19

1. IIT–JEE Syllabus
Ores & Metallurgy

2. Introduction
3 Metallurgy
3.1 Concentration Extraction of metals from their respective
3.2 Reduction of free metal
3.3
3.4
Refining or Purification
Furnaces
ores is a very scientific process and the
4 Extraction of Aluminium theme of this chapter is to explore this
4.1 Important ores of aluminium
4.2 Purification of bauxite process.
4.3 Electrolysis of fused pure alumina
4.4 Refining of aluminium

5 Extraction of Iron You will find ores of various metal that is

5.1 Important ores of iron
5.2 Extraction of cast iron found in the nature and method of
5.3 Preparation of wrought iron

6. Extraction of Copper extraction of the metals from their

6.1 Important ores of copper
6.2 Metallurgy of copper respective ores.
7. Extraction of Silver
7.1 Important ores of silver This chapter also deals with various
7.2 Metallurgy of silver

8. Extraction of Tin processes involved in the extraction of

9. Extraction of Lead metals such as carbon reduction, self
10. Extraction of Magnesium
11. Some other Important Compound
reduction, electrolytic reduction, cyanide
12. Some Important Alloy process and an introduction to various
13. Solved Problems
13.1 Subjective
types of furnaces.
13.2 Objective

14. Assignment Problems (Subjective)

15. Assignment Problems (Objective)
16. Answers to Objective
Assignments
1. IIT-JEE Syllabus
Commercially important ores of iron, copper, lead, magnesium, aluminium , tin and
silver . Carbon reduction process (iron and tin), Self reduction process (copper and
lead), Electrolytic reduction process (magnesium and aluminium), Cyanide process
(silver and gold).

2. Introduction
The earth’s crust is the main source of metals. The occurrence of metal in native or in
combined state in the earth’s crust along with a number of rocky and other impurities
depends upon the chemical nature of metals. Metals having less electropositive character
have less affinity for oxygen, moisture and occur in free or metallic or native state i.e., in
uncombined state e.g. Au, Pt , Ag etc. On the other hand metals with higher electropositive
character occurs in combined state i.e., as compounds.

The compound of a metal found in nature is called a mineral. A mineral may be a single
compound or a complex mixture. Those minerals from which metal can be economically
extracted are called ores. Thus all ores are minerals but all minerals are not ores. For e.g.
copper occurs in nature in the form of several minerals like Cu2O, Cu2S, CuFeS2, but
copper pyrites is considered as the most economical mineral for the extraction of the metal.
Hence copper pyrites is the chief ore of copper.

Ores may be divided into four groups

i) Native Ores: These ores contain the metal in free state eg. Silver gold etc.
These are usually formed in the company of rock or alluvial
impurities like clay, sand etc.
ii) Oxidised Ores: These ores consist of oxides or oxysalts (eg. carbonates,
phosphate) and silicate of metal. Important oxide ore includes,
Fe2O3, Al2O3.2H2O etc. and important cabonate ores are limestone
(CaCO3), Calamine (ZnCO3) etc.
iii) Sulphurised Ores: These ores consist of sulfides of metals like iron, lead, mercury
etc. Examples are iron pyrites (FeS2). galena (PbS), Cinnabar
(HgS)
iv) Halide ores: Metallic halides are very few in nature. Chlorides are most
common examples include horn silver (AgCl) carnallite KCl.
MgCl2.6H2O and fluorspar (CaF2) etc.

3. Metallurgy
It is the process of extracting a metal from its ores. The following operations are carried out
for obtaining the metal in the pure form.
i) Crushing of the ore
ii) Dressing or concentration of the ore.
iii) Reduction of metal.
v) Purification or refining of the metal.
RSM79-P5-CH-OM-2

3.1 Concentration

Ores usually contain soil, sand, stones and other useless silicates. These undesired
impurities present in ores are called Gangue or Matrix. The removal of these impurities from
the ores is known as concentration. The concentration process involve physical as well as
chemical method.

Physical Method

a) Gravity separation: The separation is based on the difference in the specific gravities of
the gangue particles and ore particles. The powdered ores is agitated with water or
washed with a running stream of water. The heavy ore particles of sand, clay etc. are
washed away. For this either wilfley table or hydraulic classifier is used.

b) Froth Floatation Process: Metallic sulphides are wetted by certain oil like pine oils and
not by water.

The finely divided ore is introduced into water containing small quantity of oil (e.g. Pine
Oil). The mixture is agitated violently with air a froth is formed which carries away along
with it the metallic particles on account of the surface tension forces. The froth is
transferred to another bath where gangue-free ore settles down. As the heavy metallic
material is floated upward with the froth, this process is known as froth floatation process.
The method is based upon preferential wetting of surfaces by liquids.

c) Electro Magnetic Separator: When one component either ore or the impurity is
magnetic in nature this method can be used for separation. A magnetic separator
consists of a belt moving over two rollers, one of which is magnetic. The powdered ore is
dropped on the belt at the other end. Magnetic portion of the ore is attracted by the
magnetic roller and falls near to the roller while the non-magnetic impurities fall
farther off.

Chemical Methods

a) Calcination: Calcination is a process in which the ore are usually carbonate or hydrated
oxide is subjected to the action of heat in order of expel water from hydrated oxide and
carbon dioxide from a carbonate.

Examples: ZnCO3  ZnO + CO2

CaCO3  CaO + CO2
Al2O32H2O  Al2O3 + 2H2O
2Fe2O33H2O  2Fe2O3 + 3H2O

Calcination is generally done in a reverberatory furnace.

b) Roasting: Roasting is a process in which ores (usually sulphide ores) either alone or
along with some other materials are subjected to the action of heat and air at temperatures
below their melting points in order to bring about chemical changes in them. Calcination is
also roasting but in this case we are concerned mainly with the changes due to the
expulsion of some ingredients such as water, carbon dioxide and no other chemical change
occurs. But during roasting chemical changes like oxidation, chlorination etc. takes places.
The following equations represent roasting:

2PbS + 3O2  2PbO + 2SO2

PbS + 2O2  PbSO4
2ZnS + 3O2  2ZnO + 2SO2
ZnS + 2O2  ZnSO4
CuS + 2O2  CuSO4
2Cu2S + 3O2  2Cu2O + 2SO2

Roasting is generally carried out in a reverberatory furnace or in a blast furnace.

c) Leaching: It involves the treatment of the ore with a suitable reagent as to make it
soluble while impurities remain insoluble. The ore is recovered from the solution by
suitable chemical method. e.g. bauxite ore contains ferric oxide, titanium oxide and silica
as impurities. When the powdered ore is digested with an aqueous solution of sodium
hydroxide at about 150°C under pressure, the alumina dissolves forming soluble sodium
meta aluminate while ferric oxide, TiO2 and silica remains as insoluble part.

Al2O3 + 2NaOH  2NaAlO 2 + H2O

so luble

3.2 Reduction of Free Metal

a) Smelting:The reduction of a metal from its ore by a process involving melting is known
as smelting. It is generally done in a reverberatory furnace or a blast furnace in a
controlled supply of air. Several reducing agents such as sodium, magnesium and
aluminium are used for reduction. The calcinated or roasted ore is mixed with carbon
(coal or coke) and heated in a reverberatory or a blast furnace. Carbon and carbon
monoxide produced by incomplete combustion of carbon reduce the oxide to the metal.

