Metallurgy | 1

CHAPTER

Metallurgy
General Principles up to Purification General principles and processes involved
Minerals : Naturally occuring chemical substance in in the extraction of metal from its ore :
The extraction of metal from its ore is completed in
which metal exist either in its free state or in combined state
five steps :
is called mineral.
Step I : Pulverization : The crushing of ore to powdered
Ore: Mineral from which metal can be conventionaly and state is called pulverisation.
economically extracted is called ore & impurities associated Step II : concentration or Dressing or Beneficiation of ore
with it is called gangue or matrix Step III : Conversion of Concentrated ore into oxide form
TYPES OF ORES : step IV : Reduction of oxide to the metal
• Sulphide Ores : Step V: Purification or refining of crude metal :
Galena : PbS, Cinnabar : HgS,
Step I : Pulverization :
Zinc blende : Zns, Chalcopyrite : CuFeS2
The crushing of ore to powdered state is called
Copper glance : Cu2S Fool's Gold : FeS2 pulverisation
• Oxide Ores : This process in stamp mill or ball mill
Bauxite : Al2O3. 2H2O Haematite : Fe2O3
Limonite : Fe2O3. 3H2O Tin stone or Cassiterite: Step II : Concentration or Dressing or
SnO2, Fe3O4 : Magnetite beneficiation of Ore
• Carbonate Ores : (a) By Gravity separation : Ore particles are
heavier than the gangue particles. This is used for
Siderite : FeCO3 Calamine ZnCO3
the separation of most of the gangue particles :
Malacite : Cu(OH)2CuCO3 Dolomite CaCO3.  By Wilfley Table Method
MgCO3. 2H2O Aq. Suspersion of powdered / Crushed ore
lime stone : CaCO3
• Sulphate Ores :
Gypsom : CaSO4.2H2O Anylesite PbSO4 Ore particles
Glauber's salt : Na2SO4. 10 H2O Mohr's salt :
FeSO4. (NH4)2SO4. 6H2O Gangue + water
• Halide Ores :
Rock salt : NaCl Cryolite : Na3AlF6  By Hydraulic Classifier
Fluorspar : CaF2 Carnallite : KCl. MgCl2. 6H2O Powdered/Crushed ore

• Nitrate Ores :
Chiele Saltpeter: NaNO3 Indian Salt petre : KNO3
• Native Ores : Gangue + water

Those metals which are chemically less reactive.

Water
They occur in the earth crust in form of free state
(lumbs)
e.g : Cu, Ag, Au, Hg, Pd, Pt, Bi Conc. ore

Corporate Office : Motion Education Pvt. Ltd., 394 - Rajeev Gandhi Nagar, Kota
2 | Metallurgy
OE
(b) By Magnetic separator :
S = C = S’ + Et O– K+ S=C
Powdered/Crushed Ore
S– K+
Nonmagnetic Roller Potassium
ethyl xanthate
Magnetic Roller
Depressant : KCN or NaCN
Non Magnetic Magnetic
substance
ZnS is found to be an impurity with the lead sulphide.
substance

Cassiterite or Tinstone contains impurities of Therefore to separate out PbS from ZnS depressant KCN or
wulframite or wulframates of Fe & Mn. NaCN added.
 Tin stone : SnO2  Diamagnetic PbS + NaCN  No complex formation due to very low Ksp
 Wulframites or wulframates of of PbS.
Fe & Mn : FeWO4, MnWO4  Paramagnetic. ZnS + 4NaCN  4Na+ + [Zn (CN)4]2– + S– –
Ulframates of Fe & Mn from Tin stone by magnetic (water soluble)
separator.

