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Vidyamandir Classes Basic Principle of Extraction

Basic Principle of Extraction

NEEDS FOR EXRACTION OF METALS Section - 1

We all use metals in our day to day life sometimes directly and sometimes indirectly. For example, Iron is
used making electromagnets, chains, etc. Steel is used in making machinery parts, household utensils. Silver
and gold are used in making jewellery. We can find numerous examples where we use metals. Since metals
do not occur in pure form in earth’s crusts, we need to extract metals from their ores or minerals.
Occurrence of Metals :
Metals occur in various forms. Some in native form, some in carbonate form and some in oxide form. Those
metals that are least reactive and have very little affinity for oxygen, moisture and other chemical reagents
occure in free or metallic or native state.
 Natural substances in which metals or their compounds occur in earth are called minerals.
 Those minerals form which metals can be extracted conveniently and proditably are known as ores.

llustration :
A certain metal M occurs in three compounds namely A, B, C. A has 15% of M, B has 66% of M and C has
71% of M. If we extract M from A, it costs Rs 35 per kg, if we extract it from B, it costs Rs 45 per kg and
if we extract from C, it costs Rs 1110 per kg.
Now both A, B, C are minerals as they contain M, but all cannot be called ores. Extraction of M from
mineral A would cost less but would result in a very less amount. Similarly, extraction from C would result in
large amount but it will also cost a large sum. Hence, B is the appropriate mineral from which M should be
extracted as it would give sufficient amount and would not even cost much. In that case, B is the ore of M.
for example : Bauxite (Al2O3 .2 H 2O) and Clay (Al2O3 .2SiO 2 .2 H 2O) both are minerals of Aluminium.
But still Bauxite is appropriate ore but not Clay since we can extract Aluminium more profitably and quan-
titatively from Bauxite.
Commercially Important Ores :
1. Native Ores :
These ores contain metals in the free state. They exist in free state because they are very unreactive.
Some of important metals are :
2. Sulphurised and Arsenical ores :
These ores consists of sulphides and arsenides in simple and complex forms of metals.

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Metal Name of the ore

Pb Galena PbS
Zn Zinc blende ZnS
Hg Cinnabar HgS
Ag Argentite or Silver glance Ag2S
Fe Iron pyrites FeS2
Cu Copper pyrites CuFeS2
Chalcocite or Copper glance Cu2S

3. Oxidised Ores
In these ores, metals are present as their oxides or oxy-salt as carbonates, nitrates, sulphates, phosphates,
silicates, etc.
Oxides : Haematite Fe 2O 3
Magnetite Fe3O4
Bauxite Al2O3.2H2O
Corundum Al2O3
Chromite FeO.Cr2O3
Tinstone (Cassiterite) SnO2
Pyrolusite MnO2

Carbonates : Magnesite MgCO3

Lime stone CaCO3
Dolomite CaCO3.MgCO3
Calamine ZnCO3
Malachite CuCO3.Cu(OH)2
Azurite Cu(OH)2.2CuCo3
Cerussite PbCO3
Siderite FeCO3

Nitrates : Chile saltpetre NaNO 3

Salt petre KNO 3

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Sulphates : Epsom salt MgSO4.7H2O

Gypsum CaSO4.2H2O
Glauber’salt Na2SO4.10H2O

Phosphates and Sillicates :

Fluor-apatite 3Ca3(PO4)2.CaF2
Felspar KAlSi3O8

4. Halide Ores :
Metallic halides are very few in nature. Chlorides are most common ores.
Common salt NaCl
Horn silver AgCl
Carnallite KCl.MgCl2.6H2O
Fluorspar CaF2
Cryolite Na3AlF6

Note : You Don’t need to cram all these compounds in one go. As you will read the chapter these com-
pounds will slowly set in your mind.

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METALLURGY Section - 2

The complete process of obtaining a pure metal from one of its ores is known metallurgy. The method to
extract a metal is generally not universal, as it depends upon a number of factors such as its chemical nature
and reactivity, nature of ore, nature of impurities and local conditions, etc. But still in general, metallurgy is
divided into following three steps.
I. Concentration of the Ore
II. Obtaining Crude Metal from Concentrated Ore
III. Refining of Crude Metal
Different methods are available for each of these stages. Choice of any method depends upon the nature
of metal and type of impurity present in the ore.
I. Concentration of the Ore :
Concentration of an deals with removal of unwanted impurities. Ores usually contain soil, sand, stones and
other useless silicates. These unwanted impurities are named gangue or matrix. For concentration, metal is
crushed and powdered and then it undergoes concentration. Concentration of ore involves physical as
well as chemical methods. It is also known as Dressing or Benefication of the ore.
(i) Hydraulic Washing (Gravity Separation)
Principle :
It is based on the difference in specific gravity of ore and gangue particles.
Working :
Powdered ore is agitated with running water which carries lighter particles like sand, clay away with
it.

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Type of Ore :
The oxides and carbonates type of ores are suitable for this method. For example : Tin’s ore Cassiterite
(SnO 2 ), Iron’s ore Haematite (Fe 2O3 ).

(ii) Magnetic Separation

Principle :
It is based on the magnetic and non-magnetic properties of ore and gangue.
Working :
A magnetic separator consists of a belt which moves on two rollers, one of the roller being a strong
magnet. Now, the powdered ore is dropped on the belt near the non-magnetic roller and as the ore
reaches the magnetic roller the magnetic particles get attracted and fall nearer to the roller while the
non-magnetic particles fall away from the rollers.

Type of Ore :
Separating Wolframite (Tungsten) ore from Cassiterite (Tin) ore, separating transition metal ores such
as Magnetite (Fe3O4 ), Pyrolusite (MnO2 ) and Chromite (FeO, Cr2O3 ) from unwanted gangue.
(iii) Froth Floatation
Principle :
Mineral particles are wetted by oils and the gangue particles are welled by water.
Working :
Collectors, frothing agents and froth stabilisers are added to the ore which mixed water. Collectors
enhance the non-wettability of mineral particles and froth stabilizers stabilize froth. Mineral particles
become wet by oils while gangue particles by water. Liquid mixture is agitated and air blown. Froth
is formed which carries off with it mineral particles. Light froth floats at the surface which is taken off
and from this froth mineral is recovered.

