Chapter -6 Thus, minerals can be defined as

General Principles and naturally occurring chemical substances in the

Processes of Isolation earth’s crust obtainable by mining.
Elements Ores
6.1 Introduction The minerals from which metals are
About 118 elements are discovered so extracted conveniently and economically are
far, out of which 92 occurs in nature while the called Ores. For example, two well-known
rest are artificially synthesized. Elements are minerals of aluminium are clay
the basic units of all types of matter present on (Al2O3..2SiO2.2H2O) and bauxite (Al2O3.xH2O)
the earth. Aluminium can be extracted conveniently and
Elements are classified as Metals, (eg economically from bauxite but not from clay.
Iron , Aluminium, copper etc) Non- metals Therefore, bauxite is considered as ore of
( oxygen , hydrogen etc) and Metalloids aluminium. (see table 6-1)
(antimony , tin etc ) . More than 80% of the Table 6.1: Principal Ores of Some Important
known elements are metals and exist in solid Metals
state at room temperature. However, Mercury
(Hydrargyrum) is an exception and exist as a
liquid at room temperature.
Out of total 22 non-metals, 11 are
gases, bromine is liquid while rest 10 are
solid at room temperature.
Oxygen is the most abundant non-
metal while aluminium is most abundant metal
in earth crust. In general earth crust is a huge
source of metals.
6-1.1- Occurrence of Metals
Some metals like platinum, gold, silver
etc. occur in free state or Native State while
others like iron, aluminium, copper etc occur in Gangue
combined forms in the earth’s crust. A The earthly or undesired materials
particular element may occur in a variety of impurities associated with ores are known as
compounds as oxides, sulphide, Sulphates , gangue or matrix.
carbonates, halides etc. Thus, mineral = ore + gangue
Metals usually do not occur in nature as
6-2. Metallurgy
nitrates because all metals nitrates are soluble
The entire scientific and technological
in water, hence, slowly and gradually washed
process used for isolation of the metal from its ores
with rain water into sea.
is known as metallurgy and it involves the following
Minerals steps
The form in which metals and their • Concentration of the ore,
compounds are found in nature is called • Isolation of the metal from its concentrated ore,
mineral. and
• Purification of the metal.
6-2.1- Concentration of Ore magnetic roller (fig.6.1). Magnetic part of the
Removal of the unwanted materials ore forms a heap near the magnetic roller due
(e.g., sand, clays, etc.) from the ore is known to attractive forces, whereas non- magnetic
as concentration, dressing or benefaction. part form a heap at a distance due to
It involves several steps and selection of centrifugal force.
these steps depends upon the differences in 4- Froth Flotation Method
physical properties of the compound of the This method is widely used for the
metal present and that of the gangue, the concentration of sulphide ores.
available facilities and the environmental Principal : This method is based on the
factors. difference in the wetting qualities of the gangue
1-Pulverization of Ores and sulphide ore particles with water and oil.
Before proceeding for concentration, Sulphide ores are preferentially wetted
ores are graded and crushed to reasonable size by oil, comes out with froth, while gangues are
with the help of jaw crusher and then powered wetted by water and remain in water.
in a stamp mill or ball mill. The process is Method :In this process, two types of
known as Pulverization of Ores. substances are used
2- Hydraulic Washing (i) Collectors are substances which enhance non
Principal : This is based on the – wet ability of the mineral, helpful in bringing
differences in relative density of the ore and the the froth to surface and make sulphide ore
gangue particles. water repelling e.g., pine oils, fatty acids,
Method : It is therefore a type of xanthates, etc.
gravity separation. In one such process, an (ii) Forth stabilizers are the substances which
upward stream of running water is used to stabilize the forth. e.g. , cresols, aniline.
wash the powdered ore. The lighter gangue
particles are washed away and the heavier ores
are left behind. It is suitable method for heavy
oxide ores like, hematite, tinstone etc
3- Magnetic Separation
Principal : This is based on differences
in magnetic properties of the ore and the
gangue.

Mixture of powdered ore, collectors and

froth stabilizers are poured in a vessel
containing water.
The mineral particles become wet by oils
while the gangue particles by water.
A ratting paddle agitates the mixture
Method :The ground ore is dropped and draws air in it. As a result, froth is formed
over a conveyer belt which passes over a which carries the mineral particles.
 In this process, powdered ore of gold
The froth is light and is skimmed off. It
[Calve rite: AuTe 2; Sybarite: AgAuTe 2 ] is
is then dried for recovery of the ore particles.
(iii) Depressants are the chemicals used to treated with a dilute solution of NaCN or KCN in
separate two sulphide ores. the presence of air (or O2). As a result, gold
For example in case of an ore containing from a soluble complexes [sodium
ZnS and PbS, the depressant used is NaCN. dicyanoaurate (I)] while impurities remain
NaCN react with ZnS to form a soluble complex unaffected which are filtered off.
(Sodium-tetra-cyano- zincate) and prevent it 8KCN (aq)+ 2H2O(aq) + O2(g) →
from going into the froth. On the other hand, 4[Au(CN)2]−(aq) + 4KOH−(aq)
PbS does not react with NaCN and, therefore, The filtrate is treated with Zn scraps
comes out with froth. which displaces Au from the complex in the
4NaCN + ZnS → Na2 [ Zn ( CN )4 ] + Na2S pure form as a precipitate. 4Au(s) + 2[Au(CN) 2]
5- Leaching (aq) + Zn(s) → [Zn(CN)4]2− + 2Au
This is also known as chemical method (b) Leaching of Silver
of concentration of ore. In this process, powdered ore of silver
Principal : It is based on the solubility [argentite (Ag2S) or horn silver (AgCl)]
of ore in some suitable solvent which selectively is treated with a dilute solution of NaCN or
dissolves ore but not the impurities. KCN in the presence of air (or O2). As a result,
(a) Leaching of alumina from bauxite silver from a soluble complexes [sodium
(i) The powdered bauxite ore is treated with a dicyanoargentate (I)] while impurities
concentrated solution of NaOH at 473 – 523 K remain unaffected which are filtered off.
and 35 – 36 bar pressure, Al2O3 is leached out 4Ag(s) + 8KCN (aq)+ 2H2O(aq) + O2(g) →
as sodium aluminate leaving the insoluble 4[Ag(CN)2]−(aq) + 4KOH−(aq)
impurities behind. The filtrate is treated with Zn scraps
These impurities are separated by which displaces Ag from the complex in the
filtration. pure form as a precipitate.
Al2O3(s) + 2NaOH(aq) + 3H2O(l) → 2[Ag(CN)2](aq) + Zn(s) → [Zn(CN)4]2− + 2Ag
2Na[Al(OH)4](aq) The above reaction is also an oxidation
(ii) Now CO2 gas is passed into the sodium reduction reaction (Ag → Ag+ or Au → Au+). In
aluminate to neutralized it and also to get the reaction. Au (or Ag ) is first oxidizes to Au+
hydrated Al2O3  precipitate. (or Ag+ ) by oxygen. Au+ ion (or Ag+ ) then
At this stage, the solution is seeded with combine with CN− ions to form a soluble
freshly prepared samples of hydrated Al2O3 complex .
which induces the precipitation faster: Zn reduces Au+ to Au [or Ag+ to Ag]
2Na[Al(OH)4](aq) + CO2(g) → while Zn itself oxidized to Zn+2 and combines
Al2O3.xH2O(s) + NaHCO3 (aq) with CN− ions to form soluble complex, sodium
(iii)The sodium silicate remains in the solution tetracyanozincate. Thus it involves both
and hydrated alumina is filtered, dried and oxidation and reduction.
heated to give back pure Al2O3: 6.3 Extraction of Crude Metal From
Concentrated Ore
The process of obtaining metals in free
(b) Leaching of Gold
state from concentrated ore is called
extraction. This involves two major steps viz., 2PbS + 3O2 → 2PbO + 2SO2
(a) conversion of concentrated ore to its oxide, 2Cu2S + 3O2 → 2Cu2O + 2SO2
and (b) reduction of the oxide to metal.
(a) Conversion to oxide
All metals are converted into their oxides
as they can be easily reduced to metal as
compare to ores of sulphides, carbonates etc,
The concentrated ore can be converted
into oxides either by calcinations or
roasting.
(i) Calcination:
Calcination is the process of heating the
ore below its melting point in absence of air or
limited supply of air. This process is carried out
in reverberatory furnace. Table 6-2- Difference between Calcinations and
In this process (i) the volatile matter Roasting
and moisture are expelled S.No Calcinations Roasting
(ii) metal hydroxides or metal 1 Ore is heated in Ore is heated in
carbonates are converted into metal oxide and absence of oxygen excess of oxygen
(iii) ore becomes porous and, hence, 2 Usually Carbonates, Usually Sulphide
easily workable in subsequent stages. Hydrated oxides and ores are converted
Hydroxides ores are into oxides
converted into oxides
3 Usually decomposition The decomposition
of ore is takes place of ore does not
(ii) Roasting:
takes place
Roasting is the process of heating the
(b) Reduction of oxide to the metal:
ore below its melting point in a regular supply
Metal oxides can be reduced to the
of air in a blast furnace or in reverberatory
metal by using a suitable reducing agents
furnace.
depending upon
In this process (i) the volatile matter
(i) the reactivity of the metals.
and moisture are expelled
Metal Activity Series
(ii) organic matter is destroyed.
(iii)Non-metallic impurities such as
Sulphur, phosphorus and arsenic are oxidized
and evaporated
(iv) Sulphide ores are converted into
metallic oxides.
(v) ore becomes porous and, hence, (ii)the cost of the reducing agent
easily workable in subsequent stages (iii)energy costs
2ZnS + 3O2 → 2ZnO + 2SO2
(iv)the desired purity of the metal.
 For example, sodium and magnesium
The commonly used methods for
metals are obtained by electrolytic reduction of
reduction are:
1- Electrolytic Reduction their chloride solutions in molten state. 
(Electrometallurgy)
2- Reduction by Heat (pyrometallurgy)
3- Reduction by
acid/bacteria/hydrogen
6-3.1-Role of Reducing Agents During this process, chlorine gas is

