GENERAL PRINCIPLES & PROCESSES OF ELEMENTS 81

www.thinkiit.in
Rotating paddle
Mineral froth
Pulp of ore + oil
Paddle draws in air
and stirs the pulp
Enlarged view of an air bubble
showing mineral particles attached to it
Air
Froth stabilizers : Sub like cresols and aniline, which stabilize the froth.
Depressants : These are the substances which selectively prevent certain type of particles from
forming the froth with the bubbles. For example, NaCN is added as a depressant for the separation of an
ore containing ZnS and PbS. NaCN acts as a depressant for ZnS but not for PbS. NaCN forms a layer of
zinc complex Na
2
[Zn(CN)
4
] on the surface of ZnS, thereby, preventing it from froth.
(d) Leaching : This method consists of treating the powdered ore with a suitable reagent which can
selectively dissolve the ore but not the impurities. The impurities are filtered out and ore recovered from
solution. For example, bauxite ore containing SiO
2
, iron oxide and titanium oxide are impurities concentrated
by this method.
Al
2
O
3
.xH
2
O(s)
1470 K
Al
2
O
3
(s) + xH
2
O(g)
7. Extraction of Crude Metal from Concentrated Ore : The process used to obtain metals in free state
from the concentrated ore is called extraction. It involves the following two major steps.
(a) Conversion of the ore into metal oxide and
(a) Conversion of the ore into metal oxide : The following two methods are used for conversion of ores
into their respective oxides.
(i) Calcination : It is the process of heating an ore below its melting point either in the absence or
limited supply of air. During calcination,
hydrated ores become anhydrous. For example
Fe
2
O
3
.3H
2
O Fe
2
O
3
+ 3H
3
O
Limonite Calcium oxide
carbonates are converted into their respective oxides.
Zn CO
3
heat
ZnO + CO
2
Calcium
(ii) Roasting : It is process of heating the ore below its melting point in excess of air. The following
changes occur during roasting :
Moisture is drive away.
S
8
+ 8O
2
heat
8SO
2
Sulphur dioxide
(b) Reduction of oxide to metal : The role of reducing agent is to provide G negative and large enough
to make the sum of G of oxidation of reducing agnet and reduction of metal oxide negative. The free
energy change, G is related with other thermodynamic quantities by the expression;
G = H TS
where H = enthalpy change, S = entropy change, and T = temperature in Kelvin
As heating, i.e., increase in T, favours a negative value of
r
G, therefore, the temperature is chosen such
that sum of
r
G in two combined redox processes is negative.
(i) Smelting : In this process metal oxide is reduced to metal with C or CO.
Fe
2
O
3
+ CO
500900K
2FeO + CO
2
Fe
3
O
4
+ CO
500900K
3FeO + CO
2
GENERAL PRINCIPLES & PROCESSES OF ELEMENTS 83
www.thinkiit.in
Al
2
O
3
electrolysis
2Al
3+
+ 3O
2
Cathode : Al
3+
(melt) +3
e
Al()
Anode : C(s) + O
2
(melt) CO(g) + 2
e
C(s) + 2O
2
(melt) CO
2
(g) + 4
e
2Al
2
O
3
+ 3C 4Al + 3CO
2
Carbon
anode
Carbon
clamp
+