(c) By Froth Floatation Process : This method

ZnS [Zn(CN)4]2–
is used for the concentration of sulphide ores.
• It is based on the concept that the sulphide ores are
prefrentially wetted by pine oil, camphor oil while
Thus, ZnS becomes water soluble & it remains with gangue
gangue particles are prefrentially by water.
while PbS comes out with the froth.
• This is based on the physical phenomenon of
Activator: CuSO4
adsorption.
air
From galena (PbS.ZnS) ZnS is removed
ZnS + 4NaCN 4Na++[Zn(CN)4]2–   [Cu(CN)4]
CuSO 4

3–

Powdered/crushed ore
+
+ vaS– – + ZnS 
water pine oil

(water soluble)
(more stable)
& ZnS is taken out by froth floatation second time.
Conc. Ore Gangue (ii) Chemical Method of Concentration :
+ pine oil
Frother : Pine oil, Camphor oil Leaching : It involves dissolution of metalic ore in a suitable
reagent in which metallic ore is soluble and impurities are
Surface of pine oil insoluble.
Sulphide Leaching of alumina from bauxite :
ore
air bubble Al2O3(s) + 2NaOH(aq) + 3H2O(I)  2Na[Al(OH)4](aq)
Having F2O3 as important leachant.
The aluminate in solution is acidified by adding acid and
Froth Stabilizers : They reduce surface tension of water hydrated Al2O3 is precipitated.
e.g. cresols, amines.
2Na[Al(OH) 4](aq) +H + (aq) Al(OH) 3 +H 2 O +
Collector : Sodium or Potassium xanthates. It combines with
Na+(aq). (white ppt)
sulphide ore & makes them water replent so that its affinity
Hydrated alumina is filtered, dried and heated to give back
towards pine oil increases (Adsorption tendency increases)
pure Al2O3 :
KOH + EtOH  Et O– K+ + H2O
: info@motion.ac.in, url : www.motion.ac.in, : 1800-212-1799
99, 8003899588
 Metallurgy | 3

Al(OH)3 

 Al2O3(s) + 3H2O(g) (ii) Roasting : In the presence of air the sulphide are heated
in free supply of air below m.p. Impurities of sulphur,
white (pure)
phosphorus, arsenic & antimony are converted into their
Other examples :
corresponding volatile oxide & thus get removed.
In the metallurgy of silver and gold, the respective metal/ore
is leached with very dilute solution of NaCN or KCN in the Moisture & Water of crystallisation are also removed.
presence of air (for O2) from which the metal is obtained by
displacement reaction. 3
eg. (1) PbS + O  PbO + SO2 
2 2 
4M(s) + 8CN–(aq) + 2H2O(aq) + O2(g)  4[M(CN)2]– (aq)
+ 4OH–(aq) PbS + 2O2 
 PbSO4
(M = Ag Or Au)
2[M(CN)2]– (aq) + Zn(s) [Zn(CN)4]2–(aq) + 2M(s) 3 
(2) ZnS  O 2  ZnO  SO 2 
2
Step III : Conversion of Concentrated ore
into oxide form : (Utilised in manufacturing of H2SO4)

It is done either by calcination or by roasting. ZnS  2O 2  ZnSO 4

(i) Calcination :

• Calcination is carried out for carbonate, hydrated

metal oxide & metal hydroxide ores. Step IV : Reduction of oxide to the metal :
• It is carried out in the absence of air i.e., heating in (b) Reduction of Metal oxide / conc. ore into
absence of air. free metal .

Ca++ CO 3– – Ca++ CO 3– – Ca++ O– – Ca++ O– – This can be carried out


 + CO2
CO3– – Ca++ CO 3– – Ca++ O– – Ca++ O– – Ca++ (i) chemical reduction
lattice will remain same (ii) By self reduction or auto reduction or Air
• Due to calcination ore becomes porous.
Reduction
• Volatile organic impurities get evaporated

(iii) Metal - displacement method
eg. CaCO3(S) CaO  CO2
(iv) By electrolytic Reduction

CaCO3MgCO 3 .2H2O  CaO  MgO  2CO 2  2H2O
(v) By amulgamation.

