Metallurgy

Introduction
Definition
Metallurgy
y The extaction and isolation of an element from The entire scientific and
its combined from involves various principles of technological process used for
chemistry. isolation of the metal from its
y Some general principles are common to all the ores is known as metallurgy.
extraction processes of metals.
Definition
Mineral :
y The naturally occurring chemical substances in
Those compounds of metals in
form of which the metals occur in the earth crust
which metal occurs in nature is
along with impurities are called minerals.
called minerals.
Ex. Mineral of Aluminium – Bauxite, Cryolite, Clay,
Feldspar, Mica.

Ore : Concept Ladder

y The mineral from which metal can be extracted
easily & economically
“All ores are minerals but
Ore → Metal
all minerals cannot be
Ex. Fe – Fe2O3 (Haematite), Fe3O4 (Magnetite), FeSO2 ores.”
(Iron pyrite), FeCO3 (Siderite)

Metallurgy

1.
 Metal Ores Composition

• Bauxite AlOx(OH)3-2x(where 0 < x < 1)

Aluminium • Cryolite AlF6Na3
• Kaolinite (a form of clay) [Al2(OH)4Si2O5]

• Haematite Fe2O3
• Magnetite Fe2O4
Iron
• Siderite FeCO3
• Iron pyrites FeS2

• Copper pyrites CuFeS2

• Malachite CuCO3.Cu(OH)2
Copper
• Cuprite Cu2O
• Copper glance Cu2S

• Zinc blende or Sphalerite ZnS

Zinc • Calamine ZnCO3
• Zincite ZnO

• Cerussite PbCO3
Lead • Galena PbS
• Anglesite PbSO4

Mercury • Cinnabar HgS

• Silver glance/Argentite Ag2S

Silver
• Horn silver AgCl

• Carnallite KCl.MgCl2.6H2O
Potassium
• Indian nitre KNO3

• Cryolite Na3AlF6
Fluorine
• Fluorspar CaF2

Rack your Brain

Which metal undergoes

Hydrometallurgical Process and
Metallurgy

why ?

2.
Q1 Al is absent in
(1) Bauxite
(2) Cryolite
(3) Feldspar
(4) Fluorspar

A1 (4) Fluorspar

Q2 Most abundant metal is

(1) Cu
(2) Al
(3) Fe
(4) Au

A2 (2) Al

Q3 Why Al is costly than Iron ?

A3 In extraction of Al large amount of electrical energy is used as compared to iron.

Al 2O3 . 2H2O 

→ Al (Difficult process, more electricity required)
Bauxite

Fe O
2 3 → Fe
 (Easy process)
Haematite ore

Occurrence :
1. Free form (Native form) – Less reactive Previous Year’s Questions
Ex: Noble metal/Inert metal (Au, Pt, Ag)
2. Combined form – More reactive metal
Which one is malachite from the
found in combined form i.e. Oxide, Halide,
following
Sulphide, Sulphate, Carbonate
 [NEET-2019]
Ex:
(1) CuCO3, Cu(OH)2 (2) CuFeS2
(3) Cu(OH)2 (4) Fe3O4
Metallurgy

3.
 y Oxide – Bauxite – Al2O3 2H2O, Haematite – Fe2O3,
Magnetite – Fe3O4
Concept Ladder
y Carbonate : Limes stone–CaCO3, Dolomite–
CaCO3.MgCO3, Siderite–FeCO3
Oxygen and silicon
y
constitute about 73% by
y Halides : Common salt–NaCl, Sylvine–KCl,
mass of earth’s crust.
Carnallite–KCl.MgCl2.6H2O

y Phosphate : Phosphorite– Ca3(PO4)2, Fluorapatite–

3Ca3(PO4)2.CaF2

y Sulphide : Cinnabar–HgS, Argentite or Silver Rack your Brain

glance–Ag2S
What will happen on equilibrium
y Sulphate : Glauber’s salt– Na2SO4. 10H2O,
constant when temperature is
Angelsite–PbSO4
increased?

y Metallurgy of metal involves four main processes.