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Frothing agents : Pine Oil

Collectors : Fatty acids, Sodium Ethyl Xanthate
Froth Stabilizers : Cresols and Aniline
Depressants :
These are those chemicals that are used to prevent certain type of particles from forming the froth with
the bubbles. For example : NaCN (sodium cyanide) acts as a depressant in preveting ZnS from
forming the froth as it forms a layer of Na 2 Zn(CN)4 on surface of ZnS in concentration of zine
blende (ZnS). This is also known as selective frothing.
Type of Ore :
Sulphide ores eg: Galena (Pbs), Zinc blenda (ZnS), Cinnabar (HgS).
(iv) Chemical Separation (Leaching)
Principle :
It is based on the differences in the chemical properties of the ore and the gangue.
Working :
Ore is made soluble in a solvent and is then separated from the gangue. The solvent’s choice depends
upon the ore and gangue’s chemical properties.
Example :
1. In Bayer’s process, the impurities of iron and silicon are removed from the bauxite ore.
NaOH is added to the ore and as Al is amphoteric it dissolves forming sodium aluminate.
SiO2 being acidicoxide also dissolves as silicate ions. The insoluble iron impurities are re
moved by filtering. Next, CO 2 is bubbled through the solution lowering the pH. This enables
the precipitation of Al(OH)3 (sili-cate ions remain dissolved). The Al(OH)3 precipitated is
calcined (heated strongly) to give concentrated Al2O3 .

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 Na[Al(OH) 4 ] + SiO44 
Al2O3 + SiO2 + NaOH 

Na[Al(OH)4 ] + CO2 
 Na 2CO3 + Al(OH)3 ()


Al(OH)3(s)  Al2O3 + H 2 O()

2. Cyanide’s Process
Another example is the cyanide’s process for extraction of Au (from native form) and Ag (from
Ag 2S ore). The ore containing impurities is curshed and then treated with 0.1 – 0.2% soluton of
NaCN or KCN and aerated forming a soluble complex from complex which the metal is extracted
by the addition of Zn power in the solution.
For Au : 4 Au + 8 NaCN + 2 H 2O + O 2 
 4 Na[Au(CN)2 + 4 NaOH

2 Na[Au(CN)2 ] + Zn 
 Na 2 [Zn(CN)4 ] + 2 Au()

For Ag : Ag 2S + 4 NaCN  2 Na[Ag(CN)2 ] + Na 2S

2 Na[Ag(CN)2 ] + Zn 
 Na 2 [Zn(CN)4 ] + 2 Ag()

II. Obtaining Crude Metal :

This step involves reduction of concentrated ore. The concentrated ore i.e. Metal oxides, Metal sulphides,

Metal carbonates etc. are converted to metal in this step. M n+   M reduction occurs in this step.
Metal cabonates and Metal sulphides are difficult to reduce than metal oxides therefore they are first converted
to their oxides and then metal oxides is reduced to metal.
Conversion into Oxide Forms
Metallic ores are converted to metallic oxides by the two processes.
1. Calcination :
It involves heating of the ore below its fusion temperature in absence of air. It can remove moisture
from hydrated oxides or carbondioxide from carbonates. It is suitable for carbonate ores.


CuCO3 .Cu(OH)2 
 2CuO + CO2 + H 2O


ZnCO3 
 ZnO + CO2
Calcination makes the ore porous. The step is generally performed in a reverberatory furnace.

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2. Roasting :
It involves heating of the ore strongly in the presence of excess of air below its fusion temperature. It
is suitable for sulphide ores.

2 ZnS(s) + 3O2 (g) 
 2 ZnO(s) + 2SO2 (g)
Sometimes, a part of sulphide may act as a reducing agent as in case of extraction of lead.
PbO formed by roasting is reduced to lead by PbS.

2 PbS + 3O2 
 2 PbO+ 2SO2

PbS + 2 PbO 
 3Pb + SO2
Exception :
O
2  Cu S + Fe O + 3SO
2CuFeS2  2 2 3 2
1400° C

Note : Oxide ores are suitable for reduction. So, if we obtain ore in oxide form just after concentration as in case
of aluminium, then this ore is not required to undergo calcination and roasting as it already exists in oxide
form.

Reduction to Crude Metal

When the oxide form is obtained, then the metal has to be reduced. The choice of the reducing agent is
decided by the factors of energetics and economics.
Three main categories of reduction processes are :
(A) Chemical Reduction (B) Hydrometallurgy (C) Electrolytic Reduction
Now, we will discuss few important points of each category.

(A) Chemical Reduction Process

Carbon, Aluminium, Hydrogen and some other metals are used as reducing agents. These metals replace
less electropositive metals from their oxides.
(i) Reduction by carbon :
Carbon can be used to reduce a number of oxides and other compounds, and because of the low cost
and avilability of coke this methods is widely used. The disadvantages are that a high temperature is
needed, which is expensive and necessitates the use of a blast furance. Also, many metals combine
with caron, forming carbides, some examples are :
blast 1200C
Fe2 O3  C  Fe ; ZnO  C 
 Zn
furnance
electric electric
Ca 3 (PO4 )2  C 
P ; MgO  C  Mg
arc furnance

PbO  C 
 Pb

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(ii) Reduction by another metal :

If the temperature needed for carbon to reduce an oxide is too high for economic or practical purposes,
the reduction can be done by another highly electropositive metal such as Al, which liberates a large
amount of energy on oxidation to Al2O3. This is the bases of the thermite process : -

 9Mn  4Al2O3 ;
3Mn 3O4  8Al  B2O3  2Al 
 2B  Al2O3

Cr2O3  2Al 
 2Cr  Al2O3
Magnesium being more electropositive metal as compared to Al is used to reduce halides.
1000C
TiCl4  2Mg 
 Ti  2MgCl2

(iii) Reduction of oxides with hydrogen

This method is not widely used because many metals react with hydrogen at elevated temperatures,
forming hydrides.

