Ores and Metallurgy

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Introduction
Composition of earth crust: Earth crust is the source of many elements. Oxygen is most
abundant element present in earth crust. Among metals aluminium is present in most abundance
in earth crust and iron comes second. The percentage of different elements in earth crust is:
Element O Sr Al Fe Ca Na K Mg H Other elements

% by mass 49 26 7.5 4.2 3.2 2.4 2.3 2.3 1 2
Besides earth crust some soluble salts of metals such as NaCl, MgCl2, KBr, CaBr2, KI etc. are
also found in sea water.
Occurrence of Metals: It depends upon the nature of the metals. Metals occur in nature in
two forms.
1 Native Ores: These ores contain metal in free state. For example: Silver, gold, platinum,
mercury, copper etc. Sometime lumps of pure metals are found known as nuggets.
Metals Minerals/Ores with their chemical formula
1. Copper (IB, coinage metal) a) Cuprite; Cu 2 O

b) Copper pyrites; CuFeS2 (as sulphides)
c) Copper glance; Cu 2S (as sulphides)
d) Malachite; CuCO3 ; Cu(OH) 2
d) Azurite 2CuCO3 .Cu(OH) 2
2. Silver (IB, best reductive metal) a) Horn silver (chloroapyrite); AgCl (as
halide)
b) Lunar Caustic; AgNO3 (as nitrate)
c) Silver glance or argentite; Ag 2S (as
sulphide)
d) Ruby silver or pyrogyrite; 3Ag 2S. Sb 2S3
3. Magnesium (II A, bridge metal) a) Carnalite; KCl, MgCl 2 .6H 2 O (chloride)

b) Dolomite; MgCO3 ; CaCO3 (Carbonate)
c) Magnesite; MgCO3 (carbonate)
d) Epsomite; MgSO4 .7H 2O (sulphate)
e) Kiesserite; MgSO4 .7H 2O (sulphate)
f) Asbestos; CaMg(SiO3 ) 4
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4. Zinc (II B, amphoteric metal) a) Zinc blende; ZnS (sulphide)

b) Zincite; ZnO (oxide)
c) Calamine; ZnCO3 (carbonate)
d) Willemite; Zn 2SiO 4 (silicate)
5. Aluminium (III A, amphoteric a) Bauxite; Al2 O3 .2H 2O (oxide)
metal)
b) Corundum; Al2 O3 (oxide)
c) Feldspar; KAlSi3O6 (oxide)
d) Clay silicate; Al2 O3 .2SiO 2 .2H 2O (oxide)
e) Cryolite; 2NaF. AlF3 (Na 3AlF6 ) (halide ore)
f) Alum; K 2SO 4 .Al2 (SO 4 )3 .24H 2 O
g) Diaspore; Al2 O3 .H 2O
h) Mica K 2 O.3Al2 O3 .6SiO 2 .2H 2O
i) Lapis Lazuli (Sodium aluminium silicate
with sulphur)
6. Tin (IV A, amphoteric metal) a) Cassiterite or Tin stone; SnO 2

b) Stannite; Cu 2S.FeS.SnS2
7. Lead (IV A, amphoteric metal) a) Galena; PbS

b) Cerussite; PbCO3
c) Anglessite; PbSO 4
d) White lead; 2Pb(OH) 2 .PbCO3
8. Iron (VIII, transition metal) a) Iron pyrite; FeS2

b) Siderite; FeCO3
c) Red haematite; Fe 2 O3
d) Magnetite; Fe3O 4
e) Limonite or brown haematite;
2Fe 2 O3 .3H 2O
2. In combined state: Reactive metals are found in combined state in nature. Such metals
are attacked by O2, H2O, CO2 etc. Na, Mg, Ca, Fe, Cu, Zn Al, Pb etc, occur in combined
state in nature. These metals are not found in free state.
Minerals: The natural material in which the metal is found in nature is called mineral.
Ores: Those minerals from which the metal can be extracted conveniently, economically and in
large quantity are called ore.
Thus, all the ores are minerals but all the minerals are not ores.

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Gangue or Matrix: Metallic ores are often found to contain non-metallic and rocky materials
such as sand, clay, quartz, feldspar, silicates, mica etc. These unwanted impurities are called
gangue or matrix. Gangue is a waste material present in the ore.
Flux: Ores contain some impurities which have high melting point. Flux is used to remove these
influsible impurities in the form of a fusible slag.
Infusible impurity + Flux = Fusible slag.
Slag has low melting point, it is lighter than the metal and is insoluble in molten metal. It floats
over the molten metal and is removed from the upper exit (tap hole) in the furnace. To remove
the infusible impurity ore is mixed with a flux and is then heated at high temperature. Flux are of
two types.
a) Acidic flux
b) Basic flux
a) Acidic Flux: These are used to remove the basic impurity present in the roasted ore. For
example, in the metallurgy of copper to remove the basic impurity of FeO present an
acidic flux (SiO2) is used.
FeO SiO
2 FeSiO3
Impurity flux slag
(ferrous silicate)
b) Basic flux: These are used to remove the acidic impurity present in the roasted ore. For
example, in the metallurgy of iron, to remove the acidic impurity of SiO 2 present a basic
flux lime stone (CaCO3) is used.
CaCO3 SiO
2 3 CO 2
CaSiO
flux impurity slag (calcium silicate)
Metallurgical Process
The process of extraction of metal from its ores is called metallurgy. Metallurgy involves the
following five steps:
1. Concentration (Dressing) 2. Roasting

3. Smelting 4. Reduction
5. Purification
1. Concentration (Dressing): Ores obtained from mines often contain non-metallic

and rocky materials such as sand, clay, silicates, Felspar etc. These impurities are called
gangue or matrix. The process of removing the gangue and thereby increasing the
concentration of the metal in the ore is called concentration of the ore. Ores may be
concentrated by several methods which depend upon the nature of the ore and the
impurities present in it. Following are the important methods of concentration.

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a) Gravity separation: The ore is powdered. It is then washed in running stream of

water. The lighter earthy materials and gangue are washed away while the heavy ore
particles remain behind. The oxide ore of iron Fe2O3 and Fe3O4 are concentrated by
this method. This method is also called lavigation.
b) Froth floatation process: Sulphide ores are generally concentrated by this

method.
Principle: This process is based on the preferential wetting the ore particles and
gangue by a liquid.
Method: The ore is powdered and is then Air
placed in a water tank. Now some pine oil
and potassium ethylxanthate is added in it.
A strong stream of air is passed in the tank Froth
containing water and powdered ore. The
whole mass is agitated and froth is formed.
Ore particles are preferentially wetted by
the oil and come at the surface along with
the froth. The impurities are wetted by
water and remain behind in the tank. The Gangue
ore particles are separated from the froth.
Addition of pine oil lowers the surface tension and thus stabilizes the froth. Such
substances are called frotheres. Ore particles are adsorbed on potassium ethylxanthate
and come at the surface along with the froth. The sulphide ores of Cu, Ag, Zn, Pb etc.,
concentrated by froth floatation process.
c) Magnetic Separation
Principle: This process is based upon magnetic properties of the ore and gangue. If
the ore or the impurity present is magnetic, then this process is used to separate the
magnetic substance from the non-magnetic substance.
Method: Ore is concentrated by a magnetic separator. It consists of a leather belt

moving over two rollers. One of the roller is magnetic. The powdered ore is put on the
belt. The magnetic portion of the ore falls nearer to the magnetic roller. The non-
magnetic portion falls further off the magnetic roller.
This method is used to concentrate tin Ore

stone (SnO2). It contains magnetic Belt
oxide ion (Fe3O4) as impurity. The
magnetic impurity of Fe3O4 is
collected near the magnetic roller
while the ore particles of SnO2 fall
further off the magnetic roller.
Magnetic roller

