Metallurgy 15.

Chapter
15 Metallurgy

Intext Exercise 1
1. By definition, ore is that naturally occurring mineral 7. Definition of Levigation.
from which the metal can be profitably extracted.
8. Heating in the presence of air or oxygen is called
2. Such minerals from which a metal can be extracted roasting while doing the same with limited supply
profitably are called its ore. of O2 is called calcination.
3. Cinabar is HgS 9. Smelting is a process of reducing metal oxide to
metal by means of coke or CO.
4. Froth floatation method is based on the fact that the
surface of sulphide ores is preferentially wetted by Fe2O3 + 3C → 2Fe + 3CO
oil while that of gangue is wetted by water.
Fe2O3 + 3CO → 2Fe + 3CO2
5. Haematite (Fe2O3) is a magnetic material while the
10. Heating of concentrated ore in presence of O2 is
gangue associated with this ore is non-magnetic.
called Roasting.
6. Cyanide process is used in the extraction of both
Silver and Gold because these form complex salts
with CN- ion due to presence of lone pair of electron
on nitrogen atom.
Intext Exercise 2
1. Carbon reduction, is one of the most common 6. Al being a highly electropositive metal is extracted
methods employed to reduce oxide ores. by electrolysing fused Al2O3 after adding cryolite
2. CaO is a refractory material i.e. has high M.P. and is and fluorspar.
heat resistant. Also, it is a basic oxide and hence can 7. Self reduction:- Reduction of oxide ore of a metal
combine with acid oxides to form slag. by its own sulphide 2Cu2O + Cu2S → 6Cu + SO2
3. The reduction of a metal oxide by a more 8. Cyanide process or leaching is used to extract Ag
electropositive metal is called thermal reduction. and Au.
Iron can be obtained by Alumino thermic process.
9. ZnO + CO → CO2 + Zn
4. Flux + Gangue → Slag
10. Fe2O3 + 3CO → 3CO2 + 2Fe
5. Fe2O3 + 3C → 3CO + 2Fe
Intext Exercise 3
1. Copper has a high reduction potetial and hence is 5. Zn is a highly electropositive metal and the
easily refined by electrorefining impurity cations get reduced in preference to Zn2+ if
electrorefining is used for Zn.
2.
6. Mond’s process

3. Si, Ge which are required in ultra pure state for the

manufacture of semiconductors are purified by zone
refining. 7. Van Arkel method Ti and Zn are refined by this
method. It is used for obtaining ultra pure metals.
4. 2Cu2S + 3O2 → 2Cu2O + 2SO2
8. Poling is used for purification of metal which contain
their own oxide as impurity
e.g. Cu2O in Cu; SnO2 in Sn
15.2 Chemistry
9. Hydrometallurgy is the process of dissolving the 10. Cupellation method is used when the impure metals
metal or its ore by the action of a suitable chemical contain impurity of another metal which forms
regent followed by recovery of the metal either by volatile oxide.
electrolysis or by the use of a suitable precipitating
agent.
4Au + 8KCN + 2H2O + O2 → 4K[Au(CN)2] 4KOH
air
2K[Au(CN)2] + Zn → 2Au + K2[Zn(CN)4]

