution of a salt of the metal serves as the electrolyte. On
passing an electric current through the electrolyte, the metal dissolves in the electrolyte by oxidation of
the anode and pure metal is deposited at the cathode. The impurities present in the anode either dissolve
in the electrolyte or collect below the anode as anode mud. In the electrolytic refining of copper,
impurities of iron and zinc are dissolved in the electrolyte and while gold, platinum and silver are left
behind as anode mud.

4.7 VANARKEL METHOD/MOND’S PROCESS

This is used for getting ultra pure metals. The principle involved is to convert the metal to a volatile
unstable compound and to subsequently decompose it to give the pure metal. The impurities present
should be such as not to be affected. Metals like titanium, zirconium etc. are purified by using this
method.
523 K
Ti(s) + 2I2(g)  Ti I4(g)
Impure
1700 K
TiI4(g)   Ti(s) + 2I2(g).
Pure
150-180oC
50-600C Ni(CO) (g) 
4CO(g)  4  Ni(s)+4CO(g)

4.8 ZONEREFINING
Metals of very high purity can be obtained by this method by removing an impurity, which shows
difference in solubility of the liquid and solid states of the metal. A circular heater is fitted around a rod of
impure metal and is slowly moved down the rod. At the heated zone, the rod melts and as the heater
passes on, pure metal crystallizes while impurities pass into the adjacent molten part. In this way, the
impurities are swept over one end of the rod, which is finally discarded. The heater may have to be
moved from one end to the other more than once. Ge, Si and Ga, which are used as semiconductors, are
refined in this manner; galliumarsenide and indiumantimonide are also zone refined.

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METALLURGY OF SOME METALS
1. COPPER
Ores of copper: (a) Cuprite Cu2O
(b) Copper pyrites or chalcopyrites CuFeS2 (Cu2S.Fe2S3)
(c) Copper glance or chalcocite Cu2S
(d) Malachite CuCO3.Cu(OH)2
(e) Azurite 2CuCO3.Cu(OH)2
The chief ore of copper is copper pyrites.
Froth floatation Roasting
Finely divided ore Concentrated ore Roasted ore
(Cu2S+FeS+FeSiO3
+Cu2O
Smelting (Coke+Silica)

Self-reduction
Blister copper Cu2S+FeS Slag (FeSiO3)
Matte
Reactions involved:
1. Roasting: S + O2  SO2 (S removed)
4As + 3O2  2As2O3 (As & Sb removed)
Cu 2S.Fe 2S3 +O2 
 Cu 2S+2FeS+SO2
Cu 2S.Fe 2S3 +4O 2 
 Cu 2S+2FeO+3SO2
Since iron is more electropositive than copper, its sulphide is preferentially oxidised. If any Cu2O
is formed, it is converted back into Cu2S.
2. Smelting: Coke is added to maintain the temperature and the flux is SiO2.
3
FeS+ O 2  FeO+SO2
2
FeO+SiO 2 
 FeSiO3 (slag)
High temperature keeps the mixture molten and the slag, being lighter, floats.
3. Self reduction (Bessemer converter): Raw material for Bessemer converter is matte (Cu2S + small amount
of FeS). Initially, air blasting is done for slag formation and SiO2 is added from outside.
3
FeS+ O 2  FeO+SO2
2
FeO+SiO 2 
 FeSiO3 (slag)
During slag formation, characteristic green flame is observed due to the presence of FeO. Disappearance of
green flame indicates completion of slag formation. Again air blasting is started for partial roasting.
Cu 2S+ 3 O 2 
 Cu 2O+SO 2 (Small amount of CuOis also formed)
2
Cu 2S+2Cu 2O  6Cu+SO 2

4. Refining of copper:
Poling Electrorefining
Blister copper Pure copper
Cu+Fe+S+As Electrolyte 15% CuSO
5% H2SO4

2. ZINC
Ores of zinc: Zinc blende ZnS
Calamine ZnCO3
Willemite ZnSiO3
Important ore of zinc is zinc blende, which is also known as black jack due to the presence of PbS.