The role of reducing agent is to provide liberated at anode while metals (sodium or

the change in Gibbs energy ΔG negative and magnesium) deposit at cathode.

large enough to make the sum of ΔG° of the Sometimes, a flux can be added to

two reactions (oxidation of the reducing agent improve conductivity of the molten metal

and reduction of the metal oxide) negative. Thus, the Process of extraction of metals
The change in Gibbs energy, ΔG° for any by electrolysis of their fused salts is called
process at any specified temperature, is electrometallurgy.
described by the Gibb’s Helmholtz equation: 6-4.1-Extraction of Aluminium by Hall-
ΔG° = ΔH – TΔS Heroult process.
where, ΔH is the enthalpy change and The purified Al2O3 is mixed with molten
ΔS is the entropy change for the process. Na3AlF6 ( cryolite ) or CaF2 ( fluorspar ) and is
electrolyzed in steel tank lined inside with
The change in Gibbs energy, ΔG0 for
carbon.
electrolysis process is
Carbon lining serve as cathode while
ΔG° = – n E°F
graphite rods, immersed in electrolyte, function
Where, n is number of electrons exchanged
as anode.
during reaction; E° is standard electrode
potential of redox couple and F is Faraday
constant.
6.4- Electrolytic reduction or
electrochemical principles of Metallurgy:
       The Oxides of metals which are quite high
in reactivity series can be reduced to metals
by electrolytic reduction (Electrometallurgy).
Here, electrons serve as reducing agents.
More reactive metal (lye above) will
displace the less reactive metal (lye below)
from the solution .i.e. the less reactive metal On passing electric current, the

will come out of the solution and the more aluminium metal is liberated at cathode and

reactive metal will go to the solution. collected at the bottom of the tank from where

Cu2+(aq) + Fe(s) → Cu(s) + Fe2+(aq) it is withdraws periodically. Aluminium thus

In simple electrolysis, the Mn+ ions are collected is 99.95% pure.

discharged at negative electrodes (cathodes) The oxygen liberated at anode reacts

and deposited there while anions like oxygen or with the carbon of anode producing CO and CO2

chlorine are discharged at anode. . This way for each kg of aluminium produced,
about 0.5 kg of carbon anode is burnt away.
 The bottom layer consists of molten
Because of this the anodes have to be replaced
impure aluminium containing the impurities.
from time to time.
This layer acts as anode.
The electrolytic reactions are:
When electric current is passed, Al+3 ions
Cathode: Al3+ (melt) + 3e− → Al(l)
from the middle layer go to the top layer and
Anode: C(s) + O (melt) → CO(g) + 2e−
C(s) + 2O (melt) → CO2 (g) + 4e− are deposited as pure Aluminium.

The overall reaction may be taken as: At the same time an equivalent amount

2Al2O3 + 3C → 4Al + 3CO2 of Al from the bottom layer passes into the
Function of cryolyte Na3AlF6 or CaF2  middle layer.
(i) it lowers the melting point of the The impurities remain in the bottom
molten electrolytic (alumina ) layer as they do not dissolve in the electrolyte.
(ii) increase conductivity of electrolyte The pure aluminium containing 99.99%
(iii) it acts as a solvent for the Al is removed from time to time from the top
concentrated bauxite ore. layer whereas impure aluminium is added into
Due to absence of free electrons for the bottom layer.
conduction of electricity, diamond electrodes
are not used for electrolysis. On the other hand
graphite, another allotropic form of carbon, is
widely used as electrode as it has free electrons
for the conduction of electricity.
6-4.2- Purification of Aluminium by Hoop'
Process 6.5 Pyrometallurgy and Thermodynamic
Aluminum is further purified by Hoop' Principles of Metallurgy.
Process electrolytically. Pyrometallurgy can be defined as the
Electrolytic cell is made of iron, which is process of converting a metal oxide into
lined with carbon at the bottom and filled with metallic form upon strong heating with a
three molten layers of different specific gravity suitable reducing agent.
one over the other. Some of commonly used reducing
agents are mentioned below : -
( a )Reduction by C or CO is known as
smelting. In this process the metal oxide is
mixed with coke and heated in blast furnace.
FeO(s) + C(s) → Fe(s/l) + CO (g)
ZnO(s) + C(s) → Zn(s/l) + CO (g)
Fe2O3 + CO → 2Fe + CO2
The top layer consists of pure molten PbO + CO → Pb + CO2
Aluminium and acts as cathode. CuO + CO → Cu + CO2
The middle layer consists of fused This process has a limitation of addition
mixture of fluorides of Sodium, Aluminium and of a small traces of carbon are added to the
Barium (Na3 AlF6 + Ba F2) and acts as the metal as impurity .
electrolyte. ( b ) Reduction by aluminium is known as
aluminothermy or thermite process. Metal
oxides of Cr, Mn, Ti, V, Mo and U are reduced Or 2HgS + 3O2 → 2HgO + 2SO2
with powered aluminium . 2PbS + 3O2 → 2PbO + 2SO2
MnO2 + 4Al→Al2O3 + Mn + Heat Or 2PbO + PbS → 3Pb + SO2
Fe2O3 + 2Al → 2Fe + Al2O3 + Heat To predict which element will be most
This is a highly exothermic reaction suitable reducing agent for a given metal oxide
which is made use of in thermite welding for and what would be the optimum temperature at
joining the broken pieces of heavy iron objects which reduction will proceed smoothly,
like girders, railway tracks or cracked machine Ellingham Diagram is used. Ellingham
parts. Diagram is the graphical representation of
(c) By electro positive metal : Gibbs energy ΔfGV vs T (absolute temperature)
Like Al, other electropositive metals can also 6-5.1-Ellingham Diagram
be used This was first used by H.J.T. Ellingham
B2O3 + Mg → 3MgO + 2B and it helps to select the best reducing agent
TiO2 + 2 Mg → 2MgO + Ti for various ores in the extraction process.  Main
( d ) Reduction by Hydrogen or water gas: features of the diagram are as under
Its use is limited to those ores where (a) Ellingham diagram normally consists
carbon or other reagents are not suitable of plots of ΔfGV vs T for formation of oxides of
because of its expensive nature, The ore is elements i.e., for the reaction. The graphs for
heated in small trays in the current of hydrogen most metal to metal oxide reactions show a
gas. positive slope
WO2 + H2 → W + H2O 2xM(s) + O2(g) → 2MxO(s)
In2O3 + H2 → 2In + H2O In this reaction, the gaseous amount
2NiO + CO + H2 → 2Ni + CO2 + H2O (hence molecular randomness) is decreasing
( CO +H2 is known as water gas ) from left to right due to the consumption of
(e) Reduction by Heat gases leading to a –ve value of ΔS. If the
The oxides of metals which are present temperature is raised, then T∆S becomes more
at the bottom of reactivity series can be negative. So, ∆G becomes less negative.
reduced to metals by action of heat alone e.g. (b) Each plot is a straight line except
mercury oxide can be reduced to mercury metal when some change in phase (s→liq or liq→g)
by heating it to a temperature of about 300°C.  takes place. The temperature at which such
change occurs, is indicated by an increase in
the slope on +ve side (e.g., in the Zn, ZnO plot,