Co3O4  4H 2 
 3Co  4H2O

2NH4 [MoO4 ]  7H 2 
 2Mo  8H2O  2NH 3
(iv) Self Reduction Process
The sulphide ore of less electropositive metals like lead, mercury, copper are heated in air as to
convert part of the ore into oxide or sulphate which then reacts with the remaining sulphide ore to
give the metal and SO2 gas.
No external reducing agent is used in this process.
Lead : 2 PbS  3O 2 
 2 PbO  2SO 2 (Extraction of lead from Galena, PbS)
2 PbO  PbS 
 3Pb  SO 2

Copper : 2 Cu 2S  3O 2 
 Cu 2O  2SO 2 (Extraction of copper from copper glance, Cu2S)
Cu 2S  2 Cu 2O 
 6 Cu  SO2

Mercury : 2HgS  3O 2 
 2 HgO  2SO 2 (Extraction of mercury from cinnabar, HgS)

2 HgO  HgS 
 3 Hg  SO 2

Another name for self reduction process is auto reduction process or air reduction process.
(B) Hydrometallurgy
This process is based on the principle that more electropositive metals can displace less electropositive
metals from their salt solution. The ore is treated with such chemical reagents which convert it into soluble
compound. By addition of more electropositive metals to the filtrate, the metal present in the ore can be
precipitated.

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Illustration :
Malachite ore is first calcined and the oxide obtained is dissolved in H2SO4. To the solution of CuSO4,
scrap iron is added which precipitates copper.

CuCO3 .Cu(OH) 2 
 2CuO  CO2  H 2O

CuO  H 2SO4 
 CuSO4  H 2O
(soluble)

CuSO4  Fe   FeSO4  Cu 
(soluble)
Similarly, silver can be obtained by cyanide process.
(C) Electrolytic Reduction
Oxide of highly electropositive metals like Na, K etc cannot be reduced with carbon at moderate temperature.
So, for their reduction, a very high temperature is required, at which they may combine with carbon to form
carbide. Thus, they are obtained by electrolysis of their oxides in fused or molten state.
Illustration :
Sodium is obtained by the electrolysis of fused mixture of NaCl and CaCl2 (Down’s Process) or by the
electrolysis of fused NaOH (Castner’s process).
 Na+ + Cl
NaCl (molten) 
Cathode : Na+ + le 
 Na
Anode : 2Cl 
 Cl2 + 2e

Similarly aluminium is obtained by the electrolysis of alumina mixed with cryolite.

(III) Refining of Crude Metal
The crude metal obtained is impure. The impure metal is subjected to some purifying processes
known as refining in order to remove the impurities. The processes used for refining depend upon the
nature of the metal and the nature of impurities.
(A) Distillation (B) Liquation (C) Pyrometallurgical Oxidation
(i) Cupellation (ii) Bessemerisation (iii) Poling
(D) Electrolytic Refining (E) Special Methods
(i) Mond’s Process (ii) Van Arkel Method (iii) Zone Refining

(A) Distillation
This process is used for those metals which are easily volatile such as: Zn, Hg, Cd. The impure metal is
heated in a furnace and its vapours are separately condensed in a receiver. The non-volatile impurities are
left behind in the furnace.

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(B) Liquation
This process is based on the difference in fusibility of metal and impurities. When the impurities are less
fusible than the metal, this process is employed. The impure metal is placed on the sloping hearth of the
furnace and gently heated. The metal melts and flows down leaving behind the impurities on the hearth. This
method is used to purify Bi, Sn, Pb and Hg.

(C) Bessemerisation (Pyrometallurgical oxidation)

The impure metal is heated in a furnace and a blast of compressed air is blown through the molten mass.
The impurities get oxidized. For example, the molten pig iron is taken in a Bessemer converter and compressed
air is passed which oxidizes the impurities.
2Mn + O2 
 2MnO ; Si + O2 
 SiO2
2C + O2 
 2CO ; MnO + SiO2 
 MnSiO3 (slag)

(D) Electrolytic Refining

It is different from electrolytic reduction. The impure metal is made anode and a thin sheet of pure metal is
made cathode.
As electrolysis proceeds, pure metal from anode is transferred to the cathode, whereas the impurities settle
down as anodic mud or anodic sludge. For examples Cu, Ag, Au, Pb, Zu, etc. are refined by this method.
(E) Special methods for Refining
(i) Mond’s Process
It is used mainly for refining of nickel. Impure Ni is treated with carbon monoxide at 330K  350K,
when volatile compounds Ni(CO)4 is formed.
The impurities are left behind and the volatile Ni(CO)4 is transferred into another container, where it is
heated more strongly at 450 K to give pure Ni. The CO gas produced is used again.

330  350 K 450K  470K

 Ni  CO 4  Ni  4CO
Ni  4 CO 
Im pure Volatile and (Pure)
highly toxic

(ii) Van Arkel Method

In this method, zirconium (or titanium) is heated in iodine vapour at about 870K to form volatile ZrI4.
The vapours of volatile ZrI4 are then decomposed electrically over tungsten filament to get pure metal,
and iodine is recovered.
870K 2075K
Zr  2 I2  ZrI 4 
 Zr  2 I2
(Im pure) (Vapours) (Pure)

As Van Arkel method and Mond’s process are quite related they are known as Vapour Phase
Refining.

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(iii) Zone Refining

This method is used for extracting ultra-pure metals. This method is based upon the principle that
when a molten solution of impure metal is allowed to cool, the pure metal crystallizes out, while the
impurities remain in the melt. A movable heater is fitted at one end of the rod of impure metal. The
heater is slowly moved across the rod. The metal melts at the point of heating and as the heater moves
on from one end of the rod to the other end, the pure metal crystallizes while the impurities pass into
the adjacent melted zone. This process is repeated number of times unless metal of desired purity is
obtained. The process is carried out in an inert atmosphere to prevent the oxidation of metal. For
example, Germanium, Silicon and Gallium for being used in semiconductors are purified by this method.