1. Concentration or dressing of ore.
2. Conversion of ore into oxide.
3. Conversion of oxide into pure metal. Previous Year’s Questions
4. Purification of metal.
Which one of the following is a
Metallurgy is the process in which the entire mineral of irons
technological and scientific processes used for  [AIPMT-2012]
isolation of the metal from its ores. (1) Malachite (2) Cassiterite
Those principles shall include the thermodynamic (3) Pyrolusite (4) Magnetite
and electrochemical aspects involved in the
effective reduciton of the concentrated ore to
the metal.

Q4 Which of the following ores does not represent the ore of iron
(1) Haematite
(2) Magneite
(3) Cassiterite
(4) Limonite

A4 (3) Cassiterite
Metallurgy

4.
5.
Metallurgy
 Reactivity Series
Metallurgy

6.
 (1) Concentraion/Benefaction/Enrichment/Dressing of Ore
(A) Physical Method
(i) Hydraulic washing/ gravity separation/ lavigation :

y Basic principle of this method is the difference in

Concept Ladder
specific gravity (density) of ore and gangue particle.
y Gangue particle being lighter are washed away by
Unwanted earthy
jet of water & ore particle being heavier remains.
impurities are called
y This method is mainly applicable for oxide & (ii)
gangue/matrix.
Metallurgy

7.
 (ii) Magnetic separation :

Ex.
Previous Year’s Questions

An ore of tin containing FeCrO4 is

concentrated by
Ex.  [AIPMT]
(1) Magnetic separation
(2) Froth floatation
(3) Electrostatic method
(4) Gravity separation
y Basic principle of electromagnetic separation is
the difference in magnetic property of either ore
or gangue.
Concept Ladder
y If the metal bearing particles have magnetic
nature then they can be separated from non- Michael Faraday discovered
magnetic impurities by the help of this method. that when a substance is put in
a magnetic environment, the
y On a conveyer belt (passess over a magnetic intensity of the environment
roller) the ground ore is carried. is modified by it. With this
information, he discovered
that different material can
be separated with their
Metallurgy

magnetic properties.

8.
 (iii) Froth Floatation Method : It is used for the
concentration of sulphide ores. It is a physical
method.

y In this method mainly sulphide ores are used.

y The basic principle of Froth floatation method
is the difference in wetting properties of ore &
Previous Year’s Questions
gauge particles.
Ore particles are wetted by oil & gangue particles
are wetted by water. Froth floatation process is used for
y Frother/frothing agent – pine oil/ turpentine/ the concentration of
mustard oil etc  [AIPMT]
y Collector/ floating agent – Na-alkyl xanthate (1) Oxide ores
y Froth stabiliser – Cresol/ aniline (2) Sulphide ores
y Depressant – NaCN (Concentration of galena ore) (3) Chloride ores
y Activator – Na2S activators increase the effect of (4) Amalgams
collectors. Ex. Na2S

Chemical Reaction :

ZnS + PbS + NaCN Na2 [Zn(CN)4]  + PbS

(Soluble)     Galena
(Goes away with froth)
Metallurgy

9.
 (B) Chemical Method
(i) Leaching : Rack your Brain
y In case of leaching, suitable reagent is used
which combines with ore to make it soluble while
What is the significance of
impurities like gangue remain insoluble.
Leaching?
Ex- Ag, Au, Al
y Al
Chief ore – Bauxite (Al2O3.2H2O)
(i)  Red (impurities of Fe2O3)
Concept Ladder
(ii)  White (impurities of SiO2)
Leaching is widely used
Mac-Arthur forest cyanide process (Cyanide
in the biological and food
process) :
processing industries for
the separation of sugar
(for Ag and Au)
from sugar beets with hot
Ag S + NaCN 
O2
→ Na[Ag(CN)2 ] + Na2 SO4 water.
2
(Ag − glance)

In the absence of O2, reaction becomes reversible.