EXERCISE - 1

1. In smelting, metal is obtained in a fused state. 14. The rocky and siliceous impurities associated with
an ore is called matrix or gangue.
2. Sulphide ores of zinc/copper is concentrated by
froth floatation process. 15. In calcination, moisture or hydrated water is
removed on heating.
3. Acidic flux is used. An acidic oxide (oxide of a
non-metal) like SiO2, P2O5, B2O3 (from borax). It Al2O3.2H2O → Al2O3 + 2H2O↑
is used to remove the basic impurity like CaO, FeO,
16. The most common method of extraction of metals
MgO etc. The acidic flux combines with the basic
from oxide ores is carbon reduction method. This is
impurity and forms a slag.
so because coal (carbon) is relatively cheap.
4. Smelting involves heating of oxide of the metal with
17. Pyrolusite is an oxide ore which is not concentrated
carbon or coke at very high temperature.
by froth floatation method. This method is used for
5. Both Ca and K are highly electropositive metals. sulphide ores.
When heated with C they form carbides.
18. Roasting removes Sulphur from an ore in presence
6. Pine oil is adsorbed at the surface of sulphide ore of oxygen as SO2 gas.
particles which become water repellent and come
19. Lighter gangue particles are washed in a current of
out along with froth when air is blown through the
water by a process called levigation. In levigation
mixture.
the powdered ore is agitated with water or washed
7. In froth floatation process, ore particles float because with a upward stream of running water, the lighter
their surface is hydrophobic i.e., not easily wetted particles of sand, clay etc are washed away leaving
by water but wetted by oil. behind heavier ore particles.
8. (a) Calamine is ZnCO3 and siderite is FeCO3 20. Potassium ethyl xanthate acts as a collector. KCN
and NaOH depress the floatation property of ZnS
(b) Argentite is Ag2S while cuprite is Cu2O
and FeS2 particles. Thus, only PbS particles go into
(c) Zinc blende is ZnS and iron pyrites is FeS2 the froth. Now copper sulphate is added to the tank
(d) Malachite is CuCO3 Cu(OH)2 and (mixture) which activates floating character of ZnS
azurite is 2CuCO3 Cu(OH)2 and this time only ZnS comes along with froth. The
remaining slurry is acidified and FeS2 floats along
9. In smelting, ore is reduced by C or other reductants with froth.
in molten state
21. PbS is good conductor and ZnS is poor conductor of
10. FeCrO4 being magnetic in nature can be separated electricity.
from tin ore (SnO2) which is non magnetic by Hydraulic washing or Gravity separation or
magnetic separation method. Levigation method is based on the difference in the
11. Calcination is used to remove organic matter, water densities of the gangue and ore particles.
from hydrated oxides and CO2 from carbonates. 23. Calamine is ZnCO3 and zincite is ZnO. Both are
12. Calcination is the process of heating the purified ore minerals of zinc.
in the absence of air or oxygen. Thus, option (d) is 24. Pig iron is an impure form of iron and not an ore.
calcination.
25. Chalcopyrites are sulphide minerals which are
13. SnO2 (tin stone) is also called cassiterite. concentrated by froth floatation process.
 Metallurgy 15.3
26. Galena (PbS) is an ore of Pb. an oxidation reaction (Ag → Ag+ or Au → Au+)
27. Copper sulphate activates the floating character of Ag2S(s) + 4CN–(aq) —→ 2[Ag(CN)2]–(aq) + S2–(aq)
sulphide ore (ZnS). 2Ag(CN)2–(aq) + Zn(s) —→ [Zn (Cn)4]2–(aq) + 2Ag(s)
28. Wolframite is ferrous tungstate FeWO4 which is Here Zn acts as reducing agent.
magnetic in nature.
33. Mg and Al are highly electropositive metals and
29. Fact. can not be obtained by electrolysis of the aqueous
roasting solution of their salts as they would react with water.
30. 2ZnS + 3O2 2ZnO + 2SO2 ;
1100 o C
They are obtained from electrolysis of their fused
ZnO + C Zn + CO. salt.
31. Highly reactive element Na is extracted by 34. A hydrometallurgical process for the extraction
electrolysis of fused salts. of metals from ores, concentrates, or secondary
32. (a) Self-reduction method materials essentially contains three basic steps—
dissolution of the valuable metal in the aqueous
This method is also called auto-reduction solution (leaching) purification of leach solution
method or air reduction method. If the sulphide and subsequent recovery of metal from the purified
ore of some of the less electropositive metals solutions either by electrolysis or by adding some
like Hg, Cu, Pb etc. are heated in air, a part of electropositive metal to it.
these is changed into oxide or sulphate that then
reacts with the remaining part of the sulphide 35. Al2O3.2H2O(bauxite) is concentrated by leaching
ore to give its metal and SO2. with NaOH. Al2O3 dissolves leaving other impurities
undissolve.
Cu2S + 3O2 —→ 3Cu2O + 2SO2
Al2O3.2H2O + 2NaOH → 2NaAlO2 + 3H2O
2Cu2O + Cu2S —→ 6Cu + SO2
(b) Reduction with carbon / carbon monoxide :
2Fe2O3 + 3C —→ 4Fe (spongy iron) + 3CO2
Fe2O3 + 3CO —→ 2Fe + 3CO2 36.
Fe3O4 + 4CO —→ 3Fe + CO2
(c) 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 increases
Reactions involved :
conductivity. The fused matrix is electrolysed.
2FeS + 3O2 —→ 2FeO + 2SO2
The electolysis of the molten mass is carried out
in an electrolytic cell using carbon electrodes. FeO + SiO2 —→ FeSiO3
The oxygen liberated at anode reacts with the 2Cu2S + 3O2 —→ 2Cu2O + 2SO2
carbon of anode producing CO and CO2. 2Cu2O + Cu2S —→ 6Cu + SO2 (self reduction)
Cathode : Al3+ (melt) + 3e– —→ Al(l) 37. A molten mixture of Al2O3 and Na3AlF6 is used as
Anode : C(s) + O2– (melt) —→ CO(g) + 2e– an electrolyte in the commercial electrochemical
C(s) + 2O2– (melt) —→ CO2 (g) + 4e– process for extraction of Al.
(d) Complex formation and displacement by metal : 38. In many extraction processes, an oxide is added
deliberately to combine with other impurities and
Extraction of Ag and Au. Metals like Au and
form a stable molten phase immiscible with molten
Ag can be precipitated for their salt solution by
metal called a slag. The principle of slag formation
electropositive metals for example, Zn.
is essentially the following.
Metallic Ag is dissolved from its ore in dilute Nonmetal oxide (acidic oxide) + Metal oxide (basic
NaCN solution, and the solute so obtained is oxide) —→ Fusible (easily melted) slag.
treated with scrap Zn when Ag is precipitated.
Air is blown into the solution oxidize Na2S. 39. Electrolysis of aqueous solution of NaCl (brine)
Leaching the metals like silver, gold with CN– is gives Cl2 at the anode.
15.4 Chemistry
40. Copper is obtained by self reduction or self 50. Highly electropositive elements are extracted by
electronation or auto reduction as shown below: electrolytic reduction.
2Cu2O + Cu2S —→ 6Cu + SO2 - 51. In Van-Arkel method, the metal is converted into its
41. Electrolytic reduction method is used in the stable volatile iodide which is then decomposed at
extraction of highly electropositive elements as they higher temperature to pure metal and I2.
themselves are stronger reducing agents. They lie 52. Ni combines with CO to form volatile Ni(CO)4
above hydrogen in electrochemical series. The heat which decomposes to give pure Ni metal and CO on
of formation of Al2O3 is very high and therefore, at heating.
higher temperature there will be the possibility of Heat
Ni(CO)4 Ni + CO -
formation of Al4C3 with carbon.
Volatile Metal
42. As the reduction potential of water is lower than that
53. Electrolysis is done to achieve electroplating and
of sodium, it will be discharged at the cathode and
electrorefining of metals.
chloride will be discharged at the anode to form H2
and Cl2 gases. 54. This process is used for the purification of copper
43. Cryolite is Na3AlF6 and is used in the electrolysis of and tin to remove the impurities of their oxides.
alumina. It reduces the melting point of alumina and Green wood → Hydrocarbons → CH4 ;
increase the electrical conductivity of electrolyte. 4CuO + CH4 → 4Cu (pure metal) + CO2 + 2H2O
44. In blast furnace, zone of combustion has 1500– Green wood → Hydrocarbon → CH4 ;
1600ºC temperature, zone of fusion (1200–1500ºC),
2SnO2 + CH4 → 2Sn + CO2 + 2H2O
zone of heat absorption, middle zone (800–1200ºC)
and zone of reduction (300–700ºC) are other zones 55. Silicon is purified by zone refining process.
of the furnace. Heat
56. Ni (CO) 4 Ni + 4CO
45. Electrolytic reduction method is used in the
57. Cyanide process is used for the extraction of Au,
extraction of highly electropositive elements as they
floatation process uses pine oil as a foaming agent,
themselves are stronger reducing agents. They lie
electrolytic reduction is used in the extraction of Al
above hydrogen in electrochemical series.
and zone refining process produces ultra pure Ge.
46. FeO + SiO2 " FeSiO3
(Impurities) (Flux) (slag) 58. Greater solubility of the impurity in the molten state
47. Molten iron from blast furnace is taken into sand than in the solid.
pigs for solidification. Therefore iron obtained from 59. Gallium arsenide is purified by zone refining
blast furnace is called pig iron. method.
48. In blast furnace, Fe2O3 is reduced to Fe by CO.
60. In electrorefining of copper, impure copper is
Fe2O3 + 3CO → 2Fe + 3CO2 - made anode while pure Cu strip is made cathode.
49. In Ellingham diagram, the DGº of Al2O3 lies below On passing current impurities like Fe, Zn, Ni, Co
that of CO2. If reduction is carried out at very high dissolve in the solution and Au, Ag etc. settle down
temperature, the Al produced will react with carbon below as anode mud.
forming Al4C3.
EXERCISE - 2
1. Zinc blende (ZnS) ; copper glance (Cu2S) ; Galena 5. 2MgO + 2C 2Mg + CO;
(PbS).
DGReaction = DGCO - DGMgO
2. (P) Haematite Fe2O3 = + 3
At 1000oC, DG = -439 + 941 > 0 (Non-spontaneous)
8
(Q) Magnetite Fe3O4 = + 3 At 2000oC, DG = -628 + 341 < 0 (Spontaneous)
(R) Siderite FeO = + 2
6. The purified ore, cassiterite containing 60-70%
3. Carnallite is the important ore of magnesium and it SnO2 is called as black tin.
has chemical composition KCl.MgCl2.6H2O.
7. Carbonate ores being heated in absence of air to
4. Feldspar is K2O.Al2O3.6SiO2. obtain the metal oxides is called calcination.
Beryl is Be3Al2Si6O18
 Metallurgy 15.5
8. Metal cannot be economically and conveniently 20. Process mentioned in the question is self-reduction.
extracted from salt cake (Na2SO4). Lead is extracted by this method.
2 ]3 Gg 21. It is obtained by electrolytic reduction of molten
9. 2T =-3 S anhydrous KCl.MgCl2 (other methods are not
economical/ feasible for the extraction of Mg metal).
Matte is obtained in blast furnace and that contains
mostly Cu2S and FeS. It is transferred to bessemer
converter where self reduction takes place according
to the following reactions.
2Cu2S + 3O2 —→ 2Cu2O + 2SO2 ;
∵ DS < 0, slope will be positive. 2Cu2O + Cu2S —→ 6Cu + SO2.
10. It is used to separate haematite ore as it is attracted 23. Slag floats on the molten metal. During extraction
by electromagnet. haematite is Fe2O3 which is of iron the silica impurity (SiO2) is converted to
magnetic but the impurities present in it are not. CaSiO3 by adding CaCO3.
11. The free energy change that occurs when 1 mol of 24. Na3[AlF6] —→ 3NaF + AlF3
common reactant (in this case O2) is used may be
plotted graphically against temperature for a number NaF and AlF3 both are ionic compounds and so
of reactions. This is called an Ellingham diagram. ionise to give ions. This increases the electrical
conductivity and lowers the melting point of Al2O3.
12. For a reduction process the change in the free energy,
DG must be negative and to make DG negative At cathode : Al3+ (melt) + 3e– —→ Al.
temperature should be high enough so that TDS > At anode : C(s) + O2– (melt) —→ CO (g) + 2e– ;
DH. C(s) + 2O2– (melt) —→ CO2 (g) + 4e–.
13. ZnO + C —→ Zn + CO;
25. (Y) PbS reduces PbO to Pb ; it is called self reduction.
DGo = -460 + 360 < 0 (Spontaneous) 3
26. Na2CO3 + Al2O3 2NaAlO2 + CO2 is involved
14. Calamine is ZnCO3. in Hall’s process.
15. Reduction of oxides of Mn, Cr etc., by electropositive 27. Aluminum is extracted by electrolytic reduction of
aluminium metal is called as alumino thermite mixture of molten Al2O3 + Na3AlF6 + CaF2.
process.
Due to very high energy of dissociation of Al2O3, the
16. (a) AlOx(OH)3–2x [Where 0 < x < 1] reduction at such high temperature will give carbide
(b) Al2O3 in place of metallic Al according to the following
3
(c) K2Mg2(SO4)3 reaction. 2Al2O3 + 6C Al4C3 + 3CO2.
(d) [Al2(OH)4Si2O5] 28. PbS will be reduced by self reduction as well as
Therefore, (C) is not an ore of AL. carbon reduction method.