(ii) Auto- reduction : the melting is indicated by an abrupt change in

The sulphide ores of some less active the curve).

metals ( like Hg, Cu, Pb etc.) are unstable (c) There is a point in a curve below

towards heat , hence, on roasting in a which ΔG is negative (So MxO is stable). Above

reverberatory furnace a part of these sulphides this point, MxO will decompose on its own. At

are oxides to their oxides which further react the point of intersection ΔG is zero.

with more of the sulphide ore to yield the (d) Any metal oxide with lower ΔfGo is

metal. This process is called auto reduction or more stable than the metal oxide with higher

self reduction. ΔfGo Therefore, metal oxide with lower ΔfGo

HgS + O2 → Hg + SO2 cannot be reduced by the metal oxide with

higher ΔfGo Obviously, Al2O3 .cannot be reduced the reactants and products are in equilibrium:
by Cr but Cr2O3can be reduced by Al metal. MxO + Ared l xM + AOox
o
( e)For metals like Ag & Hg , ΔfG This is not always true because the
become positive at high temperature . reactant/product may be solid. [However it
Therefore, Ag2OandHgOdecompose of their own explains how the reactions are sluggish when
at high temperature and not require any every species is in solid state and smooth when
reducing agent the ore melts down. It is interesting to note
.(f) As the ΔfGV of MxS is not here that ΔH (enthalpy change) and the ΔS
compensated hence it is difficult to reduce (entropy change) values for any chemical
sulphide or halide ores. reaction remain nearly constant even on
(g )The curve for the formation of CO varying temperature. So the only dominant
o
(g) shows a downward trend becauseΔS tends variable in equation becomes T. However, ΔS
to increase during the reaction, therefore, ΔfGo depends much on the physical state of the
is likely to become more negative with rise in compound. Since entropy depends on disorder
temperature. or randomness in the system, it will increase if
a compound melts (s→l) or vapourises (l→g)
since molecular randomness increases on
changing the phase from solid to liquid or from
liquid to gas].

6-5.3-Applications of Ellingham Diagram

(a) Reduction of iron from its oxides
From Ellingham Diagram it is clear
that the formation of oxides of carbon and iron
cross about 1073 K.
Below 1073K, CO reduces the oxides of
iron Fe2 O3 and Fe3 O4 because CO → CO2 is
below the formation of oxides of iron
3 Fe2O3 + CO → 2 Fe3O4 + CO2
Fe3O4 + 4 CO → 3Fe + 4 CO2
Fe2O3 + CO → 2FeO + CO2
Above 1073K, coke can reduces
haematite ore because the C→ CO line comes
below the Fe, FeO line
6-5.2-Limitations of Ellingham Diagram
C + CO2 → 2CO
1. The graph simply indicates whether a
FeO + CO → Fe + CO2
reaction is possible or not i.e., the tendency of
(b) Reduction of copper from its oxides
reduction with a reducing agent is indicated. It From Ellingham Diagram it is clear
does not say about the kinetics of the that the formation of cuprous oxides (Cu2O) is
reduction process (Cannot answer questions nearly at the top. This means cuprous oxides is
like how fast it could be ?). quit unstable and can be easily reduced by a
2. The interpretation of ΔGV is based on reducing agent like coke because the lines
V
K (ΔG  = – RT lnK). Thus it is presumed that representing the formation of CO and CO2 from
 external e.m.f. that is greater than 2.2 V.
coke occupy much lower position in the
Thus, Cl2 is obtained by electrolysis
diagram.
giving out H2 and aqueous NaOH as by-
(c) Reduction of Zinc from its oxides
products.
From Ellingham Diagram it is clear
Electrolysis of molten NaCl is also carried
that the formation of zinc oxides and CO cross
about 1270K. Thus ZnO is reduced by coke out. But in that case, Na metal is produced and

above 1270K. not NaOH.

(d) Reduction of Al2O3 and MgO 6-7.1-Displacement reaction :
At the point of intersection of the Al2O3 Some metals are reduced by
and MgO curves (marked “A” in diagram 6.4), displacement by a more electropositive metal
the ΔG° becomes ZERO for the reaction: from their soluble complexes.
2/3 Al2O3 +2Mg → 2MgO + 4/3Al For example, firstly Ag or Au are
Below that point magnesium can reduce reacted with cyanides like NaCN or KCN to form
alumina and above this temperature aluminum a soluble complexes which is then treated Zn .
can reduce MgO. Zn is more electropositive than Ag & Au.
6-6-Hydrometallurgy: Ag2S + 4NaCN (aq) → 2[Ag(CN)2] (aq) + Na2S
Hydrometallurgy can be defined as “the 2[Ag(CN)2] (aq) + Zn(s)
process of converting the impure metal present → 2Ag(s) + Na2 [Zn(CN)4] (aq)
in an ore into a soluble complex by treating Sodium tetracyanozincate(II)
with a suitable reagent and then recovering the Summary of Reduction method employed
pure metal from the complex by treating with a Nature of Metals in Reduction
more electropositive metal which is a strong metals decreasing method
reducing agent.” order of employed
6-6.1-Copper from Low Grade Ores and activity
Scraps More active K >Na> Ba ELECTROLYSIS
Copper is extracted by hydrometallurgy >Ca >Mg OF FUSED
from low grade ores. >Al SALTS NOT
It is leached out using acid or bacteria. AQUEOUS
2+
The solution containing Cu  is treated with SOLUTION
scrap iron or H2 . Intermediate > Zn >Cr > BY C , CO ,
+
Cu (aq) + H2(g) → Cu(s) + 2H  (aq) in activity Fe >Cd H2,Al or other
6.7- Oxidation Reduction >Co >Ni electro positive
Besides reductions, some extractions are >Ti>Pb>H metal
based on oxidation particularly for non- >Cu > Hg
metals. The extraction of chlorine from brine Less active >Ag >Au > Displacement
(chlorine is abundant in sea water as common Pt reaction
salt).
6.8- Refining
2Cl−(aq) + 2H2O(l) →
For obtaining metals of high purity, several
2OH (aq) + H2(g) + Cl2(g)
techniques are used depending upon the differences
The ΔG° for this reaction is + 422 kJ. When it is
in properties of the metal and the impurity.
converted to E (using ΔG° = – nE°F), we get
The process of purifying the crude metals is
E° = – 2.2 V. Naturally, it will require an
called refining.
Some of them are listed below. Table : Difference between Electrolytic
(a) Distillation (b) Liquation reduction &Electrolytic refining
(c) Electrolysis (d) Zone refining S.N Electrolytic Electrolytic
(e) Vapour phase refining (f ) By Poling o reduction refining
(g ) Chromatographic method 1 Fused salt of metal is An aqueous solution
(a) Distillation used as electrolyte of the salt of the
This is very useful for low boiling metals metal is used as
like bismuth, cadmium. zinc and mercury. On electrolyte
heating the impure metal is evaporated to 2 Anode and cathode Cathode is a thin
obtain the pure metal as distillate. are made up of inert strip of the same
(b) Liquation substance or pure metal whereas
In this method a low melting metal like substance of less anode is made up of
tin or lead can be made to flow on a sloping reactive than desired the impure metal
surface of a reverberatory furnace in an inert metal
atmosphere of CO. In this way it is separated 3 The anions of the At anode the impure
from higher melting impurities which left in the metal salts are metal is oxidized into
hearth. oxidized at anode cations which pass
(c) Electrolytic refining into solution
In this method, the impure metal is 4 The active metals Metals like Cu and
made to act as anode. A strip of the same like Na,K,Mg are Ag are purified
metal in pure form is used as cathode. They are isolated
put in a suitable electrolytic bath containing (d) Zone refining
soluble salt of the same metal. The more basic This method is based on the principle
metal remains in the solution and the less that the impurities are more soluble in the melt
basic ones go to the anode mud. Most of the than in the solid state of the metal.
metals such as copper, silver, gold, zinc and
chromium are refined electrolytically.
Electrolytic refining of copper
Anodes are of impure copper and pure
copper strips are taken as cathode. The
electrolyte is acidified solution of copper
sulphate and the net result of electrolysis is the
transfer of copper in pure form from the anode
A circular mobile heater is fixed at one
to the cathode:
end of a rod of the impure metal (Fig. 6.7). As
Anode:  Cu → Cu2+ + 2 e−
the heater moves forward, the pure metal
Cathode:  Cu2+ + 2e− → Cu
recrystallizes out of the melt and the impurities
Impurities from the blister copper deposit as
remain in the melt . The melt zone of the rod
anode mud which contains antimony,
moves along with the movement of the heater..
selenium, tellurium, silver, gold and platinum;
The process is repeated several times till the
recovery of these elements may meet the cost
impurities are driven completely towards one
of refining.
end and metal towards the other end. The rod
is cut off to remove impure zone, This method
is very useful for producing semiconductor and This method is based on the principle
other metals of very high purity, e.g., that different components of a mixture are

germanium, silicon, boron, gallium and indium. differently adsorbed on an adsorbent.