PbO  C  Pb  CO 

PbO  CO  Pb  CO 2  Carbon reduction process
SnO 2  2C  Sn  2CO  
Cr 2O3  2Al  2Cr  Al2O3 
Alu min ium reduction process (Gold - Schimidt alumino thermic process )
3Mn 3O4  8Al  9Mn  4Al2O3 

b) Flux:The ores even after concentration contain some earthy matter called gangue which
is heated combine with this earthy matter to form an easily fusible material. Such a
substance is known as flux and the fusible material formed during reduction process is
called slag. Slag is usually lighter and floats on the surface of the molten metal.
Concentrated ore + gangue + reduction agent + flux
heated

Metal + slag + gases

Fluxes are of the following two types:

 i) Acidic fluxes like silica, borax etc. These are used when the gangue is basic such
as lime or other metallic oxides like MnO, FeO, etc. The chemical reaction which
takes place in removing a basic gangue is as follows:

CaO  SiO 2  CaSiO 3

Basic Gangue Acidic Flux Slag

ii) Basic fluxes like CaO, lime stone (CaCO3), magnesite (MgCO3), haematite
(Fe2O3) etc. These fluxes are used when the gangue is acidic like silica, P4O10
etc. For example

SiO 2  MgCO 3 MgSiO 3  CO 2 

Acidic Gangue Basic Flux Slag

P O  6CaO  2Ca 3 (PO 4 )2

4 10
Acidic flux Basic gangue Slag

The other methods used for the reduction of metals are electrolytic reduction,
hydro metallurgy and amalgamation method.

Illustration 1: Write short notes on

(a) Amalgamation (b) Hydrometallurgy
(c) Self reduction (d) Electrolytic reduction

Solution: a) This process is used for the extractioin of noble metals like gold and silver
from the native ores. The finely crushed ore is brought into contact with
mercury which combines with the metal forming its amalgam. The metal
is then recovered by distilling the amalgam.

b) Hydrometallurgy is the process of bringing the metal into solution by the

action of suitable chemical reagents (e..g., sodium cyanide solution or
chlorine in presence of water etc.) followed by recovery of the metal by
the use of a proper precipitating agent which is a more electropositive
metal. For example, poor ores of silver are suspended in a dilute solution
of sodium cyanide and air is blown through it when the silver present
goes into solution as the argentocyanide complex. From this solution the
metal is precipitated by adding zinc turnigs.

4Ag + 8NaCN + O2 (air) + 2H2O  4Na [Ag(CN)2] + 4NaOH

or AgCl + 2NaCN  Na[Ag(CN)2] + NaCl
2Na [Ag(CN)2] + Zn  Na2[Zn(CN)4] + 2Ag

c) In some cases no extra reducing agent is required. A part of the sulphide

ore is changed to oxide or sulphate which then reacts with the remaining
part to give the metal and sulphur dioxide. Copper and lead are obtained
by this method.
2Cu2S + 3O2  2Cu2O + 2SO2
Cu2S + 2Cu2O  6Cu + SO2
2PbS + 3O2  2PbO + 2SO2
PbS + 2O2  PbSO4
PbSO4 + PbS  2Pb + 2SO2
 d) The carbon reduction methods are not applicable for the highly
electropositive and chemically active metals such as alkali metals,
alkaline earth metals, aluminium etc. The oxides of these metals are very
stable and have to be heated very strongly with carbon in order to reduce
them to metals. But at high temperatures these metals combine with
carbon to form carbides, thus creating problem. Hence these metals are
extracted by the electrolytic reduction of their fused halides. The metal is
liberated at the cathode. Aluminium is however obtained by the
electrolytic reduction of alumina (Al2O3) dissolved in molten cryolite
(Na3AlF6).

3.3 Refining or purification

The metals obtained by the application of above reduction methods from the concentration
ores are usually impure. The impure metal is thus subjected to some purifying process
known as refining in order to remove undesired impurities. Various process for this are

a) Liquation process b) Distillation process

c) Cupellation d) Poling
e) Elecrolytic refining f) Bessemerisation

3.3.1 Bassemerisation

This is a process in the metallurgy of copper. It involves the reduction of molten matte
(mixture of cuprous and ferrous sulphide) obtained after smelting of copper pyrites ore in a
Bessemer converter.

The molten matte is taken in Bessemer converter and heated by blowing hot blast of air and
sand through tuyeres. The following reactions takes place in the converter.

i) Air oxidizes iron sulphide to iron oxide and SO2

2FeS + 3O2  2FeO + 2SO2

ii) Sand reacts with iron oxide to form iron silicate

2FeO + SiO2  FeSiO3 (Slag)

iii) After the iron has been removed, hot blast of air converts a part of cuprous sulphide to
cuprous oxide.
2Cu2S + 3O2  2Cu2O + 2SO2

iv) The cuprous oxide so formed reacts immediately with remaining cuprous sulphide to
form metallic copper.
2Cu2O + Cu2S  6Cu + SO2
Since the reaction is exothermic, the heat liberated maintains the crude copper in the
molten state. The completion of the reaction is indicated by the appearance of green
flame produced by the vaporization of copper.

3.4 Furnaces

It is a device in which high temperature is produced either by burning a fuel or by using

electricity. The important ones are described below.
a) Blast Furnace: It is used for smelting iron, copper and lead ores. It has a tall structure
made of steel plates rivetted together lined inside with fire bricks. The furnace is
provided with an arrangement for blowing air near the base, a slag hole, a tapping hole
for removing the molten metal and an exit for waste gases near the top. The charge is
introduced at the top. The mouth of the furnace is closed by a special arrangement
through which the charge is introduced.
b) Reverberatory Furnace: It is used for calcination, roasting or for smelting. The charge
in the powdered form along with a flux is placed on the hearth of the furnace. The fuel is
placed on grate and the flames are deflected from its low sloping roof. This furnace is
used in case of copper, tin, lead and wrought iron.
c) Muffle Furnace: A furnace in which the charge container is heated from all sides is
called muffle furnace. The burnt materials including the vapours of the metal are allowed
to escape through the same opening. The metal is obtained by condensing the vapours.
In Belgian process for extracting zinc, the retorts act as muffles and prolongs help in
completing the condensation.
d) Bassemer Converter: It is a pear-shaped furnace made of steel plates lined inside with
lime or magnesium oxide. It is fixed on pivots and can be tilted in any direction. It is
provided with pipes through which hot air can be blown for heating purposes.

4. Extraction of Aluminium
4.1 Important ores of aluminium

1. Bauxite Al2O32H2O
2. Cryolite Na3AlF6
3. Feldspar K2OAl2O36SiO2 or KAlSi3O8
4. Mica K2O3Al2O36SiO22H2O
5. Corundum Al2O3
6. Alumstone or Alunite K2SO4Al2(SO4)34Al(OH)3
Aluminium is mainly extracted from bauxite ore.