Carbon lining
(cathode)
Molten
aluminium
Outlet for Al
Iron
Electrolytic cell for the extraction of aluminium
11.Copper from Low Grade Ores and Scraps : Copper is extracted by hydrometallurgy from low-grade
copper ores and scraps. It is leached out by using acid or bacteria.
Reduction : The solution containing Cu
2+
is treated with scrap iron or H
2
.
Cu
2+
(aq) + H
2
(g) Cu(s) + 2H
+
(aq)
Cu
2+
(aq) + Fe(s) Fe
2+
(aq) + Cu(s)
GENERAL PRINCIPLES & PROCESSES OF ELEMENTS 85
www.thinkiit.in
The impurities, which remain in the molten part, are progressively shifted to one end of the rod. The
process could be repeated many times still the desired level of purity is attained. The method is
especially useful for producing B, Ge, Si, Ga (semiconductors).
(c) To get metal of high purity, electrochemical refining is done making impure metal as anode.
In an aqueous solution: It is used in cases when the electrolyte is soluble in water and product does
not react with it. Cu, Zn, Ag and other metal are obtained by the electrolysis of aqueous solution of
their salts (ZnSO
4
, AgNO
3
, CuSO
4
). Impure metal is made anode of electrolytic cell (consists of same
metal salt) having pure metal plate of cathode. On electrolysis pure metal from crude form gets
dissolved at anode whereas at cathode pure metal is deposited. The soluble impurities pass into
solution while the insoluble ones collected below the anode as anodic mud or anode sludge.
In fused melts: Na, K, Ca, Mg etc., react with H
2
O hence they are extracted by electrolysis of fused
halides.
Na and Cl
2
are obtained by electrolysis of fused NaCl.
Al is obtained by the electrolysis of fused mixture of Al
2
O
3
and Na
3
(AlF
6
) (cryolite).
In other solvents: Electrolysis can be carried out in solvents other than water.
F
2
reacts violently with H
2
O hence it is produced by electrolysis of KHF
2
in HF.
Q.5 You are provided with samples of some impure metals such as zinc, copper and germanium.
Which methods would you recommend for the purification of each of these metals?
Ans. Zinc: distillation, electrolysis; Copper: poling, electrolysis; Germanium: zone refining
Q.6 Name the chief forms of the occurrence of the following in the earths crust:
(a) aluminium (b) calcium (c) sodium (d) lead
Ans. (a) Aluminium: Bauxite, Al
2
O
3
, 2H
2
O; Cryolite, Na
3
AlF
6
; Aluminosilicates
(b) Calcium: Limestone, CaCO
3
; Dolomite, MgCO
3
, CaCO
3
; Gypsum CaCO
3
, 2H
2
O
(c) Sodium: Rock Salt, NaCl; Feldspar, Na
3
AlSi
3
O
8
; Chile saltpeter, NaNO
3
(d) Lead: Galena, PbS; Cerrusite, PbCO
3
; Anglesite, PbSO
4
Q.7 Discuss some of the factors which need consideration before deciding on the method of
extraction of metal from its ore.
Ans. Some of the factors which need consideration before deciding on the method of extraction of metal
from its ore are:
(i) Depending upon the type of impurity, the ore may be concentrated by different methods like
(a) magnetic separation
(b) hydraulic washing
(c) froth floatation method
(d) leaching
(e) electrostatic concentration
(ii) If the ore is in the oxide form, it is directly reduced. However, if the ore is a hydroxide, carbonate
or sulphide, it is first converted to the oxide form by calcinations or roasting/ smelting.
(iii) Chemical nature of the ore greatly affects the extraction process.
For example, various oxide ores may be reduced by carbon, hydrogen, aluminium or other metals auto-
reduction, displacement method or electrolytic method depending on the nature of the metal.
(iv) Thermodynamic considerations are very important in metallurgical processes.
These can help in deciding the temperature and the choice of reducing agents in the reduction
processes.
(v) Availability of facilities greatly determines the method of extraction.
GENERAL PRINCIPLES & PROCESSES OF ELEMENTS 87
www.thinkiit.in
(ii) Moderately reactive metals like Fe, Zn, Pb, etc. also do not occur in the native state and are
found in the combined form as oxides, carbonates, sulphides, sulphates, etc.
(iii) Noble metals like Au, Ag, etc being highly unreactive occur in native form.
Q.16 How do non-metals occurs in nature? How are they extracted/isolated form their natural
sources?
Ans. Non-metals occur in nature in the elemental as well as combined form. Nitrogen, oxygen, noble gases,
hydrogen etc are some non-metals which occur in the elemental form and are available from air.
The non-metals which occur in the combined form are generally extracted by oxidation, e.g., halogens
etc. are obtained by oxidation by electrolysis.
Non-metals like carbon, sulphur and phosphorus are extracted either from native ores or by oxidation
from their compounds occurring in nature. There are no general methods of extraction of non-metals.
Q.17 Name the processes from which chlorine is obtained as a bye product.
What will happen if an aqueous solution of NaCl is subjected to electrolysis?
Ans. Chlorine is obtained as a bye product in the electrolytic reduction of metal chlorides like NaCl, KCl etc.
When an aqueous solution of NaCl is subjected to electrolysis, H
+
ions are preferentially discharged at
the cathode by accepting electrons and thereby producing H
2
gas. This pushes the dissociation equilibrium
of water in the forward direction. The net reaction at cathode can be represented as
At cathode 2H
2
O + 2e