(e) Vapour phase refining There are several chromatographic

In this method, techniques such as paper chromatography,

(i) the metal is converted into its volatile column chromatography, gas chromatography,

compound with a suitable reagent, and . etc but column chromatography is the simplest

(ii) It is then decomposed to give pure and most preferred method.

metal. Column chromatography:

Mond Process for Refining Nickel: This includes following steps

In this process, nickel is heated in a (i) Stationary Phase :

stream of carbon monoxide forming a volatile A long glass tube is packed uniformly

complex, nickel tetracarbonyl: with suitable adsorbent ( such as alumina, silica

gel, magnesium oxide, starch etc.) which is
usually taken in the form of a slurry in
The carbonyl is subjected to higher petroleum ether or hexane ( preferable non
temperature so that it is decomposed giving the polar ).
pure metal: (ii) Moving Phase :
The substance to be purified is dissolved
in a minimum volume of a suitable highly polar
Van Arkel Method for Refining solvent. This is applied on the top of the column
Zirconium or Titanium: and allowed to pass slowly through it.
This method is very useful for removing (iii) Adsorption :
all the oxygen and nitrogen present in the form As the solution moves down in the
of impurity in certain metals like Zr and Ti. The column its various components are adsorbed at
crude metal is heated in an evacuated vessel varying heights in a narrow band depending
with iodine. The metal iodide being more upon their polarity i.e. more polar components
covalent, volatilises: are adsorbed at the top while less polar
Zr + 2I2 → ZrI4 components are adsorbed near the lower end.
The metal iodide is decomposed on a (iv) Elution:
tungsten filament, electrically heated to about It is a process of extraction of the
1800K. The pure metal is thus deposited on the adsorbed components from the adsorbent with
filament. help of suitable solvents called elution. The
ZrI4 → Zr + 2I2 eluent usually employed are petroleum ether,
(f) Chromatographic methods carbon tetrachloride, benzene, alcohols etc.
This method was first developed by The adsorbed components are removed (eluted)
Tswett (1903), a Russian botanist. This is by using suitable solvents (eluant).As the
widely used for separation, purification and eluent passes down the column, it dissolves out
identification of the elements which are the different components selectively. The
available in minute quantities and the weakly adsorbed component ( closer to lower
impurities are not very different in chemical end ) is eluted first by least polar solvent while
properties from the element to be purified.. the most strongly adsorbed component is
eluted in the last by the solvent of higher
(g) By Poling
polarity. Different components of the mixture
This method is applied to those metals
are collected in the form of different fractions in which contain impurities as their own oxides.
different conical flasks . The eluent from each The crude metal is melted in a big container
fraction is then distilled off to get the various and is then stirred with green poles of wood.
components in pure form. Gaseous hydrocarbons (CH4, C2H6, C2H4, etc)
Alternately, the column is taken out of are released from green poles which reduces the
the glass tube and cut into pieces such that oxides of metals to the pure state by taking up
each piece contains a single band. The oxygen. 
component present in each piece is dissolved in (h) By Cupellation
a suitable solvent. This solution is concentrated Cupellation, separation of gold or

and pure substance is obtained by silver from impurities by melting the

crystallization. impure metal in a cupel (a flat, porous dish

For example, when a mixture of made of a refractory, or high-temperature-

naphthalene and benzophenone is passed over resistant, material) and then directing a blast of

a column of alumina, naphthalene ( less polar) hot air on it in a special furnace. The impurities,

is weakly adsorbed while benzophenone ( more including lead, copper, tin, and other unwanted

polar ) is strongly adsorbed. By using petroleum metals, are oxidized and partly vaporized and

ether containing benzene as eluent , partly absorbed into the pores of the cupel.

naphthalene eluted first and then 6-9-Metallurgy of some elements

benzophenone. Procedures followed in column 1-Metallurgy of Iron

chromatography have been depicted in Fig. 6.8. (a)Ores of Iron

2- Concentration
Haematite is concentrated by hydraulic
washing or gravity separation, while magnetite
is concentrated by magnetic separation.
The concentrated ore is then subjected
to calcination. The calcined ore is then smelted.
3- Reduction (Smelting)
Oxide ores of iron, after concentration
through calcination/roasting are mixed with
limestone and coke and fed into a Blast furnace
from its top. Here, the oxide is reduced to the
metal.
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.
in smaller amount (e.g., S, P, Si, Mn). This is
The burning of coke therefore supplies
known as pig iron and cast into variety of
most of the heat required in the process.
shapes.
The CO and heat moves to upper part of
It is used to make pipes. radiators,
the furnace. bathtubs , sinks etc. The name ‘Pig’ is derived
In upper part, the temperature is lower from the fact that when the molten iron is
and the iron oxides (Fe2O3 and Fe3O4) coming poured in the sand moulds, the ingots are
from the top are reduced in steps to FeO. Thus, formed which resemble to a sow with litter of
the reduction reactions taking place in the lower pigs.
temperature range and in the higher (b) Cast iron
temperature range. It is made by melting pig iron with scrap

These reactions can be summarized as iron and coke using hot air blast. It has slightly

follows: lower carbon content (about 3%) and is

At 500 – 800 K (lower temperature range extremely hard and brittle.

The presence of sulphur and phosphorus
in the blast furnace) –
cause iron to brittle, presence of silicon gives
3 Fe2O3 + CO → 2 Fe3O4 + CO2
fluidity and presence of manganese gives
Fe3O4 + 4 CO → 3Fe + 4 CO2
hardness to iron.
Fe2O3 + CO → 2FeO + CO2
( c)Wrought iron or malleable iron
At 900 – 1500 K (higher temperature
It is the purest form of commercial iron
range in the blast furnace):
and is prepared from cast iron by oxidising
C + CO2 → 2CO
impurities in a reverberatory furnace lined with
FeO + CO → Fe + CO2
haematite. This haematite oxidises carbon to
carbon monoxide:
Fe2O3 + 3C → 2Fe + 3CO
It is fibrous, tough .malleable and ductile
, therefore. Used to make chains, cables,
anchors etc, It does not rust easily.
Nickel steel is used for making cables,
automobiles and aero plane parts, pendulum,
measuring tapes, chrome steel for cutting tools
and crushing machines, and stainless steel for
cycles, automobiles, utensils, pens, etc.
Flux and Slag

Flux is the substance which reacts with

the infusible gangue present with ore at high
temperature and converts it into fusible slag. If
the gangue is of acidic nature (such as SiO3.]
then basic flux [such as CaO or FeO] is added

(a)Pig Iron : or vice versa

The iron obtained from Blast furnace SLAG = FLUX + GANGUE

contains about 4% carbon and many impurities Slag is generally a silicate.