4.2 Purification of Bauxite

Purification of Bauxite

Bayer’s process Hall’s Process Serpeck’s process

This process is used for red (For Red Bauxite) This process is employed for
bauxite which contains Al2O32H2O + Na2CO3 the purification of white
relatively larger quantities of  bauxite which contains silica
iron oxide as impurities. 2NaAlO2 + CO2 + 2H2O as the chief impurity. Ore is
Al2O32H2O + 2NaOH iron oxide and silica remain powdered, mixed with coke
Bauxite as residue. Sodium meta and heated to 2073 K in an
 aluminate is heated and atmosphere of nitrogen
2NaAlO2 + 3H2O stream of CO2 passed Al2O32H2O + N2 + 3C
Sodium meta aluminate through when Al(OH)3 gets 2AIN + 3CO + 2H2O
(soluble) precipitated. Aluminium nitride
Ferric oxide remains insoluble 2NaAlO2 + 3H2O + CO2 SiO2 + 2C  Si + 2CO
NaAlO2 + 2H2O  AlN +3H2O  Al(OH)3 + NH3
 2Al(OH)3 + Na2CO3
Al(OH)3 + NaOH

2Al(OH)3  
 Al2O3  3H2O (calcination of aluminium hydroxide)
1473K

Alu min a
4.3 Electrolysis of fused pure alumina (Hall & Herwlt Method)

The addition of cryolite (Na3AlF6) and fluorspar (CaF2) makes alumina a good conductor of
electricity and lowers its Fusion temperature from 2323 to 1140 K. the reaction taking place
during electrolysis.
Na3AlF6 3NaF + AlF3
AlF3 Al3+ + 3F–
At cathode
Al3+ + 3e–  Al
At anode
F–  F + e–
2Al2O3 + 12 F  4AlF3 + 3O2
2C + O2  2CO
2CO + O2  2CO2

4.4 Refining of Aluminium

The aluminium metal obtained by the electrolysis of fused almina is about 99.5% pure. It can
be further refined by Hoope’s electrolytic process.

The graphite rods dipped in pure aluminium and Cu–Al alloy rod at the bottom in the impure
aluminium work as conductors. On electrolysis, aluminium is deposited at cathode from the
middle layer and equivalent amount of aluminium is taken up by the middle layer from the
bottom layer (impure aluminium). Therefore, aluminium is transferred from bottom to the top
layer through middle layer while the impurities are left behind. Aluminium thus obtained is
99.98% pure.
Illustration -2: Aluminium cannot be prepared by the electrolysis of aqueous solution of
its salts. Why?

Solution: Discharge potential of aluminium is higher then the discharge potential of

hydrogen. Thus the aqueous solution containing Al+3 and H+ ion when
electrolysed, the H+ ions rather than Al+3 ions are discharged at cathode
and hydrogen is evolved.

5. Extraction of Iron
5.1 Important Ores of Iron
i) Haematite Fe2O3 (red oxide of iron)
ii) Limonite Fe2O33H2O (hydrated oxide of iron)
iii) Magnetite Fe3O4 (magnetic oxide of iron)
Varieties of Iron

Pig or Cast Iron Wrought Iron Steel

 most impure form  Purest form of iron It is in between pig

 2.5 – 5% carbon and other  0.1 – 0.25% carbon iron and wrought iron.
impurities like Mn, Si, S and  Its is ductile, soft and  0.25 to 2% carbon
P malleable.
 It is hard and Brittle and
hence cannot be moulded by
hammering
5.2 Extraction of Cast Iron
Iron is usually extracted from the haematite. Concentrated ore after calcination is reduced
with carbon i.e. smelted in the blast furnace.

Reactions taking place in the blast furnace

Charge
i) Zone of combustion
C  O2  CO 2
( Coke )
Cup and cone
ii) Zone of reduction arrangement
Waste gases
Fe2O3 + 3CO  Fe + CO2 200–250C

iii) Zone of reduction 400C

Fe2O3 + 3CO  2Fe + 3CO2 600C

FeO + CO  Fe + CO2
iv) Zone of slag formation 700C Refractory bricks
CaCO 3  CaO  CO 2 800–1000C
(lim e stone)

CaO  SiO 2  CaSiO 3 ; 1300C

Fusibleslag Hot air
1600C
v) Zone of fusion lower part of furnace
Tuyeres
Molten iron is heavier than from
molten slag. The two liquids are Molten slag
periodically tapped off. The molten
iron tapped off from the furnace is Molten metal
solidifed into blocks called ‘pigs’. Blast furnace

5.3 Preparation of Wrought Iron

This is done by heating cast iron with haematite (Fe2O3) which oxidises C to CO, S to SO2,
Si to SiO2, P to P4O10 & Mn to MnO
Fe2O3 + 3C  2Fe + 3CO
Where CO & SO2 escape, manganous oxide (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
Illustration 3: Cast iron is hard but pure iron is soft in nature. Explain why?
Solution: Cast iron contains 2.5 to 5% carbon which makes cast iron hard.

6. Extraction of Copper
6.1 Important Ores of Copper
i) Copper glance (chalcocite) Cu2S
ii) Copper pyrites (Chalopyrites) CuFeS2
iii) Malchite Cu(OH)2 CuCO3
iv) Cuprite or Ruby copper Cu2O
v) Azurite Cu(OH)22CuCO3
6.2 Metallurgy of Copper

Copper is extracted mainly from copper pyrites. The various steps involved are

COPPER PYRITES
(CuFeS2)
Crushed and Sieved

Concentration by froth floatation

Powdered ore + water + pine oil + air  sulphide ore in the froth

Rosting in reverberatory furnace in presence of air

S + O2  SO2; 2As + 3O2  2As2O3
2CuFeS2 + O2  Cu2S + 2FeS + SO2
Sand + Coke

Smelting in blast furnace in presence of air

2FeS + 3O2  2FeO + 2SO2; FeO + SiO2  FeSiO3 (slag)

Cu2O + FeS
Slag
(Matte)

Bessemerisation in bessemer converter in presence of air

2FeS + 3O2  2FeO + 2SO2; FeO + SiO2  FeSiO3
2Cu2S + 3O2  2Cu2O + 2SO2
Auto
2Cu2O + Cu2S  
 6Cu + SO2
reduction

Blister copper (98% Cu + 2% impurities)

*Electrolytic refining
Anode–impure copper plates
Cathode-pure copper plates
Electrolyte -CuSO4 + H2SO4

Pure copper at cathode (99.9% pure)

7. Extraction of Silver
7.1 Important Ores of Silver:
i) Argentite or silver glance, Ag2S
ii) Horn Silver AgCl
iii) Pyragyrite (Ruby Silver), Ag2S, Sb2S3
7.2 Metallurgy of silver:

Silver is mainly extracted from argentite (Ag2S) by Cyanide Process

SILVER ORE (Argentite)

Concentration by froth floatation

Powdered ore + water + pine oil + air  sulphide ore in the froth

CYANIDATION
Concentrated ore + NaCN solution (0.4 – 0.6%) + Air
Ag2S + 4NaCN 2Na[Ag(CN)2] + Na2S
4Na2S + 5O2 + 2H2O  2Na2SO4 + 4NaOH + 2S

Filtrate

Precipitation of silver with zinc

2Na[Ag(CN)2] + Zn  2Ag + Na2[Zn(CN)4]
Black ppt.

fuse
Black ppt. of Ag + KNO3   compact mass silver metal

Electrolytic refining
Anode–impure silver plates
Cathode-pure silver plates
Electrolyte -AgNO3 solution + HNO3

Pure silver at cathode

8. Extraction of Tin
The chief ore of tin is cassiterite or tin stone, SnO2. It contains about 10% of tin. The
crushed ore is washed with water to remove lighter impurities. The ore is then roasted to
remove arsenic and sulphur as volatile oxides. Tin is obtained by reducing SnO2 with carbon
at 1200- 13000C in an electric furnace.

1200 1300 C
SnO2 + 2C     Sn + 2 CO

The product often contains traces of Fe, which make the metal hard. Fe is removed by
blowing air through the molten mixture to oxidise the iron to FeO, which then floats to the
surface.