2Al(OH)3  Al 2O 3  2 H2O 
(i) & (ii) method are collectively known as Pyrometallurgy
Al2 O3.2H2O 
 Al2O3 + 2H2O  e.g. Sn, Pb, Fe, Hg, Cu, B, Zn, (Based on Ellinghum diagram)

Pb(OH)2 + PbCO3 

 2PbO + CO2  + H2O (iii) step is called hydrometallurgy — Cu, Ag, Au are
extracted
FeCO3 
 FeO + CO2 
(iv) step is called Electrometallurgy, Alkali, Alkaline earth
Fe2O3. 3H2O 
 Fe2O3 + 2H2O  metals & Al & base electrolysis
Cu(OH)2. CuCO3 
 2CuO + CO2  + H2O (v) is used for Ag & Au

Black powder

ZnCO3 
 ZnO + CO2 

Corporate Office : Motion Education Pvt. Ltd., 394 - Rajeev Gandhi Nagar, Kota
4 | Metallurgy

(I) CHEMICAL REDUCTION : (b) Gold Schmidt Thermite Reduction :

1. Smelting i.e., carbon Reduction - Reduction Thermite : Al powder
of metal oxide by coke, coal & CO
Cr2O3 + 2Al 
 2Cr + Al2O3
Reduction of the metal oxide usually involves heating it with
some other Substance acting as a reducing agent, e.g., C or (Gf = –540 kJ/mole) (G3 = –827 kJ/mole)

CO or even another metal. The reducing agent (e.g., carbon) B2O3 + 2Al 
 2B + Al2O3
combines with the oxygen of the metal oxide.
2Mn3O4 + 8Al 
 9Mn + 4 Al2O3
MxOy + yC  xM + y CO
Some metal oxides get reduced easily while others are very Fe2O3 + 2Al 
 2Fe + Al2O3
difficult to be reduced. To understand the variation in the This method is used for reduction of those metal oxides which
temperature requirement for thermal reductions and to predict are highly stable if they are reduced by coke it will occur at
which element will suit as the reducing agent for a given very high temprature & at this high temperature the liberated
metal oxide (MxOy), Gibbs energy interpretations are done, metal will combine with the coke & carbide will be formed
which is explained by ellingham diagram. hence Al powder i.e., thermite is used
? G = H – TS (c) Reduction by Hydrogen :
If H is greater than zero then reduction will be feasible on Because of inflammable nature of hydrogen its use as a
increasing temprature i.e., |TS| > |H| reducing agent is very restricted.
Flux : Additional substances which are used during metal Cu2O + H2 
 2Cu + H2O
extration to remove acidic or basic impurity are called flux
depending upon nature of impurity flux are of two types. MOO3 + 3H2 
 M0 + 3H2O

3 T0 / w
(i) Basic Flux : It is used to remove acidic impurity eg : BCl3 + H Filament
  B + 3 HCl
2
CaO, MgO, CaCO3, MgCO3 FeCO3 etc.

BCl3 + H2
(ii)Acidic Flux : It is used to remove basic impurity eg :
SiO2, B2O3, P2O5, Na2B4O7. (Borax)
Reduction by other metals :

SiCl4 + 2Mg 

 2MgCl2 + Si
Smelting : Phenomenon of slag formation by combining flux
with impurity is called smelting. Kroll process used for extraction of Ti & Zr
1000 –1150C
Flux + Impurity  Slag (Smelting) TiCl4 + 2Mg  Ti + 2MgCl2

(Basic or acidic) ZrCl4 + 2Mg 

 Zr + 2MgCl2

I.M.I Process (Imperial Metal Industries)

Properties of slag :
TiCl4 + 4Na 
 Ti + 4NaCl
(i) Slag has low melting point than metal.
(ii) By Self reduction or Auto reduction or Air
(ii) Slag is lighter than metal therfore it floats over the molten Reduction :
metal and prevents further oxidation of molten metal by air.
This method is used for extraction of copper, lead, mercury
(iii) Slag immiscible with molten metal therefore it can be i.e., it is used for the extraction of metal from their sulphide
easily separted from molten metal. ores.