 2FeS + 3O2 → 2FeO + 2SO2
Limestone is added as a flux which
decomposed to CaO and removes sulphur,
silicon and phosphorus are oxidised and passed
into the slag [CaSi O3.]
The slag being lighter floats on the
molten iron and protects iron from being
oxidised. As a result of smelting, two separate
The metal is removed and freed from the molten layers are formed at the bottom of
slag by passing through rollers. the furnace.
2-Metallurgy of Copper The upper layer consists of slag and is
(a)Ores removed as a waste while the lower layer is
i) Copper pyrite, CuFeS2. called copper matte. It chiefly consists of
ii) Cuprite or Ruby copper, Cu2O. cuprous sulphide and some unchanged ferrous
iii) Copper glance, Cu2S. sulphide.
The chief ore of copper is copper pyrite. (d) Bessemerisation
The ore is crushed and then The molten matte is transferred to a
concentrated by froth-floatation process Bessemer converter.
(b) Roasting The Bessemer is mounted on a
The concentrated ore is heated strongly horizontal axis and is fitted with small pipes
in the reverberatory furnace, in excess of air. called tuyeres through which a blast of hot air
During roasting, and fine sand is admitted.
i) Moisture is removed. Any sulphur, arsenic and antimony still
ii) The volatile impurities are removed. present escape as their respective oxides.
iii) Sulphur, phosphorus, arsenic and Ferrous sulphide present in matte is oxidised to
antimony which are present as impurity are ferrous oxide which combines with silica to form
removed as volatile oxides. slag
2FeS + 3O2 → 2FeO + 2SO2
FeO + SiO2 → FeSiO3 (slag)

Some of the cuprous sulphide undergoes

oxidation to form cuprous oxide which then
iv) The copper pyrite is partly converted into
reacts with more cuprous sulphide to give
sulphides of copper and iron.
copper metal. The solidified copper obtained
has blistered appearance due to the evolution
of SO2and so it is called blister copper. It is
( c) Smelting about 98% pure.
The roasted ore is mixed with powdered 2Cu2S + 3O2 → 2Cu2O + 2SO2

coke and sand and is heated in a blast furnace. 2Cu2O + Cu2S → 6Cu + SO2

It is made of steel plates lined inside ( e )Refining

with fire clay bricks. Blister copper contains about 2% of

Hot air at 800°C is introduced from the impurities and it is purified by electrolytic

tuyers near the base of the furnace. As a result, Refining. On passing current ,Pure copper get

the following changes occur. deposited on the cathode impurities settle near
the anode in the form of sludge called anode 1. It is widely used for galvanizing iron
mud. sheets.
(f) Uses 2. It is used in the extraction of gold and
1. It is extensively used for making silver by the cyanide process.
electric cables and other electric appliances. 3. Zinc plates and rods are used in
2. It is used for making utensils, batteries and dry cells.
containers, calorimeters, coins, ...... etc. 4. Zinc dust and granulated zinc are
3. It is used in electroplating. used in laboratory as reducing agents.
4. It is alloyed with gold and silver for 3-Metallurgy of Silver
making coins and jewellery. (a)Ores
5- Important alloys of Copper i) Argentite or silver glance, Ag2S

i- Brass Cu = 60-80, Zn = 20-40 % ii) Horn silver or chlor-argyrite, AgCl

ii- Bronze Cu = 75-90, Sn = 10-25% iii) Pyrargyrite or Ruby silver,

iii- Gun metal Cu -87, Sn -10, Zn - 3% Ag2S . Sb2 S3

3-Metallurgy of Zinc Silver is extracted from the argentite ore by

(a)Ores the Mac-Arthur and Forrest’s cyanide

The important ores of zinc are process. The crushed ore is concentrated by
i) Zinc blende, ZnS froth-floatation process.
ii) Calamine, ZnCO3 (b)The concentrated ore is treated with 0.4-
iii) Zincite, ZnO 0.6% solution of sodium cyanide for several
The chief ore of Zinc is Zinc blende. hours and the ore is converted into soluble
The ore is crushed and then sodium argento complex.
concentrated by froth-floatation process.
The concentrated ore is then roasted in
the presence of excess of air at about 1200 K. The solution is filtered and filtrate is
treated with zinc dust, silver gets precipitated.

(b) Reduction
(c)Electrolytic refining
Zinc oxide is mixed with powdered coke
The impure silver is further purified by
and heated to 1673 K in a fire clay retort, in
electrolytic refining.
which ZnO is reduced to zinc metal.
The impure silver is made the anode
while a thin sheet of pure silver act as the
cathode.
(c) Purification
The electrolyte is silver nitrate acidified
Zinc is purified by electrolytic refining. In
with 1% nitric acid.
this process, Impure Zinc is anode and cathode
On passing electricity pure silver gets
is of pure thin sheet of Zinc. The electrolyte is
deposited at the cathode.
ZnSO4 solution containing a little of dil.H2SO4.
(d)Uses of silver
On passing electric current, pure zinc
i) Silver salts are used in silvering of
get deposited at the cathode.
mirrors
(d) Uses of zinc
ii) AgBr is used in photography
 iii) Silver salts are used in silver plating.
iv) Silver is used in making electrodes.
(d)Uses of Chromium
v) Silver leaf is used in medicine, while
1. The articles to be plated with
silver amalgam is employed in dental filling.
chromium are made the cathode in an
3-Metallurgy of Chromium
electrolytic bath consisting of chromic acid and
(a)Ores
sulphuric acid while the anode is made of a
The chief ore of chromium is chromite
plate of lead. During electrolysis chromium
ore, FeO Cr2O3.
deposits on the article (cathode). Generally the
The crushed ore is concentrated by
articles are first plated with nickel and then
gravity separation method.
subjected to chromium plating.
(b) Roasting
2. Chrome nickel steel is used for
The concentrated ore is mixed with
armour plates.
excess of Na2CO3 and a small amount
3. Chromium salts are used as mordants
of lime and roasted in a reverberatory furnace
and in the manufacture of coloured glass and
at 900-1000°C to convert it into soluble
pottery.
sodium chromate.
4. Chromium compounds are used in
Now,Na2CrO4 is treated with a
dyeing as pigments and in tanning of leather.
calculated quantity of H2SO4 followed by
( e)Alloys of chromium
heating with carbon and treatment with H2O, to
1-Ferrochrome Cr = 65% Fe = 35%
obtain Chromic oxide (Cr2O3) precipitate.
It is used in manufacture of
burglar proof safe.
2-Stainless steel Cr = 11-13%
C = 0.1 - 0.4% Fe = 73% Ni = 8%
3-Nichrome
Cr = 15%, Ni = 60% Fe = 25%
4-Stellite
Cr = 20-35% Co = 40-80%.
Ni = 0.25% C = 0.75 - 2.5%
( C) Reduction
It is used in surgical instruments,.....etc
Chromic oxide is reduced to chromium
Summary
by Alumino-thermic process.
1-Metals occur in nature sometimes in
Chromic oxide is mixed with powdered
free or native state, but most of these occur in
Aluminium in the ratio 3:1 and is placed in a
nature in the form of chemical combination,
large fire clay crucible.
i.e., in the form of their stable compounds
A mixture of barium peroxide and Mg
which are associated with gangue or matrix.
powder is placed over this. The crucible is
2-The natural material in which the
surrounded by sand which prevents loss of
metal or their compounds occur in the earth is
heat by radiation.
known as mineral. A mineral from which a
The mixture is ignited by a piece of Mg
metal can be profitably extracted is called an
ribbon. During this process a large amount of
ore. Ores of the metal are associated with
heat is liberated, in which Cr2O3 is reduced to
many impurities called gangue or matrix.
chromium.
 3-The entire scientific and technological best reducing agent for various ores in the
process used for isolation of the metal from its extraction process. 
ores is known as metallurgy and it involves 8- Several methods are employed in
the following steps refining the metal such as
• Concentration of the ore, (a) Distillation (b) Liquation
• Isolation of the metal from its (c) Electrolysis (d) Zone refining
concentrated ore, and (e) Vapour phase refining
• Purification of the metal. (f ) Chromatographic method
4-Removal of the unwanted materials 9- Metals and their alloys are very
(e.g., sand, clays, etc.) from the crushed and widely used and have contributed significantly
powered ore is known as concentration, in the development of a variety of industries.
dressing or benefaction which depends upon NCERT SOLVED
the differences in physical properties of the
Example 6.1
compound of the metal present and that of the
Suggest a condition under which magnesium
gangue, the available facilities and the
could reduce alumina.
environmental factors. This includes
Solution
(i)Gravity separation process or hydraulic
The two equations are:
washing
(a) 4/3 Al + O2 →2/3 Al2O3
(ii) Froth flotation process
(b) 2Mg +O2 → 2MgO
(iii) Electromagnetic separation process
At the point of intersection of the Al2O3
(iv) Chemical method or leaching
and MgO curves (marked “A” in diagram 6.4),
5- Concentrated ore is converted into
the ΔG° becomes ZERO for the reaction:
their oxides by calcination or roasting before
2/3 Al2O3 +2Mg → 2MgO + 4/3Al
reducing to the metal.
Below that point magnesium can reduce
6- Metal oxides can be reduced to the
alumina.
metal by using a suitable reducing agents
Example 6.2 
depending upon the reactivity of the metals.
Although thermodynamically feasible, in
(i)The oxides of most reactive metals
practice, magnesium metal is not used for the
like alkali metals, alkali earth metals, Al etc can
reduction of alumina in the metallurgy of
be extracted by electrolytic methods.
aluminium. Why ?
(ii )The oxides of less reactive metals
Solution
can be extracted by heating the ore with a
Temperatures below the point of
suitable reagent like C, CO , H2,Al or other
intersection of Al2O3 and MgO curves,
electro positive metal or Auto reduction. This is
magnesium can reduce alumina. But the
also known as Chemical reduction or pyro
process will be uneconomical.
metallurgy.
Example 6.3
(iii) The non -metals and some very less
 Why is the reduction of a metal oxide
reactive metals are extracted by
easier if the metal formed is in liquid state at
Hydrometallurgy
the temperature of reduction?
7- Ellingham Diagram was first used
Solution
by H.J.T. Ellingham and it helps to select the
The entropy is higher if the metal is in
liquid state than when it is in solid state. The
 value of entropy change (ΔS) of the reduction Bauxite usually contains silica, iron oxide, and
process is more on +ve side when the metal titanium oxide as impurities. In the process of
formed is in liquid state and the metal oxide leaching, alumina is concentrated by digesting
being reduced is in solid state. Thus the value the powdered ore with a concentrated solution
of ΔG° becomes more on negative side and the of NaOH at 473-523 K and 35-36 bar. Under
reduction becomes easier. these conditions, alumina (Al2O3) dissolves as
Example 6.4 sodium meta-aluminate and silica (SiO2)
At a site, low grade copper ores are dissolves as sodium silicate leaving the
available and zinc and iron scraps are also impurities behind.
available. Which of the two scraps would be
more suitable for reducing the leached copper
ore and why?
Solution
Zinc being above iron in the
electrochemical series (more reactive metal is The impurities are then filtered and the solution