17. ZnS + 4NaCN → Na2[Zn(CN)4] + Na2S 29. Cu metal is extracted by self-reduction method.
PbS + NaCN → No such complex formation. 30. Copper pyrite the chief ore of copper contains FeS as
18. (a) PbS + 2PbO —→ 3Pb + SO2 impurity which is converted into FeO and separated
(Self reduction process) as slag by adding SiO2 as flux. the slag formed has
the formula of FeSiO3.
(b) PbSO4 + PbS —→ 2Pb + 2SO2
(Self reduction process) 31. Copper matte contains Cu2S and FeS.
(c) 2PbS + 2O2 —→ 2PbO + 2SO2 32. Cathode : Al3+ (melt) + 3e– —→ Al
(Roasting) Anode : C + O2– (melt) —→ CO + 2e–;
19. The solidified copper obtained after bessemerisation C + 2O2–(melt) → CO2 + 4e–
is impure and contains Fe, Ni, Zn, Ag, Au etc., as 33. The most important property which allows a
impurity. It has blistered like appearance due to the substance to be used as a refractory material is its
evolution of SO2 and so it is called blister copper.
ability to withstand high temperatures.
15.6 Chemistry
34. NaCl and CaCl2 both being ionic compounds ionise 42. The Hoop’s process is a process for the electrolytic
to give ions which lowers the melting point and refining of aluminum. Impure Al forms the anode
increase the conductivity of the mixture. and pure Al forms the cathode of the Hoop’s cell
which contains three liquid layers. The bottom layer
35. Sulphide ore of Hg, Cu, Pb are heated in air, a part is molten impure Al, the middle is a fused salt layer
of these is changed in to oxides or sulphate that then containing sodium fluoride, aluminum fluoride and
react with the remaining part of the sulphide ore to barium fluoride, and the top layer is pure Al. At
give its metal and SO2. This is called self reduction, the anode (bottom layer), Al passes with solution
auto reduction or air reduction method. as aluminum ion (Al3+), and at the cathode (top
36. Cathode (reduction) Cu2+ (aq) + 2e– —→ Cu(s). layer), these ions are reduced to the pure metal. In
operation, molten metal is added to the bottom of the
37. Factual. cell and pure aluminum is drawn off the top.
38. P represents the Van Arkel process and is used for At anode : Al —→ Al3+ + 3e–
Ti. Q represents self reduction or Auto reduction and
can be used for Cu, Pb, Hg etc. At cathode : Al3+ + 3e– —→ Al.