Definition
Na[Ag(CN)2 ] 
Zn
→ Na2 [Zn(CN)4 ] + Ag
The process of removal of
Similarly, Au can be extracted by using KCN. volatile impurities (CO2, H2O
etc.) from an ore in the absence
(ii) Oxide formation : of air is known as Calcination.
(a) Calcination : Strong heating in the absence of
air
(1) PbCO3 
∆
→ PbO + CO2
Cerrusite litharg e

Previous Year’s Questions

(2) ZnCO3 
∆
→ ZnO + CO2
Cala mine

(3) CaCO3 

∆
→ CaO + CO2 The following reactions take place in
lime stone the blast furnace int he preparation
(4) FeCO3 
∆
→ FeO + CO2 of impure iron. Identify the reaction
Siderite
pertaining to the formation of the slag
(5) CuCO3 .Cu(OH)2 
∆
→ CuO + CO2 + H2O  [AIPMT-2011]
(1) CaO(s) + SiO2 → CaSiO3(s)
(6) Al 2O3 .2H2 O 
∆
→ Al 2O3 + 2H2O (2) 2C(s) + O2(g) → 2CO(g)
(alumina)
(3) Fe2O3(s) + 3CO(g) → 2Fe(l) + 3CO2(g)
(7) Fe2O3 .3H2O 
∆
→ Fe2O3 + 3H2O
Hametite (4) CaCO3(s) → CaO(s) + CO2
Metallurgy

(8) Al (OH)3 

∆
→ Al 2O3 + H2O
alumina

10.
 Note : Calcination is carried out in case of carbonate,
hydroxide, hydrated oxide Concept Ladder

Advantage of calcination
y Organic matter is destroyed Calcination and roasting
y Ore becomes porous & easily workable (rate of may be carried out in
reaction increase) the same reverberatory
y Moisture is removed. furnace.
y Oxide is formed.

(b) Roasting :

Definition

The removal of excess sulphur

contained in the form of SO2 from
Metallurgy

sulphide ore by the heating and

presence of air called as Roasting.

11.
 y Strong heating in the presence of air

PbS + O2 
→ PbO + SO2 ZnS + O2 
→ZnS + SO2
galena zinc blend

Advantage of Roasting :
y Impurities of Arsinic, Sb, P are removed in the Previous Year’s Questions
form of their volatile oxides.
y In the form of SO2 excess sulphur can be removed. In the extraction of copper from
y Metal oxide is formed. its sulphide ore, the metal is finally
obtained by the reduciton of cuprous
Roasting in the Fe-metallurgy : oxide with
FeO + O2 → Fe2O2 + SiO2 → No reaction  [AIPMT-2012]
FeO + SiO2 → FeSiO3 (1) Copper (I) sulphide (Cu2S)
(slag)
(2) Sulphur dioxide (SO2)
 Wastage of iron is prevented by roasting of (3) Iron sulphide (FeS)
FeO → Fe2O3 (4) Carbon monoxide (CO)

Roasting in Cu-metallurgy :
Chief Ore – Copper pyrites (CuFeS2)
CuFeS2 →+ O2
partial roasting
Cu2S.FeS+ SO2 + CU2O.FeO
(major) (minor)

Principles of metallurgy : Rack your Brain

Gibbs free energy (DG) = DH – TDS
where DH = change in enthalpy, DS = change Why all ores are rosted and not
in entropy, T = absolute temperature reduced directly?
DG is also related to equilibrium constant (K).
DG° = –RT ln K
If DG° is –ve, then K will be positive, reaction
will proceed towards forward direction.

Note : Concept Ladder

y The feasibility of reaction at any temperature
is when DG of the reaction is negative. Thus, on If DG is positive, the
increasing the temperature, DS becomes positive, reaction can still be made
the value TDS will increase and DG will be negative. to occur by coupling it with
(TDS > DH). This will proceed the reaction in forward another reaction having
direction. large negative DG, as a
result of the two reactions
is negative.
Metallurgy

12.
Ellingham Diagram :
It helps use in predicting the feasibility of the
thermal reduction of an ore.
Previous Year’s Questions
2x M(s) + O2(g) 2MxO(s)
Gases have higher entropy than liquids and solids.
Considering Ellingham diagram,
Therefore, during this reaction, DS becomes
negative. Thus, if temperature is increased, TDS which of the following metals
becomes more and more negative. DG increases with can be used to reduce alumina?
increase in temperature (normally, DG decreases  [NEET-2018]
with increase in temperature). In other words, DfG° (1) Fe (2) Zn
vs T lines have +ve slopes for most of the reactions (3) Mg (4) Cu
involving the formation of metal oxides, MxO (s) as
shown in figure.