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Froth floatation Roasting Smelting
Finely divided ore Concentrated ore Roasted ore Impure zinc
Depressant and
Activator are to Refining
be added.
Fractional or Electrorefining
distillation

Reactions involved:
1. Froth floatation: ZnS+4NaCN (depressant)   Na 2 [Zn(CN)4 ]+Na2S
CuSO4 (activator)is added later to activate ZnS.
2. Roasting (Reverberatory furnace at 9500C):
3
ZnS+ O 2   ZnO+SO 2
2
ZnS+2O 2  ZnSO 4
950
ZnSO 4 
0C
 ZnO+SO 2 +O 2
3. Smelting:
ZnO+C 
 Zn+CO
2ZnO+C 
 2Zn+CO 2
CO 2 +C 
 CO
4. Fractional distillation:
Cd bp = 7670C T > 7670C T > 9200C
Crude Zn Pb + Fe
Fe Zn (Fe + Pb)
bp of Zn = 9200C bp > 15000C Cd is vaporised Zn is vaporised
Pb

Electrorefining:
Electrolyte:ZnSO4 +H 2SO4
Cathode: Alsheet (Zn dissolves readilyin dil.H 2SO 4 )
Anode: impure zinc

3. Aluminium

Ores of aluminium: (a) Bauxite Al2O3.2H2O

(b) Diaspore Al2O3.H2O
(c) Corundum Al2O3
(d) Cryolite Na3AlF6 (3NaF.AlF3)
(e) Spinel MgO.Al2O3
(f) Feldspar KAlSi3O8 (K2O.Al2O3.6SiO2)
Aluminium is generally extracted from bauxite. Bauxite is of two types.
1. Red bauxite: Al2O3.2H2O + Fe2O3 (major product) + SiO2 + TiO2
2. White bauxite: Al2O3.2H2O + Fe2O3 + SiO2 (major product) + TiO2

I.CONCENTRATION OF THE ORE:

1.Bayer’s process (for red bauxite)
Residue (Fe2O3 + TiO2)
Calcination Digested with
y powdered bauxite Calcined ore
Removes organic 45% NaOH
Filtrate (NaAlO2 + Na2SiO3)
matter
diluted with water or
CO2 is sent

Filtrate Residue 11000C

Al2O3
Na2SiO3 + NaOH Al(OH)3

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Reactions involved:
Step II: Al2O3 and SiO2, both being more acidic Fe2O3 and TiO2, react with NaOH.
Al2 O3 +NaOH 
 Na[Al(OH) 4 ]
SiO 2 +NaOH 
 Na 2SiO3 +H 2 O
Step III: Al2O3 is less acidic than SiO2. As a result, when CO2 gas is sent into a mixture of NaAlO2 and
Na2SiO3, Al(OH)3 gets precipitated.
Al(OH) 4 - +H 2 CO 3 
 Al(OH) 3 +HCO 3 - +H 2 O

2. Hall’s process (for red bauxite):

Residue (Fe2O3 + TiO2)
Calcination Fused at 11000C
Finely powdered bauxite Calcined ore
Removes organic with Na2CO3 +
CaCO3 Filtrate (NaAlO2 + Na2SiO3)
matter
diluted with water or
CO2 is sent

Filtrate Residue 11000C

Al2O3
Na2SiO3 + Na2CO3 Al(OH)3
When bauxite is fused with Na2CO3 and CaCO3, following reactions happen.
Al2 O 3 +Na 2 CO 3 
 2NaAlO 2 +CO 2
SiO 2 +Na 2CO3 
 Na 2SiO 3 +CO 2
CaO+SiO 2 
 CaSiO 3
Some Fe 2O 3 may also react with Na 2 CO3
Fe 2 O3 +Na 2CO3 
 2NaAFeO 2 +CO 2
3. Serpeck’s process (for white bauxite):
CO + Si
Heated at 18000C
Finely powdered bauxite
in a current of
N2 gas AlN(s) + Fe2O3 + TiO2
Step I

Step II hot and dilute NaOH

NH3 is escaped

Filtrate
Filtrate Residue
NaOH + Na2CO3 CO2
Na[Al(OH)4] Fe2O3 + TiO2
Residue

Al2O3 Al(OH)3
Reactions involved:
Step I Al2 O3 +C+N 2 
 AlN+CO
SiO 2 +C 
 Si+CO
Step II AlN+NaOH+H 2O 
 Na[Al(OH) 4 ]+NH 3

II.ELECTROLYTIC REDUCTION OF PURE Al2O3:

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Electolyte: Molten Al2O3 (20%), Cryolite, 3NaF.AlF3 (60%), Flourspar, CaF2 (20%)
Cathode: Iron tank with carbon lining
Anode: Graphite rod
A layer of powdered coke is maintained at the top. Oxygen liberated at anode may corrode the anode
surface producing CO or CO2. Coke layer prevents this by consuming the oxygen (difference between
carbon block and powdered carbon).
Reactions:
At cathode Al+3 +3e- 
 Al
At anode 2O -2  O 2 +4e-
Cryolite and flouspar help reduce the melting temperature of the electrolyte and increase its electrical
conductivity.
It is believed that an alternate set of reaction may happen during electrolysis.
At cathode Al+3 +3e- 
 Al
At anode 2F- 
 F2 +2e-
F2 +Al 2 O3 
 AlF3 +O2
III.ELECTROREFINING OF Al:

Electrorefining of aluminium is different from that of other metals because of two reasons:
1. Aqueous solution of any aluminium salt can’t be used because H2 is liberated in that case.
2. Molten Al2O3 and molten AlCl3 are high melting solids and poor conductors of electricity.
In electrorefining, an iron tank with carbon lining is used as anode and there are three layers in the tank.
Layer I: Pure aluminium which acts as cathode. Graphite rods dipped in this layer act as electrodes.
Layer II: Molten mixture of cryolite (Al2O3 + BaF2). BaF2 is added to maintain the density so that layer II stays in
the middle.
Layer III: Melt of impure Al and Cu. Cu melt is added to make the layer III sufficiently dense so that it stays at the
bottom.
Reactions: At cathode: Al+3 + 3e-   Al At anode: Al  +3
 Al + 3e
-

4. IRON
Ores of iron: (a) Haematite: Fe2O3
(b) Magnetite: Fe3O4
(c) Corundum Al2O3
(d) Limonite: Fe3O4.3H2O
(e) Siderite: FeCO3
(f) Iron pyrites: FeS2

Fe3O4
Gravity separation Roasting
Fe2O3 Concentrated ore + Roasted ore
Fe2O3 .2H2O CO2, SO2 and As2O3 Smelting
SiO2 is removed small amount of SiO2
FeCO3 are removed Roasted ore :
Blast Coke :Lime stone
furnace = 8:4:1

Molten metal Slag

Reactions involved:
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I. Roasting:
Fe3O 4 
 FeO+Fe2 O3
FeCO3 
 FeO+CO 2
1
2FeO+ O 2   Fe2 O3
2
Fe2 O3 .3H 2 O 
 Fe2 O3 +3H 2 O
S+O 2 
 SO2
As+O 2 
 As2 O3
Conversion of FeO into Fe2O3 prevents the formation of FeSiO3.
II. Smelting: The calcined ore mixed with lime stone (CaCO3) as flux and coke as reductant in the ratio 8 : 1 : 4 is
called charge. The charge is sent into the blast furnace from the top. Hot air is sent from the bottom. Blast
furnace has different temperatures at different heights. The reactions happening in different zones are given
below.
1.Reduction zone(Upper most zone, 250 - 7000 C) 1.Slag formation zone (Central zone, 800 - 10000 C)
3Fe 2 O3 +CO 
 2Fe3O4 +CO 2 CaCO3 
 CaO+CO 2
Fe3O4 +CO 
 3FeO+CO 2 CaO+SiO 2 
 CaSiO 3
FeO+CO 
 Fe+CO2 MnO 2 +2C 
 Mn+2CO
P4 O10 +10C 
 4P+10CO
SiO 2 +2C 
 Si+2CO
2Ca 3 (PO 4 ) 2 +3SiO 2 +10C 
 3(2CaO.SiO 2 )+4P+10CO
3Fe+P 
 Fe3p

3. Combustion zone (Lowest portion, 1500 -16000 C)

C+O 2 
 CO 2
1
C+ O 2  CO
2
CO 2 +C 
 2CO
4. Zone of fusion: It is just above the zone of combustion. The spongy iron formed in the reduction zone collects
at the bottom and melts while the slag, being lighter, floats.
Iron obtained from the blast furnace is called pig iron, which contains 93% Fe, 4% C along with Si, Mg,
P, S and Mn that are formed from their compounds in the reducing atmosphere of the furnace. Cast iron is
different from the pig iron and is made by melting pig iron with scrap iron and coke using hot air blast. Cast iron
has slightly lower carbon content (3%) and is extremely hard and brittle.

III. Purification of iron (preparation of wrought iron/Bessemerisation): Wrought iron is the purest form of
commercial iron and is prepared from cast iron by oxidising impurities in a reverberatory furnace lined with a
basic oxide like CaO or Fe2O3. Molten iron from blast furnace is exposed to a jet of O2 gas for about 20 minutes.
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The impurities are oxidised and the resultant acidic oxides react with CaO to yield a molten slag. Various
reactions taking place in the furnace are:
S+O 2 
 SO 2 C+O2 
 CO2
3S+2Fe2 O3 
 4Fe+3SO2 3Si+2Fe2O3 
 4Fe+3SiO2
3Mn+Fe2O3 
 2Fe+3MnO MnO+SiO 2 
 MnSiO3 (slag)
Fe2 O3 +3C 
 2Fe+3CO P+O 2 
 P2O5
Fe2 O3 +P2O5 
 2FePO4 (slag) P2 O5 +CaO 
 Ca 3 (PO 4 ) 2 (slag)
Mn+O 2 
 MnO