R represents electrolytic reduction with cryolite and 43. Cupellation is employed to purity such metals which
fluorspar and is used for the extraction of Aluminum. contains impurities whose oxides are relatively
volatile.
39. Lead is purified by Electro-refining. Zone refining
is used for the purification of Si and Ge. 44. Molten silver preferentially dissolves in molten zinc
forming silver-zinc alloy - Which is lighter and has
40. Anode mud obtained in electrolytic refining of lead higher melting point.
contains, Sb, Cu, Ag and Au. Less electropositive
metals than the metal being purified remains in 45. Electro refining is used to purity metals like Cu, Pb.
the anode mud while more electropositive metals 46. Anode mud contains the impurity of Au only.
remain in the electrolytic solution. The only impurity present in Ag which is less
41. Zinc and lead do not form an alloy and hence electropositive than Ag.
separate into different layers when molten in the 47. Mond’s process — Nickel
presence of organic solvent. Silver forms alloys with
48. It is not called van Arkel method. Van Arkel method
both Zn and Pb and hence is found in both layers.
is used for the purification of Zr and Ti. Reaction (c)
silver forms alloy with Zn more readily as both are
is simple thermal decomposition of Ag2CO3.
d-block metals and thus more Ag is present in X.
49. This method is used for the purification of those
impure metals which contain the impurities of their
own oxides as impurities for example CuO in Cu
and SnO2 in Sn.