Important Terms
1. Flux
Flux is a substance which is added to remove non-fusible impurities by forming slag and decrease the
melting point of the melt during reduction. Flux can be of three types :
(a) Acidic flux - It is used to remove basic impurities. Examples of acidic flux include SiO2 (in
smelting of Cu) and borax.
(b) Basic Flux - It is added to remove acidic impurities. Examples include Fe2O3, CaCO3 (in
blast furnance) etc.
2. Furnance
A furnance is a structure built to produce high temperature. Examples of some farnaces are
reverberatory furnance, blast furnance and muffle furance.
3. Refractory materials
These are compounds / mixtures which can withstand very high temperature without melting and are
not affected by slags. They are used in the form of bricks for internal lining of furnaces.
Referectory materials may be of three types :
(a) Acid Refractories - SiO2, quartz.
(b) Basic Refractories - CaO(lime), magnesite, dolomite.(in blast furnance)
(c) Neutral Refractories - Graphite (used in Hall Heroult Process), Chromite, bone ash.

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IN - CHAPTER EXERCISE - A

1. List five ores which are smelted and give equations to show what occurs during smelting.
2. Name the process(es) used for concentration of tinstone.
3. Explain the role of collectors and froth stabilisers in Froth floation process.
4. Why is reduction by hydrogen not widely used.
5. Name three ores which undergo autoreduction give balanced equations.
6. Explain thermite process.

NOW ATTEMPT IN-CHAPTER EXERCISE-A REMAINING QUESTIONS IN THIS EBOOK

EXTRACTION OF IMPORTANT METALS Section - 3

GROUP 1
LITHIUM
Sources :
Lithium occurs mainly as silicate minerals like spodumene (LiAlSi2O6), Lepidolite.
SODIUM
Sources :
Sodium is the most abundant alkali metal. It is found in sea water, as rock salt (NaCl), Saltpetre (NaNO3),
Borax, Glauber’s salt (Na2SO4 . 10H2O), cryolite.
Extraction :
Sodium is obtained on large scale by two processes :
(A) Castner’s process :
In this process, electrolysis of fused NaOH is carried out at 330°C using iron as cathode and nickel
anode.

 Na   OH 
NaOH 

At Fe cathode: Na   e 
 Na

At Ni anode : 4OH   2H 2O  O2  4e

water formed at the anode gets partly evaporeted and is partly broken down to form H2 at cathode.
(B) Down’s process :
Sodium metal is manufactured mainly by this process. It involves the electrolysis of fused sodium
chloride (40%), calcium chloride (60%) and potassium fluoride using iron as cathode and graphite as
anode at about 600C.

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 Na+ + Cl
NaCl 
At Iron cathode Na   e 
 Na
At carbon anode 2Cl 
 Cl2  2e 

The electrolysis of pure NaCl presents the following difficulties :

 The fusion temperature of NaCl is high, i.e., 803C. At this temperature both sodium and chlorine are
corrosive.
 Sodium forms a metallic fog at this temperature.
To remove above difficulties, the fusion temperature is reduced to 600C by adding CaCl2 and KF.

POTASSIUM
Sources :
Potassium occurs mainly as deposits of KCl and carnallite (KCl . MgCl2 . 6H2O)

Extraction :
A cell similar to down’s cell can be used to obtain potassium by electrolysing fused KCl.

GROUP 2
MAGNESIUM

Sources : Magnesium salts occur in sea water. Entire mountain ranges (eg Dolomites in Italy) consist of the
mineral dolomite [MgCO3 . CaCO3] . It also occurs as magnesite (MgCO3) and carnallite.
Extraction :
(A) Dow’s sea water process :
Sea water contains MgCl2 . Water is treated with Ca(OH)2 which precipitates MgCl2 as Mg(OH)2.

MgCl2  Ca(OH)2 
 CaCl2  Mg(OH)2 
(in sea water)

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This is then converted back to MgCl2 .

 MgCl2   MgCl2 . 6H 2O   2H 2O
Mg(OH)2  2HCl 
dry HCl
MgCl2 . 6H2O  MgCl2 (anhydrous)
The obtained anhydrous MgCl2 is then electrolysed in fused state.
(B) From magnesite

MgCO3 
 MgO  CO2

MgO  C  Cl2 
 MgCl2  CO
(anhydrous)

MgCl2 is then electrolysed.

(C) Electrolysis of Fused Carnallite

Magnesium is prepared by electrolysis of fused MgCl2.

Anhydrous magnesium chloride is first prepared as in (A), (B) above

In order to lower fusion temperature of anhydrous MgCl2 and to increase the conductivity of electrolyte
NaCl or KCl (30%) is added. The electrolysis of MgCl2 is carried out at 700C. An air tight Iron vessel
serves as cathode. A carbon rod serves as anode and is enclosed by a porcelain tube. This arrangement
prevents the contact between magnesium and chlorine. Before starting the electrolysis, air above the electrolyte
is replaced by coal gas. This precaution is necessary because at about 700C magnesium reacts rapidly
with O2, N2 and CO2 present in air.

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 Mg2+ + 2 Cl
MgCl2 
At Fe cathode Mg2+ + 2e 
 Mg
At Carion anode 2 Cl 
 Cl2 + 2e

(D) In silico-thermic process / Pidgeon process :

Here calcined dolomite (CaO + MgO) is reduced by ferrosilicon at about 1200C in an electric
furnace working under reduced pressure (3mm) where pure magnesium distils over.

1200 C
CaO  2MgO  Si 
 2Mg  CaSiO3
3mm

CALCIUM
Sources :
It occurs in many common minerals like limestne, marble and chalk (CaCO3), dolomite, gypsum, Fluorspar
and also as coral.

Extraction by Electrolysis :
Calcium is obtained by electrolysis of a fused mass consisting six parts calcium chloride and one part
calcium fluoride at about 700C in an electrolytic cell made of graphite which acts as anode and a water
cooled cathode of iron which is suspended from the top in the fused mass. On passing current, calcium is
discharged at cathode. It gets solidified as cathode is water cooled.
 Ca 2   2Cl
CaCl2 
At graphite anode : 2Cl 
 Cl2  2e 
At Fe cathode : Ca 2   2e  
 Ca
Since metallic calcium is soluble in fused CaCl2 at electrolysis temperature, cathode is raised and Ca is
removed as soon as it is deposited.