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2. Calcination: The concentrated ore is heated in absence of air below its melting point.
This process is called calcinations. On calcinations metal carbonates and metal
hydroxides are decomposed to give metal oxide. Moisture, water of hydration and other
volatile impurities present in the ore are removed. On calcinations, the ore becomes
porous. Thus ore is heated uniformly. Following are the examples of calcinations.
a) Aluminium hydroxide on calcination gives alumina.
1500C Al2 O3 3H 2O
2Al(OH)3
b) Limonite is the ore of iron. This on calcination gives anhydrous ferric oxide.
Fe 2 O3 3H 2 O Heat
Fe 2O3 3H 2O
c) Siderite is the ore of iron. This on calcination gives ferrous oxide
FeCO
3
Heat
FeO CO 2
d) Calamine is the ore of zinc. This on calcination gives zinc oxide.
ZnCO
3
Heat
ZnO CO 2
e) Sodium bicarbonate on calcination gives sodium carbonate
2NaHCO
3
Heat
2 CO3 CO 2
Na H 2O
f) Calcination of lime stone gives CaO and CO2.
CaCO
3
Heat
CaO CO 2
3. Roasting: The concentrated ore is heated alone or mixed with some other substance
below its melting point in the presence of air. The ore and impurities get oxidized.
Impurities of sulphur and arsenic are removed as volatile oxides. Following are the
examples of roasting.
a) In the extraction of iron the concentrated and calcined ore is roasted. The impurities of
S and As are removed as volatile SO2 and As2O3. Any ferrous oxide present in the ore
is oxidized into ferric oxide.
S O
2
SO 2
4As 3O
2 2As2 O3
4FeO O
2 2Fe2O3
b) In the extraction of zinc its ore zinc blende (ZnS) is roasted to get ZnO.

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c) On roasting the copper ore chalcopyrite (CuFeS 2) the impurities of S and As present
in it are removed as volatile SO 2 and As2O3. CuFeS2 is converted into cuprous
sulphide and ferrous sulphide.
S O
2 SO 2
4As 3O
2 2As 2 O3
2CuFeS2 O
2 2S 2FeS
Cu SO 2
Some part of cuprous sulphide and ferrous sulphide is converted into Cu2O and FeO.
2FeS 3O
2
2FeO 2SO 2
2Cu 2S 3O
2 2O 2SO 2
2Cu
4. Smelting: In this process the roasted ore is mixed with coke and a suitable flux and is
then heated in the presence of air at high temperature. Following reactions take place
during smelting.
a) Roasted ore is reduced into metal or a compound containing that metal.
b) Impurity present in the roasted ore is removed as slag.
c) Melting point of slag is lower than that of the metal and it is also lighter than the
metal. Slag is insoluble in the molten metal and floats over the molten metal. Slag is
removed from the upper exit (tap hole).
Following are the examples of smelting.

i) In the extraction of iron the roasted ore is mixed with coke and lime stone (flux) and
is then heated in the presence of air at high temperature in a furnace. Impurity of SiO 2
is removed as calcium silicate (CaSiO3, slag). Lime stone acts as flux. Iron oxide is
reduced into iron.
C O
2 CO 2
CO 2 C
2CO
Fe 2 O3 3CO
2Fe 3CO 2
CaCO
3
CaO CO 2
CaO SiO
2 CaSiO3
flux impurity slag
ii) In the extraction of copper the roasted ore is mixed with silica (SiO 2, flux) and is then
heated in the presence of air at high temperature in a furnace. FeS is present as an
impurity. It is converted into FeO and then removed as ferrous silicate (FeSiO 3, slag).
SiO2 acts as flux.
Cu 2 O FeS
2S FeO
Cu

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2FeS 3O
2
2FeO 2SO 2
FeO SiO
2 FeSiO3
impurity flux sla g
Thus in smelting a mixture of Cu2S and FeS is obtained. This molten mixture of FeS and
Cu2S is called matte. Copper is then extracted from matte.
5. Purification of metals: Several methods are used to purify metals. The method
used depends upon the nature of the metal and the impurity present in it.
a) Electrolytic Process: Copper, silver, gold, lead etc. are purified by this method.
It is an important method for the purification of metals. Pure metal is made cathode
and impure metal anode. Aqueous solution of a salt of the metal acts as electrolyte.
Anode : Impure metal
Cathode : Pure metal
Electrolyte : Aqueous salt solution of the metal
On passing electric current pure metal deposits on cathode. Equivalent mass of anode
dissolves in the form of a salt and comes in the solution. The impurities either remain
dissolved in solution or settle down as anode mud near anode.
In the purification of copper, pure copper made cathode, impure copper is anode, and
aqueous solution of copper sulphate acts as electrolyte. On passing electric current
pure copper deposits on cathode. Equivalent mass of anode dissolves in the form of
CuSO4 and comes in solution. Impurities of less reactive metals such as Ag, Au, Pt
etc. are removed as anode mud.
b) Liquation method: Zn, Pb, Sn, Bi etc., pure copper rods
metals are purified by this method. This method impure

copper rods
is used to purify those metals which have low
melting point and the impurity present has high
melting point. Impure metal is heated on an
inclined hearth. Metal melts and flows down.
Impurities remain behind.
anode mud CuSO4 solution

Purification of copper by electrolytic process
c) Distillation method: Cd, Zn, Hg, etc., metals are purified by this method. This
method is used to purify those metals which are volatile. The metal is heated and the
vapours formed are condensed. Mercury is purified by distilling it under reduced
pressure.
Extraction of Iron
Concentration of the ore
1. Dressing of the ores: The iron ores are first broken into small pieces 3-5 cm in size.
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2. Roasting: During roasting S, As, P are oxidized to the respective oxides.
S + O2 SO2
4As + 3O2 2As2O3
FeCO3 decomposes as,
FeCO3 FeO + CO2
Fe2O3.3H2O loses water
Fe2O3. 3H2O Fe2O3 + 3H2O
Fe3O4 is decomposed to ferrous oxide and ferric oxides.
Fe3O4 FeO + Fe2O3
Ferrous oxide reacts with silica to forms ferrous silicate at high temperature.
FeO + SiO2 FeSiO3
But the conversion of FeO into Fe2O3 will prevent the formation of FeSiO3. Thus the mass
of the ore becomes porous casting the increase in the effective surface area.
3. Smelting in the Blast furnace: Blast furnace is a shaft furnace made of steel
plate of 20-30 in with 4 - 6 diameter.
Extraction of Cast Iron
Iron is usually extracted from the haematite. Concentrated ore after calcinations is reduced with
carbon i.e. smelted in the blast furnace.
Reactions taking place in the blast furnace are
i) Zone of combustion :
C + O2 CO2
(Coke)
CO2 + C 2CO ; H = +ve (Newmanns inversion reaction)
ii) Zone of reduction: The following reduction reactions are called indirect reduction, which
is done by CO, which is unstable at higher temperature (See Ellingham diagram).
Fe2O3 + 3CO 2Fe + 3CO2

FeO + CO Fe + CO2
iii) Zone of slag formation :
CaCO3 CaO + CO2

(lime stone)
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CaO + SiO2
aSiO3 ;
C
Fusible slag
iv) Zone of fusion (lower part of furnace):
Cup and cone

arrangement Waste gases
200-250C
400C Refractory bricks
600C
700C
800-1000C
1300C Hot air
1600C
Tuteres
Molten
slag
Molten metal
Molten iron is heavier from molten slag. The two liquid are periodically tapped off. The molten
iron tapped off from the furnace is solidified into blocks called plags.
Preparation of Wrought Iron: This is done by heating cast iron with haematite (Fe 2O3)
which oxidizes C to CO, S to SO2, Si to SiO2, P to P4O10 and Mn to MnO
Fe2O3 + 3C 2Fe + 3CO
Where CO and SO2 escape, manganous oxides (MnO) and Silica (SiO2) combine to form slag.
MnO + SiO2 MnSiO3
Similarly phosphorus pentoxide combines with haematite to form ferric phosphate slag.
2Fe2O3 + P4O10 4FePO4
Bosh: The diameter of the furnace gradually increases from the top down wards. Widest part of
the furnace is called Bosh. At above 2m, tubes are there through which hot air blast is blown into
the furnace.
Hearth: Below the bosh this region exists. (1) slag notch is at higher height and (2) tap hole for
metal passage at lower position from the bottom. At the top of the furnace the hopper is there
which is cup and cone arrangement. Through this charge is introduced till the charge bed in the
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furnace is 4/5th of the furnace. Hot air at 700C is forced into the furnace through the tubes. The
thermal gradient inside exists from 1800C (hearth) to 400C-900C in the upper region. Near the
both the reactions temperature varies from 1200-1300.
Chemical reactions which have placed are:

1. At 1200C near the tuyeres,
C + O2 CO2 ; CO2 + C 2CO
2. Above bosh 600 - 900C, ferric oxide is partially reduced by CO as

2Fe + 3CO2
Fe2O3 + 3CO
3. CaCO3 900C CaO + CO2

2CO 1000 1300C CO2 + C
Fe2O3 + 3C 2Fe + 3CO
CaO + SiO2 CaSiO3 (slag)
4. The reaction at 1500C, MnO2 is reduced to

MnO2 + 2C Mn + 2CO
Ca3(PO4)2 3CaO + P2O5
CaO + SiO2 CaSiO3
2P2O5 + 10C P4 + 10CO
5. Collection of Cast Iron : Metal is cast into ingots or in the ladle for further refining like
steel making.
Wrought Iron: Minimum % of carbon is 0.1 to 0.25% and other impurities like S, P, Mn, Si
less than 0.3%.
Manufacturing process
Cast iron is taken in pudding furnace and melted by hot blast of air. The chemical reactions,
which occur are
S + O2 SO2 ; 3S + 2Fe2O3 4Fe + 3SO2
3Si + 2Fe2O3 4Fe + 3SiO2
3Mn + Fe2 O3 2Fe + 3MnO
MnO + SiO2 MnSiO3
3C + Fe2O3 2Fe + 3CO
4P + 5O2 2P2O5 ; Fe2O3 + P2O5 2FePO4 (slag)
The impurities are removed from iron, the melting point of the metal rises and it becomes a semi
solid mass. Metal taken out from the furnace in the form of balls with the help of the rubbles. The
balls are then beaten under hammer to separate out of the slag. The product formed, is thus called
wrought iron.

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Some Important Alloy

Sl. No. Name Composition
1. Stainless steel Fe, Cr, Ni
2. Invar Fe, Ni
3. Alnico Fe, Al, Ni, Co
4. Brass Cu, Zn
5. Bronze Cu, Zn, Sn
6. Gun metal Cu, Sn
7. Bell Metal Cu, Sn
8. German Silver Cu, Zn, Ni
9. Solder, pewter Pb, Sn
10. Babbitt metal Sn, Sb, Cu
Extraction of Tin
The chief ore of tin is cassiterite or tin stone, SnO 2. It also contains silica and wolframite iron
(tungstate, FeWO4), iron pyrites and arsenical pyrites and sometimes copper pyrites. The ore is
concentrated, and then smelted to give crude tin which is finally refined.
Roasting: The impure tin stone is roasted in current of hot air in an inclined revolving tube-
furnace, when arsenic and sulphur are expelled as volatile oxides; most of the iron is converted to
the magnetic oxide, Fe3O4 and copper forms oxide and sulphate
Smelting: The black tin is mixed with one-fifth of its weight of crushed anthracite coal and
some lime and fluorspar to act as a flux and smelted at 1200-1300C in a reverberatory furnace
when the tin oxide is reduced to the metal. The molten tin and slag form two layers and are
runout separately
SnO2 + 2C Sn + 2CO
The liquid tin is cast into ingots or else refined to a higher purity.
A good amount of tin goes into the slag, because of the amphoteric nature of tin dioxide, the slag
may contain 10 to 25% tin. Tin is recovered from the slag by smelting it at a much higher
temperature with carbon, flux and some scrap iron to decompose the tin oxide.
SnSiO3 CaO Sn + CaSiO3 + CO

SnSiO3 + Fe Sn + FeSiO3 ; SnO2 + 2C Sn + 2CO
Refining
i) The crude tin is refined by liquation or sweating i.e. by heating the ingots on the slopping
hearth of a reverberatory furnace, when the easily fusible tin (melting point 232C) melts
and runs away leaving behind a dross of an alloy of tin with iron, copper, tungsten and

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arsenic Bismuth and Lead because of their low melting points go with tin and remain in
the sweated tin.
ii) The liquated tin is further treated by poling, i.e. the liquid tin stirred with poles of green
wood so that a large surface is exposed to the air, when the remaining impurities are
oxidized and separated as scum on the surface and are skimmed off. The tin so obtained is
of over 99% purity. The scum and dross contain much tin and are worked up by smelting.
Extraction of Copper
Copper glance or Chalcocite : Cu2S
Chalcopyrites (copper pyrites) : Cu2S.Fe2S3
Cuprite : Cu2O
Malachite : [CuCO3.Cu(OH)2]
Azurite : [2CuCO3.Cu(OH)2]
Extraction of Metallic Copper
1. Concentration of the ore by froth floatation process: Copper pyrites

contains only (2-3)% of copper. The rest of the ore contains iron or sulphide, silica,
silicious materials, sulphur, arsenic etc. as impurities. Froth flotation by Xanthate and
pine oil. The froth is collected and dried when concentrated ore is obtained which
contains 25-30% of Cu.
2. Roasting
2CuFeS2 + O2 Cu2S + 2FeS + SO2
2CuFeS2 + 4O2 Cu2S + 2FeO + 3SO2
2Cu2S + 3O2 2Cu2O + 2SO2
Cu2O + FeS Cu2S + FeO
3. Smelting of the roasted ore in blast furnace : material required

a) Roasted ore
b) Lime stone
c) Coke (used as fuel)
d) Silica (used as flux)
e) Lime stone (used to remove excess silica)
Reactions occurring given as follows
2FeS + 3O2 2FeO + 2SO2

Cu2O + FeS Cu2S + FeO
FeO + SiO2 FeSiO3 (removed as slag)
CaO + SiO2 CaSiO3 (removal as slag)
4. Self reduction in Bessemer Converter

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Reactions involved are,
2FeS + 3O2 2FeO + 2SO2

FeO + SiO2 FeSiO3 (Slag)
2Cu2S + 3O2 Cu2O + 2SO2
Cu2S + 2O2 Cu2SO4
When approximately 2/3rd of the cuprous sulphide is oxidized, the blast of air is stopped.
The produced Cu2O and Cu2S are reduced by the rest of cuprous sulphide to produce
metallic copper with the evolution of SO2.
Cu2S + 2Cu2O 6Cu + SO2

Cu2SO4 + Cu2S 4Cu + 2SO2
As the molten cools, it gives off the dissolved of SO 2. The SO2 gas escaping in the form of
bubbles, leaves the surface of the metal with full of cavities which gives the metal is blistered
appearance. This is why the metal thus obtained is by blister copper.
5. Refining
Electrorefining
Anode : Impure copper obtained above
Cathode : Pure copper
Electrolyte : 15% CuSO4 solution + 5% H2SO4
When electric current is passed through the electrolyte, the anodes gradually dissolve and pure
copper is deposited on the cathodes which gradually grow in size. The impurities like Fe, Zn, Ni
etc., dissolved in the solution as sulphates while gold, silver, platinum settle down below the
anode as anode mud.
Reaction coming are as follows
CuSO4 +2+
Cu + SO4
2
At anode : Cu Cu+2 + 2e
At cathode : Cu+2 + 2e Cu
Extraction of Lead
Lead is mainly extracted from galena. After the concentration of the ore by froth flotation
process, the ore is roasted in a reverberatory furnace for about six hours at a moderate
temperature in a current of air. Part of galena is converted into lead oxide and lead sulphate. After
this, the supply of air is stopped and small quantities of carbon, quicklime and cheap iron ore are
added along with increase of temperature. At this stage, unreacted sulphide reacts with the lead
oxide and sulphate giving metallic lead :
PbS + 2PbO 3Pb + 2SO2