EXERCISE - 3
1. Hydrometallurgy or leaching is used for less reactive Fe2O3 + CO —→ 2FeO + CO2
metals like Ag, Au etc. At 900–1500 K (higher temperature range in the
2. [MxOy + Al
3
Al2O3 + xM blast furnace):
Thermite process used for extraction of B, Mn, Cr, C + CO2 —→ 2CO; FeO + CO —→ Fe + CO2
Zn, Sn and Cu are less reactive and can be reduced 5. (i) Dolomite CaCO3.MgCO3
by other reducing agents like coke.
(ii) Malachite CuCO3.Cu(OH)2
3. [FeSO4, TiSO4 and CuSO4.5H2O are paramagnetic.] (iii) Calcite ZnCO3
4. C and CO are the two reducing agents used. At 500 – (iv) Copperpyrities CuFeS2
800 K (lower temperature range in the blast furnace)
(v) Sylvine KCl
3 Fe2O3 + CO —→ 2Fe3O4 + CO2
(vi) Cryolite Na3AlF6
Fe3O4 + CO —→ 3Fe + 4CO2
(vii) Siderite FeCO3
(viii) Iron pyrite FeS2
 Metallurgy 15.7
(ix) Argentite Ag2S CuFeS2 —→ No leaching
So, answer is (i), (ii), (iii) and (vii) PbS —→ No leaching
6. ZrI4 (l = 4) MgCl2 —→ No leaching;
Gas involved in Mond’s process is CO (m = 3). FeCO3 —→ No leaching
Thomas slag is Ca3(PO4)2 (n = 3 + 2 = 5) 2Cu2O(s)+4H2SO4(aq)+O2(g)→4CuSO4(aq)+4H2O(l)
7. Name of ore Composition of ore HgS —→ No leaching
(i) Carnallite KCl.MgCl2.6H2O 10. DGº = + nFEºcell MgCl2 —→ Mg + Cl2
(ii) Cuprite Cu2O 2 × 96500 × 2.02
= 1000 = 390 kJ/mole
(iii) Cassiterite SnO2 11. 2HgS + 3O2 —→ 2HgO + 2SO2;
(iv) Chromite FeO.Cr2O3 2HgO + HgS —→ 3Hg + SO2
(v) Cinnabar HgS Cu2S + 3O2 —→ 3Cu2O + 2SO2 ;
(vi) Calamine ZnCO3 2Cu2O + Cu2S —→ 6Cu + SO2
(vii) Cerussite PbCO3 2PbS + 3O2 —→ 2PbO + 2SO2 ;
(viii) Chalcopyrite CuFeS2 2PbO + PbS —→ 3Pb + SO2
(ix) Chalcocite Cu2S
12. Physical Method : I, II, III, IV
So, answer is (ii), (iii) & (iv)
Chemical Method : V, VI, VII, VIII, IX
3
8. (1) B2O3 + 2Al 2B + Al2O3 (aluminothermic 13. Fe2+ and Fe3+
process-extraction of boron)
3 Number of Fe3+ = 2 × Number of Fe2+
(2) Cr2O3 + Al 2Cr + Al2O3 (extraction of
chromium) \ EF = 2Fe3+.Fe2+O42– = Fe0.75O

(3) TiCl4 + 2Mg

3
Ti + 2MgCl2 (Kroll 14. 2Na[Ag(CN)2] + Zn —→ Na2[Zn(CN)4] + 2Ag
process-extraction of titanium) 0.5 × 500
3
1000 = 0.25 moles
(4) PbS + 2PbO 3Pb + SO2 (extraction of 0.25
lead) moles of Zn = 2
(5) 3Fe2O3+CO—→2Fe3O4+CO2(Indirect reduction) 0.25 65
mass of Zn = 2 × 65 = 8 × 8 = 65
(6) Fe3O4+CO—→3FeO+CO2 (Indirect reduction)
(7) 2Cu2O + Cu2S —→ 6Cu + SO2 (Self reduction) 15. The metals which are more electropositive than Al
(Li → Al). They are extracted by electrolysis of their
3
9. Al2O3 + 2NaOH + 2H2O 2NaAlO2 + 3H2O; molten salts. i.e. Li, Ba, Na, Al, Ca, Mg.
Ag2S + 2CN– —→ [Ag(CN)2 + S2– ]–
Au + 2CN– + 2H2O + O2 —→ [Au(CN)2]– + 4OH–;