Note : Na or K is obtained by electrolysis of fused NaOH or KOH respectively but calcium cannot be obtained in
the same manner as Ca(OH)2 decomposes into CaO (quick lime) which is difficult to fuse.

GROUP 3 - 7
 Ti is refined by Van Arkel - de-Boer method :

Note : TiO2 is very stable and can’t be reduced by C or CO as it forms carbides and hence is reduced by Na or
Mg.

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 Zirconium (Zr) is also refined by Van Arkel - de-Boer methods :

 Molybdenum and Tungsten are chemically reduced by H2

MoO3  H2 
 Mo  H2O ; WO3  H2 
 W  H 2O

GROUP 8
IRON
Sources :
Iron is the second most abundant metal and fourth most abundant element in the earth’s crust. It is extracted
from haematite (Fe2O3), magnetite (FeIIFe2IIIO4) and iron pyrites (FeS2) Famously called Fools Gold.

Extraction :

1. Crushing and Concentration :

The ore is crushed and washed with water (i.e., concentrated by levigating in a stream of water-
gravity separation or hydraulic washing) and then concentrated by electromagnetic process.

2. Roasting :
The concentrated ore is roasted in shallow kilns in the presence of excess of air. In roasting,
 Most of the moisture is removed.
 Impurities (like C, S, P, As and Sb) are removed in the form of their volatile oxides.
S + O2   SO
2
; 4As + 3O2   2AS O
2 3
; P + O2  P O
2 3
 Carbonates and sulphides are converted into oxides.
FeCO3   FeO + CO ; 4FeS + 11O 
2 2 2
 2Fe O + 8 SO
2 3 2
 Ferrous oxide is oxidised to ferric and thus avoids formation of slag with sand in further
processing.
4FeO + O2   2Fe O
2 3
(Otherwise FeO + SiO2   FeSiO )
3
 The entire mass becomes porous which makes reduction easy.
3. Smelting or Reduction :
The roasted ore (8 parts) mixed with coke (C), a reducing agent (4 parts) and limestone, a flux (1
part) is smelted (reduced) in a blast furnace lined with dolomite. Hot air blast is introduced near the
bottom of the furnace. Since the blast furnace has different temperature at different zones, different
reactions take place at different zones.
(a) Zone of Combustion : (1500°C -1600°C)
This zone is near the bottom of furnace and little above the tuyeres.
2C + O2 
 2CO + 58 Kcal
C + O2 
 CO + 97 Kcal
2
Both reactions are exothermic, a high temperature of about 1500C 1600C is attained.

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FeO  CO 
 Fe  CO2
CO 2  C 
 2CO
FeO  C 
 Fe  CO

(b) Zone of Fusion : (1200°C -1500°C)

It is just above the zone of combustion. Here the iron produced in upper zones melts and trickles
down in hearth while the slag being lighter floats over the molten iron and thus prevents oxidation of
Fe by blast of hot air. The molten metal and slag are removed from different outlets.
(c) Zone of Heat Absorption : (or middle zone) (800°C -1200°C)
In this middle part of furnace, rising CO2 (produced in the zone of combustion) is reduced to carbon
monoxide.
CO2 + C 
 2CO ; H = +39 kcal
The reaction being endothermic lowers the temperature of the zone. In addition to this, following
reactions also take place here.
(i) Limestone decomposes forming CaO which reacts with SiO2 forming slag.

CaCO3   CaO + CO2
CaO + SiO2 
 CaSiO3 (slag)
(ii) Any Fe3O4 which escapes reduction in the zone of reduction is reduced in this zone.
 3FeO + CO 
Fe3O4 + CO  2

(iii) Some impurities are reduced and get mixed up with Iron.
MnO + C   Mn + CO

SO2 + 2C 
 S + 2CO

SiO2 + 2C 
 Si + 2CO

P2O5 + 5C 
 2P + 5CO

Ca3(PO4)2 
 3CaO + P O
2 5

(d) Zone of Reduction : (300°C -700°C)

It is near the top of the furnace. Here the roasted ore is reduced by rising carbon monoxide CO. The
following reactions taking place in this zone are all reversible in nature.
300C  400C
3Fe2O3 + CO   2Fe3O4 (spongy iron) + CO2

680C  700C
Fe3O4 + CO   3FeO + CO2

FeO + CO 
 Fe + CO2

Fe3O 4 + 4 CO 
 3 Fe+ 4 CO 2

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 Iron obtained is impure. The product from blast furnace in called as Pig Iron. The net
productof blast furnace consists of Pig Iron, slag and fuel gases.
 The overall process for the extraction of Fe is thus :

3C  Fe 2O3 
 4Fe  3CO2

CaCO3  SiO2 
 CaSiO3  CO2

Cast Iron : The cast iron is specially made by igniting Pig iron with scrap iron and coke in a specially
designed furnace by blast of hot air. It contains 3% carbon in the form of graphite and carbide
and is extremely hard and brittle.

GROUP - 11
COPPER
Sources :
The most common ore is chalcopyrites CuFeS2. Other ores include Cu2S (Copper glance / chalocite),
basic copper carbonate CuCO3 . Cu(OH)2 (called malachite and is green) and cuprite Cu2O (is ruby red)

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Extraction :
It is a self reduction method. It can be achieved by two ways.
I. Pyrometallurgical II. Hyderometallurgical
(A) Pyrometallurgical Method :
1. Concentration of Ore : The ore is finely divided and concentrated by froth floatation method.
Here froth is made from pine oil and water by bubbling air into the mixture. Concentrated ore
adheres to the surface of froth leaving behind impurities.
2. Roasting : The concentrated ore is heated strongly in presence of air in a reverberatry furnace.
Sulphur, arsenic and antimony are removed in the form of their volatile oxides while the proper
ore is converted into a mixture of cuprous and ferrous sulphides. These sulphides are partially
oxidised to oxides.

