Metallurgy

METALLURGY
1. 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. So all minerals are not ores but all ores are minerals. 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 (e.g. carbonates, phosphates,
sulphates and silicates ) 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.

2. SECTION (A) : ORES & METHOD OF CONCENTRATION

Important ore :

2.1. Oxide ore :

(i) Bauxite  Al2O3.2H2O (Major ore of Al)
(ii) Haematite  Fe2O3
(iii) Zincite = ZnO
(iv) ***Cassiterite or tin stone  SnO2 (Black Tin = 60 – 70% SnO2)

2.2. Carbonate ore :

(i) Lime stone  CaCO3
(ii) Dolomite  CaCO3.MgCO3
(iii) Siderite  FeCO3
(iv) Malachite  CuCO3.Cu(OH)2
(v) Azurite  2CuCO3.Cu(OH)2
(vi) ***Calamine  ZnCO3
(vii) ***Cerussite  PbCO3

2.3. Sulphate ore :

Epsom salt  MgSO4.7H2O

2.4. Silicate ore :

Feldspar  KAlSi3O8

2.5. Sulphurised ore :

Consist of sulphides of metal like Iron, lead, zinc & mercury.
(i) Iron pyrites  FeS2
(ii) Copper glance  Cu2S
(iii) Copper pyrite or chalcopyrite  CuFeS2
(iv) Zinc Blende  ZnS
(v) Galena  PbS
(vi) Cinnabar  HgS

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2.6. Halide ore :
(i) Cryolite  Na3AlF6
(ii) Sylvine  KCl
(iii) **Carnallite  KCl.MgCl.6H2O
(iv) Fluorspar  CaF2
(v) Horn silver  AgCl
Note : Mg obtained from both sea water & earth crust.

Solved Example
Example 1. Which metals are supposed to occur in the native state in nature ?
Solution: Elements below hydrogen in the electrochemical series like Cu, Ag, Au etc, exist native ores.
Example 2. Match the ores listed in Column-I with their correct chemical formula listed in Column-II.
Column  Column 
(A) Cassiterite (p) FeCO3
(B) Siderite (q) SnO2
(C) Cerussite (r) PbSO4
(D) Anglesite (s) PbCO3
Solution: SnO2 is called as cassiterite or tin stone, FeCO3 is called as siderite, PbCO3 is called as
cerussite and PbSO4 is called anglesite. So correct match is (A)  (q), (B)  (p), (C)  (s) and
(D)  (r).

3. 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.
Chart1:
Metallurgy

Pyrometallurgy Hydro metallurgy Electrometallurgy

(Thermal treatment) (use of aqueous chemistry) (use of electrodes)

Chart2: Steps involved in metallurgy.

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3.1. Physical Method :

3.1.1 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.

3.1.2 Concentration :
The removal of unwanted useless impurities from the ore is called dressing, concentration or
benefaction of ore.
It involves several steps and selection of these steps depends upon the difference in physical
properties of the compound of metal and that of gangue. Some of the important procedures are
described below.
(i) Hydraulic washing or Gravity separation or Levigation method : It is based on the
difference in the densities of the gangue and ore particles. In this, the powdered ore is agitated
with water or washed with a upward stream of running water, the lighter particles of sand, clay
etc. are washed away leaving behind heavier ore particles. For this either hydraulic classifier or
Wilfley table is used. This method is generally used for the concentration of oxide and native
ores.
(ii) Electromagnetic separation :
It is based on differences in magnetic properties of the ore components.

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It is used when either the ore or the impurities
associated with it are magnetic in nature. A magnetic
separator consists of a belt (of leather or brass)
moving over two rollers, one of which is magnetic.
When the powdered ore is dropped on the belt at the
other end, magnetic component of the ore is
attracted by the magnetic roller and falls nearer to the
roller while the non-magnetic impurities fall away
from it.
Examples : Chromite ore(FeO.Cr2O3) is separated
from non–magnetic silicious impurities and cassiterite
ore (SnO2) is separated from magnetic Wolframite
(FeWO4 + MnWO4).

(iii) Froth floatation process : This method is commonly used for the concentration of the low grade
sulphide ores like galena, PbS (ore of Pb) ; copper pyrites Cu2S.Fe2S3 or CuFeS2 (ore of copper) ;
zinc blende, ZnS (ore of zinc) etc., and is based on the fact that gangue and ore particles have
different degree of wettability with water and pine oil; the gangue particles are preferentially wetted
by water while the ore particles are wetted by oil. In this process one or more chemical frothing
agents are added.
(a) Frothers : These form stable froth which rises to the top of the flotation cell. Oils like pine oil,
camphor oil etc., are used as frothers. These are added in small quantity. The stabiliser are
added to the frothers so that the froth can last for longer period.
(b) Collectors : 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.
(c) Activating and depressing agents : When a mineral contains other minerals as impurities.
The addition of these agents activates or depresses the flotation property of other minerals
present as impurities and thus helps in separating the impurities. For example galena (PbS)
usually contains the minerals namely zinc blende (ZnS) and pyrites (FeS2) as impurities.
Flotation is carried out by using potassium ethyl xanthate (used as a collector) along with NaCN
and Na2CO3 (used as depressing agent). The addition of NaCN and Na2CO3 depresses the
flotation property of ZnS and FeS2 grains, so mainly PbS passes into the froth when air is
blown in. After PbS has been collected with the froth, the process is repeated by adding CuSO 4
(activator) which activates the flotation property of ZnS grains which are now removed with the
froth. The acidification of the remaining material left in the flotation cell leads to the flotation of
FeS2.