zinc), the reduction will be faster in case zinc is neutralized by passing CO2 gas. In this

scraps are used. But zinc is costlier metal than process, hydrated Al2O3 gets precipitated and

iron so using iron scraps will be advisable and sodium silicate remains in the solution.

advantageous. Precipitation is induced by seeding the solution

NCERT INTEXT with freshly prepared samples of hydrated

Question 6.1: Al2O3.

Which of the ores mentioned in Table 6.1 can

be concentrated by magnetic separation
method?
Hydrated alumina thus obtained is filtered,
 Answer
dried, and heated to give back pure alumina
If the ore or the gangue can be attracted by the
(Al2O3).
magnetic field, then the ore can be
concentrated by the process of magnetic
separation. Among the ores mentioned in table Question 6.3:
6.1, the ores of iron such as haematite (Fe2O3), The reaction,
magnetite (Fe3O4), siderite (FeCO3), and iron
pyrites (FeS2) can be separated by the process
of magnetic separation. is thermodynamically feasible as is apparent
from the Gibbs energy value.
Why does it not take place at room
Question 6.2:
temperature?
What is the significance of leaching in the
 Answer
extraction of aluminium?
The change in Gibbs energy is related to the
 Answer
equilibrium constant, K as
In the extraction of aluminium, the significance
of leaching is to concentrate pure alumina .

(Al2O3) from bauxite ore. At room temperature, all reactants and

products of the given reaction are in the solid
 state. As a result, equilibrium does not exist The reduction potentials of zinc and iron are
between the reactants and the products. Hence, lower than that of copper. In hydrometallurgy,
the reaction does not take place at room zinc and iron can be used to displace copper
temperature. However, at a higher from their solution.
temperature, chromium melts and the reaction
takes place.
But to displace zinc, more reactive metals i.e.,
We also know that according to the equation
metals having lower reduction potentials than
zinc such as Mg, Ca, K, etc. are required. But all
Increasing the temperature increases the value
these metals react with water with the
of  making the value of   more and evolution of H2 gas.
more negative. Therefore, the reaction becomes
more and more feasible as the temperature is
As a result, these metals cannot be used in
increased.
hydrometallurgy to extract zinc.
Hence, copper can be extracted by
Question 6.4: hydrometallurgy but not zinc.
Is it true that under certain conditions, Mg can Question 6.2:
reduce SiO2 and Si can reduce MgO? What are What is the role of depressant in froth floatation
those conditions? process?
 Answer  Answer
In the froth floatation process, the role of the
depressants is to separate two sulphide ores by
selectively preventing one ore from forming
froth. For example, to separate two sulphide
The temperature range in which   is ores (ZnS and Pbs), NaCN is used as a
depressant which selectively allows PbS to
lesser than , Mg can reduce SiO2 to Si.
come with froth, but prevents ZnS from coming
to froth. This happens because NaCN reacts
On the other hand, the temperatures range in
with ZnS to form Na2[Zn(CN)4].

which   is less than , Si can

reduce MgO to Mg. Question 6.3:
Why is the extraction of copper from pyrites
The temperature at which ΔfG curves of these more difficult than that from its
two substances intersect is 1966 K. Thus, at oxide ore through reduction?
temperatures less than 1966 K, Mg can reduce  Answer
SiO2 and above 1966 K, Si can reduce MgO. The Gibbs free energy of formation (ΔfG) of
NCERT EXERCISE
Cu2S is less than that of  and .
Question 6.1:
Therefore, H2 and C cannot reduce Cu2S to Cu.
Copper can be extracted by hydrometallurgy
On the other hand, the Gibbs free energy of
but not zinc. Explain.
 Answer formation of   is greater than that of .
Hence, C can reduce Cu2O to Cu.
 immiscible. Al2O3 column is usually used as the
stationary phase in column chromatography.
Hence, the extraction of copper from its pyrite
The mobile phase may be a gas, liquid,
ore is difficult than from its oxide ore through
or supercritical fluid in which the sample extract
reduction.
is dissolved and forced to move through the
Question 6.4:
stationary phase.
Explain: (i) Zone refining (ii) Column
The component that is more strongly
chromatography.
adsorbed on the column takes a longer time to
 Answer
travel through it than the component that is
(i) Zone refining:
weakly adsorbed. The adsorbed components
This method is based on the principle that
are then removed (eluted) using a suitable
impurities are more soluble in the molten state
solvent (eluant).
of metal (the melt) than in the solid state.
In the process of zone refining, a circular
mobile heater is fixed at one end of a rod of
impure metal.
As the heater moves, the molten zone of
the rod also moves with it. As a result, pure
metal crystallizes out of the melt and the
impurities pass onto the adjacent molten zone.
This process is repeated several times,
which leads to the segregation of impurities at
one end of the rod. Then, the end with the
impurities is cut off. Silicon, boron, gallium,
indium etc. can be purified by this process.

Question 6.5:
Out of C and CO, which is a better reducing
agent at 673 K?
 Answer

(ii) Column chromatography:

At 673 K, the value of  is less than
Column chromatography is a very useful
technique used for the purification of elements that of . Therefore, CO can be reduced
available in minute quantities or are not very more easily to CO2 than C to CO. Hence, CO is a
different in chemical properties from the better reducing agent than C at 673 K.
element to be purified. Question 6.6:
Chromatography is based on the Name the common elements present in the
principle that different components of a mixture anode mud in electrolytic refining
are differently adsorbed on an adsorbent. of copper. Why are they so present ?
In chromatography, there are two  Answer
phases: mobile phase and stationary phase. In electrolytic refining of copper, the common
The stationary phase is immobile and elements present in anode mud are selenium,
 tellurium, silver, gold, platinum, and antimony.  Answer
These elements are very less reactive The different steps involved in the extraction of
and are not affected during the purification zinc from zinc blende (ZnS) are given below:
process. Hence, they settle down below the (i) Concentration of ore
anode as anode mud. First, the gangue from zinc blende is removed
Question 6.7: by the froth floatation method.
Write down the reactions taking place in (ii) Conversion to oxide (Roasting)
different zones in the blast furnace during the Sulphide ore is converted into oxide by the
extraction of iron. process of roasting. In this process, ZnS is
 Answer heated in a regular supply of air in a furnace at
During the extraction of iron, the a temperature, which is below the melting point
reduction of iron oxides takes place in the blast of Zn.
furnace.
In this process, hot air is blown from the
(iii) Extraction of zinc from zinc oxide
bottom of the furnace and coke is burnt to raise
(Reduction)
the temperature up to 2200 K in the lower
Zinc is extracted from zinc oxide by the process
portion itself. The temperature is lower in the
of reduction. The reduction of zinc oxide is
upper part.
carried out by mixing it with powdered coke and
The reactions taking place in the lower
then, heating it at 673 K.
temperature range (500 − 800 K) in the
blast furnace are:
(iv) Electrolytic Refining
Zinc can be refined by the process of
electrolytic refining. In this process, impure zinc
is made the anode while a pure copper strip is
The reactions taking place in the higher made the cathode. The electrolyte used is an
temperature range (900 − 1500 K) in the acidified solution of zinc sulphate (ZnSO4).
blast furnace are: Electrolysis results in the transfer of zinc in pure
from the anode to the cathode.