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PbS + PbSO4 2Pb + 2SO2
The obtained lead contains impurities such as Cu, Ag, Bi, Sb and Sn. Silver is removed by
Parkes process where molten zinc is added to molten impure lead. The former is immiscible with
the latter. Silver is more soluble in molten zinc than in molten lead. Zinc-silver alloy solidifies
earlier then molten lead and thus can be separated. After this, crude lead is refined electrolytically
(Electrolyte; lead silicoflyuoride, PbSiF6 and hydrofluosilicic acid, H2SiF6 with a little gelatin,
anode; crude lead and cathode; pure lead).
Extraction of Magnesium
Extraction of magnesium: Magnesium is commonly obtained by the electrolysis of fused

magnesium chloride containing a little (25%) sodium chloride and sodium fluoride at 700C in an
air-tight iron pot which itself serves as the cathode, the anode being a graphite rod which dips
into the electrolyte. The anode is surrounded by a perforated porcelain tube for the exit of
chlorine. The electrolysis is carried out in the atmosphere of coal gas so as to prevent the attack
of atmospheric oxygen and nitrogen on magnesium. Molten magnesium being lighter then the
electrolyte, it floats over the fused electrolyte and is withdrawn.
Graphite anode
Cl2
Porcelain hoood
Inert gas Inert gas (coal gas)
Iron cathode
Mg
Molten electrolyte
Iron cell
In Dow process, magnesium is recovered from seawater as magnesium chloride which is then
electrolysed using cell described in above figure.
Dows Sea Water Process: Sea water contains 0.13% Mg2+ ions.
Mg2+ (seawater) + Ca(OH)2 (from oyster shells) Mg(OH)2 + CaCl2

CO2
(calcined dolomite) MgCl22H2O
MgCl2.1.5H2O
dry HCl
MgCl2.2H2O
spray drying
heat MgCl2
Dows Natural Brine Process:
MgCO3CaCO3
MgO.CaO

heat dil. HCl
CaCl2(aq)+MgCl2(aq)
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(dolomite) (calcined dolomite)

CO2
MgCl2(aq)+CaCO3
(calcined dolomite)
The reaction is : CaCl2.MgCl2(aq) + MgO.CaO + 2CO2 2MgCl2(aq) + 2CaCO3
Electrolysis: Anhydrous carnallite (KCl.MgCl2.6H2O) may also be employed as the starting

material of magnesium chloride. The cathode may be a layer of molten lead on the floor of the
cell and anode may be graphite rods which are suspended above the molten lead. Magnesium
liberated at the cathode dissolves in molten lead. The alloy of lead-magnesium is subjected to
electrolysis to obtain pure magnesium (electrolyte : fused carnallite, anode-lead-magnesium alloy
and cathode-steel rods).
Extraction of Aluminium
Important ores of aluminium
Bauxite Al2O3.2H2O
Cryolite Na3AlF6
Feldspar K2O.Al2O3.6SiO2 or KAlSi3O8
Mica K2O.3Al2O3.6SiO2.2H2O
Corundum Al2O3
Alumstone or Alunite K2SO4.Al2(SO4)3.4Al(OH)3
Aluminium is mainly extracted from bauxite ore.
Purification of Bauxite: By Bayers process commercially it is being carried out (for red
bauxite not for the white bauxite).
Flow sheet of Baeyers process for the preparation of pure Al2O3.
Finely powdered bauxite

containing Fe2O3, TiO2.SiO2 as
impurities
Calcination (FeO Fe2O3)
Organic matters are removed
Calcined ore (Digested with 45%, NaOH with at

150C under 80 lb pr. Filtered)
Residue Filtrate
(Fe2O3, TiO2) (NaAlO2 + Na2SiO3)
Freshly prepared Al(OH)3 Seeding agent filtered
Precipitate Filtrate
(Al(OH)3 (NaOH, Na2SiO3)
1000C
Al2O3 Pure
Alumina

SM-OM-CH-18
Halls process: Crude bauxite at 1100C reacts with Na 2CO3, Na2SiO3, NaFeO2, NaAlO2 are
formed.
Al2O3 + Na2CO3 2NaAlO2 + CO2

Fe2O3 + Na2CO3 2NaFeO2 + CO2
SiO2 + Na2CO3 Na2SiO3 + CO2
Then at 50-60C CO2 is passed through NaAlO2 solution and produces thereby Al(OH)3
2NaAlO2 + CO2 + 3H2O 2Al(OH)3 + Na2CO3

2Al(OH)3 100C Al2O3 + 3H2O
Serpecks Process: Bauxite containing high percentage of silica can be purified by

Serpecks process. In this process finely powered bauxite is mixed with coke and the mixture is
heated to 1800C in a current of nitrogen. The AIN thus obtained is reacted with hot and dilute
NaOH, produced NaAlO2 and excess AIN is hydrolysed and Al(OH)3 is formed.
Al2O3 + 3C + N2 3AlN + 3CO

SiO2 + 2C Si + 2CO
AlN + NaOH NaAlO2 + NH3
NaAlO2 2H2O Al(OH)3 + NaOH
AlN + 3H2O Al(OH)3 + NH3
2Al(OH)3
1100C Al2O3 + 3H2O
(cryolite)
Electrolytic reduction of Al2O3: Pure alumina melts at about 2000C and is a bad
conductor of electricity. If fused cryolite AlF3.3NaF and CaF2 (Fluorspar) is added the mixture
melts at 900C and Al2O3 becomes a good conductor of electricity. Metallic Al is liberated at the
cathode.
Electrolysis of molten mixture
Cathode : Carbon
Anode : Graphite rods
Electrolyte : 60 parts cryolite + 20 parts fluorspar + 20 parts pure Al2O3
Temperature : 900C
Reaction
According to the 1st theory of the following reaction occurs
Al2O3 +3
2Al + 3O
2
At cathode : 2Al+3 + 6e 2Al

At anode : 3O2 3O2e
SM-OM-CH-19
As cryolite has greater electrochemical stability it does not dissociate. It only increases the
dissociation of Al2O3
But the second theory states that, cryolite undergoes electrolytic dissociation first then Al +3 goes
to the cathode, produced F2 at anode then reacts with Al2O3 produces AlF3.
AlF3.3NaF +3 +
Al + 3Na + 6F

At cathode : Al+3 + 3e Al
At anode : 6F 3F2 + 6e
Al2O3 + 6F2 4AlF3 + 3O2
Refining of aluminium: The aluminium metal obtained by the electrolysis of fused almina
is about 99.5% pure. It can be further refined by Hoopes electrolytic process.
Extraction of Silver
Occurrence: It occurs in free state. The chief and important ore of silver is silver glance
(Ag2S), which is present as such or is associated with galena, PbS.
Cyanide Process (Mac Arthur Forest) Process: The finally powdered ore after being
concentrated by froth floatation process is treated with dilute (0.7%) NaCN solution and a current
of air is blown into it. The silver present in the ore dissolves forming a complex soluble
argentocyanide.
Ag2S + 2NaCN 2AgCN + Na2S

AgCN + NaCN Na[Ag(CN)2]

Ag2S + 4NaCN 2Na[Ag(CN)2] + Na2S
or Ag2S + 4CN 2[Ag(CN)2]1 + S2
The reaction is reversible and in order to prevent backward reaction it is essential to remove
sodium sulphide from the sphere of action. The oxygen of the air converts sodium sulphide into
sodium sulphate and free sulphur and thus makes the above reaction irreversible.
4Na2S + 5O2 + 2H2O Na2SO4 + 4NaOH + 2S
In case the ore is silver chloride then, too, it goes into solution forming sodium argtentocyanide.
AgCl + 2NaCN Na[Ag(CN)2] + NaCl

or AgCl + 2CN [Ag(CN)2] + Cl
The solution of sodium argentocyanide, obtained as above, is treated with finally powdered zinc.
Zinc being more electropositive than silver displaces it from the solution. A black precipitate of
silver is thus obtained.
2Na[Ag(CN)2] + Zn Na2[Zn(CN4] + 2Ag

SM-OM-CH-20
The precipitated silver is mixed with potassium nitrate and fused when the impurities are
oxidized and removed as a scum from the surface of molten metal. On cooling a compact shining
mass of silver is formed.
This is the best method of extracting silver from its ore especially when the % of silver is low.
Refining of Silver: Silver so obtained is purified by electrolytic process. It consists of
Cathode : Pure Ag
Anode : Impure Ag
Electrolyte : AgNO3 solution containing 1% HNO3
On passing electric current pure silver is deposited on cathode while the same amount dissolves
out from anode. The more electro positive metals like copper and zinc remain in solution while
less electro positive gold comes down as anode mud.
Reaction: AgNO3
Ag+ + NO3
Ag + e Ag(Cathode)
+
Extraction of Gold
Occurrence: Gold occurs in free and combined state.
i) Native state: It is generally found in free state because it is a noble metal. The two
important sources are
a) Quartz veins: In this state, the fine particles of gold along with silver and
platinum remain embedded.
b) Alluvial sands: This is present in those rivers, which passes over auriferous
rocks.
ii) Combined sands: Its compounds in nature are few. Bismuth surite AuBi, Calaverite
Au Te2.
Extraction: Gold is extracted from quartz veins and alluvial sands by the following methods :
i) Amalgamation process
ii) Cyanide process
iii) Chlorination process
Cyanide process (Mac Arthur Forrests): This is very good process for the removal of
traces of gold from tailings of amalgamation process or from even poorer ores. It is based on the
fact that gold dissolves in dilute solution (0.3%) of sodium cyanide in presence of atmosphere
oxygen with the formation of complex cyanide.