5. TIN
An important ore of tin is casseterite or tin stone (SnO2). The impurities present are SiO2, pyrites of Cu &
Fe (Cu2S + FeS2) and a magnetic impurity, wolframite (FeWO4 + MnWO4).
Gravity separation Roasting Magnetic
Finely divided ore Concentrated ore SnO2 + Black tin
SiO2 is removed Pyrites of Cu and Fe separation 75% SnO
are removed as Wolframite 2
sulphates
Carbon
Metallic Sn
reduction
CaCO3 +
anthracite
Smelting Slag
Metallic Sn FeSiO3 +
C + CaCO3
SnSiO3

Reactions involved:
1. In roasting, the pyrites of Cu and Fe are converted into sulphates because the roasting is done at
moderate temperature. As both CuSO4 and FeSO4 are soluble in water, they can be washed away with
water.
2. In smelting step, CaCO3 is added to remove SiO2 as slag. But some SnO2 also reacts with SiO2
forming SnSiO3. This SnSiO3 separates out with slag. Slag is further smelted along with CaCO3 to
convert any SnSiO3 into Sn.
SnSiO 3 +CaO+C 
 Sn+CaSiO 3 +CO
Refining of tin:
Crude tin with Liquation Poling Electrorefining
impurities Fe, Cu & W Pure Sn
Electrolyte: SnSO4 +H2SO4
Cathode : pure Sn
Anode : impure Sn
In liquation, the low melting Sn separates out upon melting the crude Sn.

6. SILVER
Silver occurs both in combined state as well as free state. The important ores of silver are:

Ores of (a) Argentite: Ag2S (b) Siver copper glance:

silver: Ag2s.Cu2S
(c) Horn silver: AgCl (d) Ruby silver: 3Ag2S.Sb2S3

Cyanide process or Mc-Arthur Forrest process is one of the methods for the extraction of silver.

Residue (impurity)
Froth foatation Digested with
Finely divided ore Concentrated ore
SiO2 is removed with little silica 5% NaCN in the Filtrate Na[Ag(CN)2]
presence of air
Zn powder
in excess

Residue Filtrate
Crude Ag Na2[Zn(CN)2 ]

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Reactions involved:
 Na[Ag(CN) 2 ]+Na 2S
1.Ag 2S+ ex NaCN 
Na 2S+O 2 +H 2 O 
 Na 2SO 4 +NaOH+S
Oxygen drives the first equilibrium in the forward direction by removing Na2S from time to time.
2. 2Na[Ag(CN)2] + Zn   Na2[Zn(CN)2] + 2Ag
Refining of silver:
It is done by electrorefining. Crude silver contains Zn, Cu and Au as impurities.
Electrolyte: AgNO3 + HNO3
Cathode: pure silver
Anode: impure silver

7. GOLD
Gold is obtained in the earth’s crust in the native state. Like silver, gold is also extracted by Cyanide or Mc-Arthur
Forrest process.
Residue (impurity)
Filtrate
Finely divided gold Digested with Zn powder
5% NaCN in the Na2[Zn(CN)2]
containing rock in excess
presence of air Filtrate Na[Au(CN) 2 ]

Residue
Crude Au
Reactions involved:
Au+ ex NaCN+H 2 O+O 2 
 Na[Au(CN) 2 ]+NaOH
Na[Au(CN) 2 ]+Zn 
 Na 2 [Zn(CN) 2 ]+Au
Refining of Au:

Crude Au with dil.H2SO4 Cupellation heated with

impurities Zn, Pb, ZnSO is removed Au (Pb, Cu & Ag) Au (Cu+Ag) Au + Ag
Cu and Ag. 4 removes Pb as borax powder
volatile PbO and washed with
water
Conc
H2SO4

Au

1. Cupellation is a metallurgical process in which a mixture of metals are heated under high temperatures in order
to separate noble metals like gold and silver from base metals like lead, zinc etc. Base metals get oxidised while
the noble metals do not.