9. Extraction of Lead
The principal ore of lead is Galena, PbS. The ore is first concentrated by froth floatation
process. The concentrated ore is roasted in air to convert it into lead oxide PbO and lead
sulphate. Some galena is also left unchanged. If the air supply is now reduced, the
unreacted PbS reacts with PbO and PbSO4 to produce metal
 3PbS + 5O2  2PbO + PbSO4 + SO2
2PbO + PbS  3Pb + SO2
PbSO4 + PbS  2Pb + 2SO2

10. Extraction of Magnesium

Magnesium from sea-water is obtained by the Dow's process. It consists of electrolysis of
molten magnesium chloride using an iron cathode and a graphite anode. Following are the
steps that involved during the process.

a) Mg+2 is precipitated as magnesium hydroxide by the addition of slaked lime, Ca(OH)2 to

the sea water.

Mg2+ + Ca(OH)2  Mg(OH)2 + Ca2+

b) Magnesium hydroxide on treatment with hydrochloric acid is converted to chloride which

is crystallised as MgCl2.6H2O

Mg(OH)2 + 2HCl  MgCl2 + 2H2O

c) Now for electrolysis, magnesium chloride is fused as follows:

On passing a current of dry HCl gas it get partially dehydrated and the chloride thus
obtained is added to a molten mix. of sodium chloride and calcium chloride (temp. range
973 - 1023 K).Under this condition MgCl2 melt with the loss of water.

If magnesium chloride hydrate is heated strongly, it hydrolyses to yield magnesia

(magnesium oxide ) which is a refractory.

MgCl2.6 H2O  MgO + 2HCl + 5H2O

d) Molten mixture of MgCl2 , NaCl and CaCl2 is electrolysed. Magnesium is formed at the
cathode and chlorine is evolved at the anode. The chlorine is used to make HCl acid
which in turn is required for making magnesium chloride.

Cathode : Mg2+ + 2e-  Mg

Anode : 2Cl-  Cl2 + 2e-

Illustration 4: NaCl is added during electrolysis of fused anhydrous MgCl2. Why?

Solution: NaCl is added as to lower the fusion temperature of MgCl2 and to make the
mixture a good conductor of electricity.

11. Some Other Important Compounds

1. MgCO3 Magnesite 2. MgCO3CaCO3 Dolomite
3. MgSO47H2O Epsomsalt 4. KClMgCl26H2O Carnallite
5. MgAl2O4 Spinal 6. H2MgSiO3 Talc
7. Ca2Mg5Si8O22(OH)2 Asbestos 8. KAlSi3O8 Feldspar
 9. Cu(OH)2CuCO3 Malachite 10. Cu(OH)22CuCO3 Azurite
11. PbS Galena 12. Fe3O4 Magnetite
13. 3Fe2O33H2O Cimonite 14. AgNO3 Lunar Caustic
15. ZnSO47H2O White Vitriol 16. SnCl25H2O Butter of Iron
17. CaO Quick lime 18. Na2SO410H2O Glauber’s salt
19. Pb3O4 Red lead 20. Pb(OH)22PbCO3 White lead
21. Na2CO3 Soda ash 22. NaOH Caustic Soda
23. KOH Caustic potash 24. Ca(OH)2 Slaked lime
25. CaSO42H2O Gypsum 26. (CaSO4)2H2O Plaster of Paris
27. FeSO47H2O Green Vitriol 28. Hg2Cl2 Calomel
Corrosive
29. HgCl2 30. PbSO4 Anglesite
Sublimate
31. PbO Cittarge 32. ZnO Philosopher’s wool
33. HgS Cinnabar 34. BaSO4 Baryte or heavy spar
35. ZnS Zinc blende

12. 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

13. Solved Problems

13.1 Subjective

Problem 1: A student suggested that calcium should be made if CaO is reacted with
Aluminium powder. Was student correct?
Given Gf0 (CaO) = – 604.2 kJ/mol
Gf0 (Al2O3) = –1582 kJ/mol

Solution: 2Al + 3CaO  Al2O3 + 3Ca

G° = Gof (Al2O3) – 3 Gof (CaO)
–1582 – 3  (–604.2)
 = –1582.0 + 1812.6 = + 130.6
G° = +ve  reaction is non spontaneous hence not possible. So student
was wrong.

Problem 2: 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
Δ
HgS + 2HgO  3Hg + SO2
( unstable)
Δ
PbS + 2PbO  3Pb + SO2
( unstable)

ZnS + 2ZnO 
 3Zn +SO2
X
( stable)

Problem 3: Explain the following

a) 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.

Solution: a) Au dissolved in aquaregia forming soluble HAuCl4 but Ag forms insoluble

AgCl
Au + 4HCl + 3HNO3  HAuCl 4 + 3NO2 + 3H2O
so luble
Ag + HCl + HNO3  AgCl + NO2 + H2O
inso luble
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
Problem 4: 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
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+2  equivalent of KMnO4

10  N = 10  0.02  5  10–3
 N = 0.1N
Strength = Normality  equivalent wt. = 0.1  56 = 5.6 gm/ litre
% of Fe+2 = 56%

b) CuSO4 + 4KI  Cu2I2 + 2K2SO4 + I2

Equivalent of Cu+2 = equivalent of I2 = equivalent of Na2S2O3
Equivalent of Cu+2 in 10 ml = 10  0.02  1  10–3
Equivalent of Cu+2 in 1000 ml = 100  10  0.02  10–3 = 0.02
Strength = Normality  equivalent weight
63.5
= 0.02  = 12.7 g
2
or percentage of Cu = 12.7%

Problem 5: a) MgO is used for the lining in steel making furnace.

b) Which of the metals Na, Ag and Fe are extracted by
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  MgSiO 3 

3MgO  P2O5  Mg 3 (PO 4 )2  Slag
MgO  SO 2  MgSO 3 

b) (i) Ag, (ii) Fe, (iii) Na

13.2 Objective

Problem 1: The material used in semiconductors

(A) Si (B) Sn
(C) Ti (D) Cs

Solution: (A)
Problem 2: 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 3: Which of the following is manufactured by Siemens Martin process?
(A) Pig iron (B) Cast iron
(C) wrought iron (D) steel

Solution: (D)
Problem 4: 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 5: Bordeaux mixture is

(A) CuSO4 +MgSO4 (B) FeSO4 + CuSO4
(C) CuSO4 and lime (D) NiSO4 + lime

Solution: (C)

Problem 6: The main function of roasting is

(A) to remove the volatile impurities
(B) oxidation of metal
(C) reduction of metal
(D) to make slag

Solution: (B)

Problem 7: Which method of purification is represented by the following equation

o o
70
Ni + 4CO  C  Ni(CO)  180
 C  Ni + 4CO
4

(A) van Arkel (B) zone refining

(C) mond process (D) cupellation

Solution: (C)

Problem 8: The process of converting hydrated alumina into anhydrous alumina is called
(A) roasting (B) calcination
(C) smelting (D) dressing

Solution: (B)

Problem 9: Zone refining is a method to obtain

(A) Very high temperature (B) Ultra pure Al
(C) Ultra pure metal (D) Ultra pure oxides

Solution: (C)

Problem 10: Thomas slag is -

(A) Ca3(PO4)2 (B) MnSiO3
(C) CaSiO3 (D) FeSiO3

Solution: (A)
14. Assignments (Subjective Problems)
LEVEL – I

1. Complete the following reactions:

a) Al(OH)4– + CO2  ? + ? + ?
b) Ag+ + Na2S2O3  ? + ?
c) MnO 
4 + H2S  ? + ?

2. A sulfide ore (A) on roasting leaves a residue (B). (B) on heating with chlorine gives
(C), soluble in water, addition of excess potassium iodide to a solution of (C) gives a
solution (D). A brown precipitate (E)is formed when a solution of ammonium sulfate
is added to an alkaline solution of (D). Identify (A) to (E).