Froth floatation process

Solved Example
Example 1. How does NaCN act as a depressant in preventing ZnS from forming the froth?
Solution: NaCN reacts with ZnS and forms a layer of Na2[Zn(CN)4] complex on the surface of ZnS and
thus prevents it from the formation of froth.

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Example 2. What is the role of stabiliser in froth floatation process ?
Solution: Froth can last for a longer period in presence of stabiliser.

3.2. Chemical Method :

(iv) Leaching : Leaching is often used if the ore is soluble in some suitable solvent, e.g, acids, bases
and suitable chemical reagents. e.g. Al ore, Ag ore, Au ore, low grade copper ore.
Leaching of alumina from bauxite :
The principal ore of aluminium, bauxite, usually contains SiO 2, iron oxide and titanium oxide
(TiO2) as impurities. Concentration is carried out by digesting the powdered ore with a
concentrated solution of NaOH at 473-523 K and 35-36 bar pressure. This way, Al 2O3 is
leached out as sodium aluminate (and also SiO2 as sodium silicate) leaving behind the
impurities, iron oxide and titanium oxide.
Al2O3(s) + 2NaOH(aq) + 3H2O(l)  2Na[Al(OH)4 ](aq)
The aluminate in solution is neutralised by passing CO 2 gas and hydrated Al2O3 is precipitated.
At this stage, the solution is seeded with freshly prepared samples of hydrated Al 2O3 which
induces the precipitation.
2Na[Al(OH)4] (aq) + CO2(g)  Al2O3.xH2O(s) + 2NaHCO3(aq)
The sodium silicate remains in the solution and hydrated alumina is filtered, dried and heated to
give back pure Al2O3 :
1470K / calcination
Al2O3.xH2O(s)   Al2O3(s) + xH2O(g)
These steps comprises the Bayer’s process.
Other examples : In the metallurgy of silver and that of gold, the respective metal/ore is
leached with a dilute solution of NaCN or KCN in the presence of air (or O 2) from which the metal
is obtained later by displacement with zinc scrap.
4M(s) + 8CN–(aq) + 2H2O(aq) + O2(g)  4[M(CN)2]– (aq) + 4OH–(aq) (M= Ag or Au)
2[M(CN)2]–(aq) + Zn(s)  [Zn(CN)4]2–(aq) + 2M(s)

3.2.1 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 as given below.
(i) Conversion to oxide
(ii) Reduction of the oxide to metal.
(i) Conversion to oxide :

Conversion into oxide

By calcination By Roasting
(absence of air) (in air)
Whose: carbonate, oxide ore, hydrated oxide ore means Whose: Sulphide ore
heating

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.,
 
FeCO3 (siderite)   FeO + CO2 ; PbCO3 (cerrussite)  PbO + CO2

CaCO3 (calcite ore / lime stone)   CaO + CO2

ZnCO3 (calamine)   ZnO + CO2

CuCO3.Cu(OH)2 (malachite)   2CuO + H2O + CO2

MgCO3.CaCO3 (dolomite)   MgO + CaO + 2CO2
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(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. Roasting is an exothermic process once started it does not require
additional heating. The process of roasting does the following things :
(a) Roasting at moderate temperature. Some portion of the sulphide ores like galena (PbS), Zinc
blende (ZnS) is converted into metallic oxide. If the temperature is fairly low (about 500ºC) and
the concentration of SO2 in the gaseous environment is more, sulphate may be produced that
are stable, and high temperature is needed to decompose them.
 
2PbS + 3O2   2PbO + 2SO2 ; 2ZnS + 2O2   2ZnO + 2SO2 ,.
 
PbS + 2O2   PbSO4 ; ZnS + 2O2   ZnSO4
* Some times roasting may not bring about complete oxidation.
2CuFeS2 (copper pyrite) + 4O2  Cu2S + 2FeO + 3SO2
(b) Roasting at high temperature. The sulphide ores of some of the metals like Cu, Pb, Hg, Sb etc.,
when heated strongly in the free supply of air or O2 are reduced directly to the metal rather than
to the metallic oxides, e.g.,
Cu2S (copper glance) + O2  2Cu + SO2
PbS (galena) + O2  Pb + SO2
HgS (cinnabar) + O2  Hg + SO2
The reduction of the sulphide ore directly into metal by heating it in air or O 2 is called by various names
like self-reduction, auto-reduction, air-reduction etc. The SO2 produced is utilised for manufacturing of
H2SO4 .
(c) It removes easily oxidisable volatile impurities like arsenic (as As2O3) sulphur (as SO2),
phosphorus (as P4O10) and antimony (as Sb2O3).
4M (M = As, Sb) + 3O2  2M2O3 
S + O2  SO2  ; P4 + 4O2  P4O10 
These oxides are volatile and hence escape as gases through the chimney.

(d) When the concentrated tin stone ore SnO2 (ore of Sn) is heated strongly in a free supply of air
(roasting), the impurities of CuS and FeS present in the ore are converted into CuSO4 and
FeSO4 respectively.
 
CuS + 2O2   CuSO4 ; FeS + 2O2  FeSO4
Both calcination and roasting are generally carried out in a reverberatory furnace. In case of roasting,
the air holes are kept open while they are partially or completely closed during calcination.