: info@motion.ac.in, url : www.motion.ac.in, : 1800-212-1799

99, 8003899588
 Metallurgy | 5

In this method the sulphide ore is roasted in free supply of EFe  / Fe  –0.40
air to its metal oxide & then air supply is cut off followed by
heating by increasing temprature & metal is extracted by  ECell  0.74  G < 0

self reduction. • Iron is found to be an impurity in the copper ores

hence if Zn is added to extract copper, iron will also
3
PbS + O2  PbO + SO2  be displaced along with copper & that is why iron
2
is used.
PbS + 2O2 
 PbSO4
• Both metals which extracted & by which we
Now air supply is cut off followed by heating extracted are water insoluble

PbS(s) + 2PbO(s) 

 3Pb(?) + SO2 
(iv) Electro Metallurgy : The metal is extracted by passing
Self reduction is responsible for acid rain than roasting
electricity into its fused salt or in aqueous solution.
because SO2 dissolves in air, (3927cc CO2 in 1000cc of H2O)
Extraction of sodium :
(iii) By Metal Displacement Method or By
Hydrometalurgy :  By electrolysis of Aq. NaCl solution :
Li K Ca Na Mg Al Zn Fe Sn Pb H NaCl(s) + x H2O Na+(aq) + Cl–(aq)

More Electropositive H2O H+ + OH–

than Hydrogen
• On passing electricity
Cu Ag Hg Au
At cathode : 2H+ + 2e–  H2 
Less Electropositive
 EH / 1/ 2H ; G  –nFE 
2 0
In this method the concentrated ore is treated/ leached with
specific chemical reagent that converts the ore into water ENa / Na  –2.7 V ; G = – n FE°
soluble salt. Now, on adding more electropositive metal into
 Na+ does not discharge at cathode
the aqueous salt solution the metal (less electro positive) is
displaced At anode : 2Cl–  Cl2 + 2e–
e.g.
E1/ 2 Cl / Cl –
 –1.36 Volt
2
Extraction of Copper from Malacite :

Cu(OH)2 CuCO3 + H2SO4  2CuSO4 + CO2 E1/ 2O –  –0.44 V

2 / OH

 + 2H2O
In sol : Na+ + OH–  NaOH
or
 By electrolysis of fused NaCl :
Cu(OH)2.CuCO3 
 2CuO + CO2  + H2O

NaCl( s )  Na   Cl–
? ? ? ? ? ??
CuO + H2SO4  CuSO4 + H2O Molten state

H2SO4  leaching agent, it leached out Cu as CuSO4 On Passing electricity

Now, on adding more electropositive metal :
At cathode : 2Na+ + 2e–  Na
CuSO4 + Fe  FeSO4 + Cu 
At Anode : 2Cl– +
 Cl2  2e
–

Fe Reducing agent)

ECu  / Cu  0.34
In sol. Na+ + OH–  NaOH


Corporate Office : Motion Education Pvt. Ltd., 394 - Rajeev Gandhi Nagar, Kota
6 | Metallurgy

Electrochemical Principles of Metallurgy : (A) By Physical Method :

We have seen how principles of thermodynamics are applied (a) Liquation Method :
to pyrometallurgy. Similar priniciples are effective in the Metal M.P.

reductions of metal ions in solution or molten state. Here Sn 232°C

they are reduced by electrolysis or by adding some reducing Impurities Fe 1535°C
element.
Mn 1244°C
In the reduction of molten metal salt, electrolysis is done.
W 3380°C
Such methods are based on electrochemical principles which impurities
(or Dross)
could be understood through the equation,
G° = –nE°F ..................... (16) Molten
Metal
Here n is the number of electrons and E° is the electrode
potential of the redox couple formed in the system. More
Fire
reactive metals have large negative values of the electrode
potential. So their reduction is difficult. If the difference of This method is used for refining of those metal which have
two E° values corresponds to a positive E° and consequently very low m.p. in comparison to impurity present in them.
negative G° in equation (16), then the less reactive metal e.g.  Sn, Pb, Hg, Bi, Zn
will come out of the solution and the more reactive metal
will go to the solution, e.g., (b) Distillation Method : It is used for refining of those
Cu2+(aq) + Fe(s)  Cu(s) + Fe2+(aq) metals which are volatile & hence it is used for refining of
Zn, Cd, Hg (i.e., is of filled d orbital metal)
In simple electrolysis, the Mn+ ions are discharged at negative
electrodes (cathodes) and deposited there. Precautions are (c) Zone Refining : (Si, Ge, Pb, B, Ga, In)

taken considering the reactivity of the metal produced and 1800ºC

SiO2 + 2C Si + 2CO
impure
suitable materials are used as electrodes. Sometimes a flux
2Cl2
is added for making the molten mass more conducting. SiCl4
distillation
SiCl4
Mg
Si
Zone
Si
Volatile Pure Pure refining Ultra
Pure
9
[1 : 10 ]