3. Write the balanced chemical equations for the following

a) Pb3O4 is treated with nitric acid
b) Zinc oxide is treated with excess of sodium hydroxide solution
c) Dilute nitric acid is slowly reacted with metallic tin
d) Gold is dissolved in aqua regia
e) Iron reacts with cold dilute nitric acid
f) Sodium thiosulphate is added slowly to silver nitrate
g) Heating of ZnCl22H2O

4. In moist air copper corrodes to produce a green layer on the surface. Explain.

5. Why does AgNO3 produce a black stain on the skin.

6. How is ferrochrome produced? What are its application?

7. State the composition of Cu alloys used for coinage.

8. State the composition and use of

i) Monel metal
ii) German silver

9. Complete the following reactions

i) Zn + conc. HNO3 
ii) Zn + 2NaOH 

10. How does the composition of cast iron differ from wrought iron and steel?
 LEVEL – II
1. What is solvent extraction

2. What is Goldsmidt Thermite Process:?

3. What is the main differences between cupellation and poling?

4. Complete and balance the following equations

a) Zn + Fe2(SO4)3  ? + ?
b) CuSO4   ? + ?
heat

c) Al + conc. H2SO4  ? + ? + ?
d) Al2O3 + C + N2   ? + ?
heat

e) Pb + O2 + H2O  ?

5. a) Egg shell is made up of a chemical. In which of the two ores this chemical is
present.
b) How we can remove impurity of Pb in silver and impurity of Cuprous oxide in
copper.

6. Explain the following terms

i) Zone refining (Fractional crystallization)
ii) Electro-refining:
iii) Van-Arkel Method:

7. What is meant by passivity of iron.

8. List the reaction which occur at the various part of the blast furnace during
manufacture of cast iron.

9. The most stable chlorides of Cu, Ag and Au have the stoichiometric composition
CuCl2 AgCl and AuCl3 in which the oxidation states are +2, +1, +3 respectively.
Justify.

10. Complete the reaction

i) 3Cu + conc. 4HNO3 
ii) Cu + conc. 2H2SO4 
iii) Cu2O + 4NH4OH 
iv) 2CuSO4 + 4KI 
15. Assignments (Objective Problems)
LEVEL – I

1. Cupric oxide is reduced to copper by

(A) H2 (B) C
(C) CO (D) All of these

2. Cupric chloride is converted into cuprous chloride by

(A) Zinc (B) SO2
(C) copper (D) All of these

3. White lead is -
(A) Pb(OH)2.PbCO3 (B) 2PbCO3.Pb(OH)2
(C) Pb(OH)2.Pb(CH3COO)2 (D) PbCO3.PbO

4. Cerussite is
(A) PbS (B) PbCO3
(C) PbSO4 (D) SnO2

5. Which alloy of aluminium is used in aircraft industry

(A) duralumin (B) Magnalium
(C) Nickeloy (D) alunico

6. The common impurities present in the bauxite ore are

(A) Fe2O3 and CuO (B) Fe2O3 and PbO
(C) Fe2O3 and SiO2 (D) SiO2 and CuO

7. Froth floatation process is based on

(A) specific gravity of the ore particle
(B) magnetic properties of the ore particle
(C) wetting properties of the ore particle
(D) electrical property o the ore particle

8. The iron manufactured by pudding process is called as

(A) Pig iron (B) cast iron
(C) wrought iron (D) white cast iron

9. Which of the following is a highly deliquescent solid?

(A) FeCl3 (B) FeSO4
(C) CuSO4 (D) All of these

10. The compound undergoing photoreduction is

(A) AgCl (B) AgF
(C) AgNO3 (D) AgBr

11. In aluminotermic process aluminium acts as

(A) an oxidising agent (B) a reducing agent
(C) a flux (D) a solder
12. Poling process is used
(A) for the removal of Cu2O from Cu (B) for the removal of Al2O3 from Al
(C) for the removal Fe2O3 from Fe (D) in all the above

13. Calcination is used in metallurgy to remove

(A) H2O and H2S (B) H2O and CO2
(C) CO2 and H2S (D) H2O and H2S

14. Mac-Aurthur forrest process is used for the extraction of

(A) Zn (B) Cu
(C) Fe (D) Ag

15. Duralumin is an alloy of

(A) Al and Mg (B) Al, Mg, Ni
(C) Al, Mg, Mn, Cu (D) Al and Ni

16. Which of the following precipitates Ag from AgNO3?

(A) Phosphine (B) Arsine
(C) Stibine (D) All of these

17. Schwitzer’s reagent has the composition of

(A) [Ag(NH3)2]Cl (B) Fe4[Fe(CN)6]3
(C) [Cu(NH3)4]SO4 (D) K2[HgI4]

18. The moleten matte obtained after the treatment of copper pyrites in the blast furnace,
has the composition of –
(A) Cu2S (B) Cu2S + FeS
(B) Cu2S + Fe2S3 (D) CuS + Fe2S3

19. Green coloured ore among the following is

(A) Cu2O (B) CuFeS2
(C) CuCO3.(Cu(OH)2 (D) 2CuCO3. Cu(OH)2

20. Bromine is added to cold dilute aqueous solution of sodium hydroxide. The mixture is
boiled. Which of the following statements is not true?
(A) During the reaction bromine is present in four different oxidation states.
(B) The greatest difference between the different oxidation states of bromine is 5.
(C) On acidification of the final mixture, bromine is formed
(D) Disproportionation of bromine occurs during the reaction

21. Zeolite, which shows ion exchange ability -

(A) is an ion exchange resin
(B) is a closed packed assemblage of Si and O – atoms
(C) can provide H+ ions in place of Na+ ions
(D) is a sodium aluminum silicate

22. Stainless steel contains -

(A) Fe, Cr, Cu (B) Fe, Cr, Ni
 (C) Fe, Ni, C (D) Fe, Ni, Cu

23. Books, periodicals, magazines and calendars are printed in large numbers. Type
metal used in printing presses as alphabet letter printing contains -
(A) sulphur (B) chromium
(C) lead (D) copper

24. The metallic lustre exhibited by sodium is explained by the presence of -

(A) Na+ ions (B) conducting electrons
(C) free protons (D) a body centred cubic lattice

25. During Hoope’s process for electrolytic refining of Al, the middle layer is of -
(A) Pure aluminum (B) impure aluminum
(C) cryolite and BaF2 (D) alloys of Al, Ca, Si

26. The silver halide, which is least soluble in NH4OH is

(A) AgF (B) AgCl
(C) AgBr (D) AgI

27. Complex formation method is used for the exraction of

(A) Zn (B) Ag
(C) Hg (D) Cu

28. Auto reduction process is used in the extraction of

(A) Cu and Hg (B) Zn and Hg
(C) Cu and Al (D) Fe and Pb

29. Van Arkel method of purification of metals involves converting the metal to a
(A) Volatile stable compound (B) Volatile unstable compound
(C) non volatile stable compound (D) none of the above

30. Which of the following is not a basic flux?

(A) CaCO3 (B) CaO
(C) SiO2 (D) MgO

LEVEL - II More than one choice

1. Highly pure dilute solution of sodium in liquid ammonia

(a) shows blue colour (b) exhibits electrical conductivity
(c) produces sodium amide (d) produces hydrogen gas