Metallurgy

13.
 Rack your Brain

Metal sulphides occur mainly in

rocks and metal halides in lakes and
seas. Why?
Metallurgy

14.
(2) Conversion of ore into oxide
(i) Red (impurities of Fe2O3) : Rack your Brain
(a) Bayer’s process
Fe2O3    +   NaOH → no reaction What is the purpose of using
(impurity)    (Base) cryolite and CaF2 in electrolytic
reduction of Al2O3.
Al 2O3 + NaOH 
→ NaAlO2 
H2O
excess
→ Al(OH)3
(So luble gelateneous
complex) white ppt

(b) Hall’s process

Concept Ladder
Fe2O3 + Na2CO3 
→ no reaction
(impurity ) (base)
Beach sands of Kerala
Al 2O3 + Na2CO3 
→ NaAlO2 
H2O
excess
→ Al(OH)3 and Tamilnadu contain a
(So luble gelateneous
complex) white ppt useful mineral monazite
used for the extraction of
(ii) White (impurities of SiO2) :
thorium and rare earths.
(a) Serpeck’s process

Previous Year’s Questions

Alumino-thermic process is used for

2Al(OH)3 
1500°C
→ Al 2O3 + 3H2O
metallurgy of
 → Si + CO ↑  [AIPMT]
SiO + 2C 
2
(impurity ) (1) Pb (2) Ag
(3) Al (4) None

(3) Reduction to obtain Crude Metal (impure) :

Metallurgy

15.
 Smelting (C-reduction) :
C blast
Metal Oxide + impurities + flux →
(coke) furrance
metal (molten) + slag + C O / CO2

y Slag is lighter than metal, forms a protective layer Concept Ladder

on molten. Metal which decreases the negativity
of molten metal. Slag also decreases the melting The reduction of metal
point (fusion temperature) of impurity. oxide easier if the metal
y In the metallurgy of iron impurity is acidic. So, flux formed is in liquid state
used is basic. at the temperature of
y In the metallurgy of Copper impurity is basic. So, reduction.
flux used is acidic.

CaO + SiO2 

→ CaSiO 3 Copper SiO 2 + FeO 
→ FeSiO 3
(Basic flux) (imp) (metallurgy of iron) (acidic flux) (imp) (metallurgy of copper)

y Neutral flux is used in metallurgy of Al

(Na3 AlF6 + CaF2 )
cryolite flourouspar

Previous Year’s Questions

Purification of aluminum, by
electrolytic refining, is known as.
 [1999]
(1) Hoope’s pocess
(2) Baeyer’s process
(3) Hall’s process
(4) Serpeck’s process
y Neutral flux decreases the melting point of Al2O3 &
increases conductivity of salt.

ZnO 
C
→ Zn + CO / CO2 PbO 
C
→ Pb + CO / CO2
Fe2O3 
C
→ Fe + CO / CO2 SnO2 
C
→ Sn + CO / CO2

Rack your Brain

Why carbon and hydrogne are

suitable reducing agents for metal
sulphides?
Metallurgy

16.
Smelting of iron metallurgy :

Metallurgy

17.
 Pudding process :

Smelting of copper metallurgy :

Cu2O + FeS 
→ Cu2S + FeO FeO + SiO2 
→ ↓ FeSiO3 (slag)

Self-reduction :
(Pb, Hg, Cu)
PbS + O2 
→ PbO + SO2 PbS + PbO 
→ Pb + SO2

Self-reduction in Cu-metallurgy (Bessemerisation) :

Cu2S + FeS + FeO + SiO2 + O2 (air) 
→ Cu + SO2 + FeSiO3
(copper (basic (acidic (Blister (slag)
matte) impurities) flux) Copper)

Mechanism :