4. SECTION (B) : THERMODYNAMIC PRINCIPLES OF METALLURGY

(ii) Reduction of a metal oxide :
The free metal is obtained by reduction of a compound, using either a chemical reducing agent or
electrolysis.
1. 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.
(A) Reduction with carbon :
PbO + C  Pb + CO (extraction of lead)
2Fe2O3 + 3C  4Fe (spongy iron) + 3CO2
1200ºC
ZnO + C   Zn + CO (extraction of zinc)

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1800ºC
SnO2 + 2C (anthracite)   Sn + 2CO (extraction of tin)
1200ºC
MgO + C   Mg + CO
electric furnace
(B) 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
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

2. 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 AI 2O3. The
process is known as Goldschmidt or aluminothermic process and the reaction is known as
thermite reaction.
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
1000–1150ºC
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.
3. 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 SO 2.
Examples : 2HgS + 3O2  2HgO + 2SO2
2HgO + HgS  2Hg + SO2
Cu2S + 3O2  3Cu2O + 2SO2
2Cu2O + Cu2S  6Cu + SO2
2PbS + 3O2  2PbO + 2SO2
2PbO + PbS  3Pb + SO2
The extraction of Pb by heating its sulphide ore (PbS) in air can also be represented as
PbS + 2O2  PbSO4
PbSO4 + PbS  2Pb + 2SO2
4. 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
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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.
THERMODYNAMICS OF EXTRACTION : ELLINGHAM DIAGRAM OF A METAL
The standard electrode reduction potential of metal provides a very good indicator or the ease or
difficulty of extracting the metal from its compounds. However, since most metals of industrial
importance are obtained by chemical reduction of their oxide, the free energy changes occurring during
these processes are of more fundamental importance. Despite the fact that redox reactions do not
always reach equilibrium thermodynamics can at least be used to identify which reactions are feasible.
For a spontaneous reaction the change in free energy G must negative, G = H – TS.
It is sufficient to consider G because it is related to the equilibrium constant through, G = – RTInK.
Here a negative value of G corresponds to K > 1 and, therefore, a favourable reaction. Reaction rates
are also relevant, but at high temperature reactions are often fast and we can normally assume that any
thermodynamically permissible process can occur.
The problem of extracting a metal from its ore is essentially concerned with decomposing the oxide of
the metal (apart from simple binary compounds such as metal sulfides and chlorides that occur in
nature). Most metal ores consist essentially of a metal oxide in association with one or more nonmetal
oxides. Ores like carbonates, sulphides etc., are also converted to oxides, prior to reduction.
The free energy of formation G is the standard free energy of the reaction.
y
xM + O2  MxOy ......... (1)
2
2x 2
M + O2  MxOy ........... (2)
y y
G is the free energy of formation per mole of O2 consumed.
If the standard free energy of formation G has a negative sign at a given temperature, then the oxide
can be expected to form spontaneously from the metal plus oxygen. If G has a positive sign, the
oxide will be expected to decompose spontaneously to its elements.
The free energy of formation of an oxide can
now be determined, provided we know the
entropy of formation.
G = H – TS ........... (3)
In reaction (2) oxygen is used up in the course
of reaction. Gases have a more random
structure (less ordered) than liquid or solids. In
this reaction the entropy or randomness
decreases, and hence S is negative (provided
that neither the metal nor its oxide MxOy are
vaporized). Thus, if the temperature is raised
then TS becomes more negative. Since TS is
subtracted in equation (3), G then becomes
less negative. Thus, the change in free energy
decreases with increase in temperature.
The free energy change that occurs when 1 mol
of common reactant (in this case O2) is used
may be plotted graphically against temperature
for a number of reaction of metals to their
oxides. This graph is shown in following figure
and is called an Ellingham diagram for oxides.
Similar diagrams can be produced for 1 mol of
S, giving Ellingham diagram for sulphides and
similarly for halides using 1 mol of halogen.