2. Which of the following statements is/are correct about the making of blue prints ?
(a) ferric oxalate or citrate are reduced to ferrous salt on being exposed to light
(b) ferrous salts give blue colour with K3[Fe(CN)6]
(c) ferrous salts give blue colour with K3[Fe(CN)6]
(d) white lines are obtained in place of the ink drawing on a deep blue ground.
3. Amongst the following statements, which is/are not correct ?
(a) [Fe(CN)6]3- is more stable than [Fe(CN)6]4-
(b) [Fe(CN)6]3- is less stable than [Fe(CN)6]4-
(c) [Fe(CN)6]3- gets easily oxidized to [Fe(CN)6]4- in alkaline medium
(d) [Fe(CN)6]3- is reduced to [Fe(CN)6]4- in alkaline medium
4. On going down the group from V to Nb, the metallic radius increases from 134 to 146 pm
whereas the radius of Ta belonging to next higher period in the same group is the same as
that of Nb. This is due to
(a) very poor shielding effect of f-electrons orbital
(b) high shielding effect of f-electrons orbital
(c) lanthanide contraction
(d) actinide contraction

5. Identify the correct statements of the following

(a) Transition metals have high enthalpies of sublimation
(b) the atomic sizes of third series of transition metals are not very much different from
those of second series in respective groups.
(c) Most of the transition metals of first series have negative reduction potentials and hence
react readily with dilute acids to liberate H2.
(d) Cr, Mo and W are very hard metals because of greater number of the covalent bonds
involving unpaired electrons.

6. Which of the following statements is/are correct ?

(a) Anhydrous ferric chloride can be obtained by heating hydrated ferric chloride
(b) A solution of ferric oxalate in dilute H2SO4 will decolorise KMnO4.
(c) Ferric salts are more stable than ferrous salts
(d) The Mohr’s salt is resistant to oxidation by atmospheric oxygen.

7. Which of the following ions disproportionate in aqueous solution ?

(a) Cu+ (b) Cu2+
(c) Au3+ (d) Au+

8. Which of the following complex ions that zinc can form

(a) [Zn(CN)6]4- (b) [Zn(CN)4]2-
2+
(c) [Zn(NH3)4] (d) [Zn(CNS)4]2-

9. Which of the following are correctly matched ?

(a) Hg2Cl2  corrosive sublimate
(b) Hg2Cl2  calomel electrode
(c) HgCl2 + KI (excess) + NH4+  red precipitate
(d) Hg2Cl2  purgative in medicine

10. Which of the following statement is/are true?

(a) Both Hg2+ and Hg22  ions show the divalency
(b) The ionization potentials of 12 group metals are fairly greater then those of coinage
metals yet more reactive than the latter
(c) ionization potential of Hg is smaller than that of Cd
(d) Zn, Cd and Hg exhibit positive oxidation potentials.
 LEVEL - III Other Enginering Exams
1. Cinnabar is an ore of
(a) Hg (b) Cu
(c) Pb (d) Zn

2. Main ore of aluminium is

(a) Bauxite (b) Corundum
(c) Cryolite (d) magnetite

3. The ore carnalite is represented by structure :

(a) Na2Al2O3 (b) Na3AlF6
(c) KCl.MgCl2 6H2O (d) Fe3O4

4. Forth floatation process is used for the concentration of

(a) Oxide ores (b) Sulphide ores
(c) Chloride ores (d) Amalgams

5. Copper pyrites are concentrated by

(a) Electromagnetic method (b) Gravity method
(c) Froth floatation process (d) All the above methods.

6. Heating of pyrites in air for oxidation of sulphur is called.

(a) Roasting (b) Calcination
(c) Smelting (d) Slagging

7. The substance with is mixed with the ore for removal of impurities is termed as
(a) Slag (b) Gangue
(c) Flux (d) Catalyst

8. In the manufacture of iron lime stone added to the blast furnace, the calcium ion ends in the
form of
(a) Slag (b) Gangue
(c) Calcium metal (d) CaCO3
9. The slag obtained during the extraction of copper from copper pyrites is composed mainly of
(a) CaSiO3 (b) FeSiO3
(c) CuSiO3 (d) SiO2

10. Silver obtained from argentiferrous lead containing lead impurity is purified by
(a) Distillation (b) Froth floatation
(c) Cupellation (d) Treatment of KCN

SECTION - III
A Matrix-Match Type

1. Match the following column I and Column II

Column – I Column - II
(A) Zn (p) Self reduction
 (B) Ag (q) Fused salt electrolysis
(C) Ca (r) Carbon reduction
(D) Cu (s) Amalgamation
2. Match the following column I and Column II
Column – I Column - II
(A) Galena (p) PbS
(B) Cassiterite (q) KCl. MgCl2. 6H2O
(C) Bauxite (r) Al2O3. 2H2O
(D) Carnallite (s) SnO2

B Linked Comprehension Type

Comprehension - I
Metals are extracted from their ores by a wide variety of techniques. The most common ores
are oxides MnO2,Al2O3,SnO2), sulfides (PbS, ZnS), chlorides (NaCI, KC1, CaCI2, MgCl2),
and phosphates (Ca3 (PO4 )2). Most metals are obtained by direct treatment of their ores
with chemical agents, but the extraction of certain other requires electrolysis. An example of
the former type of process is the extraction of iron from its oxide, described by the following
equation :
Fe2O3 + 3C  2Fe + 3CO
The relative case of extraction of a metal from its oxide can be estimated using the
Ellingham diagram, which is shown in Figure -1. This diagram plots the free energies of
formation of various oxides per mole of consumed oxygen as a function of absolute
temperature.
G°f
(kJ)
CO O3
Fe2 CO2

1000 2000 T(K)

Electrolytic extraction proceeds in three steps (see equations). In the first step, the crystalline
lattice of the ore is thermally disintegrated to form a liquid containing free metal cations. In
the second step, the metal cations are stabilized by solvating them with some thermally
stable non-aqueous solvent (NAS). In the final step, an applied electric potential reduces the
cations to neutral atoms.
Step-1 Ore(s)  Mn+ (l)
Step-2 Mn+ (l)  Mn+ (solvated)
Step-3 Mn+ (solvated) + ne  M

Extraction of a metal is usually preceded by enrichment of the ore. Some ores can be
concentrated after pulverization by the use of specific collectors such as salts of organic
acids and bases, which make the ores hydrophobic and thus separable from hydrophilic
admixtures. Other enrichment techniques include density separation and magnetic
separation.

1. All of the following agents could be used to extract lead from its oxide EXCEPT.
(a) molecular fluorine (b) molecular boron
 (c) molecular nitrogen (d) elemental carbon

2. If for a certain ore the enthalpies of steps-1 and 2 were 248.50 and 250.25 kJ, respectively,
which of the following would determine the rate of extraction?
(a) The lattice energy of the ore
(b) The solvation energy of the metal cations
(c) The magnitude of the electric potential used
(d) The size of the metal cations

3. For the extraction : 2CaO (s) + C (s) —— 2Ca (s) + CO2 (g)
the standard free energy change of the forward reaction is 814.1 kJ. According to this data,
standard conditions are likely to favor :
(a) the forward reaction
(b) the reverse reaction
(c) both forward and reverse reactions
(d) neither the forward not the reverse reaction

4. Which of the following best explains why the free energy of formation of Fe2O3 become less
negative as the temperature increases?
(a) The free energy of formation is independent of the absolute temperature
(b) Entropy drops as a result of the consumption of oxygen
(c) At low temperature, the free energy of formation become less dependent on the enthalpy
of formation
(d) As entropy increases, the free energy of formation increases