Fe + S O2 
→ FeO + SWO2 FeO + SiO2 
→ FeSiO3 ↓
(slag)

Cu2S + O2 
→ Cu2O + SO2 Cu2S + Cu2O 
→ Cu + SO2
(limited) Blister
Metallurgy

18.
Thermal Reduction :
1
(i) (a) Ag 2S + O2 
→ Ag 2O (b) Ag 2O 

→ 2Ag + O2
2
1
(ii) (a)HgS + o2 
→ HgO + SO2 (b)HgO 

→ Hg + O2
2

Previous Year’s Questions

The following reactions take place in the

blast furnace in the preparation of impure
iron. Identify the reaction pertaining to the
formation of the slag. [2011]
(1) Fe2O3( s) + 3COg → 2Fe(  ) + 3CO2( g )
(2) CaCO3( s) → CaOs + CO2( g )
(3) CaO( s) + SiO2( s) → CaSiO3( s)
(4) 2C( s) + O2( s) → 2CO( g )

Hall-Heroult Process (electrolytic reduction of Al2O3) :

Metallurgy

19.
 Electrolyte :
Al2O3 + Na3AlF6 + CaF2 Rack your Brain
(cryolite) (fluorspar)
Can the value of equilibirum
Al2O3 ionises as : constant be affected by change in
concentration of reactant ?
Al 2O3 
 Al 3+ + AlO33−

Cathode :

Carbon (inner lining) Concept Ladder

Al 3+ + 3e → Al
Na, K, Mg, Ca, Al etc. (Highly
Anode : electropositive metals) are
extracted from their molten
Graphite rods salts by using electricity is
4AlO33− → 2Al 2O3 + 3O2 + 12e known as electrometallurgy.
Overall chemical reaction

2Al 2O3 

→ 4Al + 3O2
Previous Year’s Questions
Note: 99.8% pure aluminium is obtained from
this process.
minium is rumina (Al2O3) by
Note: O2 
→ CO / CO2
C electrolysis of a molten mixture of
 [AIPMT-2012]
y Due to the formation of CO corrosion of anode (1) Al2O3 + HF + NaAlF4
starts so the main drawback of this process is (2) Al2O3 + CaF2 + NaAlF4
anode must be replaced time to time. (3) Al2O3 + Na3AlF6 + CaF2
(4) Al2O3 + KF + Na3AlF6

Aluminothermic Process (gold Schmidt’s process) :

Ex- Cr2O3, Mn3O4, B2O3, TiO2 etc.

Metallurgy

20.
 4. Refining to obtain ultra-pure Metal

(a) Liquation :
y Liquation process based on the difference in Rack your Brain
fusibility of the metal & impurities.
y This method used to purify the metals like Pb,
Why distillation process is use for
Sn, Sb, Bi.
low boiling metals.

(b) Distillation :
y In this case metals having lower values of BP are
purifies easily.
y This method used to purify the metals like Zn,
Cd, Hg.
Concept Ladder
(c) Zone Refining :
y The basic concept of zone refining is “Impurities In Zone refining, very high
are more soluble in molten state of m e t a l purity semi-conductors are
than in solid state of metal.” obtained.
y This method used to purify the metals like
Metallurgy

Silicone, germanium, gallium.

21.
 Chemical process :
(a) Cupellation – It is used to refine silver Concept Ladder
containing impurity of lead.
(b) Polling – Wooden pole (green wood) %
hydrocarbon more. Goldmine in Kolar
It is used to refine metal which has impurity of (Karnataka) is the deepest
its own oxide. mines of the world.

(c) Electrolytic Refining

(Cu, Zn, Pb, Al, Ag, Au, etc )

Anode : impure metal

Rack your Brain
Cathode : Thin strip of pure metal
Electrolyte : aqua solution of metallic salt.
Refining of iron : Fe3C – cementite Does German Silver consists of
silver ?
Metallurgy

22.
(d) Vapour phase refining :
(i) Mond’s process :

(ii) Van Arkle’s Method :

Small amount of Ti, Zr or Bi can be produced by this
method.