This figure shows a number of oxide plots with slopes defined by G / T = –S. It is noted that the
entropy change in reaction (2) is roughly the same for all metal oxides provided that the boiling point of
neither the metal nor oxide is exceeded. Thus, below the boiling point of metal the slope of all the
graphs are roughly the same, since TS factor is same whatever be the metal. When the temperature
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is raised a point will be reached where the graph crossed the G = 0 line. Below this temperature the
free energy of formation of oxide is negative, so the oxide is stable. Above this temperature the free
energy of formation of the oxide is positive, and the oxide becomes unstable and should decompose
into metal and oxygen. This explains why HgO, for instance, decomposes spontaneously into its
elements when heated. Theoretically, all oxides can be decomposed to give metal and oxygen if a
sufficiently high temperature can be attained. In practice, that are easily attainable and these metals
can be extracted by thermal decomposition of their oxides. The diagram predicts that MgO and ZnO
ought to decompose if heated strongly enough, but it does not hold out much hope for obtaining say
pure Mg by straight forward heating of the oxide to a high temperature where the boiling point of the
metal is exceeded. However the slope increases since the reaction is now involving a larger entropy
change as the randomness increases in reactants. For example, 2 Mg(g) + O 2(g)  2 MgO(s)
Here, three moles of gas phases are converted into solid phase in the reaction. This takes place above
1120ºC, which is the boiling point of Mg.
Similarly Hg–HgO line changes slope at 365ºC. Several of the plots show abrupt changes in the slopes.
These breaks occur at temperature at which the metal undergoes a phase transition. A smaller effect is
seen at the melting point. If, however the oxide undergoes a phase change, there will be an increase in
the entropy of the oxide, and at such a point the curve becomes less steep. For example in the case of
Pb, the oxide (PbO) boils while lead is liquid. In these instances the entropy change becomes positive
for the reaction and hence the slope G/T changes sign, the situation reverting to normal once the
boiling point of Pb is reached.
In principle, when the plot of one metal lies below that of another, the first metal is capable of reducing
the oxide of the second. A vertical line drawn on the Ellingham plot of the metal oxides at any T gives
the sequence of the stabilities of metal oxides. A metal forming a more stable oxide (higher – G) will
be potential reducing agent for a less stable oxide. If the two lines intersect, the free energy change for
the reduction will be zero at that temperature and equilibrium results, but a change of temperature will
make the reaction proceed provided no kinetic barriers (activation energy) exist. Thus, Mg metal will
reduce CuO and FeO but not CaO. Also, it is seen that at room temperature (27ºC) the order of
reducing ability approximates that of standard electrode potential.
Although the SiO2 line is above the MgO line, Si can successfully reduce MgO to free metal. Upto
1100ºC, the normal boiling point of Mg, the G plot for formation of SiO2 and MgO are parallel.
However, above 1100ºC the plot for MgO changes slope owing to the increased entropy effect, and
above 1700ºC the reaction between Si and MgO proceeds with decrease in free energy. In practice, the
reaction is further enhanced by the distillation of Mg metal from the reaction mixture.
2 MgO + Si  2 Mg + SiO2
Carbon or carbon monoxide as reducing agent.
In figure the plot corresponding to the change C (s) + O 2(g)  CO2(g) is shown by a horizontal line.
For this reaction S is relatively small because in this case one mole of gaseous product is formed
while one mole of gaseous reactant is used up. G for this reaction is almost independent of
temperature. The plot for CO2 is relatively high in the figure, and at low temperature C will reduce only a
few of metal oxides shown. However, the slopes of the plots for several of the metals are such that
they cross the CO2 plot; hence theoretically these metals can be reduced by C at elevated temperature.
An alternative reaction involving carbon and oxygen is the formation of CO.
2 C(s) + O2(g)  2 CO(g)
Since two of gaseous product is formed from one mole of gaseous reactant, this process is
accompanied by an increase in entropy. Hence, the slope of the corresponding line is negative as
shown by the downward sloping line in the figure. If the temperature is high enough, C should reduce all
the metal oxides, being converted into CO. The plot for the reaction of CO with oxygen is also shown.
There are three curves for carbon, corresponding to complete oxidation of C to CO 2, partial oxidation to
carbon monoxide, and oxidation of CO to carbon dioxide. The three curves pass through a common
point at 710ºC. Thus, the free energies of formation of CO 2 from carbon monoxide and carbon dioxide
from carbon are identical.
2CO(g) + O2(g)  2 CO2(g)  G = x kJ/mol
C(s) + O2(s)  CO2(s) G = x kJ/mol
Subtracting one equation from the other and rearranging, the following is obtained :
CO2(g) + C(s) 2CO(g) G = 0
That is, an equilibrium is set. It is clear below a temperature of 710ºC, CO is a more effective reducing
agent than carbon, but above this temperature the reverse is true. All three oxidation curves for the
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carbon system lie above that for oxidation of zinc, until a temperature of approximately 1000ºC is
reached. At this point, carbon 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)

It is interesting to note that the value of carbon as reducing agent is due to marked increase in disorder
that takes place when carbon (an ordered solid) reacts with one mole of oxygen to give two moles of
CO. The net effect is an extra mole of gas and hence an increase in disorder (an increase in entropy). It
is a fact that in the region of 2000ºC, carbon is thermodynamically capable of reducing most metal
oxides to metal.
Thus, for most metal oxides, a reducing agent is required and we should consider the overall reaction
obtained by subtracting the metal oxidation from one of carbon oxidation as
Goverall = G(C) – G(M)
Metals as reducing agents :
Metal oxide reduction is thermodynamically favourable for temperatures at which the line for the metal
oxide is above any one of the lines for carbon oxidation, for the G for metal oxide reduction by carbon
is negative.
Note : The Gibb’s energies of formation of most sulphides are greater than that for CS 2. In fact, CS2 is an
endothermic compound. There, the ƒG of MXS is not compensated. So reduction of MXS is difficult.
Hence it is common practice to roast sulphide ores to corresponding oxides prior to reduction.
Similar principles apply to other types of reduction. For instances if the plot of G(M) lies above G(M’)
from M’ is now taking the place of C. When G = G(M’) – G(M) is negative, the reaction, MO + M’ 
M + M’O is feasible.
Hydrogen as a reducing agent :
Hydrogen is not very effective reducing agent for obtaining metals from their oxides.
The reason is that S is negative for the reaction :
2H2(g) + O2(g)  2H2O(g)
3 moles of gas 2 moles of gas
as the products are less disordered. The plot of G against T therefore rises with temperature, meaning
that not many metal oxide plots are intersected. H2 will therefore reduces oxides such as Cu(I) oxide
and Cu(II) oxide, but not the oxides of AI, Mg, and Ca. Oxides of iron are reduced only with difficulty. In
the case of magnetic iron oxide Fe3O4 an equilibrium composition is readily established.
In the case of W, Mo, and Co G is above that of H2O so H2 can be reduce these oxides.