SM-OM-CH-21
4Au + 8NaCN + 2H2O + O2

4Na[Au(CN)2 + 4NaOH Sod.
aurocyanide
or 4Au + 8CN + 2H2O + O2 4[Au(CN)2] + 4OH
The molten matte is finally transferred to Bessemer converter. A blast of sand and air is blown in
the converter through tuyeres which are situated a little above the bottom. This causes removal of
S and As oxides and ferrous oxide as slag (reaction iv). At the same time Cu 2S is oxidized mostly
into Cu2O (reaction ii) and partly into CuO and CuSO4. All these reaction with Cu2S giving
copper. The reactions are
ii) 2Cu2S + 3O2 2Cu2O + 2SO2

2Cu2S + 5O2 2CuSO4 + 2CuO
2Cu2O + Cu2S 6Cu + SO2
CuSO4 + Cu2S 3Cu + 2SO2
Cu2S + 2 CuO 4Cu + SO2
Finally, copper may be refined electrolytically (electrolyte; copper sulphate: anode; impure
copper and cathode; pure copper).

SM-OM-CH-22
Solved Problems
Subjective
Problem 1: Explain the followings:
i) Why is chalcocite roasted and not calcined in the extraction of copper?
ii) Magnesium oxide is used for the lining of steel making furnace.
Solution: i) Air is necessary to convert impurities such as sulphur, arsenic and

antimony into volatile oxides and for partial oxidation of the pyrite ore.
Calcination does not use oxygen while roasting is done in presence of air.
Thus, roasting and not calcination is done in the metallurgy of copper.
ii) MgO is basic in nature. It removes acidic impurities present is cast iron
used for making steel.
MgO SiO 2 MgSiO 3
Slag
3MgO P2 O 5 Mg 3 (PO 4 ) 2
MgO is also a refractory material as it can tolerate very high temperature
of the furnace.
Problem 2: A student suggested that the calcium should be made if CaO is reacted with
Aluminium powder. Was the student correct?
Given Gf0 (CaO) = 604.2 kJ/mol
Gf0 (Al2O3) = 1582 kJ/mol
Solution: 2Al + 3CaO Al2O3 + 3Ca

G = Gf (Al2O3) 3 Gof (CaO)
o
1582 3 (604.2) = 1582.0 + 1812.6 = + 130.6

G = +ve reaction is non spontaneous hence not possible. So student was
wrong.

SM-OM-CH-23
Problem 3: Addition of NH 4 Cl can also precipitate Al(OH)3 from soluble Na[Al(OH) 4 ].

Explain.
Solution: NH 4Cl solution is acidic due to hydrolysis:

NH 4Cl H 2O
NH 4OH HCl
hence addition of NH 4 Cl solution precipitates Al(OH)3 when added to
NaAl(OH) 4
Na[Al(OH) 4 ] HCl
NaCl 3
Al(OH) H 2O
Problem 4: Cinnabar (HgS) and galena (PbS) on roasting often gives their respective
metals but zinc blende (ZnS) does not. Explain.
Solution: On roasting all these sulphides ores are partly converted into their respective
oxides. Since the oxides of Hg and Pb are unstable. While that of zinc is
stable, therefore, oxides of Hg and Pb bring about the reduction of their
sulphides to metals, but zinc oxides does not reduce ZnS to Zn metal

HgS + 2HgO
unstable
3Hg + SO2

PbS + 2PbO 3Pb + SO2
unstable
CaO SiO
2 CaSiO3
Slag
Problem 5: i) An ore (A) on roasting with sodium carbonate and lime in the presence of
air gives two compounds, (B) and (C).
ii) The solution of (B) in conc. HCl on treatment with potassium ferrocyanide
gives a blue colour or precipitate of compound (D).
iii) The aqueous solution of (C) on treatment with conc. H 2 SO 4 gives a
yellow coloured compound (E).
iv) Compound (E) when treated with KCl gives an orange red compound (F),
which is used as an oxidizing reagent.
v) The solution of (F) on treatment with oxalic acid and then with an excess
of potassium oxalate gives blue crystals of compound (G).
Solution: (A) FeCr2 O 4 or FeO. Cr2 O3 (B) Fe 2 O3

(C) Na 2 CrO 4 (D) Fe 4 [Fe(CN) 6 ]3 (blue)
(E) Na 2 Cr2 O 7 (yellow) (F) K 2 Cr2 O 7 (orange-red)
(G) K 3 [Cr(C2 O 4 )3 ](blue)
Problem 6: Copper pyrites, CuFeS2, is the important source of copper. 10g of it was
leached with dil. H2SO4 and solution diluted to 1 L.
a) 10 ml of this solution required 10 ml of 0.02 M KMnO4 in acidic solution

SM-OM-CH-24
b) 10 ml of this solution was treated with excess of KI and liberated iodine

required 10 ml of 0.02 M hypo solution. What is percentage of Cu and Fe
in copper pyrites?
Solution: CuFeS2 + 2H2SO4 CuSO4 + FeSO4 + 2H2S

a) Equivalent of Fe equivalent of KMnO4
+2
10 N = 10 0.02 5 103
N = 0.1N
Strength = Normality equivalent wt. = 0.1 56 = 5.6 gm/ litre
% of Fe+2 = 56%
b) CuSO4 + 4KI Cu2I2 + 2K2SO4 + I2

+2
Equivalent of Cu = equivalent of I2 = equivalent of Na2S2O3
Equivalent of Cu+2 in 10 ml = 10 0.02 1 103
Equivalent of Cu+2 in 1000 ml = 100 10 0.02 103 = 0.02
Strength = Normality equivalent weight
63.5
= 0.02 = 12.7 g
2
or percentage of Cu = 12.7%
Problem 7: Excess of carbon is added in zinc metallurgy. Explain.
Solution: Carbon play two roles in the metallurgy of zinc.

a) It reduces zinc oxide to zinc.
ZnO C Zn CO
ZnO CO Zn CO 2
b) It reduces CO 2 into CO, which is used as a fuel.
CO 2 C 2CO
Problem 8: When iron ore is reduced in a blast furnace, some of the SiO 2 impurity is also
reduced by reaction with carbon to give elemental silicon and carbon
monoxide. The silicon is subsequently reoxidised in basic oxygen process, and
the resulting SiO2 reacts with CaO, yielding slag, which is then separated
from the molten steel. Write balanced equations for the three reactions
involving SiO 2 .
Solution: SiO 2 (s) 2C(s)

Si(s) 2CO(g)
Si(s) O 2 (g) SiO 2 (s)
CaO(s) SiO 2 (s) CaSiO 3 (l ) (slag)
Problem 9: a) MgO is used for the lining in steel making furnace.