Step V: Purification or refining of crude Quartz tube

Moving
metal : Heating
Coil Pure silicon rod

(A) By physical Methods : Ar gas

(a) liquation Molten zone

Recrystalized of Si-rod
Si +
(b) Distillation impurities

(c) Zone refining Concept : Impurities are more soluble in the melt than in

(B) By Chemical Methods the solid state. (Fractional crystallization)

(a) Oxidation
(B) By Chemical Methods :
(b) Poling
(a) Oxidation : (Fe, Sn, Pb)
(c) Vapour Phase Refining
eg. Pig iron : M.P. 1080
(C) By Electrolytic Refining
Impurities : C, P, Mn, Si
: info@motion.ac.in, url : www.motion.ac.in, : 1800-212-1799
99, 8003899588
 Metallurgy | 7

50C 230C
O Ni  4Cu   Ni(CO) 4   Ni  CO 
Cu 2 SnO 2
Sn+O2
–200 FeO
impure volatile unstable pure

–300 /2O 2
Fe + 1
–400 80kg
–500 ZnO
/2O2 MnO
–600 Zn + 1 O2 (C) By Electrolytic Refining :
/2
–700 Mn + 1 SiO 2
2C Anode : Impure metal
–800 Si + O 2 +O
–500 2

2C
O
cathode : Pure metal
Electrolyte : Aq. salt sol. of metal/fused metal salt
+ Acid
Anode Mud : Metals which are less electropositive
100ºC Temp
than the metal to be refined.
CaO
P4  5O 2  P4 O10  Ca 3 (PO 4 )2 In electrolyte : More electropositive metals are found.
Si  O 2  SiO 2 (acidic ) eg. in Cu : Ag, Au, Fe, Zn

1
Mn + O 2  MnO (Basic) In electrolyte
2

MnO + SiO2  MnSiO3 + Heat H.J.T. Ellingham Diagram

Slag Ellingham diagram -

1 x
C O 2  CO M(s) + O  MO
2 2 2(g)  2 x(s)
This method is used for the refining of metals in which G = H – TS
impurtities are more oxidisable than metal itself.  For forward rxn S < 0
When impurities oxidise they are converted into either volatile
0
oxides or non volatile oxides Non-volatile oxides are removed
either by slag formation or by removing their skum Oxidation )
–100 (s
O
x

is known by various names : bassemerization (Fe), M

2

–200


Cupellation (Ag), Softening (Pb) or Puddling (for iron), )

(g
x O
2

tossing (for iron) G

(kg/mole) ) 2


(s
M
(b) Polling : When along with impurities the metal to be
refine is also oxidised part then this method is used. In this
method the molten impure metal is steared with green wood Temp
log, The hydrocarbons released from the log reduce metal (Ellingham diagram for formation of M2Ox)
oxide into metal while impurity oxides are not reduced. This
Ellingham diagram is a plot of formation of an
method is used for refining of Cu & Tin. In both metals
during poling iron get oxidised into FeO which in turn is element oxide between G & T
oxidised into Fe2O3 while in case of Sn, SnO2 is reduced to EXAMPLE 1
tin (Sn) & in case of Cu copper (I) oxide i.e., cuprous oxide
Which of the following statements are true :
is reduced to Cu,
Cu2O  Cu 1
A  Mg(s) + O (g) 
T1 MgO(s)
2 2
1
(c) Vapour Phase Refining : Impure metal is allowed B  Mg(?) + O2(g)  T2 MgO(s)
2
to react with a suitable reagent such that a volatile unstable 1
compound is formed & then the compound is decomposed C  Mg(g) + O (g) 
T3 MgO(s)
2 2
to pure free metal when it is subjected to heat.
• Mond's Process : used for refining of Ni

Corporate Office : Motion Education Pvt. Ltd., 394 - Rajeev Gandhi Nagar, Kota
8 | Metallurgy