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MoO3 + 3H2  Mo + 3H2O
GeO2 + 2H2  Ge + 2H2O
Co3O4 + 4H2  3Co + 4H2O
WO3 + 3H2  W + 3H2O
This method is not widely used because many metals react with H2 at elevated temperature forming
hydride. There is also a risk of explosion for H2 and oxygen in the air.

Solved Example
Example 1. The reaction Cr2O3 + 2Al  Al2O3 + 2Cr (Gº = –421 kJ) is thermodynamically feasible as is
apparent from the Gibb's energy value. Why does it not take place at room temperature ?
Solution: Certain amount of activation energy is essential even for such reactions which are
thermodynamically feasible, therefore heating is required.
Example 2. Is it true that under certain conditions, Mg can reduce Al 2O3 and Al can reduce MgO? What are
those conditions ?
Solution: Below 1350°C Mg can reduce Al2O3 and above 1350°C. Al can reduce MgO as evident from
the Ellingham diagram.

5. SECTION (C) : METALLURGY OF SOME USEFUL METALS

Smelting :
Slag formation : In many extraction processes, an oxide is added deliberately to combine with other
impurities and form a stable molten phase immiscible with molten metal called a slag. The process is
termed smelting.
The principle of slag formation is essentially the following:
Nonmetal oxide (acidic oxide) + Metal oxide (basic oxide)  Fusible (easily melted) slag
Removal of unwanted basic and acidic oxides: For example, FeO is the impurity in extraction of Cu
from copper pyrite.
2CuFeS2 + 4O2  Cu2S + 2FeO + 3SO2
+ SiO2  FeSiO3 (Fusible slag) + Cu2S (matte)
(roasted pyrite) (upper layer) (lower layer)

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

To remove unwanted acidic impurities like sand and P4O10, smelting is done in the presence of limestone.
CaCO3  CaO + CO2
CaO + SiO2  CaSiO3 (fusible slag)
6CaO + P4O10  2Ca3(PO4)2 (fusible slag - Thomas slag)
Properties of a slag :
(i) Slag is a fusible mass.
(ii) It has low melting point.
(iii) 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 (oxide of a non-metal) like SiO2, P2O5, B2O3 (from borax). It is
used to remove the basic impurity like CaO, FeO, MgO etc. The acidic flux combines with the
basic impurity and forms a slag.
(b) Basic flux : It is a basic oxide (i.e., oxide of a metal) like CaO (obtained from lime stone,
CaCO3), MgO (from magnesite, MgCO3), haematite (Fe2O3) etc. It is used to remove the acidic
impurity like SiO2, P2O5 etc. The basic flux combines with the acidic impurity and forms a slag.
Thus, slag can be defined as a fusible mass, which is obtained when a flux reacts with an
infusible acidic or basic impurity present in the oxide ore.

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5.1. Metallurgy of Some Important Metals

1. Extraction of iron (Fe)
Ore: Haematite

Oxide ores of iron, after concentration through calcination/roasting in reverberatory furnace (to remove
water, to decompose carbonates and to oxidise sulphides) 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.
Thermodynamics helps us to understand how coke reduces the oxide and why this furnace is chosen.
One of the main reduction steps in this process is :
FeO(s) + C(s)  Fe(s/l) + CO (g) .............. (11)
It can be seen as a couple of two simpler reactions. In one, the reduction of FeO is taking place and in
the other, C is being oxidised to CO :
1
FeO(s)  Fe(s) + O2 (g) [G(FeO, Fe)] .............. (12)
2
1
C(s) + O2 (g)  CO (g) [G(C, CO)] .............. (13)
2
When both the reactions take place to yield the equation (10), the net Gibbs energy change becomes:
G (C, CO) + G (FeO, Fe) = rG .............. (14)
Naturally, the resultant
reaction will take place
when the right hand side
in equation (14) is
negative. In Gº vs T plot
representing reaction
(12), the plot goes
upward and that
representing the change
C, CO (C, CO) goes
downward. At
temperatures above
1073K (approx.), the C,
CO line comes below the
Fe, FeO line [G(C, CO) <
G(Fe, FeO)]. So in this
range, coke will be
reducing the FeO and will
itself be oxidised to CO.
In a similar way the
reduction of Fe3O4 and
Fe2O3 at relatively lower
temperatures by CO can
be explained on the basis
of lower lying points of
intersection of their
curves with the CO, CO2
curve in the given figure.

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In the Blast furnace, reduction of iron oxides takes place in different temperature ranges. Hot air is
blown from the bottom of the furnace and coke is burnt to give temperature upto about 2200K in the
lower portion itself. The burning of coke therefore supplies most of the heat required in the process. The
CO and heat moves to upper part of the furnace. In upper part, the temperature is lower and the iron
oxides (Fe2O3 and Fe3O4) coming from the top are reduced in steps to FeO.
Reactions involved : The reactions proceed in several stages at different temperatures. Since the air
passes through in a few seconds, the individual reactions does not reach equilibrium.
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 and cast into variety of shapes. 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
Limestone is added as a flux and sulphur, silicon and phosphorus are oxidised and passed into the
slag. The metal is removed and freed from the slag by passing through rollers.
2. Extraction of copper :
(a) From cuprous oxide [Copper() oxide] : In the graph of rG0 vs T for formation of oxides the
Cu2O line is almost at the top. So it is quite easy to reduce oxide ores of copper directly to the
metal by heating with coke (both the lines of C, CO and C, CO 2 are at much lower positions in
the graph particularly after 500-600K). However most of the ores are sulphide and some may
also contain iron. 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  2Cu + CO
(b) From copper glance / copper pyrite (self reduction) : In actual process the ore is heated in
a reverberatory furnace after mixing with silica. In the furnace, iron oxide ‘slags of’ as iron
silicate and copper is produced in the form of copper matte. This contains mostly Cu2S and
some FeS.
2CuFeS2 + 4O2  Cu2S + 2FeO + 3SO2
Cu2S + FeO + SiO2  FeSiO3 (fusible slag) + Cu2S (matte)
Waste gases
Chimney
Tuyere Hopper