The silicate impurity of the ore is

removed as slag by calcium oxide (CaO), which Question 6.9:
is formed by the decomposition of limestone State the role of silica in the metallurgy of
(CaCO3). copper.
 Answer
During the roasting of pyrite ore, a mixture of
FeO and Cu2O is obtained.

Question 6.8:
Write chemical reactions taking place in the
extraction of zinc from zinc blende.
 The role of silica in the metallurgy of copper is carbon monoxide to form nickel tetracarbonyl,
to remove the iron oxide obtained during the which is a volatile complex.
process of roasting as ‘slag’. If the sulphide ore
of copper contains iron, then silica (SiO2) is
added as flux before roasting. Then, FeO
Then, the obtained nickel tetracarbonyl is
combines with silica to form iron silicate,
decomposed by subjecting it to a higher
FeSiO3 (slag).
temperature (450 − 470 K) to obtain pure
nickel metal.

Question 6.10:
What is meant by the term “chromatography”? Question 6.13:
 Answer How can you separate alumina from silica in
Chromatography is a collective term bauxite ore associated with silica? Give
used for a family of laboratory techniques for equations, if any.
the separation of mixtures. The term is derived  Answer
from Greek words ‘chroma’ meaning ‘colour’ To separate alumina from silica in bauxite ore
and ‘graphein’ meaning ‘to write’. associated with silica, first the powdered ore is
Chromatographic techniques are based on the digested with a concentrated NaOH solution at
principle that different components are 473 − 523 K and 35 − 36 bar pressure. This
absorbed differently on an absorbent. There are results in the leaching out of alumina (Al2O3) as
several chromatographic techniques such as sodium aluminate and silica (SiO2) as sodium
paper chromatography, column silicate leaving the impurities behind.
chromatography, gas chromatography, etc.
Question 6.11:
What criterion is followed for the selection of
the stationary phase in
chromatography?
 Answer Then, CO2 gas is passed through the resulting
The stationary phase is selected in such a way solution to neutralize the aluminate in the
that the components of the sample have solution, which results in the precipitation of
different solubility’s in the phase. Hence, hydrated alumina. To induce precipitation, the
different components have different rates of solution is seeded with freshly prepared
movement through the stationary phase and as samples of hydrated alumina.
a result, can be separated from each other.
Question 6.12:
Describe a method for refining nickel.
 Answer
During this process, sodium silicate remains in
Nickel is refined by Mond’s process. In this
the solution. The obtained hydrated alumina is
process, nickel is heated in the presence of
filtered, dried, and heated to get back pure
alumina.
 For example, there are many minerals
containing zinc, but zinc cannot be extracted
profitably (conveniently and economically) from
Question 6.14:
all these minerals. Zinc can be obtained from
Giving examples, differentiate between
zinc blende (ZnS), calamine (ZnCO3), Zincite
‘roasting’ and ‘calcination’.
(ZnO) etc.
 Answer
Thus, these minerals are called ores of zinc.
Roasting is the process of converting sulphide
Question 6.17:
ores to oxides by heating the ores in a regular
Why copper matte is put in silica lined
supply of air at a temperature below the
converter?
melting point of the metal.
 Answer
For example, sulphide ores of Zn, Pb,
Copper matte contains Cu2S and FeS.
and Cu are converted to their respective oxides
Copper matte is put in a silica-lined converter
by this process.
to remove the remaining FeO and FeS present
On the other hand, calcination is the
in the matte as slag (FeSiO3). Also, some silica
process of converting hydroxide and carbonate
is added to the silica-lined converter. Then, a
ores to oxides by heating the ores either in the
hot air blast is blown. As a result, the remaining
absence or in a limited supply of air at a
FeS and FeO are converted to iron silicate
temperature below the melting point of the
(FeSiO3) and Cu2S is converted into metallic
metal. This process causes the escaping of
copper.
volatile matter leaving behind the metal oxide.
For example, hydroxide of Fe,
carbonates of Zn, Ca, Mg are converted to their
respective oxides by this process.
Question 6.15:
How is ‘cast iron’ different from ‘pig iron”?
 Answer Question 6.18:
The iron obtained from blast furnaces is known What is the role of cryolite in the metallurgy of
as pig iron. It contains around 4% carbon and aluminium?
many impurities such as S, P, Si, Mn in smaller  Answer
amounts. Cryolite (Na3AlF6) has two roles in the
Cast iron is obtained by melting pig iron and metallurgy of aluminium:
coke using a hot air blast. It contains a lower 1. To decrease the melting point of the mixture
amount of carbon (3%) than pig iron. Unlike pig from 2323 K to 1140 K.
iron, cast iron is extremely hard and brittle. 2. To increase the electrical conductivity of
Question 6.16: Al2O3.
Differentiate between “minerals” and “ores”. Question 6.19:
 Answer How is leaching carried out in case of low grade
Minerals are naturally occurring chemical copper ores?
substances containing metals. They are found  Answer
in the Earth’s crust and are obtained by mining. In case of low grade copper ores, leaching is
Ores are rocks and minerals viable to be used carried out using acid or bacteria in the
as a source of metal.
 presence of air. In this process, copper goes Reduction of ZnO to Zn is usually carried out at
into the solution as Cu2+ ions. 1673 K. From the above figure, it can be
observed that above 1073 K, the Gibbs free
energy of formation of CO from C and above
The resulting solution is treated with scrap iron 1273 K, the Gibbs free energy of formation of
or H2 to get metallic copper. CO2 from C is lesser than the Gibbs free energy
of formation of ZnO. Therefore, C can easily
reduce ZnO to Zn.
Question 6.20:
Why is zinc not extracted from zinc oxide
through reduction using CO?
 Answer
The standard Gibbs free energy of formation of
ZnO from Zn is lower than that of CO2 from CO.
Therefore, CO cannot reduce ZnO to Zn. Hence,
Zn is not extracted from ZnO through reduction
using CO.
Question 6.21:

The value of   for formation of Cr2O3 is − 540

kJmol−1 and that of Al2 O3 is − 827 kJmol−1. Is On the other hand, the Gibbs free energy of
the reduction of Cr2O3 possible with Al? formation of CO2 from CO is always higher than
 Answer the Gibbs free energy of formation of ZnO.

The value of  for the formation of Cr2O3 from Therefore, CO cannot reduce ZnO. Hence, C is a

Cr (−540 kJmol−1) is higher than that of better reducing agent than CO for reducing

Al2O3 from Al (−827 kJmol−1). Therefore, Al can ZnO.

reduce Cr2O3 to Cr. Hence, the reduction of Question 6.23:

Cr2O3 with Al is possible. The choice of a reducing agent in a particular

Alternatively, case depends on thermodynamic factor. How

far do you agree with this statement? Support
your opinion with two examples.
 Answer

Subtracting equation (ii) from (i), we have A plot of Gibbs energy   vs. T for formation
of some oxides show that a metal can reduce
the oxide of other metals, if the standard free

energy of formation  of the oxide of the

As   for the reduction reaction of Cr2O3 by Al former is more negative than the latter. For

is negative, this reaction is possible. example, since   is more negative

Question 6.22:
than  , Al can reduce Cu2O to Cu, but
Out of C and CO, which is a better reducing
Cu cannot reduce Al2O3. Similarly, Mg can
agent for ZnO ?
reduce ZnO to Zn, but Zn cannot reduce MgO
 Answer
 because   is more negative In the electrometallurgy of aluminium, a fused
mixture of purified alumina (Al2O3), cryolite
than  .
(Na3AlF6) and fluorspar (CaF2) is electrolysed. In
this electrolysis, graphite is used as the anode
Question 6.24: and graphite-lined iron is used as the cathode.
Name the processes from which chlorine is During the electrolysis, Al is liberated at the
obtained as a by-product. What cathode, while CO and CO2 are liberated at the
will happen if an aqueous solution of NaCl is anode, according to the following equation.
subjected to electrolysis?
 Answer
In the electrolysis of molten NaCl, Cl2 is
obtained at the anode as a by product.