• Aluminium can be extracted from Alumina by

(s) carbon reduction but the method is highly
O 3
Al 2
 (C) uneconomical because -

3 O2( g)
)  2 (i) As the smelting occurs above 200°C hence a part of
l(s gO
2A 
M the aluminium will go into vapour phase (M.P. =
1 O2
G –1000  2 (B)
2520°C)
Mg

–1100 (A) (ii) At this high temperature the liberated Al will

T2 T3 1350°C combine with the carbon & aluminium carbide will
Temp. be formed.
(iii) Hfor of alumina is high – ve value
I : Below 1350° Mg can reduce Al2O3
 It is thermodynamically more stable & reduction is
II : Above 1350° C Mg Will reduce Al2O3 more difficult
III : Below 1350° Al can reduce MgO • To extract metal from sulphide ore is carried out by
IV : Above 1350° Al can reduce MgO firstly roasting it into metal oxide & followed by its
smelting. Metal sulphide or sulphide ore is not
V : At 1350° C there is no change in free energy i.e., G = 0
directly smelted to metal.
then Above 1350C
Sol. 3MgO  2Al    Al 2O 3  3Mg, G < 0
2PbS + C 
 2Pb + CS2
(Its G high) (Its G less)
(Thermodynamically Not feasible)
Al2O3 + 3 Mg     3 MgO + 2Al
Below 1350C

3
At 1350° C both reactions have same G Pbs + O  PbO + SO2
2 2 

 G = 0 
PbO + C  Pb + CO   Thermodynamically feasible
To carry out smelting below 800°C, CO is used as reducing 

Gf of PbS = –21.9 kcal/mol
agent while above 800°C, smelting is carried out by coke.
Gf of CS2 = +17.15 kcal/mol
2C(s) + O2(g)  2CO (g) H = –221.0 kJ/mole
Gf of PbO = –45.1 kcal/mol
S = + 179.4 J kJ/mol
Gf of SO2 = –71.7 kcal/mol
C(s) + O2(g)  CO2(g) H = – 393.5 kJ/mol
Gf of CO = – 32.8 kcal/mol
S = 2.89 JK–1 mole–1
Extraction of Au, Ag, Fe, Cu, Pb, Sn, Zn,
Al, Na, Ca, Mg
1. Gold :
Occurence :
–100 1 O  CO 2
–200 CO  2 2 Found mostly in free state in quartz veins called auriferous
–300
–400 quartz.
–500 C  O2  CO2
–600 Extration of gold from native ore :
G 2C
–500 O3
(kJ/mole) –600 Al 2  O
2
(A) Crushing and concentration :
 2
CO
–700 3 O2
l 2 The gold ore is crushed, powdered finely and concentrated
–800 2 A
–900 by washing with water.
–1000
–1100 (B) (Treatment with 0.25–1% sodium cyanide or potassium
2000°C
cyanide solution) Extraction of Au, from Native ore by Mac-
710°C
Temp Arthur forrest cyanide process.

: info@motion.ac.in, url : www.motion.ac.in, : 1800-212-1799

99, 8003899588
 Metallurgy | 9

4Au + 8NaCN + 2H2O + O2  4Na[Au(CN)2] + 4NaOH (C) Electrolytic refining :

air soluble
Anode : Impure Ag
2Na[Au(CN)2] + Zn  Na2[Zn(CN)2] + 2Au Cathode : Pure Ag
(Impure)
Electrolyte : AgNO3(aq) + HNO3.
Impure Au is purified by Electrolytic refining method or by
amalgamation.
Silver from (commercial lead) argentiferous
lead by Parke’s process :
(C) Electrolytic refining method :
Desilverisation of Lead :
Anode : Impure Au
Cathode : Pure Au Lead extracted from galena (PbS) contains impurities of Cu,

Electrolyte : 4% AuCl 3 solution Ag, Bi, As, Fe Zn, Sn, etc. and is called commercial lead or
acidified with 10% HCl argentiferous lead. This contains Ag upto 2% which is

Purple of Cassius : It is of colloidial gold solution : extrated by parkes process. Commerical lead is mixed with

2AuCl3 + 3SnCl2  2Au + 3SnCl4 a large quantity of Zn and the mixture is melted, where Zn-