Fire brick

Charge


     Reverberatory furnace
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. Following reactions take place:
2FeS + 3O2  2FeO + 2SO2 ; FeO + SiO2  FeSiO3
2Cu2S + 3O2  2Cu2O + 2SO2 ; 2Cu2O + Cu2S  6Cu + SO2 (self reduction)
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Bessemer convertor
The solidified copper obtained has blistered appearance due to the evolution of SO 2 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 CuSO 4 solution and Cu gets
precipitated (Metal displacement method).
CuSO4 (aq) + Fe(s)  FeSO4 (aq) + Cu(s) .
Cu2+ (aq) + H2(g)  Cu(s) + 2H+ (aq) .... (15)
3. Extraction of lead :
Ore: PbS (Lead sulphide)
There are two methods of extracting the element :
(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
3PbS(s)   PbS (s) + 2PbO(s)  3Pb() + SO2(g)
air absence of air
Chart3:

Solved Example
Example 1. Auto reduction process is used in extraction of :
(A) Cu (B) Hg (C) Al (D) Fe
Solution: (A) and (B) : Cu2S + 2Cu2O  6Cu + SO2 ; HgS + 2HgO  3Hg + SO2

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Example 2. Why the sulphide ore is roasted to convert it in to the oxide before reduction?
Solution: fG of most sulphide ore are greater than those of CS2 and H2S. Hence neither carbon nor
hydrogen is a suitable reducing agent for the metal sulphides. Moreover, the roasting of a
sulphide to the oxide is quite advantageous thermodynamically because fG of oxides are
much lower than those of SO2.

4. Extraction of zinc :
Ore: ZnS (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. The temperature in this case is higher than that in case
of copper. For the purpose of heating, the oxide is made into brickettes with coke and clay.
Coke, 1673 K
ZnO + C   Zn + CO
The metal is distilled off and collected by rapid chilling.
Note : ZnO may be reduced by carbon monoxide at 1473 K (i.e. 1200°C) in smelter. The reaction is reversible,
and the high temperature is required to move the equilibrium to the right. At this temperature the Zn is
gaseous. If the gaseous mixture of Zn and CO2 was simply removed from the furnace and cooled, then
reoxidation of Zn would occur. Thus the zinc powder obtained would contain large amounts of ZnO.
ZnO + CO Zn + CO2

Chart4 :

5. Extraction of tin from cassiterite (SnO2) : It involves following steps.

(A) Purification :
(i) Crushing and concentration : The ore is crushed and washed with a stream of running water
to remove the lighter earthy and silicious impurities.
(ii) Electromagnetic separation : The concentrated ore is subjected to the electromagnetic
separation to remove magnetic impurity of Wolframite.
(iii) Roasting: The ore is then heated in presence of air, when volatile impurities (S as SO2, As as
As2O3 and Sb as Sb2O3) are removed.The impurities of pyrites of copper and iron are
converted into their respective oxides and sulphates
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 is reduced to metal using carbon at 1200–1300°C in an electric furnace. The
product often contains traces of Fe, which is removed by blowing air through the molten mixture
to oxidise FeO which then floats to the surface.
SnO2 + 2C  Sn + 2CO
2Fe + O2  2FeO

Chart5:

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Extraction of Mercury

Chart6:

6. SECTION (D) : ELECTROCHEMICAL PRINCIPLES OF METALLURGY

Medium :
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 AI 2O3 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
G
If the potential difference of the external source exceeds, 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 Eº values corresponds to a positive Eº and consequently negative Gº 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 :
(A) Extraction of Ag and Au : Metals like Au and Ag can be precipitated for their salt solution by
electropositive metals for example, Zn.

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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 Na 2S. 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.
(B) Extraction of Aluminium : It involves the following processes
(a) Purification of bauxite :
(i) Bayer’s Method (ii) Hall's Method (iii) Serpeck’s Method
(used for red bauxite containing (used for red bauxite containing (used for white bauxite containing
Fe2O3 and silicates as impurities) Fe2O3 and silicates as impurities) silica as impurities)
Fuse
Al2O3.2H2O + 2NaOH 

190ºC
Al2O3.2H2O + Na2CO3   Al2O3.2H2O+3C+N2 
1800ºC
8 atm Electric furnace
2NaAlO2(soluble) + CO2 + 2H2O
2NaAlO2(soluble) + 3H2O 60ºC 2AlN + 3CO + 2H2O
2NaAlO2 + 3H2O + CO2  
Fe2O3 (insoluble) separated as red 2AlN + 3H2O  Al(OH)3 + NH3
mud by filteration solution is 2Al(OH)3+ Na2CO3 SiO2 + 2CO  2CO2 + Si
diluted with water and seeded with Silicone volatilises at this temp.
1473 K 
freshly prepared Al(OH)3. It 2Al(OH)3   Al2O3+3H2O 2Al(OH)3  1473 K 
 Al2O3+3H2O
induces the precipitation of
Al(OH)3. Al(OH)3 is filtered leaving
behind silicates in solution.
NaAlO2+2H2ONaOH+Al(OH)3
1473 K 
2Al(OH)3   Al2O3+3H2O
(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 CO 2. 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.