S + O2 
 SO
2
2As2S3 + O2 
 2As O + 6SO
2 3 2

2Sb2S3 + O2 
 2SbO + 6SO
3 2

2CuFeS2 + O2 
 Cu S + 2FeS + SO
2 2

Minor Reaction : 2Cu2S + 3 O2 

 2Cu2O + 2SO2
2FeS + 3O2 
 2FeO + 2SO2

3. Smelting (Auto Reduction) : The roasted ore is mixed with sand (flux) and coke (fuel) and then heated
in water jacketed blast furnace called smelter. The oxidation of ferrous sulphide which started during roasting
now goes up a step further, ferrous oxide, formed reacts with sand to form ferrous silicates (slag). Here
some FeS reacts with Cu2O to form Cu2S again.

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FeO + SiO2 (sand) 

 FeSiO3 (Slag)
Cu2O + FeS   Cu2S + FeO
Slag, forming upper layer and molten mass consisting of Cu2S and little FeS, forming lower layer called
‘COPPER MATTE’ are removed from separate holes.
4. Bessemerisation : Molten matte is heated in Bessemer converter and blast of air mixed with sand is
blown through the molten mass. Here Iron (FeS) is completely removed as slag. A part of Cu2S is
oxidised to Cu2O and a part of Cu2S reduces Cu2O to metallic copper.
2Cu2S + 3O2 
 2Cu2O + 2SO2

2Cu2O + Cu2S 
 6Cu + SO2

The molten copper is poured off into sand moulds. As it cools, it gives up dissolved SO2 which forms
blister on the metal surface. The copper thus obtained is called as BLISTER COPPER (98% Cu).

5. Refining of Copper :
(a) Furnace or thermal Refining : Blister copper is melted in a reverberatory furnace provided with
silver lining and air is blown in where the impurities oxidise. Some of oxides escape and other form
a slag with silica.
The slag is removed.
(b) Poling : Molten Cu is stirred with poles of green wood to reduce Cu2O to Cu by CO and H2 from
green wood.
Cu2O + CO 
 2Cu + CO2
Cu2O + H2 
 2Cu + H2O

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(c) Electrorefining : The electrolyte bath contains an acidified solution of copper sulphate, impure copper
(blister copper) acts as anode while pure copper strip acts as cathode. The cathode grows in thickness
and pure Cu is scraped off.
Anode : Impure Cu
Electrolyte: 3.55% CuSO4 + 15% H2SO4 :  Cu2+ + 2e
Cu 
Cathode : Pure Cu
Temperature: 50C : Cu2+ + 2e 
 Cu (Pure)

Note : The impurities (Au, Ag, Pb ......) collect below the anode and is called anode mud.

(B) Hydrometallurgical Method :

Low grade ore is crushed and exposed to air and water when copper sulphide is oxidised to copper
sulphate. Some iron sulphate and sulphuric acid is also produced. This process takes one year.

(a) CuFeS2 + 4O2 

 CuSO4 + FeSO4

(b) 2Cu2S + 5O2 

 2CuSO4 + 2CuO
Cu glance

CuS + 2O2 
 CuSO4 (pale green liquid)

In NON-SULPHIDE ores, the crushed ore is leached with dilute H2SO4.

(c) CuCO3.Cu(OH)2 + 2H2SO4 
 2CuSO4 + CO2 + 3H2O
Malachite
The pale green liquor draining from the bottom to the heaps is collected in pans and treated with iron scraps
which precipitate out copper.
CuSO4 + Fe 
 FeSO4 + Cu
The precipitated copper is dried, melted and refined.

SILVER AND GOLD

Sources :
Silver is mainly found as sulphide ore Ag2S (argentite) Gold occurs mainly as grains of metal disseminated in
quartz veins.

Extraction :
Au, Ag are both first crushed and concentrated by froth floatation. Silver then directly undergoes leaching
while gold is leached after roasting.

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Leaching is done by Cyanide process.

1. Ag ore is leached with NaCN (or KCN) solution in presence of air when silver and its solt are
converted to soluble complex.
O
Ag 2S  4CN  

2
2[Ag(CN) 2 ]  S2 
Argento Cyanide
(so lub le)

O2(air) is pumped to force the reaction in forward direction.

4S2   5O2  2H2O 

 2SO42   2S   4OH 
Zinc dust is then added to precipitate Ag.

[ Ag(CN) 2 ]  Zn 
 Ag   [ Zn(CN) 4 ]2 
(pure)

2. The leaching process used for Au is called Mac Arthur Forest Cyanide Process :
Concentrated ore is taken in large vats made of cement or iron. It is then treated with dilute (0.5%)
solution of KCN in presence of air to form a soluble complex.

4 Au  8KCN  2H 2O  O 2 
 4 K[Au(CN) 2 ]  4KOH
(ore) Potassium Aurocyanide
(Soluble)

Note : If excess conc. KCN is used then

4Au  1 6CN   O 2  2H 2O 
 4[ Au(CN)4 ]3  4OH 
(excess)

Zinc dust is then added :

2K[Au(CN)2 ]  Zn 
 K 2 [Zn(CN)4 ]  2Au 
(pure)

The obtained Gold (or Silver) still contains traces of impurities and thus electrolytic refining is performed.
The electrolyte used is AgNO3 + 10% HNO3(for silver) and AuCl3 + 10% HCl (for gold). Anode is the
impure metal while cathode is made of pure metal.
 Ag is also obtained from argnetiferrous lead (PbS . Ag2S) by Parke’s Process or Pattinson’s
Process :
 Ag, Au can also be extracted from anode mud formed during electrolytic refining of copper.
 Another method of extraction is amalgamation. Powdered ore is first converted to its amalgam and
then distilled to remove Hg in the form of vapour leaving behind pure metal.

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GROUP - 12
ZINC
Sources :
Zinc is found as Zinc Blende (ZnS), Colomine (ZnCO3) and zincite (ZnO)
Extration :
1. Concentration
The ore is concentrated first by gravity method and then by froth floatation process. If Fe2O3 is
present as an impurity, it is removed by magnetic separation.
2. Roasting
The concentrated ore is then roasted at 900C  1000C to convert ZnS and ZnSO4 to ZnO.
2ZnS + 3O2   2ZnO + 2SO2
ZnS + 2O2   ZnSO4
ZnSO4   2ZnO + 2SO2 + O2

Note : If calamine is used as the source, only calcination is required at high temperature.