2 OH

(aq) + H
2
(g)
Cl

ions are preferentially liberated at the anode.

Cl + e

Cl + Cl Cl
2
(g)
The overall reaction during the electrolysis of aqueous solution of sodium chloride is
2Na
+
(aq) + 2Cl

(aq) + 2H
2
O 2Na
+
(aq)
+ 2OH

(aq) + H
2
(g) + Cl
2
(g)
Q.18 Name the chief ores of tin, iron and aluminium. What methods are employed for the
concentration/purification of their ores?
Ans. Tin Cassiterite, SnO
2
Concentration by hydraulic washing
Roasting to remove arsenic and sulphur as volatile oxides
Smelting in a reverberatory furnace to reduce metal oxide
Refining by liquation method.
Iron Haematite, Fe
2
O
3
Concentration by hydraulic washing and magnetic separation Magnetic, Fe
2
O
3
Roasting to remove moisture and remove arsenic and sulphur as
volatile oxides and to convert FeO to Fe
2
O
3
.
Limonite, (Fe
2
O
3
)
2
, 3H
2
O
Smelting in a blast furnace which yields pig iron.
Pig iron is purified /alloyed/treated in different ways to get different varieties of iron and steel.
Aluminium Bauxite, Al
2
O
3
.2H
2
O Bauxite is the most commonly used ore.
Different steps involved in extraction are
Cryolite, Na
3
AlF
6
Purification of bauxite by either Baeyers process, Halls process or Serpecks process.
Aluminosilicates
Electrolysis of fused aluminium oxide to obtain metal.
Refining by Hoops electrolytic process.
GENERAL PRINCIPLES & PROCESSES OF ELEMENTS 89
www.thinkiit.in
(v) Rourkela Steel plants, Rourkela, Orissa
(vi) Salem Steel plants, Salem, Tamil Nadu
(vii) Visvesvaraya Iron and Steel plants, Bhadravati, Karnataka
Q.25 Name the metals which are associated with the following terms in their extraction from their ores:
(i) Bessemers converter
(ii) Blast furnace
(iii) Alumino thermic process
(iv) Magnetic separation
Ans. (i) Bessemers converter: Copper, iron. (ii) Blast furnace: Iron, Copper
(iii) Alumino thermic process : Chromium, manganese.
(iv) Magnetic separation: Tin, iron, chromium and manganese.
Q.26 What do you understand by the following terms
(i) Roasting (ii) Calcination (iii) Smelting
Ans. (i) Roasting is the process of converting an ore into its metallic oxide by heating strongly below its
melting point in excess of air. The following changes occur during roasting:
(a) Moisture is removed
(b) Organic matter is destroyed
(c) Non-metallic impurities like that of sulphur, phosphorus & arsenic are oxidized & are removed as
volatile gases
S
8
+ 8O
2
8SO
2
(g)
P
4
+ 5O
2
P
4
O
10
(g)
4As + 3O
2
2As
2
O
3
(g)
(d) Ores are generally converted into metallic oxides
2ZnS + 3O
2
2ZnO + 2SO
2
(g)
2PbS + 3O
2
2PbO + 2SO
2
(g)
(e) It makes the ore porous and hence easily workable in subsequent changes.
(ii) Calcination is the process of converting an ore into its oxide by heating it strongly below its
melting point either in absence or limited supply of air.
During the process of calcinations, the following chemical changes occur:
(a) moisture is driven out
(b) volatile impurities of S, As and P are removed as their volatile oxide.
(c) water is removed from hydrated oxides and hydroxide ores.
(d) carbonate ores are converted into their respective oxides by loss of carbon dioxide.
(e) It makes the ore porous and hence easily workable in subsequent stages.
(iii) Smelting is he process of extracting the metal by fusing of its oxide ore with carbon is called smelting.
In this process, the roasted or the calcined ore is mixed with a calculated quantity of carbon and