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Solved Example
Example 3. Common impurities present in Bauxite are :
(A) CuO (B) ZnO (C) Fe2O3 (D) SiO2
Solution: (C) Red Bauxite contains Fe2O3 as impurity. (D) white Bauxite contains SiO2 as impurity.
Therefore, (C) and (D) are correct options.
Example 4. Which metals are generally extracted by the electrolytic reduction and why ?
Solution: Sodium, aluminium, magnesium etc. are extracted by the electrolytic reduction of their fused
salts because being more reactive and electropositive elements they themselves acts as strong
reducing agents. Hence they can not be extracted by any of the chemical methods.

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 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 MgCl 2.6H2O
(c) Preparation of anhydrous magnesium chloride :
 (calcination)
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).
(iii) 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
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7. Extraction of gold and silver (MacArthur-Forrest cyanide process) :
(a) From native ores : Extraction of gold and silver involves leaching the metal with CN–. 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] –.
Chart7:

(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].
Chart8:

7. SECTION (E) : PURIFICATION OR REFINING OF IMPURE METALS

(D) Purification or Refining of metals :
Metals obtained by reduction processes still contain some objectionable impurities and have to be
refined. Refining techniques vary widely from metal to metal and also depend on the use to which a
metal has to be put. Sometimes during refining some substances may have to be added to impart some
desirable characteristic to the metal. In some cases a metal is refined to recover some valuable by-
products, for example, Ag, Au, Pt etc., may be present as impurities. 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 present in it are not, i.e., the impurities are infusible. In other words,
we can say that the melting point of the metal to be purified should be lower than that of each of
the impurities associated with the metal. This process is used for the purification of Sn and Zn,
and for removing Pb from Zn-Ag alloy, which is obtained at the end of Parke’s process and
contains Pb as impurity.

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Examples :
Purification of impure tin metal : The
impure tine metal contains Cu, Fe, W
etc. as impurities This meals is placed
on the slopping heat of a reverberatory
furnace and gently heated. When the
temperature of the furnace reaches the
melting point of tin metal, this metal, on
account of its lower melting point melts
earlier than the impurities and hence
flows down the inclined hearth and the
solid infusible (non-fusible) impurities
(called dross) are left behind on the
hearth. The pure tin metal is collected in
a cast iron vessel in the molten state.
The metal obtained in this manner is
called pig tin.
Purification of crude zinc : The crude zinc or the spelter is melted on the slopping hearth of a
reverberatory furnace. Molten zinc flows down while the non-fusible impurities are left on the hearth.
(iii) 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.
(iv) Zone refining method (Fractional crystallisation method) :
This process is used when metals
are required in very high purity, for
specific application. For example
pure Si and Ge are used in
semiconductors 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.
Germanium metal, which is used in semiconductor devices, is refined (purified) by the zone refining
method. The impure germanium metal to be refined is taken in the form of a rod. A circular heater H is
fitted around this rod and this heater is slowly moved along the length of the rod. When the heater is at
the extreme left end of the impure germanium rod, it melts a narrow zone (narrow region) of the
germanium rod at that place. Now, when the heater moves on a little to the right side, then the molten
metal at the previous position cools down and crystallizes to give pure metal at region X of the rod. The
impurities, which were initially present in region X of germanium rod, now pass on to the region Y in the
adjacent molten zone. Now, as the heater is shifted more and more to the right side on the germanium
rod, the impurities also keep on shifting to the right side in to the newer and newer molten zones.
Ultimately, the impurities reach the extreme right end Z of the germanium rod. This end Z of the
germanium rod containing all the impurities is then discarded. The remaining rod is now of highly pure
germanium metal. In addition to germanium, silicon and gallium used as semiconductors are also
refined by the zone refining method.
(v) 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.
Different components are adsorbed at different levels on the column. Later the adsorbed components
are removed (eluted) by using suitable solvent (eluant). Depending upon the physical state of the
moving medium and the adsorbent material and also on the process of passage of the moving medium,
the chromatographic method is given the name. In one such method the column of Al 2O3 is prepared in
a glass tube and the moving medium containing a solution of the components is in liquid form. This is
an example of column chromatography. This is very useful for purification of the elements which are
available in minute quantities and the impurities are not very different in chemical properties from the
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element to be purified. There are several chromatographic techniques such as paper chromatography,
column chromatography, gas chromatography, etc. Procedures followed in column chromatography
have been depicted in the following figures.

Fig. Schematic diagrams showing column chromatography

7.1. 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. Then these oxides may be removed as follows :
(a) These oxide may form a scum on the surface of the metal. This scum can easily be removed by
skimming.
(b) If the oxides are volatile, they escape from the mouth of the furnace.
(c) The oxides may form a slag with the lining on the inside surface of the furnace and may thus be
removed. In the formation of the slag, the lining acts as a flux.
This method is usually employed for refining metals like Pb, Ag, Cu, Fe, etc. In this method the molten
impure metal is subjected to oxidation by various ways.
(i) Bessemerisation (Purification of iron) :
The iron obtained from a blast furnace is a brittle material called cast iron or pig iron. It
contains about 4% elemental C and smaller amounts of other impurities such as elemental Si,
P, S and Mn that are formed from their compounds in the reducing atmosphere of the furnace.
The most important of several methods for purifying the iron and converting it to steel is the
basic oxygen process or oxidative refining. 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) + 5O2(g)  P4O10(l)
6 CaO(g) + P4O10(l)  2Ca3(PO4)2(l)
Basic oxide acidic oxide slag
Mn also passes into the slag because its oxide is basic and reacts with SiO2 yielding molten
manganese silicate.
This process produces steel that contains about 1% carbon but only very small amount of P
and S. Usually the composition of liquid steel is monitored by chemical analysis and the amount
of oxygen and impure iron used are adjusted to achieve the desired concentration of carbon
and other impurities.
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(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 SnO 2.
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 (AI 3+), 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
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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 CuSO 4. 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.