(Very dil.) Ag alloy is formed and Pb remains in the molten state. The
alloy is strongly heated where Zn is distilled of leaving Ag.
The gold thus precipitated is absorbed by Sn (OH)4 formed
by hydrolysis of SnCl4 This silver contains some Pb impurity which is removed by

SnCl4 + 4H2O  Sn(OH)4 + 4HCl cupellation process. Impure Ag is melted in a cupel (a boat

This form of gold is purple in colour named after its shaped dish made of bone ash) by passing Hot blast of air.
discoverer, Cassius. Pb is oxidised to PbO (litherge) which is either absorbed by
cupel or carried away by blast of air leaving pure Ag.

2. Silver :
Zn
Ores : (i) Siliver glance or argentite Ag2S (main ore)
Molten Zn is Distillstion
(Ag + Pb) (Zn + Ag)
(ii) Ruby silver or pyrargyrite 3Ag2S. Sb2S3 Argentiferous head
teken as solvent
Zn is more miscible
having 2% Ag with ag than Pb metal Ag (Impure)
(iii) Horn silver or chlorargyrite AgCl. Impure Ag having some
Pb impurity is further
purified by cepellation

Extraction of silver from silver glance :

Separation of silver from gold (Parting with
(A) Crushing and concentration : The ore is
conc. H2SO4)
crushed, powdered and concentrated by froth floatation
process. Alloy (Au < 20%) is boiled with conc. H2SO4 where Ag is
(B) Extraction of Ag by Mac-Arthur forrest dissolved as Ag2SO4 and Au remains as spongy mass.
cyanide process : (Treatment with 0.4-0.7%
sodium cyanide solution)
Atm air Ag2SO4 + Zn  2Ag + ZnSO4
Ag2S + 4NaCN 2Na [Ag(CN)2] + Na2S
(sparingly (Metaldisplacement reaction)
soluble
soluble solution)
The role of air is to oxidise Na2S so that reaction proceed in
the forward direction. If alloy contains Au > 20%, then some Ag is added to it so as to

Impure Ag is purified by Electolytic refining method or by reduce the % Au below 20.

amalgamation.

Corporate Office : Motion Education Pvt. Ltd., 394 - Rajeev Gandhi Nagar, Kota
 10 | Metallurgy

Silver from silver coin or silver ornaments:

dissolve in
(Ag + Cu) 
conc. HNO 3
 Ag+(aq) + Cu2+(aq) + 3NO3– (aq)

2+ –
dil. HCl
   AgCl + Cu (aq) + 3NO3

Recovergy of Ag from AgCl :

(i) By treating with KCN solution :
Reverberatory Furance
2AgCl + 2NaCN 2Na[Ag(CN)2] + 2NaCl
S + O2  SO2  ; 4As + SO2  2As2O3 ; 4Sd + 3O2
soluble complex  2Sb2O3
2Na[Ag(CN)2] + Zn(dust)  2Ag + Na2[Zn(CN)4] Volatile impurities are removed in this step.
(ii) Boiling with caustic soda and glucose. (C) Slag formation :
2AgCl + 2NaOH  Ag2O + 2NaCl + H2O 
 C6H12 O6
Roasted ore mixed with sand and strongly heated in
2Ag + C6H12O7 (Gluconic Acid) furnace.
FeO + SiO2  FeSiO3
1
(iii) 2AgCl + Na2CO3 
Fuse
 2Ag + CO2 + 2 O2 + 2NaCl flux slag
Upper layer containing slag is removed and lower
3. Copper :
layer contains mostly Cu2S (98%) with little amount
Ores :
of FeS(2%) is called matte.
Copper pyrites or Chalcopyrites CuFeS2 (main ore);
Cuprite or ruby copper Cu 2O ; Malachite
(D) Bessemerisation : (Self – reduction)
CuCO3Cu(OH)2(green);
2FeS + 3O2 

 2FeO + 2SO2
Azurite 2CuCO3.Cu(OH)2(Blue) ; Copper glance
Cu2S, bornite (peacock ore) Cu5FeS4. FeO + SiO2 
fuse
 FeSiO3(slag)