2.In the third step, soluble copper metaborate is formed which is washed away with water.
Na 2 B4O7 .10H 2O 
 2NaBO 2 +B2O3
NaBO 2 +Cu +2 
 Cu(BO2 ) 2

8. LEAD
Important ores of lead are Galena – PbS and Anglesite – PbSO4. Commercially, lead is extracted from galena.
When % of impurity is high, lead is extracted by carbon reduction and when % impurity is low, it is extracted by
self reduction.
Carbon reduction:
Froth foatation Roasting in the Smelting
Concentrated ore PbO + PbSO4 + SiO2 Molten Pb
Finely divided ore Coke + CaO + + Slag
NaCN is also added presence of lime
as depressant Fe2O3
Reactions involved:
1. Froth floatation: ZnS (impurity) + NaCN 
 Na2[Zn(CN)2] + Na2S
PbS + NaCN 
 No reaction
2. Roasting:
3
PbS+ O 2 
 PbO+SO 2
2
PbS+2O2  PbSO 4 (minor)
PbO+SiO 2 
 PbSiO3 (minor)
Lime is added to prevent PbO from reacting with SiO2 as CaO is more basic than PbO.
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2. Smelting:
PbO+C 
 Pb(l)+CO
Pb+CO 
 Pb(l)+CO
PbS(unreacted)+PbO 
 Pb(l)+SO 2
Slag formation
CaO+SiO 2 
 CaSiO3
Fe2 O3 +CO 
 FeO+CO 2
FeO+SiO 2 
 FeSiO 3
Self reduction: In this process, roasting is done partially. As a result, PbS is only partially converted into PbO or
PbSO4.
Reactions involved:
Roasting:
3
PbS+ O 2  PbO+SO 2
2
PbS+2O 2 
 PbSO4 (minor)
Self reduction
PbS+PbO 
 Pb+SO 2
PbS+PbSO 4 
 Pb+SO 2
Refining of lead:

Crude Pb with Softening of lead Desiverisation Elecrorefining

Soft lead Pb + Au Pure Pb
impurities Cu, Ag, Pb + Ag + Au Electrolyte:PbSiF6+H2SiF6
Au, Sn, Sb, Bi.
Impuritues make Anode: Impure Pb
lead hard Cathode: Pure Pb
Softening of lead: Crude Pb is melted in the presence of air. All the impurities (except Ag and Au) are converted
into oxides and are removed as scum.

9. MAGNESIUM
Ores of (a) Magnesite: MgCO3
magnesium:
(b) Dolomite: MgCO3.CaCO3
(c) Epsom salt: MgSO4.7H2O
(d) Carnallite: KCl.MgCl2.6H2O
(e) Kieserite: MgSO4.2H2O
The compound known as Epsom salt (Magnesium sulphate) was isolated from spring water in Epsom (England)
in 1795.Davy isolated the metal in the impure state in 1809 electrolytically and called it “Magnium”, which was
later changed to Magnesium.
Magnesium is extracted by
1. Modern Electrolytic method
2. Electrolysis of MgO
3. Reduction of MgO
4. Sea water
MODERN ELECTROLYTIC METHOD
1. From fused MgCl2 :
Magnesium is obtained by the electrolysis of fused MgCl2 but the process is met with the following
difficulties:
(i) Fusion temperature of MgCl2 is quite high.
(ii) It is not good conductor of electricity.
(iii) Anhydrous MgCl2 can’t be prepared by heating MgCl2.6H2O as it hydrolyses first to oxychloride. As a
result it is obtained by heating MgCl2.6H2O in the current of HCl.
Δ  MgCl .2H O 
MgCl2 .6H 2O  Δ  MgOCl 
ΔΔ  MgO
2 2 2

Δ
MgCl2 .6H 2O   MgCl 2 +6H 2O
in the presence of HCl
(iv) On electrolysis of MgCl2, Mg metal liberated at cathode may come in contact with chlorine which is
liberated at anode.
(v) O2 and N2 of the air present in the vessel may react with molten metal.
To overcome the above difficulties:

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(a) The electrolyte used is fused MgCl2 to which some NaCl has also been added. The later reduces the
melting point, increases the conductivity of the electrolyte and prevents the hydrolysis of magnesium
chloride.
(b) The air of the apparatus is displaced by an inert gas such as coal gas or hydrogen.
(c) The electrolysis is carried out in iron cell which acts as cathode. A graphite anode is surrounded by a
porcelain hood to escape chlorine.
On electrolysis magnesium is liberated and being lighter floats on the surface of the electrolyte and is
drawn off. It is about 92.0% pure.

ALLOYS

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
9. Solder, pewter Pb, Sn
10. Babbitt metal Sn, Sb, Cu
11. Aluminium bronze Al 10%, Cu 90%
12. Duralumin Al 95%, Cu3% Mn1%
Mg1%
13. Magnalium Al 90%, Mg 10%
14. Y-alloy Al 92.5%, Cu 4%, Ni 2%, Mg 1.5%

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