heated to a high temperature above its melting, when carbon reduces the metal oxide to the free
metal. For example,
Zn + C Zn + CO; Pb + C Pb + CO
The carbon monoxide thus produced can also bring about the reduction of metal oxides to free metals.
Fe
2
O
3
+ 3CO 2 Fe + 3CO
2
(g)
PbO + CO Pb + CO
2
(g)
GENERAL PRINCIPLES & PROCESSES OF ELEMENTS 91
www.thinkiit.in
Exercise1
Q.1 Copper and silver lie below in the electrochemical series and yet they are found in the combined state
as sulphides in nature. comment.
Q.2 What types of ores are roasted ?
Q.3 What is the role of flux in metallurgical processes ?
Q.4 What is gangue ?
Q.5 What name is given to carbon reduction process for extra cting the metal ?
Q.6 What are fluxes ? How are they useful ?
Q.7 Name one each of (a) acidic flux (b) basic flux
Q.8 An ore sample of galena (PbS) is contaminated with zinc blende (ZnS). Name one chemical which can
be used to concentrate galena selectively by froth floatation method .
Q.9 Indicate the temperature at which carbon cambe used as a reducing agent for FeO.
Q.10 What is a slag ?
Q.11 What is meant by beneficiation process ?
Q.12 What is liquation ?
Q.13 What is the principle of zone refining ?
Q.14 When is electrolytic reduction applied for getting a metal ?
Q.15 Give two requirements for vapour phase refining
Q.16 What should be the considerations during the extraction of metals by electrochemical method
Q.17 The purest form of iron is prepared by oxidizing impurities from cast iron in a reverberatory furnace.
Which iron ore is used to line the furnace ? Explain by giving reaction ?
Q.18 Although carbon and hydrogen are better reducing agents but they are not used to reduce metallic
oxides at high temperatures. Why ?
Q.19 Differentiate between a mineral and an ore.
Q.20 Why is it that only sulphide ores are concentrated by froth floatation process ?
Q.21 Account for the following facts :
(a) the reduction of a metal oxide is easier if the metal formed is in liquid state at the temperature of
reduction.
(b) the reduction of Cr
2
O
3
with Al is thermodynamically feasible, yet it does not occur at room
temperature.
(c) pine oil is used in froth floatation method.
Q.22 (a) Name the method used for refining of
(i) Nickel (ii) Zirconium
(b) The extraction of Au by leaching with NaCN involves both oxidation and reduction. Justify giving
equations.
Q.23 Explain the following
(i) NaCN acts as depressant in preventing ZnS from forming the froth.
(ii) Role of cryolite in the metallurgy of aluminum.
Q.24 Out of C and CO, which is better reducing agent at 673 K.
Q.25 How is the concept of coupling reactions useful in explaining the occurrence of non-spontaneous
thermochemical reactions ? Explain giving an example.
Q.26 Free energies of formation (G
p
) of MgO(s) and CO(g) at 1273 K and 2273 K are given below.

f
G[MgO(s)] = 94 KJ/mol at 1273 K

f
G[MgO(s)] = 314 KJ/mol at 2273 K

f
G[CO(g)] = 439 KJ/mol at 1273 K

f
G[CO(g)] = 628 KJ/mol at 2273 K
On the basis of abve data, predict the temperature at which carbon can be used as a reducing agent
for MgO(s).
Q.27 Explain the following :
(i) Generally sulphide ores are converted into oxides before reduction.
(ii) Carbon and hydrogen are not used as reducing agents at high temperature.
(iii) Silica is added to sulphide ore of copper in the reverberatory furnace.