b) Which of the metals Na, Ag and Fe are extracted by

SM-OM-CH-25
i) Complex formation
ii) Reduction with carbon
iii) Electrolysis of fused salts
Solution: a) Magnesium oxide acts as a flux to remove impurities of Si, P and S

through slag formation
MgO SiO 2 MgSiO3

3MgO P2 O5 Mg 3 (PO 4 ) 2 Slag
MgO SO 2 MgSO3

b) (i) Ag, (ii) Fe, (iii) Na
Objective
Problem 1: Electrolytic bath electrolytic refining of lead contains

(a) H2SiF6 only
(b) PbSiF6 only
(c) H2SiF6 in presence gelatin
(d) H2SiF6 and PbSiF6 in presence of gelatin
Solution: (d)
Problem 2: The process of producing a hard coating of iron nitride on the surface of steel
is called
(a) Annealing (b) Quenching
(c) Tempering (d) Nitriding
Solution: (d)
Problem 3: The main function of roasting is

(a) to remove the volatile impurities
(b) oxidation of metal
(c) reduction of metal
(d) to make slag
SM-OM-CH-26
Solution: (a)
Problem 4: The process of converting hydrated alumina into anhydrous alumina is called
(a) roasting (b) calcination
(c) smelting (d) dressing
Solution: (b)
Problem 5: Thomas slag is -

(a) Ca3(PO4)2 (b) MnSiO3
(c) CaSiO3 (d) FeSiO3
Solution: (a)
Problem 6: The material used in semiconductors

(a) Si (b) Sn
(c) Ti (d) Cs
Solution: (a)
Problem 7: Which of the following is manufactured by Siemens Martin process?

(a) Pig iron (b) Cast iron
(c) wrought iron (d) steel
Solution: (d)
Problem 8: Bordeaux mixture is
(a) CuSO4 +MgSO4 (b) FeSO4 + CuSO4
(c) CuSO4 and lime (d) NiSO4 + lime
Solution: (c)
Problem 9: Which method of purification is represented by the following equation

Ni + 4CO 70 C Ni(CO)4 180 C Ni + 4CO
o o
(a) van Arkel (b) zone refining

(c) mond process (d) cupellation
Solution: (c)
Problem 10: Zone refining is a method to obtain

(a) Very very high temperature (b) Ultra ultra pure Al
(c) Ultra ultra pure metal (d) Ultra ultra pure oxides
Solution: (c)

SM-OM-CH-27
Subjective Assignments
LEVEL I (CBSE LEVEL) Review Your Concept
1. What is Goldsmidt Thermite Process?
2. Al2 O3 cant be reduced by carbon to get Al metal. Explain.
3. Cu can reduce Ag to metallic Ag but Ag cant reduce Cu 2 to metallic Cu. Explain.
4. A metal is in combined state as sulphide. Identify the steps (A), (B), (C)

SM-OM-CH-28
Sulphide A Oxide B Impure metal
Pure metal C
5. Write chemical equations for metallurgical processes to represent:

a) roasting of galena (PbS),
b) reduction of Cu 2 O using charcoal as a reducing agent,
c) deposition of pure silver from an aqueous solution of Ag ,
6. Why zinc and not copper is used for the recovery of metallic silver from the complex
[Ag(CN) 2 ] .
7. Sodium is prepared by the electrolysis of molten NaCl but not by the electrolysis of its
aqueous solution.
8. Elements of alkali metal group are strong reducing agent. Explain.
9. In the metallurgy of iron, limestone is added to the ore.
10. What is the actual reducing agent of haematite in blast furnace?
LEVEL II Brush up Your Concepts
1. Write chemical equations to represent the most probable outcome in each of the
following. If no reaction is likely to occur, state so:

a) CdCO3
b) MgO

c) SnO 2 CO
d) CdSO 4 (aq)
electrolysis
e) 2HgO

f) MgO Zn
SM-OM-CH-29
2. Why graphite is used as anode but not diamond?
3. The following reactions take place during the extraction of copper from copper ore:
a) 2Cu 2S(l ) 3O 2 (g) l ) 2SO 2 (g)
2Cu 2O(
b) 2Cu 2 O(l ) Cu 2S(l
) l ) SO 2 (g)
6Cu(
Identify the oxidizing and reducing agents.
4. Dolomite ( MgCO3 .CaCO3 ) can also be treated to get MgCl2 which in turn is
electrolysed to get Mg. (Dow natural brine process). Ggive reactions of this process.

5. [CaCO3 .MgCO3
]

CaO. MgO 1150
Fe / Si
C
Mg Fe Ca 2SiO 4
Name this process.
6. Convert Mg into MgO.
7. i) A black mineral (A) on treatment with dilute sodium cyanide solution in presence of
air gives a clear solution of (B) and (C).
ii) The solution of (B) on reaction with zinc gives precipitate of a metal (D).
iii) (D) is dissolved in dilute HNO3 and the resulting solution gives a white precipitate
(E) with dilute HCl.
iv) (E) on fusion with sodium carbonate gives (D).
v) (E) dissolves in aqueous solution of ammonia giving a colourless solution of (F).
Identify compounds (A) to (F) and give chemical equations for reactions in steps
(i) to (iv).
8. Name two metals which are used for reduction in metallurgical process. Give one
chemical equation for each
9. Aluminium metal is frequently used as a reducing agent for the extraction of metals such
as chromium or manganese from their respective oxides. Why?
10. What is the function of basic furnace linings in steels manufacture?
LEVEL III Check Your Skills
1. Write down reactions involved in the extraction of Pb. What is the oxidagtion number of
lead in litharage? [IITJEE 2003]
2. A1 and A2 are two ores of metal M. A1 on calcinations gives black precipitate, CO2 and
water.

SM-OM-CH-30
ion Black solid + CO 2 H 2 O

inat
calc
A1 dil. A
2
Roasting
Metal + gas
HC
KI l K 2 Cr2 O7 H 2SO 4
I 2 + ppt
green water
[IITJEE 2004]
3. i) Zinc and not copper is used for the recovery of Ag from the complex [Ag(CN)2]
ii) Aluminium metal is frequently used as a reducing agent for the extraction of metals
such as chromium manganese etc.
43. Gold is also extracted by cyanide process as in case of silver. Outline the reactions.
54. How is Ag extracted from silver coin?

65. In the purification of bauxite ore as preliminary step in the production of Al, [Al(OH) 4 ]
can be converted to Al(OH)3 by passing CO 2 through it. Write an equation for the
reaction that occurs.
76. When the ore haematite is burnt in air with coke around 2000C along with lime, the
process not only produces steel, but also produces a silicate slag that is useful in making
building material such as cement. Discuss the same and show through balanced chemical
equation.
87. Explain the following:

i) Partial roasting of sulphide ore is done in the metallurgy of copper.
ii) Zinc and hot copper is used for the recovery of silver from complex [Ag(CN)2].
iii) In the metallurgy of iron, lime-stone is added to the ore.
9. Explain the following

a)ii) Although Au is soluble in aqua-regia, Ag is not.
b) Zinc and hot copper is used for recovery of Ag from the complex [Ag(CN)2]
c) Aluminium metal is frequently used as a reducing agent for extraction of metal such
as chromium manganese etc.
d) Partial roasting of sulphide ore is done in the metallurgy of copper.
810. Give balanced equation for the extraction of silver from sulphide ore.

SM-OM-CH-31
Objective Assignments
LEVEL I
1. Which alloy of aluminium is used in air craft industry
(a) duralumin (b) Magnalium
(c) Nickeloy (d) alunico
2. The common impurities present in the bauxite ore are

(a) Fe 2 O3 and CuO (b) Fe 2 O3 and PbO
(c) Fe 2 O3and SiO 2 (d) SiO 2 and CuO
3. The material used in solar cell contains

(a) Si (b) sn
(c) Ti (d) Cs
4. Sulphide ores are generally concentrated by

(a) froth floatation (b) roasting
(c) gravity (d) reduction by carbon
5. Which method of purification is represented by the following equations?