If a metal is used instead of graphite as the

anode, then O2 will be liberated. This will not
At cathode:  only oxidise the metal of the electrode, but also
convert some of the Al liberated at the cathode
At anode: 
back into Al2O3. Hence, graphite is used for
preventing the formation of O2 at the anode.
The overall reaction is as follows: Moreover, graphite is cheaper than other
metals.

If an aqueous solution of NaCl is electrolyzed, Question 6.27:

Cl2 will be obtained at the anode but at the Outline the principles of refining of metals by
cathode, H2 will be obtained (instead of Na). the following methods:
This is because the standard reduction potential (i) Zone refining
of Na (E°= − 2.71 V) is more negative than (ii) Electrolytic refining
that of H2O (E° = − 0.83 V). Hence, H2O will (iii) Vapour phase refining
get preference to get reduced at the cathode  Answer
and as a result, H2 is evolved. (i) Zone refining:
This method is based on the principle
that impurities are more soluble in the molten
At cathode:  state of metal (the melt) than in the solid state.
(ii) Electrolytic refining;
At anode: 
Electrolytic refining is the process of refining
impure metals by using electricity. In this
process, impure metal is made the anode and a
strip of pure metal is made the cathode.
Question 6.25:
What is the role of graphite rod in the The more basic metal remains in the solution
electrometallurgy of aluminium? and the less basic ones go to the anode
 Answer mud.
 wrought iron from cast iron. How can the
impurities of sulphur, silicon and phosphorus be
removed from cast iron?
(iii) Vapour phase refining
Answer :29.
Vapour phase refining is the process of refining
Fe2O3 + 3C → 2Fe + 3CO
metal by converting it into its volatile
Limestone is added as flux and sulphur, silicon
compound and then, decomposing it to obtain a
and phosphorus change to their oxides and
pure metal. To carry out this process,
pass into the slag.
(i) the metal should form a volatile compound
Q-30. How is copper extracted from low grade
with an available reagent, and
copper ores?
(ii) the volatile compound should be easily
Answer :30.
decomposable so that the metal can be easily
Copper is extracted by hydrometallurgy from
recovered.
low grade copper ores. It is leached out using
Nickel, zirconium, and titanium are refined
acid or bacteria. The solution containing Cu2+ is
using this method.
treated with scrap iron, Zn or H2.
Question 6.28:
Cu2+(aq) + H2(g) → Cu(s)+ 2H+ (aq)
Predict conditions under which Al might be
Cu2+ + Fe(s) →Fe2+(aq)+ Cu(s)
expected to reduce MgO.
Q-31. Write two basic requirements for refining
 Answer
of a metal by Mond process and by Van Arkel
Above 1350°C, the standard Gibbs free energy
Method.
of formation of Al2O3 from Al is less than that of
Answer :31.
MgO from Mg. Therefore, above 1350°C, Al can
Basic requirements for both processes are :
reduce MgO.
(i) The metal should form a volatile compound
NCERT EXEMPLER
with an available reagent.
Q-27. Why is an external emf of more than
(ii) The volatile compound should be easily
2.2V required for the extraction of Cl2 from
decomposable, so that recovery of metal is
brine?
easy.
Answer :27.
Q-32. Although carbon and hydrogen are better
For the reaction
reducing agents but they are not used to
2Cl–(aq) + 2H2O (l) → 2OH–(aq)+ H–(g)+Cl–(g)
reduce metallic oxides at high temperatures.
Value of ΔGΘ is + 422kJ. Using the equation
Why?
ΔGΘ = – nFEΘ the value of EΘ comes out to be –
Answer :32.
2.2V. Therefore extraction of Cl2 from brine will
It is because at high temperature carbon and
require an external emf of greater than 2.2V.
hydrogen react with metals to form carbides
Q-28. At temperatures above 1073K coke can
and hydrides respectively.
be used to reduce FeO to Fe. How can you
Q-33. How do we separate two sulphide ores by
justify this reduction with Ellingham diagram?
Froth Floatation Method? Explain with an
Answer :.
example.
As per Ellingham diagram at temperatures
Answer :33.
greater than 1073 K ΔG(C, CO) < ΔG(Fe, FeO).
Two sulphide ores can be separated by
Hence coke can reduce FeO to Fe.
adjusting proportion of oil to water or by using
Q-29. Wrought iron is the purest form of iron.
depressants. For example, in the case of an ore
Write a reaction used for the preparation of
containing ZnS and PbS, the depressant NaCN Q-39. What should be the considerations during
is used. It forms complex with ZnS and the extraction of metals by electrochemical
prevents it from coming with froth but PbS method?
remains with froth. Answer :39.
Q-34. The purest form of iron is prepared by Generally two things are considered so that
oxidising impurities from cast iron in a proper precautions can be taken.
reverberatory furnace. Which iron ore is used to (i) reactivity of metal produced.
line the furnace? Explain by giving reaction. (ii) suitability of electrodes.
Answer :34. Q-40. What is the role of flux in metallurgical
Haematite processes?
Fe2O3 + 3C → 2Fe + 3CO Answer :40.
Q-35. The mixture of compounds A and B is Flux is used for making the molten mass more
passed through a column of Al2O3 by using conducting. It also combine with gangue to
alcohol as eluant. Compound A is eluted in form slag and remove them.
preference to compound B. Which of the Q-41. How are metals used as semiconductors
compounds A or B, is more readily adsorbed on refined? What is the principle of the method
the column? used?
Answer :35. Answer :41.
Since compound ‘A’ comes out before Semiconducting metal is produced by zone
compound ‘B’, the compound ‘B’ is more readily refining method which is based on the principle
adsorbed on column. that the impurities are more soluble in melt
Q-36. Why is sulphide ore of copper heated in a than in the solid state of metals.
furnace after mixing with silica? Q-42. Write down the reactions taking place in
Answer :36. Blast furnace related to the metallurgy of iron in
Iron oxide present as impurity in sulphide ore of the temperature range 500-800 K.
copper forms slag which is iron silicate and Answer :42.
copper is produced in the form of copper matte. 3Fe2O3 + CO → 2Fe3O4 + CO2
FeO + SiO2 → FeSiO3 Fe3O4 + 4CO → 3Fe + 4CO2
Q-37. Why are sulphide ores converted to oxide Fe2O3 + CO → 2FeO + CO2
before reduction? Q-43. Give two requirements for vapour phase
Answer :37. refining.
Sulphides are not reduced easily but oxides are Answer :43.
easily reduced. (i) The metal should form a volatile compound
Q-38. Which method is used for refining Zr and with available reagent.
Ti? Explain with equation. (ii) The volatile compound should be easily
Answer :38. van Arkel method is used for decomposable so that the recovery is easy.
refining Zr and Ti. In this method crude metal is Q-44. Write the chemical reactions involved in
heated with iodine. the extraction of gold by cyanide process. Also
Zr + 2I2 → ZrI4 give the role of zinc in the extraction.
Answer :44.
4Au (s) + 8CN–(aq) + 2H2O (aq) + O2 (g) → 4
[Au (CN)2– (aq) + 4OH– (aq)
2[Au(CN)2]–(aq) + Zn(s) → 2Au(s) +
[Zn(CN)4]2–(aq)
In this reaction zinc acts as a reducing agent.
Q-45 Explain the following :
(i) Silica is added to the sulphide ore of copper
in the reverberatory furnace.
Answer :
Sulphide ore of copper contains iron as
impurity. Silica is added to remove iron
impurity as iron silicate (slag)
FeO +SiO2 → FeSiO3
(ii) Carbon and hydrogen are not used as
reducing agent at high temperature.
Answer :
Because at higher temperature carbon and
hydrogen can react with metal to form their
carbides and hydrides respectively,
ADDITIONAL QUESTIONS
1- What is gravity separation ?
2- Define Metallurgy.
3. What are the major steps involved in the
metallurgical process ?
4- What is meant by electrolytic refining? Give
example.
5-. What is anode mud?
6-What is smelting ? Explain the process with
example.
7- How nickel is extracted by Mond’s process?
Write the various reactions involved in the
process.
8- Write short notes on alumino thermic
process?
9- List the ores of silver. How silver is extracted
from Argentite?
10. Briefly explain the extraction of zinc from
zinc blende.