EXERCISE - 4
1. Ore is heated below its melting point in a 3. (a) Tin-cassiterite (SnO2)
reverberatory furnace in the presence of air (b) Zinc-calamine (ZnCO3)
to convert it into its oxides. It removes easily
oxidisable volatile impurities like arsenic as As2O3, (c) Iron-siderite (FeCO3)
antimony as Sb2O3 and sulphur as SO2. Roasting (d) Lead-Cerrusite (PbCO3)
is an exothermic process; once started it does not 4. (a) When the oxide undergoes a phase change, there
require additional heating. will be an increase in the entropy of the oxide.
2. At lower temperature following reactions occur in (b) It is true statements, HgO
3
Hg + 1/2O2
blast furnace.
(c) For a reduction process the change in the free
3Fe2O3 + CO —→ 2Fe3O4 + CO2 ; energy, DGo must be negative and to make DGo
Fe3O4 + CO —→ 3Fe + 4CO2 ; negative temperature should be high enough so
Fe2O3 + CO —→ 2FeO + CO2 that TDSo > DHo.
15.8 Chemistry
5. Fact based. 18. Zone refining method is based on the principle that an
impure molten metal on gradual cooling will deposit
6. Sulphide ores are concentrated using froth floatation
crystals of the pure metal, while the impurities will
method.
be left in the remaining part of the molten metal.
7. The Gibb’s free energy of most sulphides are less
19. Potassium or sodium ethyl xanthate get attached
than that for CS2. In fact, CS2 is an endothermic
with the particle of the sulphide ore and thus make
compound. Therefore, the DGo of MxS is not
them water repellent i.e. hydrophobic.
compensated. So reduction of MxS is difficult.
Hence it is common practice to roast sulphide ores 20. In smelting the concentrated oxide ores like
to corresponding oxides prior to reduction. haematite, tin stone even after concentration, is
heated with flux to remove the acidic or basic
8. A hydrometallurgical process for the extraction
impurities forming the slag. All other processes are
of metals from ores, concentrates, or secondary
used for removing the earthy/silicious impurities.
materials essentially contains three basic steps—
dissolution of the valuable metal in the aqueous 21. (a) Sulphides ores are generally concentrated by
solution (leaching) purification of leach solution froth floatation.
and subsequent recovery of metal from the purified roasting
(b) 2CuFeS2+ 4O2 Cu2S + 2FeO + 3SO2
solutions either by electrolysis or by adding some
electropositive metal to it. Cu2S + FeO + SiO2 —→
50 C o
FeSiO3 (fusible slag) + Cu2S (matte)
9. Ni(s) + 4CO (g) [Ni(CO)4] (g) ;
200 o C (c) Bessemerisation
[Ni(CO)4] (g) Ni(s) + 4CO (g).
2FeS + 3O2 —→ 2FeO + 2SO2
10. Ore bauxite, Al2O3.2H2O of aluminum occurs as
oxide ore in nature. FeO + SiO2 —→ FeSiO3
2Cu2S + 3O2 —→ 2Cu2O + 2SO2
11. Slag is fusible mass having lower melting point; not
miscible with molten metal and lighter than molten 2Cu2O + Cu2S —→ 6Cu + SO2 (self reduction).
metal. Roasting. It is a process of heating the concentrated
leaching ore (generally sulphide ore) strongly in the excess of
12. Al2O3 (bauxite) + 2NaOH (aq) + H2O (l)
air or O2 below its melting point.
2Na[Al(OH)4] (aq). Roasting at high temperature. The sulphide ores of
13. For examples SiO2 + CaO —→ CaSiO3 (metal some of the metals like Cu, Pb, Hg, Sb etc., when
silicate) or FeO + SiO2 —→ FeSiO3. heated strongly in the free supply of air or O2 are
reduced directly to the metal rather than to the
14. Cupellation is used when lead is present in traces. metallic oxides.
In argentiferous lead the silver is removed by Calcination. It is a process of heating the
Parke’s process because silver has higher solubility concentrated ore strongly in a limited supply of air
in molten zinc than lead. or in the absence of air.
Silver has higher solubility in molten zinc than lead 23. (a)
3G 3G
is slope in Ellingham
and thus forms zinc-silver alloy from which zinc T =-3 S, T
can be distilled off leaving behind the silver. diagram. Which is same below the boiling point.
< 1800 K (b) Below the boiling point slope is same as factor
15. Zr (impure) + 2I2 ZrI4
TDS is same.
> 1800 K
ZrI4 Zr (pure) + 2I2 and hence over (c) Above DG = 0 line free energy becomes positive
1800ºC practically no reaction can take place so oxide decomposes.
between Zr and I2.
(d) Randomness of reactant increases i.e. DS
16. The process is truly adsorption as gangue particles increases, so slope also increases.
are wetted with water and sulphide ore particles are
24. X → [Ni(CO)4]sp3, diamagnetic.
wetted with pine oil.
25. (A) true (C) small amount of Mn is added to molten
17. CaO + SiO2 —→ CaSiO3 (slag) (Haematite ore
steel to remove sulphur and oxygen.
contains silica as impurities).
Slag being lighter and insoluble in molten metal 26. Mg and Al are extracted by electrolytic reduction.
floats over and thus forms upper layer.
 Metallurgy 15.9
27. (a) White bauxite contains the impurity of silica 39. In poling process of purification of Cu, O2 oxidises
which is removed by heating with coke in a S, Sb, As and Fe into their oxides.
stream of N2
40. All processes are correct.
1800 o C
SiO2 + 2C Si - + 2CO ; Fe2O3 + 4CO —→ 3Fe + 4CO2
1800 o C
Al2O3 + 3C + N2 2AlN + 3CO ZnO + C —→ Zn + CO
lower temperature
(b) 2PbS + 3O2 air
2PbO + SO2 ; 2Cu2O + Cu2S —→ 6Cu + SO2
2PbO + PbS
higher temperature
3Pb + SO2 PbO + C —→ Pb + CO

(c) SnO2 (black tin contains 60–70% SnO2) + 2C 41. PbS, HgS, Cu2S all can be obtained by self-
3
Sn + 2CO. reduction.