ZnCO3 
 ZnO + CO2

3. Reduction by coke
The oxide, ZnO is reduced with coke at about 1500C to obtain metallic zinc which is distilled of and rapidly
cooled.
ZnO + C 
 Zn + CO

ZnO + CO 
 Zn + CO2

4. Electrolytic Refining
Zn thus produced contains impurities like Pb, Cd, and Fe. These impurities are removed by liquation. The
pure zinc is obtained by electrolysing the Zinc in presence of acidified ZnSO4 (ZnSO4 + dil H2SO4) as
electrolyte. Impure zinc is made the anode and pure zinc, the cathode.
Note : Zinc can also be extracted by electrolytic method. ZnS is first roasted at 700C to produce ZnO. Then, the
oxide ZnO is leached with H2SO4 to convert to sulphate (ZnSO4). After removing impurities by treating with
milk of lime, ZnSO4 is acidified and electrolysed to give pure zinc on cathode.

MERCURY
The most important ore is cinnabar (HgS) which is bright red coloured. The ore is first crushed and
concentrated by froth floatation method. It then undergoes Auto / self reduction

HgS  O2 
 HgO  SO 2

HgO  HgS   Hg  SO2

Refining is done by either liquation or distillation.

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GROUP - 13
ALUMINIUM :
Sources :
Aluminium is the most abundant metal and is commercially important. The most important ore of aluminium
is bauxite. This is a generic named for several minerals with formulae varying between Al2O3. H2O and
Al2O3 . 3H2O

Extraction (Electrolytic method from Bauxite) :

1. Purification of Bauxite
Bauxite contains mainly Iron oxide (Fe2O3) and silica as impurity. If iron oxide is the main impurity, it
is called red bauxite and if SiO2 is the main impurity, it is called white bauxite. It is difficult to remove
iron or silicon from aluminium, so the ore is purified before hand. It can be achieved by either of the
following processes.
(a) Bayer’s Process (for ores containing iron oxide as major impurity) :
Finely grounded ore is roasted at a low temperature to convert FeO to Fe2O3 and digested
with a concentrated solution of NaOH in an autoclave. Al2O3 (Amphoteric) dissolves forming
NaAlO2, while Fe2O3 (basic) remains undissolved. Fe2O3 is removed by filtration.

Al2O3.2H2O + 2NaOH 
 2NaAlO2 + 3H2O
The filtrate containing sodium aluminate is diluted, treated with a seed crystal of pure Al(OH)3
and then agitated, when pure Al(OH)3 is precipitated.

NaAlO2 + 2H2O 
 NaOH + Al(OH)3 
The precipitated Al(OH)3 is filtered, washed and ignited to give pure alumina, Al2O3.

2Al(OH)3   Al2O3(pure) + 3H2O

(b) Serpek’s Process (For ores containing silica, SiO2) :

The powdered ore is mixed with carbon and heated to 1800C in a current of nitrogen,
where aluminium nitride is formed. SiO2 is reduced to silicon, which volatilises away.
1800ºC
Al2O3 + 3C + N2 
 2AlN + 3CO

SiO2 + C 
 Si(volaties off) + 2CO
Aluminium nitride is hydrolysed by water to Al(OH)3 which on ignition gives pure alumina.

AlN + 2H2O 
 Al(OH)3 + NH3
1100C
2Al(OH)3  Al2O3(pure) + 3H2O

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(c) Hall’s Process [mainly for Red Bauxite] :

Crude bauxite reacts with Na2CO3 at 1000 C to give sodium aluminate and impurities Fe2O3 and
SiO2 form NaFeO2 and Na2SiO3 respectively.
 2NaAlO2 + CO2
Al2O3 + Na2CO3 
CO2 at a temperature of around 60C is passed into sodium aluminate solution producing Al(OH)3.
60C
2NaAlO2 + CO2 + 3H2O  2Al(OH)3  + Na2CO3

2Al(OH)3   Al2O3 (pure) + 3H2O
1100C

2. Electrolytic reduction of alumina (Hall - Heroult Process)

Aluminium can’t be isolated by electrolysis of aqueous solution of Al2O3, since aluminium is more
electropositive than hydrogen, so its electrolysis gives H2 at cathode.
Al2O3 is infusible (M.P. = 2050C), so it can’t be electrolysed. So pure alumina, dissolved in molten
Cryolite (Na3AlF6) containing some CaF2 or NaF is electrolysed at about 800C1000C. Cryolite
decreases melting point and increases conductivity while CaF2 and NaF are added only to increase
conductivity. The electrolysis is carried out in an iron cell lined with graphite (cathode). The anode is a
series of graphite rods.

 Al3+ + 3F
AlF3 
At cathode : Al3+ + 3e 
 Al

At the same time, Al2O3 dissociates into Al3+ and O2–.

Since ‘O’ is below F in the electronegativity series, O2 ions are selectively discharged at the anode as
oxygen.
 4 Al3+ + 6 O2
2 Al2O3 
At anode :  3 O2 + 12 e
6 O2 

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The oxygen liberated at anode combines with carbon of anode to form CO and CO2 so anode, which burn
away have to be replaced periodically. Molten Al collects at the bottom of cell (99% pure)
3. Electrolytic Refining
The cells layers contain three fused layers.
(a) The bottom anode layer of an alloy of Al, Cu, Si
(b) The middle layer of Cryolite and BaF2
(c) The top cathode layer of pure aluminium.
When a current is passed, Al3+ ions from the fused middle layer get discharged at the cathode, while an
equivalent amount of aluminium moves into the middle layer. Impurities (Cu etc) remain at the bottom.

GROUP - 14
TIN :
Sources :
It is mainly obtained from Cassiterite (SnO2) which contains Wolfromite (FeWO4 . MnWO4) as an impurity.
Extration :
1. Concentration of ore :
Ore is crushed to a fine powder and concentrated by gravity process. Ore is washed with the stream
of water to remove gangue and other silicon impurities. Tinstone and wolframite are left. Wolframite
is then removed by magnetic seperation.
2. Roasting :
The ore is roasted to remove volatile impurities.
S + O2   SO
2

2As2S3 + 9O2 
 2As O + 6SO
2 3 2

The roasted ore is washed with water to remove soluble impurities and dried. It contains 60 – 70% of
tin as SnO2 called Black Tin.