5. Elemental carbon is most likely to reduce Fe2O3 in which of the following temperature
ranges?
(a) 500- 1000 K (b) 500-1500 K
(c) Below 1000 K (d) Above 1000 K

6. When ferric oxide is reduced to obtain iron metal, CO 2 or CO can be produced. The
production of CO :
(a) is directly proportional to the temperature
(b) is inversely proportional to the temperature
(c) is independent of the temperature
(d) requires cooling of the CO

Comprehension - II
Standard Electrode Potentials and Metallurgy: The method employed for extracting a
metal from its ore /depends on the nature of the metal, that of the ore and may be related to
the position of the metal in the electrochemical series. In general, metals with reduction
potential less than  0.5 volt yield compounds which are very difficult to reduce. Such metals
are isolated by electrolysis. On the other hand noble metals with reduction potential + 0.5
volt form easily reducible compounds.
The standard electrode potential of a metal is a measure of its tendency to go into solution
as hydrated ion. On the other hand, in metallurgical extractions we generally come across
ores which are to be reduced to the metallic state. Thus, it may be said that a metal higher
up in the electrochemical series should be more difficult to reduce to metallic form. As we
move down, the reduction becomes more and more easy. However, it must be borne in
mind that this is a very general statement and cannot be strictly applied because metals are
seldom extracted from aqueous solutions.
 Energy Factors and Electrode Potentials - The heat of sublimation (5) of solid metal, the
ionization energy (I) of gaseous metal atom and the heat of hydration (H) of gaseous ion are
the contributory factors towards electrode potential (£). These factors may be consolidated
in a Born-Haber type of cycle.
M E M++ 
(so
lid
) (a
q) e

S
H

M I + 
(g
ase
ous) M
(g
ase
ous)+e
Thus, E = + S + I  H
S and I are positive because energy is supplied while H is negative as the process of
hydration is an exothermic one liberating heat.
As expected, ionization energies of alkali metals follow the trend : Li > Na > K > Rb > Cs. It
means Li has the least tendency to lose electron among a alkali metals. However, from
electrochemical series we find that lithium is the most reducing in character (E° for
Li
 3.05 volt ). The anomalous behavior of Li is understandable from the fact that heat of
Li
hydration of its ion is highest because of small size. The contribution of this hydration factor
towards electrode potential makes Li even more reducing than Na or K.

7. Arrange the metals A, B, C, D, E in order of electrochemical series if:

A  H2SO4   ASO4  H2 ; ACl2  C   CCl2  A
ECl2  C 
Noreaction; 2BCl  D 
DCl2  2B
(a) ABCDE (b) ECADB
(c) BDAEC (d) ADBEC

8. The standard reduction potentials at 298 K for the following half reactions are given against
each
Zn2+ (aq) + 2e Zn(s)  0.762
Cr3+ (aq) + 3e Cr(s)  0.740
2H+(aq) + 2e H2(g) 0.000
3+ 2+
Fe (aq) + 3e Fe (aq) 0.770
which is the strongest reducing agent?
(a) Zn(s) (b) Cr(s)
(c) H2(g) (d) Fe2+(aq)

9. The incorrect statement among the following is

(a) the first ionisation potential of Al is less than the first ionisation potential of Mg
(b) the second ionisation potential of Mg is greater than the second ionisation potential
of Na
(c) the first ionisation potential of Na is less than the first ionisation potential of Mg
(d) the third ionisation of Mg is greater than third ionisation of Al.

10. Which is the correct order of degree of hydration of the following ions?
(a) Na+ >K+ > Rb+ >Cs+ > Li+ > Be2+
(b) Cs+> Rb+> K+> Na+ > Be2+ > Li+
(c) Li+ >Be2+ >Na+ > K.+ > Rb+ > Cs+
(d) Be2+ > Li+ > Na+ > K+ > Rb+ > Cs+
11. How can alkali metals be extracted?
(a) Reduction of their oxides
(b) Displacement from their salt solution by any other element
(c) Electrolysis of their fused salts
(d) Electrolysis of their aqueous salt solutions

12. The Born Haber cycle for rubidium chloride (RbCl) is given below (the energies are
in kcal-mol1)

105
R
b(s) +1
/2C
l(
2g) R
bCl(s)
2
8.7
5
+
20.5
x 
159.5
l
C
l(g
)
C (g)
+
R
b(g
) 9
6.0 R
b (g
)
What is the electron affinity of chlorine.
(a)  105 kcal/mole (b)  90.75 kcal/mole
(c) 14.5 kcal/mole (d) 25.75 kcal/mole

Comprehension - III

Electrolysis is an imporant technique for extraction of metals, and each ion of the solution
needs a minimum voltage to get discharged and this value is expressed in terms of
dischanrge potential. For some metal ions the discharnge potentials follow the order given
below:
Li+ > K+ > Ca2+ > Na+ > Mg2+ > Al3+ > Zn2+ > Fe2+ > Ni2+ > H3O+ > Cu2+ > Hg22+ > Ag+ > Au3+
For some anions the discharge potentials are in the order :
SO42- > NO3- > OH > Br > I

13. When aqueos solution of cupric bromide is electrolyzed the product obtained at cathode will
be
(A) Cu (B) H2
(C) Br2 (D) O2

14. The product formed at anode and cathode, when dilute H2SO4 is electrolysed are :
(A) SO2, H2 (B) SO3, H2
(C) H2S2O8, H2 (D) O2, H2

15. A mixture containing chlorides of soidum, calcium and zinc is electrolysed in presence of
water. The product obtained at cathode will be:
(A) Na (B) H2
(C) Ca (D) Cl2

16. When conc. H2SO4 is electrolysed with high current using Pt electrodes, the product
obtained at anode is
(A) SO2 (B) SO3
(C) O2 (D) H2S2O8
 16. Answers to Objective Assignments
LEVEL – I
1. (D) 2. (D)
3. (B) 4. (B)
5. (A) 6. (C)
7. (C) 8. (C)
9. (D) 10. (D)
11. (B) 12. (A)
13. (C) 14. (D)
15. (C) 16. (D)
17. (C) 18. (B)
19. (C) 20. (A)
21. (D) 22. (B)
23. (C) 24. (C)
25. (C) 26. (D)
27. (B) 28. (A)
29. (A) 30. (C)

LEVEL - II

1. (A), (B) 2. (A), (B), (D) 3. (B), (C) 4. (A, (C)

5. (A), (B), (D) 6. (B), (C), (D) 7. (A), (D) 8. (B), (C), (D)
9. (B), (D) 10. (A), (B)

LEVEL - III

1. (A) 2. (A) 3. (C) 4. (B)

5. (C) 6. (A) 7. (C) 8. (A)
9. (B) 10. (C)

LEVEL - IV
A B
Match the following Write-up
1. (A) – (r) 1. (A) 2. (C)
(B) – (s) 3. (B) 4. (B)
(C) – (q) 5. (A) 6. (C)
(D) – (p) 7. (B) 8. (A)
2. (A) – (p) 9. (B) 10. (D)
(B) – (s) 11. (C) 12. (B)
(C) – (r) 13. (A) 14. (D)
(D) – (q) 15. (B) 16. (D)
 Ores and Metallurgy
Subjective Problems
LEVEL – I

1. a) 2Al(OH)4  CO 2  2Al(OH)3  CO 32   H2O

b) Ag+ + 2Na2S2O3  Na3[Ag(S2O3)2] + Na+
c) MnO 4 + H2S  Mn2++ SO2 + 2OH–

exc es s of KI
HgS   HgO 
 HgCl2      K2HgI4
roas ting Cl2
2.
(A) (B) (C) (D)

alkaline (NH4)SO4

HgOHg(NH2)I
(Brown ppt)
(E)