28. (c) is incorrect statement as 42. C can reduce those metal oxides to metal at a given
temperature whose Ellingham diagram lines lie
3
2CuFeS2 + 4O2 Cu2S + 2FeO + 3SO2. above the carbon line.
29. (i) Slag is a fusible mass. 43. Those metals whose M.P. is lower than the M.P. of
(ii) It has low melting point. the impurities present in the metal can be purified by
Liquation.
(iii) It is lighter than and immiscible with the molten
metal. It is due to these impurities that the slag 44. [X] = CuCO3.Cu(OH)2 or 2CuCO3.Cu(OH)2 ;
floats as a separate layer on the molten metal and [Y] = Cu2S or CuFeS2
can thus be easily separated from the metal. The CuCO3.Cu(OH)2 —→ CuO (s) + CO2 + H2O ;
layer of the slag on the molten metal prevents
the metal from being oxidised. It is used as one [Y] = Cu2S or CuFeS2
of the constituent of cement and in building 2Cu2S + 3O2 —→ 2Cu2O + 2SO2 ;
material.
Cu2S + 2Cu2O —→ 6Cu (M) + SO2(g)
30. Proustite → Ag3AsS3 5SO2 + 2IO3– + 4H2O —→ I2 + SO42– + 8H+
31. Sodium and Aluminium reacts with water so often I2 + strach —→ blue colour
extracted from their fuses salts as they are highly
electropositive metals. 45. It is sulphide ore (Cu2S or CuFeS2) & is called as
copper glance or copper pyrite; S2– gives yellow ppt.
32. siderite → FeCO3 fool’s gold → FeS2 of CdS with CdCO3 suspension.
chalcopyrite → CuFeS2 limonite → FeO(OH).nH2O 46. G1 = SO2 ; It can increase its oxidation state from +4
33. Cynide process used for Au and Ag complexes to +6 & decrease from +4 to 0 or –2.
formed in this, are : Na[Au(CN)2], Na[Ag(CN)2], 47. CuCO3 + 2HCI —→ CuCl2 + CO2 + H2O;
Na2[Zn(CN)4]. Cu is not involved with cyanide
CuCl2 + 2KI —→ CuI2 + 2KCI;
process.
2CuI2 —→ Cu2I2 + I2
34. The separation of gold from a mixture of gold and
3
silver is called parting. Since, gold not dissolve in 48. CuCO3.Cu(OH2) CuO↓ (black) + CO2 + H2O
nitric acid, sulphuric acid or chlorine while silver CuCO3.Cu(OH)2+4HCl—→2CuCl2 + 3H2O + CO2;
does, therefore these can be used for parting of gold.
2CuCl2 + 4KI —→ Cu2I2↓ (white) + I2 + 4KCI
35. X → CO2; Y → CO
49. (a) Langebeinite → K2Mg2(SO4)3
36. Smelting of iron in a blast furnace does not involve HCl, 3
sublimation. (b) MgCl2.6H2O MgCl2 + H2O. If heated
alone it forms MgO instead of anhyd. MgCl2.
37. Liquation process is used for the purification of
(c) Fact.
those metals which are more fusible than impurities
present. 50. Hydrated magnesium chloride in MgCl2.6H2O.
38. Bauxite → Al2O3, Limonite —→ Fe2O3.3H2O 51. NaCl and CaCl2 are added to lower the fusion
temperature and increase the conductance of MgCl2.
Cinnabar —→ HgS, Casseterite —→ SnO2
15.10 Chemistry
52. Zn can be obtained by carbon reduction. Na is (b) Copper pyrites is CuFeS2. During smelting /
obtained by electrolytic reduction while Cr, Mn by roasting and bessemerisation the impurity of
thermite reduction. iron sulphide is removed as fusible slag, FeSiO3.
Roasting
53. Liquation is a method of purification of metals 2CuFeS2 + 4O2 Cu2S + 2FeO + SO2
having a M.P. lower than the impurities present in it. 2FeS + 3O2 —→ 2FeO + 2SO2
54. Zincite→ZnO, Malachite green → CuCO3.Cu(OH)2 FeO + SiO2 —→ FeSiO3 (slag)
Anglesite → PbSO4, Magnetite → Fe3O4 (c) Carnallite (KCl.MgCl2.6H2O)
3 ]calcinationg
55. Vapour phase refining is the same as Van Arkel Dry HCl (g)
MgCl2 + 6H2O
process. Mg extraction is done by electrolytic reduction
56. (a) FeO + SiO2 —→ FeSiO3 (slag); this reaction of molten mixture of anhydrous MgCl2 + NaCl +
occurs in extraction of copper from copper CaCl2.
pyrites in smelting as well as in bessemerisation (d) Bauxite is Al2O3;
processes. 1275 K
2Al(OH)3 Calcination
Al2O3 + 3H2O; Extraction
(b) Reduction of oxides of Mn, Cr with of Al from purified Al2O3 is done by electrolytic
electropositive metal aluminum is called reduction of molten alumina dissolved in cryolite or
thermite process. fluorspar.
(c) Self reduction generally occurs in bessemer
58. (a) Poling : Impure molten metal is stirred with
converter in extraction of copper from copper
green wood poles. The reducing gases liberated
pyrites.
reduce the oxide of the metal to free metal. This
(d) Conversion of Al(OH)3 into Al2O3 by heating in method is used for the purification of those
absence of air represents the calcination. metals which contain the impurities of their own
(e) Displacement of silver from its salt solution by oxides. For example CuO in Cu and SnO2 in tin.
more electropositive zinc. (b) Cupellation : It is used when impurities are of
57. (a) Haematite is Fe2O3. To remove the impurity other metals and is mainly used for the removal
of FeCO3, the ore is heated in absence of air of lead from silver.
(calcination). (c) Liquation : This process is used for the
At 500 – 800 K (lower temperature range in the blast purification of the metal, which it self is readily
furnace) fusible but the impurity present in it are not i.e.
impurities are non-fusible. This process is used
3Fe2O3 + CO —→ Fe3O4 + CO2
for purification of Sn and Zn.
Fe3O4 + CO —→ 3Fe + 4CO2
(d) Van Arkel method : (vapour phase refining)
Fe2O3 + CO —→ 2FeO + CO2 Metals like titanium, zirconium, thorium and
At 900 – 1500 K (higher temperature range in the uranium are purified by this method.
blast furnance):
C + CO2 —→ 2 CO
FeO + CO —→ Fe + CO2