Previous Year’s Questions

Which of the following pairs of

This method is very expansive. metals is purified by van Arkel
method?  [2011]
(1) Ga and In (2) Zr and Ti
(3) Ag and Au (4) Ni and Fe

Q5 Name the form of copper which is termed as blister copper?

A5 The solidified copper obtained has blistered appearance due to the evolution of
SO2 , so it is called blistered copper.

Q6 Electrode potentials of both zinc and copper are less than that of Ag, then
also zinc is used but not copper for the recovery for metallic silver from the
complex [Ag(CN)2]–, Explain why ?

A6 Zinc reacts at faster rate as compared with copper, further zinc is cheaper than
copper

Q7 Write the name with percentage of constituents of German silver?

A7 Cu = 25-30%, Zn = 25-30%, Ni = 40-50%

Metallurgy

23.
 Q8 What is hydrometallurgy ? Give one example where it is used for metal
extraction.

A8 Leaching followed by reduction is called hydrometallurgy. It is used in extraction

of copper.

Q9 Name the elements present in anode mud during refining of copper. Why does
it contain such elements ?

A9 Au and Ag. They are not oxidized at anode. They are less electropositive than
copper.

Q10 Write names of any three ores concentrated by froth floatation process?

A10 Galena (PbS), Zinc blende (ZnS), Cinnabar (HgS).

Q11 What is the difference between the oxidation state of sulphur in product and
reactant?

A11

Q12 What is the oxidation state of Fe in fools gold?

A12
Metallurgy

24.
 Find the number of native ores out of given ores
Q13 Pyrolusite, Chromite, Siderite, Cassiterite, Calamine, Argentite, Lime stone,
Chalcopyrite.

A13 All the ores given in question are combining ore.

Q14 Total no. of metals given below which can replace Mg2+ ion from aq. solution
of MgCl2
Sodium, Gold, Copper, Lithium, Aluminium, Silver, Zinc

A14 It is not possible to displace Mg2+ ion from aqueous solution due to high reactivity
of Mg

Q15 Predict conditions under which Al might be expected to reduce MgO.

A15 Above 1350°C, the standard Gibbs free energy of formation of Al2O3 from Al is less
than that of MgO from Mg. Therefore, above 1350°C, Al can reduce MgO.

Q16 Why can’t aluminium be reduced by carbon ?

A16 Al is stronger reducing agent than carbon.

Q17 Name the most important form of iron. Mention its one use.

A17 Cast iron is one of the most important form of iron. It is used for making railway
sleepers, gutter pipes, castings, toys etc.
Metallurgy

25.
 Chapter Summary

1. (i) Abudance of elements in earth crust (by weight)

O > Si > Al > Fe > Ca > K
(ii) Abudance of elements in earth (by no. of atoms/100 g)
O > Si > Al > H > Na > Ca > Fe
2. Noble metals (Au, Ag) are obtained by cyanide or amalgamation process.
3. Iron is never manufactured by thermite process because Al is much more expensive
than Fe. Thermite process produces lot of heat so it is used for welding of iron.
4. Carbon reduction is not possible with alkaline erath metals as they form carbide
on reaction with carbon.
5. Sea weeds are source of iodine.
6. Types of metallurgy
Pyrometallurgy : Heat ios used. Ex.- oxides sulphides
Hydrometallurgy : Aqueous solution is used. Ex.- Ag, Au
Electro metallurgy : Electrolysis is done. Ex.- Na, K, Ca.
7. Pulverisation is process of grinding crushed ore into fine powder.
8. Pickling - Process of removing layers of basic oxides from electrode.
9. Amalgamation - Process of combining metal with Hg to form alloy.
10. Bassemerisation is process of passing hot blast of air through impure molten metal
in a bessmer convertor to oxidise impurities. e.g.- Pig iron and copper are purified by
this method.
11. Most electropositive metals are isolated from their ores by electrolysis of fused
ionic salts.
12. Molten zinc is converted into granulated zinc by adding water to it.

Metallurgy

26.
Š Refining: 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) Electrolytic refining (f) Bessemerisation
Š Hydrometallurgy (solvent extraction): 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.

Metallurgy

27.