3. a) Pb3O4 is a mixed oxide, 2PbO, PbO2, with nitric acid PbO is converted to
Pb(NO3)2 while PbO2 remains as such
Pb3O4 + 2HNO3  PbO2 + Pb(NO3)2 + H2O
b) ZnO is dissolved as Zincate ion
ZnO + 2NaOH  Na2ZnO2 + H2O
c) Tin reduces nitric acid (dilute) to ammonia
4Sn + NO 3 + 10H+  4Sn2+ + NH 4 + 3H2O
d) Gold dissolves in aqua regia as HAuCl4
Au + 4HCl + 3HNO3  HAuCl4 + 3NO2 + 3H2O

e) 4Fe + 10HNO3  4Fe (NO3)2 + NH4NO3 + 3H2O

f) White precipitate changes to yellow, brown and finally becomes black
S2O32   Ag  Ag2S2O3
( white)

Ag2S2O3  H2O  Ag2S H2SO 4

(Black)


g) ZnCl22H2O  ZnCl(OH) + HCl + H2O

4. In presence of moist air a thin film of green basic copper carbonate is formed on its
surface and hence copper corrodes

2Cu + O2 + H2O + CO2  CuCO 3  Cu(OH)2

green
5. In presence of organic matter (skin) and light, AgNO3 decomposes to produce a
black stain of metallic silver
2AgNO3  2Ag + 2NO2 + O2

6. FeOCr2O3 + 4C   2Cr + Fe + HCO

electric
furnace
Ferrochrome (Fe 35%, Cr 65%) is used in steel industry.

7. Ni coins = Cu 75% + Ni 25%

Guinea gold = Au 91%, Cu 9%

8. i) Monel metal: Cu30% + Ni 67% + Fe, Mn 3% used for acid pumps and acid
container.
ii) German silver: Cu 50% + Zn 25% + Ni 25% used for utensils, resistance coils.

9. i) Zn + conc. HNO3  Zn(NO3)2 + 2H2O + 2NO2

ii) Zn + 2NaOH  Na2ZnO2 + H2

10.
C% Si % S% Mn% P%
Cast iron 2 – 4.5 0.7 – 3.5 0.1 – 0.3 0.5 – 1.0 0 – 0.3
Steel 0.1 – 1.5 0.03 – 2.0 0.02 – 0.2 0.1 – 4.0 0.04 – 0.07
Wrought iron 0.04 – 0.25 0 – 0.14 0.02 – 0.15 Up to 0.25% 0.04 – 0.2

LEVEL – II

1. Solvent extraction is the latest separation technique and has become popular
because of its elegance, simplicity and speed. The method is based on preferential
solubility principles.

Solvent or liquid-liquid extraction is based on the principle that a solute can distribute
itself in a certain ratio between two immiscible solvents, one of which is usually water
and the other an organic solvent such as benzene, carbon tetrachloride or
chloroform. In certain cases, the solute can be more or less completely transferred
into the organic phase. The technique can be used for purpose of preparation,
purification, enrichment, separation and analysis.

2. 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.

Cr2O3 + 2Al  Al2O3 + 2Cr

3Mn3O4  4Al2O3 + 9Mn

The reaction is highly exothermic and the heat produced is sufficient to melt the
metal.

3. Both cupellation and poling are used for refining of metals, cupellation is contain
impurities of other metals with traces of lead are removed from silver by heating
 impure silver with a blast of air in a cupel (an oval shaped pan made up of bone ash)
in which lead is oxidised to lead oxide (PbO) which being volatile escapes leaving
behind pure silver.

Poling is used for refining of such metals which contain impurities of its own oxide. In
this process, the molten impure metal is stored with green wooden poles. At the high
temperature of the molten metal, wood liberates methane which reduces the oxide of
the metal to free metal.

3Cu2O + CH4  6Cu + 2H2O + CO

4. a) Zn + Fe2(SO4)3  ZnSO4 + 2FeSO4


b) CuSO4  CuO +SO3
c) 2Al + conc. 6H2SO4  Al2(SO4)3 + 3SO2 + 6H2O

d) Al2O3 + 2C + N2  2AlN + 3CO
e) 2Pb + O2 + 2H2O  2Pb (OH)2

5. a) Limestone CaCO3
Dolomite CaCO3.MgCO3
b) Impurity of lead in silver can be removed by cupellation method and impurity of
cuprous oxide in copper can be removed by poling.

6. i) Zone refining (Fractional crystallization) This method is employed for preparing

extremely pure metals. This method is based upon the principle that when a
molten solution of the impure metal is allowed to cool, the pure metal crystallizes
out while the impurities remain in the melt.

ii) Electro-refining: In this method, the impure metal is converted into a block which
forms the anode while cathode is a rod or plate of pure metal. These electrodes
are suspended in an electrolyte which is the solution of a soluble salt of the metal
usually a double salt of the metal. When electric current is passed, metal ions
from the electrolyte are deposited at the cathode in the form of pure metal while
an equivalent amount of metal dissolves from the anode and goes into the
electrolyte solution as metal ion. The soluble impurities present in the crude
metal anode go into the solution while the insoluble impurities settle down below
the anode as anode mud.

iii) Van-Arkel Method: In this method, the metal is converted into it volatile unstable
compound such as iodide leaving behind the impurities. The unstable compound
thus formed is decomposed to get the pure metal.
1700K
Ti(s) + 2I2(s) +   TiI4(g) 
540K
 Ti + 2I2(g)
Ti( s )

7. When iron is treated with concentrated HNO3 it stops showing its normal behaviour
such as liberation of H2 from dil. H2SO4 and precipitation of Cu from CuSO4 solution.
This phenomenon, when iron shows chemical inertness, is called passivity.

If iron is treated with certain oxidizing agents such as H2CrO4, KMnO4 etc., then also
it becomes passive. In fact passivity of iron is suggested as formation of thin
protective layer of Fe2O3 which prevents reaction of iron at room temperature.
8. Zone of fusion (1200°C – 1500°C)
C + O2  CO2
CO2 + 2CO
Top section (4000°C – 900°C)
400°°C
Fe2O3 + 3CO 2Fe + 3CO2
500-700°C
3Fe2O3 + CO 2Fe3O4 + CO2
700-900°C
Fe3O4 + CO 3FeO + CO2
FeO + CO Fe + CO2
Fe2O3 + 3C 2Fe  3CO 
Spongy iron

Middle section (900°C)

CaCO3 CaO + CO2
CaO + SiO2 CaSiO3 (slag)
2Ca3(PO4)2 + 6SiO2 + 10C  6CaSiO3 + 10CO + 4P
3Fe + P  Fe3P

9. The (+1) state is expected to be the common and most stable for Cu, Ag and Au as
they posses table d10 configuration. But only Ag+ is stable both in solid state and
solution, which Cu+ and Au+ disproportionate very fast in H2O
[Cu 2  ]
2Cu+ Cu2+ + Cu K= = 1.6  106
[Cu  ]2
[ Au3  ]
3Au+ Au3+ + 2Au K= = 1  1010
[ Au ]3

10. i) 3Cu + conc. 4HNO3 Cu(NO3)2 + 2NO2 + 2H2O

ii) Cu + conc. 2H2SO4  CuSO4 + SO2 + 2H2O
iii) Cu2O + 4NH4OH  2[Cu(NH3)2]OH + 3H2O
iv) 2CuSO4 + 4KI  2CuI2 + 2K2SO4