3. Smelting :
The ore is mixed with 1/5 th of its weight of powdered anthracite and a little limestone and heated in
reverberatory furnace. SnO2 is reduced to metallic state and silica is removed as slag.
SnO2 + 2C 
 Sn + 2CO

4. Refining :
It is refined by any of the following processes.
(a) Liquation : The crude tin is melted on the sloping hearth of a reverberatory furnace when tin
alone melts and flows out. The process is called sweating and the impure tin left is called
dross.

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(b) Electrolytic Refining : The electrolyte consists of hydrofluorosilicic acid (H2SiF6) containing
stannic sulphate (SnSO4) and H2SO4. A block of impure tin is anode and a thin strip of pure
tin the cathode.

LEAD
Sources :
Galena (PbS) is the principal ore.
Extraction :
(A) Self Reduction or Air reduction process :
This is used for samples of galena rich in lead. In this process roasting and smelting are done in same
furnace, but at different temperatures.
(i) Crushing and Concentration
The ore is crushed, finely powdered and concentrated by froth floating process. NaCN is
used as a depressant to prevent ZnS (if present) from coming out as froth. The concentrated
ore contains 50  60% of lead.
(ii) Roasting
The concentrated ore is roasted at a moderate temperature in a reverberatory furnace and in
a limited supply of air.
lim e
2PbS + 3O2 
 2PbO + 2SO2

PbS + 2O2 
 PbSO
4

(iii) Reduction (Smelting)

Air supply is cut off, fresh galena is added to roasted ore and the temperature is raised.
Galena reduces lead oxide and lead sulphate to metallic lead.

2PbO + PbS 
 3Pb + SO2

PbSO4 + PbS 
 2Pb + 2SO2
Molten lead is drawn from time to time and purified.

(B) Carbon Reduction Process :

This process is suitable when the ore contains more impurity (silica) and has low amount of lead. Here
roasting and smelting are done in different furnaces.
(i) Crushing and Concentration
This is done as in above process.

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(ii) Roasting
Concentrated ore is mixed with lime (CaO) and heated in presence of air when PbS is oxidised
mainly to PbO.
2PbS + 3O2 
 2PbO + 2SO2
Lime performs two important functions.
(a) Being more basic than PbO, lime preferentially reacts with SO2 (formed in the above
oxidation) to form calcium sulphite and thus favours the oxidation of galena in the
forward direction.
(b) It decomposes lead silicate (formed by reaction of PbSO4 with silica present as
impurity) to PbO which would otherwise have gone as slag.
PbS + 2O2   PbSO4
2PbSO4 + 2SiO2 
 2PbSiO3 + 2SO2 + O2
PbSiO3 + CaO 
 CaSiO3 + PbO

(iii) Smelting
The roasted mass is mixed with coke and lime (flux) and smelted in a blast furnace. Following
reactions occur.
PbO + C 
 Pb + CO
PbO + CO  Pb + CO2
CaO + SiO2  CaSiO3 (slag)

PbSiO3 + CaO  CaSiO3 + PbO

Little hematite is added to reduce any unchanged PbS to Pb.
2PbS + Fe2O3 + 3C 
 2Pb + 2FeS + 3CO

(iv) Refining
Impurities are Cu, As, Sb, Fe, Zn, Bi, Ag and sulphur. These are refined by either of flowing
processes :
(a) Oxidation or softening where impure metal is heated in current of air where Cu, Fe, Sn etc are
oxidised before lead.
(b) Desilverisation by Parke’s or Pattinson method to remove Ag.
(c) Electrorefining : Electrolysis of 1-15% Lead silica fluoride (PbSiF6) and 5-10%
(hydrofluorosilicic acid, H2SiF6) is carried out between pure lead sheets serving as cathode,
and crude impure lead as anode.

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Basic Principle of Extraction Vidyamandir Classes

IN - CHAPTER EXERCISE - B

1. Cinnabar (HgS) and galena (PbS) on roasting often give their respective metals but zinc blende
(ZnS) does not.
Explain :
2. A metal is in combined sate as sulphide. Identify the steps (A), (B) and (C)


3. Why Zinc and not copper is used for the recovery of metallic silver from the complex  Ag  CN  2 
4. Describe the extraction of magnesium from sea water.
NOW ATTEMPT IN-CHAPTER EXERCISE-B REMAINING QUESTIONS IN THIS EBOOK
NOW ATTEMPT OBJECTIVE WORKSHEET BEFORE PROCEEDING AHEAD IN THIS EBOOK

SOLUTIONS - IN - CHAPTER EXERCISE - A

1. Fe 2O3  C 
 Fe ; ZnO  C 
 Zn  CO 2  CO(gases)
(haematite) (zincite)

PbO  C   Pb ; MgO  C   Mg ; Ca 3 (PO4 ) 2  C  P

2. Tinstone is concentrated first by gravity seperation and then magnetic seperation is used to remove magnetic
impurities like wolframite.
3. Collectors enhance the non wettability of mineral particles and froth - stabilizers stabilize the froth.
4. Reduction by hydrogen is not widely used because many metals react at elevated temperartures, forming
hydrides. There is also a risk of explosion.
5. Galena (PbS), Chalcocite (Cu2S) and cinnabar (HgS).
6. In the thermite process, Al is used to reduce metal oxide to metal while it itself gets oxidised to Al2O3 which
produces a large amount of heat (1675 kJ/mol). This is utilised to join broken railway tracks.

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Vidyamandir Classes Basic Principle of Extraction

SOLUTIONS - IN - CHAPTER EXERCISE - B

1. This is because HgS and PbS can undergoe self reduction while ZnS doesnot.
2. A = roasting, B = reduction, C = refining
4. Sea water contains MgCl2 which is precipitated as Mg(OH)2 (using Ca(OH)2). This is then converted back
to MgCl2(by HCl) and dried. MgCl2 is then electrolysed.

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My Chapter Notes

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Illustration - 1

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