1. Siderite – FeCO3 4. Dolomite : CaMg(CO3)2

Calamine – ZnCO3 Malachite : CuCO3∙ Cu(OH)2
Kaolinite – Al2(OH)4.Si2O5 Copper pyrite : CuFeS2
Malachite – Cu(OH)2.CuCO3 Azurite : Cu3(CO3)2(OH)2
2. Purest form is wrought iron. 5. Metal present lower in the Ellingham diagram at any
given temperature can reduce oxides present above
3. A + BO2 → B + AO2 it at that temperature. Thus, Al can be used to reduce
ΔG = –ve ZnO at all temperatures as per the given diagram.
Only above 1400°C
 Metallurgy 15.11
6. Reduction of Alumina by Carbon is called Hall 9. The process is known as Van Arkel method.
Heroult’s process.
10. It is true that statement (C) has no significance for
7. Galena = PbS roasting sulphide ores to the oxides.
For sulphide ores froth floatation is carried out. The Gibb’s energies of formation of most sulphides
are greater than that for CS2. In fact, CS2 is an
8. (a) In this process, carbon anode is oxidized to CO endothermic compound. There, the DGo of MXS is
and CO2. not compensated. So reduction of MXS is difficult.
(b) It is a fact Hence it is common practice to roast sulphide ores
(c) At cathode, Al3+ from Al2O3 is reduced to Al. to corresponding oxides prior to reduction.
(d) Al2O3 is the electrolyte, which is undergoing the
redox process. So, Al2O3 serves as electrolyte
and Na3AlF6, although an electrolyte, serves as
solvent.

1. Calamine – ZnCO3 SiO2 + FeO → FeSiO3(slag)

Malachite – CuCO3.Cu(OH)2 During slag formation, the characteristic green flame
Magnetite – Fe3O4 is observed at the mouth of the Bessemer converter
which indicates the presence of iron in the form of
Cryolite – Na3AlF6
FeO. Disappearance of this green flame indicates
2. Common ore of Ag – Ag2S, Cu – CuFeS2, that the slag formation is complete. Then air blasting
Pb – PbS, Sn – SnO2, Mg – KCl.MgCl2.6H2O, Al– is stopped and slag is removed.
Al2O3. xH2O Again air blasting is restarted for partial roasting
So answer is (A) before self reduction, until two-thirds of Cu2S is
converted into Cu2O. After this, only heating is
3. In extraction of silver, Ag2S is leached with KCN or continued for the self reduction process.
NaCN in presence of air : 3
Cu2S + 2 O2 → Cu2O + SO2↑
Ag2S + NaCN + O2 Na [Ag(CN)2] + Na2SO4
Cu2S + 2Cu2O → 6(I) + SO2↑ ( s e l f
Thus, O2 is oxidant.
reduction)
2Ag(CN)2– + Zn [Zn(CN)4]2– + 2Ag
and Cu2S + 2O2 → Cu2SO4
4. In haematite(Fe2O3), Fe is present in (III) oxidation Cu2S + Cu2SO4 → 4Cu + 2SO2 ↑ (self reduction)
state and in magnetite (Fe3O4) which is a mixed
oxide of FeO and Fe2O3, Fe is present in (II) and Thus the molten Cu obtained is poured into large
(III) oxidation state. container and allowed to cool and during cooling the
dissolved SO2 comes up to the surface and forms
5. Reaction is reversible so to get the maximum yield blisters. It is known as blister copper.
of the product, the reaction is carried out in presence
2Na[Au(CN)2 ] + Zn → Na2 [Zn(CN)4] + 2Au ↓
of oxygen. Also oxygen oxidises silver to silver (I)
ion which then produces soluble complex with CN– 7. (a) 2Na[Al(OH)4](aq) + CO2 → Na2CO3 + H2O +
ions. 2Al(OH)3 (↓) or Al2O3.2H2O (ppt)
1 (b) Function of Na3AlF6 is to lower the melting
2Ag+4NaCN+ 2 O2+H2O 2Na[Ag(CN)2]+2NaOH
point of electrolyte.
6. PbS + 2PbO → 3Pb + SO2 (c) During electrolysis of Al2O3, the reactions at
Self reduction is taking place between PbS and PbO. anode are :
At anode
In the Bessemer converter : The raw material for the [2Al3+(l)+3O2- (l) O2 (gas) +
Bessemer converter is matte, i.e., Cu2S + FeS (little). 2e-]
Here air blasting is initially done for slag formation C(graphite) + O2 → CO (↑) + CO2 (↑)
and SiO2 is added from external source. (d) The steel vessel with a lining of carbon acts as
3 cathode
FeS + 2 O2 → FeO + SO2↑
15.12 Chemistry
8. CN-, Q T 13. PbS + O2 → Pb + SO2
Au →R → Au + Z
H 2O 103
Moles of O2 consumed = 32
Au + 2CN- + O2 → [Au(CN)2]-
103
[Au(CN)2]- + Zn → Au + [Zn(CN)4]-2 Moles of Pb formed = 32
9. Impure Cu is used as anode pure Cu deposited at 103
\ Mass of Pb formed = 32 ×207 = 6468.75 gm
cathode. Electrolyte is acidified solution of CuSO4.
Impurities settle as anode mud. = 6.46875 kg
10. Cu2 + 2Cu2O —→ 6Cu + SO2 = 6.47 kg
Cu2S + 2CuO —→ 4Cu + SO2 14. (P) Siderite — FeCO3
Cu2S + CuSO4 —→ 3Cu + 2SO2 (Q) Malachite — CuCO3.Cu(OH)2
11. SnO2 and Fe2O3 are reduced by C reduction method. (R) Bauxite — AlOx(OH)3–2x
Al2O3 and MgCO3.CaCO3 are reduced by electrolytic (S) Calamine — ZnCO3
reduction. (T) Argentite — Ag2S
12. Important ore of tin is cassiterite (SnO2). 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
Fe + O2 —→ FeO