Ti 2I 2 523 K
TiI4 1700 K Ti 2I 2
(a) cupellation (b) poling
(c) Van Arkel (d) zone refining.
6. The function of flux during smelting of ores is to:

(a) make the ore porous (b) remove gangues
(c) facilitate reduction (d) precipitate slag
7. The chemical composition of slag formed during the smelting process in the extraction of
copper is:
(a) Cu2O + FeS (b) FeSiO3
(c) CuFeS2 (d) Cu2S + FeO
8. The chemical process in the production of steel from haemotite ore involves:
(a) reduction (b) oxidation
(c) reduction followed by oxidation (d) oxidation followed by reduction.
9. In the commercial electrochemical process for alumniuim extraction, the electrolyte

used is
(a) Al(OH)3 in NaOH solution (b) an aqueous solution of Al2(SO4)3
(c) a molten mixture of Al2 O3 and Na 3AlF6
(d) a molten mixture of AlO(OH) and Al(OH)3

SM-OM-CH-32
10. Cyanide process is used for the extraction of:

(a) Ag (b) Hg
(c) Cu (d) Zn.
LEVEL II
1. Poling process is used
(a) for the removal of Cu 2 O from Cu (b) for the removal of Al2 O3 from Al
(c) for the removal Fe 2 O3 from Fe (d) in all the above.
2. Which of the following is not a basic flux?
(a) CaCO3 (b) CaO
(c) SiO 2 (d) MgO
3. Zone refining is a method to obtain
(a) Very high temperature (b) Ultra pure Al
(c) Ultra pure metal (d) Ultra pure oxides.
4. Calcination is used in metallurgy to remove
(a) H 2 O and H 2S (b) H 2 O and CO 2
(c) CO 2 and H 2S (d) H 2 O and H 2S .
5. The metallic luster exhibited by sodium is explained by the presence of
(a) Na ions (b) conducting electrons
(c) free protons (d) a body-centred cubiclattice.
6. Stainless steel contains
(a) Fe, Cr, Cu (b) Fe, Cr, Ni
(c) Fe, Ni, C (d) Fe, Ni, Cu.
7. Cryolite is
(a) Na 3 AlF6 and is used in the electrolysis of alumina for descreasing electrical
conductivity.
(b) Na 3 AlF6 and is used in the electrolysis of alumina for lowering the melting point of
alumina.
(c) Na 3 AlF6 and is used in the electrolytic purification of alumina
(d) Na 3 AlF6 and is used in the electrolysis of alumina.
8. Ag 2 S NaCN (A)
(A) Zn (B)
(B) is a metal. Hence, (A) and (B) are
(a) Na 2 [Zn(CN) 4 ], Zn (b) Na[Ag(CN) 2 ], Ag
(c) Na 2 [Ag(CN) 4 ], Ag (d) Na 3 [Ag(CN) 4 ], Ag .
9. Copper pyrites ore is concentrated by
(a) electromagnetic method (b) gravity method
(c) froth floatation process (d) all.
SM-OM-CH-33
10. In the metallurgy of iron, when limestone is added to the blast furnace, the calcium ion
ends up in:
(a) slag (b) gangue
(c) metallic Ca (d) CaCO3 .
Answer to Subjective Assignments
LEVEL I
1. Certain oxides are not satisfactorily reduced by carbon. In such cases aluminium is used
as a reducing agent. A mixture of metallic oxide and aluminium powder is ignited in a
closed crucible by means of lighted magnesium ribbon. Metals like chromium,
manganese etc. are extracted by thermite process as illustrated below.
Cr2 O3 2Al Al2O3 2Cr
3Mn 3O 4 8Al
4Al2O3 9Mn
The reaction is highly exothermic and the heat produced is sufficient to melt the metal.
2. Al has greater affinity for O 2 than that carbon has, hence C cant be used to reduce
Al2 O3 to Al. Thermodynamically for this reaction:
Al2O3 3C 2Al 3CO

G is positive hence reaction is non-spontaneous.
f

3. Cu 2Ag 2Ag Cu 2

2
2Ag Cu X (no reaction)
In ECS, Cu is above Ag hence Cu can reduce Ag to metallic Ag.
4. (A) : roasting
(B) : reduction by carbon or more electropositive metal.
(C) : electrolysis
5. a) 2PbS 3O 2
2PbO 2SO 2

b) Cu 2O C 2Cu CO

c) Ag e
Ag (at cathode)
6. E OP of Zn is more positive than E OP of Cu and thus Zn is more powerful reductant than

Cu and thus Zn can easily replace Ag from [Ag(CN) 2 ] . Furthermore, Zn being cheaper
in comparison to Cu.
7. On the electrolysis of an aqueous solution of the NaCl, the Na ions are not discharged at
cathode, on the contrary H ions get discharged to form H 2 . While it is not so in the case
of fused NaCl. Therefore molten NaCl is used to prepare sodium.

SM-OM-CH-34
8. The members of group 1 i.e. alkali metals have low ionization potential and thus possess
high electropositive character as well as high oxidation potential which enables them to
get easily oxidized.
9. In the metallurgy of iron, limestone (CaCO 3 ) acts as a flux and form calcium silicate
CaSiO3 (slag).
CaCO
3
CaO 2
CO
CaO SiO
2 CaSiO3
Flux Slag
10. Carbon monoxide is actual reducing agent of haematite in blast furnace.

C O
2 2
CO
CO 2 C
2CO
Fe 2 O3 CO

2FeO 2
CO
FeO CO Fe 2
CO
LEVEL II

1. a) CdCO3
CdO CO 2
b) No reaction

c) SnO 2 CO Sn 2CO 2
CdSO 4 (aq)
current
2SO4 O 2
H Cd
{
d) 1 4 2 4 43
a t an ode at cathode

e) 2HgO
2Hg O2
f) No reaction
Non-spontaneous G being positive,
2. There exist free electrons between two parallel sheets of graphite. Hence it helps in
electron conduction. On the other hand diamond is a bad conductor because it does not
have free electrons.
3. Oxidising agent Reducing agent

a) O 2 (itself reduced to O )
2
S (in Cu 2S ) oxidized to SO 2
2
b) Cu 2 O oxidizes S2 of Cu 2S to Cu 2S , reduces Cu 2O to Cu, and itself

SO 2 also reduced to Cu.
4. MgCO3 . CaCO
3
calination

MgO CaO 2CO 2
HCl
MgCl 2 CaCO 3 CO 2
MgCl 2 CaCl 2

SM-OM-CH-35
On passing CO 2
into aq MgCl2 and CaCl 2 solution, CaCO3 is precipitated leaving MgCl2 soluble.
5. It is called Pidgeon process.
6. Mg HNO3

Mg(NO 3 )2

MgO
Cl2 ,

MgCl
2
KOH

Mg(OH) 2
7. (A): Ag 2S (a black mineral) (B): NaAg(CN) 2

(C): Na 2 S (D): Ag
(E) : AgCl (F): Ag(NH 3 ) 2 Cl
8. (1) Al (2) Fe
Cr2 O3 2Al Al2O 3 2Cr
HgS Fe
Hg FeS
9. Aluminium metal is frequently used as a reducing agent for the extraction of metals such
as Cr and Mn from their respective oxides because aluminium is more electropositive
than Cr or Mn. The process of reduction is known as Aluminothermy.
Cr2O3 2Al Al2O3 2Cr ; H ve
3Mn 3O 4 8Al
4Al2O3 9Mn ; H ve
10. Basic lining of lime (CaO) or magnesia (MgO) used to remove the acidic impurities such
as P4 O10 or SO2 .
6CaO P4O l0 2Ca 3 (PO 4 ) 2
MgO SO
2 MgSO 3
LEVEL III
1. Lead is extracted from its galena mineral (PbS). It is firstly concentrated by froth
floatation process and then roasted in reverbratory furnace. Therefore, galena mineral is
oxidsed ito PbSO4 and PbO.
2PbS 3O 2
2PbO 2
2SO
PbS 2O2 PbSO 4
The roasted mineral is smelted into lead
2PbO PbS 3Pb SO 2
PbSO 4 PbS 2Pb 2SO 2
This lead is purified by any suitable method. In litharj (PbO) oxidation state of lead is +2.
2. A1 will be malachite i.e., CuCO3, Cu(OH)2

A2 will be copper glance i.e., Cu2S
The confirmatory reactions are
SM-OM-CH-36
a) For malachite
i) CuCO3 Cu(OH) 2 2CuO
CO 2
calcination
H 2O
Black solid
ii) CuCO3 Cu(OH) 2