Solved Example
–
Example 1. Sketch an electrolytic cell suitable for e– + – e
electroplating a silver spoon. Describe the Battery
+
electrode and the electrolyte. Label the anode Silver
and cathode, and indicate the direction of anode
electron and ion flow. Write balanced equations – Spoon
for the anode and cathode half reaction. + cathode
Ag (aq)
Solution: Anode : Ag(s)  Ag+(aq) + e– NO3– (aq)
Cathode : Ag+(aq) + e–  Ag(s)
The overall reaction is transfer of Ag metal from
silver anode to the silver spoon.

(V) KROLL’S PROCESS :

1000–150ºC
TiCI4 + 2 Mg   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. These can be fabricated into metal parts
using “powder forming” techniques and sintering in an inert atmosphere. Zr is also produced by Kroll’s
process.

(VI) VAPOR PHASE REFINING :

(i) Extraction of Nickel (Mond’s process) :
Nickel is extracted from sulfide ore by roasting followed by reduction with carbon, but the
process is complicated by the fact that nickel is found in association with other metals. The
refining is rather unusual, for nickel forms a complex with carbon monoxide tetracarbonylnickel
(O) [Ni(CO)4]. This substance is molecular in molecular in structure and readily volatilized
(boiling point 43ºC). It is made by heating nickel powder to 50ºC, in a stream of CO and then
decomposed at 200ºC. Any impurity in the nickel sample remains in the solid state and the gas
is heated to 230ºC, when it decomposes, giving pure metal and CO, which is recycled. Ni(CO) 4
is gaseous and may be produced by warming nickel with CO at 50ºC.
The sequence of reaction is
H2O(g) + C  CO(g) + H2
50ºC
Ni(s) + 4 CO(s)   [Ni(CO4)] (g)
200ºC
[Ni (CO)4](g)   Ni + 4CO(g)

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(ii) Van Arkel–De Boer process :
Small amounts of very pure metals (Ti, Zr, or Bi) can be produced by this method. This
process is based on the fact that iodides are the least stable of the halides. The impure element
is heated with iodine, producing a volatile iodide, TiI 4, ZrI4 or BiI3. These are decomposed by
passing the gas over an electrically heated filament of tungsten or tantalum that is white hot.
The element is deposited on the filament and the iodine is recycled. As more metal is deposited
on the filament, it conducts electricity better. Thus, more electric current must be passed to
keep it white hot. Thus the filament grows fatter and eventually the metal is recovered. The
tungsten core is distilled out of the center and a small amount of high purity metal is obtained.
50–250ºC 1400ºC
Impure Ti + 2I2   TiI4   Ti + 2I2
Tungsten filament
The method is very expensive and is employed for the preparation of very pure metal for
specific use.
(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.

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8. MISCELLANEOUS SOLVED PROBLEMS (MSPS)

Problem 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?
Solution: 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.
Problem 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).
Solution: (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+ + ne–  m
Problem 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+.
Solution: (i) 2PbS + 3O2 2PbO + 2SO2; PbS + 2O2 PbSO4
(ii) Cu2O + C 2Cu + CO
(Electrolysis)
(iii) Ag+ + e–   Ag (at cathode)

Problem 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
Solution: The positive value of Gº 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.

 Mg + CI2
(A) (B) (C) (D)
Problem 5. Sea water   Mg(OH)2   Mg CI2. 6H2O   MgCI2 
Identify the reagents and processes (A) to (D) and give the name of this process.
Solution: 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
Calcination (C)
MgCI2 6H2O   MgCI2 + 6H2O
 Dry HCl
Electrolysis(D)
MgCI2()   Mg2+ + 2CI–
+2e– CI2
Mg CI2
(cathode) (anode)
Name of the process is Dow’s process.

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 Metallurgy
Problem 6. Convert magnesite into anhydrous MgCI2.

Solution: Mg CO3   MgO + CO2. ; MgO + C + CI2 MgCI2 + CO
Problem 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
Solution: Lead is purified by Electro-refining. Zone refining is used for the purification of Si and Ge.
Therefore, (B) option is correct.
Problem 8. Tin stone, an oxide or of tin is amphoteric in nature. Explain.
Solution: 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
Problem 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.
Solution: Lead  self reduction; 2PbO + PbS 3Pb + SO2
Tin  carbon reduction, SnO2 + 2C Sn + 2CO
Therefore, (C) option is correct.
Problem 10. Which of the following is not an ore of iron ?
(A) limonite (B) cassiterite (C) magnetite (D) none of these
Solution: SnO2, cassiterite is an ore of tin.
Therefore, (B) option is correct.
Problem 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

Solution: 2Cu2O + Cu2S   6Cu + SO 2 Therefore, (C) option is correct.

Problem 12. Which of the following is a carbonate ore ?

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

Problem 13. 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 ;
Solution: (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

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