HCl 2 CO
CuCl 2 H 2O
CuCl2
KI
2 I 2
Cu KCl I 2
ppt (D)
b) For copper glance

Cu 2
S Cu 2 O SO 2
Roasting
O2
Cu 2S Cu 2 O
Cu SO 2
SO2 is the gas which gives green colour with acidified K2Cr2O7 as
3SO 2 K 2 Cr2 O7 H 2SO
4 K 2SO 4 Cr2 (SO
4 )3 4H 2O
green
3. i) Zinc is more powerful reducing agent in comparison to copper. Zinc is also cheaper
than copper.
ii) Aluminium has great affinity for oxygen. It acts as a reducing agent when the metal
having high melting point is to be extracted from is oxide.
Cr2O3 + 2Al 2Cr + Al2O3
43. In the cyanide process, crushed rock containing traces of gold is treated with 0.10.2%
solution of NaCN and aerated. O 2 (air) oxidizes free metal to Au which complexes
with CN
4Au 8CN 2H 2O O 2 4[Au(CN) 2 ] 4OH
The pure metal is diplaced from solution by an active metal.
2[Au(CN) 2 ] Zn [Zn(CN)4 ]2 2Au
54. conc. HNO3 (Cu 2

Silver coin (Cu Ag) Ag ) NO3
NaCl
AgCl (white ppt)

2AgCl Na 2CO
3 3
Ag 2CO 2NaCl
1
Ag 2CO
3
2Ag 2
O2
CO
2
Or use cyanide process with AgCl.

65. Aqueous solution of CO 2 is acidic. Hence CO 2 when passed into [Al(OH) 4 ] solution
makes it acidic hence Al(OH)3 is precipitated.
CO 2 2H 2O H3O HCO 3

[Al(OH) 4 ] H 3O 3
Al(OH) 2H 2 O
76. Haematite ( (Fe 2 O3 ) on burning with coke and lime at 2000C results in following:
C O
2 2 C
CO 2 ; CO 2CO

SM-OM-CH-37
3CO Fe 2O
3 2Fe 3CO 2
(Steel)
SiO 2 CaO CaSiO 3

(lim e) (slag)
CaSiO3 (slag) is used as the building material.

87. i) The concentrated ore is roasted in reverberatory furnance in a current of air. The
volatile impurities such as free sulphur, arsenic and antimony are removed as volatile
oxides and the ore is partially oxidized.
4As 3O 2 2As 2O 3 ;4Sb 3O 2
2Sb 2O 3; S O 2 SO 2
2CuFeS2 O
2 2S 2FeS
Cu SO 2
2CuFeS2 O
2 2S
Cu
2FeS SO 2
2Cu 2S 3O
2 2O
2Cu 2SO 2
A mixture of sulphides and oxides is formed. The Cu 2 O so formed reacts with
unconverted Cu 2S to form copper.
Cu 2S 2Cu 2 O
6Cu SO 2
ii) Zinc is cheaper as well as stronger reducing agent in comparison to copper.
Zn 2[Ag(CN) 2 ]
2Ag [Zn(CN) 4 ]2
iii) Lime stone is added as a flux. It is decomposed in the furnace into CaO and CO 2 .
CaO reacts with gangue silica and forms infusible stag, CaSiO3 .
CaCO 3
CaO CO 2
9. aii) Au dissolved in aquaregia forming soluble HAuCl4 but Ag forms insoluble AgCl
Au + 4HCl + 3HNO HAuCl 4 3NO + 3H O
3 2 2
soluble
Ag + HCl + HNO3 AgCl + NO2 + H2O

insoluble
b) zinc is powerful reducing agent in comparison to copper and zinc is cheaper also
than copper.
c) Auminium metal is frequently used as a reducing agent for the extraction of metals.
Such as Cr and Mn from their respective oxides because aluminium is more
electropositive than Cr or Mn. The process of reduction is called alumino thermy.
Cr2O3 + 2Al Al2O3 + 2Cr
3Mn3O4 + 8Al 4Al2O3 + 9 Mn
d) Partial roasting of sulphide ore forms some oxide. The oxide then reduces the
remaining sulphide ore into metal.
2CuS + 3O2 2CuO + 2SO2
2CuO + CuS 3Cu+ + SO2
108. Ag 2S 4NaCN 2 ] Na 2S
2Na[Ag(CN)
2Na[Ag(CN) 2 ] Zn 4 ] 2Ag
Na 2 [Zn(CN)

SM-OM-CH-38
Objective
LEVEL I
1. a 7. b
2. c 8. c
3. a 9. c
4. a 10. a
5. c
6. d
LEVEL II
1. a 7. d
2. c 8. b
3. c 9. c
4. c 10. a
5. c
6. b

SM-OM-CH-39


Ores and Metallurgy

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SM-OM-CH-3

Element O Sr Al Fe Ca Na K Mg H Other elements

1. Copper (IB, coinage metal) a) Cuprite; Cu 2 O

3. Magnesium (II A, bridge metal) a) Carnalite; KCl, MgCl 2 .6H 2 O (chloride)

NARAYANA IIT ACADEMY

4. Zinc (II B, amphoteric metal) a) Zinc blende; ZnS (sulphide)

6. Tin (IV A, amphoteric metal) a) Cassiterite or Tin stone; SnO 2

7. Lead (IV A, amphoteric metal) a) Galena; PbS

8. Iron (VIII, transition metal) a) Iron pyrite; FeS2

NARAYANA IIT ACADEMY

Infusible impurity + Flux = Fusible slag.

1. Concentration (Dressing) 2. Roasting

1. Concentration (Dressing): Ores obtained from mines often contain non-metallic

NARAYANA IIT ACADEMY

a) Gravity separation: The ore is powdered. It is then washed in running stream of

b) Froth floatation process: Sulphide ores are generally concentrated by this

ore particles are separated from the froth.

Method: Ore is concentrated by a magnetic separator. It consists of a leather belt

This method is used to concentrate tin Ore

NARAYANA IIT ACADEMY

a) Aluminium hydroxide on calcination gives alumina.

c) Siderite is the ore of iron. This on calcination gives ferrous oxide

d) Calamine is the ore of zinc. This on calcination gives zinc oxide.

e) Sodium bicarbonate on calcination gives sodium carbonate

f) Calcination of lime stone gives CaO and CO2.

NARAYANA IIT ACADEMY

a) Roasted ore is reduced into metal or a compound containing that metal.

b) Impurity present in the roasted ore is removed as slag.

Following are the examples of smelting.

NARAYANA IIT ACADEMY

b) Liquation method: Zn, Pb, Sn, Bi etc., pure copper rods

metals are purified by this method. This method impure

anode mud CuSO4 solution

2. Roasting: During roasting S, As, P are oxidized to the respective oxides.

Fe3O4 is decomposed to ferrous oxide and ferric oxides.

Fe3O4 FeO + Fe2O3

FeO + SiO2 FeSiO3

Extraction of Cast Iron

Reactions taking place in the blast furnace are

Fe2O3 + 3CO 2Fe + 3CO2

iii) Zone of slag formation :

CaCO3 CaO + CO2

iv) Zone of fusion (lower part of furnace):

Cup and cone

Fe2O3 + 3C 2Fe + 3CO

MnO + SiO2 MnSiO3

2Fe2O3 + P4O10 4FePO4

Chemical reactions which have placed are:

2. Above bosh 600 - 900C, ferric oxide is partially reduced by CO as

3. CaCO3 900C CaO + CO2

4. The reaction at 1500C, MnO2 is reduced to

NARAYANA IIT ACADEMY

Some Important Alloy

SnSiO3 CaO Sn + CaSiO3 + CO

NARAYANA IIT ACADEMY

Extraction of Metallic Copper

1. Concentration of the ore by froth floatation process: Copper pyrites

3. Smelting of the roasted ore in blast furnace : material required

Reactions occurring given as follows

2FeS + 3O2 2FeO + 2SO2

4. Self reduction in Bessemer Converter

Reactions involved are,

2FeS + 3O2 2FeO + 2SO2