Extraction of copper from copper pyrites : 2Cu2S + 3O2 


 2Cu2O + 2SO2 (partial roasting)

(A) Crushing and concentration : Ore is first crushed and (limited air)
high temp.
then powedered finely and powdered ore is concentrated by Cu2S + 2Cu2O   6Cu + SO2 (self reduction)
froth floatation process. (R.A.) (impure)
Impure copper obtained has blister appearances and therefore
(B) Roasting : Concentrated ore along with SiO2 is heated called blister copper.
in excess of air in a reverberatory furnace. Waste gase Acidic
lining
(Cu2S + FeS + FeS2) of SiO2
2CuFeS2 + O2  Cu2S + 2FeS + SO2 Tuyer

2FeS + 3O2  2FeO + 2SO2(Major oxidation)

Hot
2Cu2S + 3O2 2Cu2O + 2SO2(Minor oxidation) air
Cu2O + FeS Cu2S + FeO

: info@motion.ac.in, url : www.motion.ac.in, : 1800-212-1799

99, 8003899588
 Metallurgy | 11

Poling : Molten Cu is stirred with poles of green wood to 5. Tin :

reduce any copper oxide impurity into Cu. Ores : (i) Cassiterite or Tin stone SnO2 (Main ore) (It
contains impurities of pyrites of Cu and Fe and magnetic
Electrolytic refining : impurity of wolframite which is a mixture of FeWO4 +
Anode - impure Cu ; MnWO4).
This mineral is also called black tin to distinguish it from
Cathode - Pure Cu ;
the metal Sn which is also called white tin.
Electrolyte CuSO4 + H2SO4.
The more electropositive impurities like Zn, Fe, Ni Extraction of Sn from cassiterite :
etc. get dissolved in solution and less positive (i) Crushing and concentration :
impurities like Ag, Au collect below anode as anode The ore is crushed and washed with a stream of runing water
mud. to remove lighter silicious impurities followed by magnetic
separation method to remove the magnetic impurity of
Wolframite.
4. Lead :
Ores : Galena PbS (Main ore) ; Anglesite PbSO4 ; Cerussite (ii) Roasting :
PbCO3 Concentraed ore is heated in pressence of air, and volatile
impurities (S as SO2, As as As2O3 and Sb as Sb2O3) are
Extraction of lead from galena :
removed. The impurities of pyrites of Cu and Fe are converted
Crushing and conentration : The ore is crushed, grinded
into their respective oxides and sulphates.
finely and concentrated by froth floatation process.
Roasting : In reverberatory furnance, limited supply of air (iii) Washing :
is passed at moderate temperature. Sulphates of copper and iron are dissolved in water. The ore
PbS + 2O2 

 PbSO4 ; 2PbS + 3O2 

 2PbO + thus obtained contains 60–70% SnO2 and is called as black
tin.
2SO2
Self reduction : Air supply is cut off and the temperature is
Carbon reduction :
increased to melt the change in reverberatory furnace.
The black tin is mixed with anthracite coal and heated to
high temp.
PbS + 2PbO  Δ
 3Pb + SO
2 about 1300°C. If SiO2 is present as impurity then CaO is
(R.A.) impure added as flux.
high temp.
PbS + PbSO4  2Pb + 2SO2
Δ

(R.A.) impure
SiO2 + CaO (flux) 
 CaSiO3 (slag)
fuse

PbSiO3 + CaO (lime)  PbO + CaSiO3 (slag)

In this way, lime (CaO) prevents formation of PbSiO3.

Impure Pb is purified by electrolytic refining method or by
liquation and poling.
Electrolytic refining :
Anode - Impure Pb
Cathode - Pure Pb
Electrolyte - PbSiF6 + H2SiF6 + gelatine

Corporate Office : Motion Education Pvt. Ltd., 394 - Rajeev Gandhi Nagar, Kota
12 | Metallurgy

Refining : (i) Combustion Zone (155 - 1700°C)

(i) Liquation and poling : (a) (Combustion zone) a blast of dry preheated air is blown
Impure Sn is melted on the sloping hearth where Sn(m.pt. into the furnace from near the bottom of the furnace. Near
232°C) is first melt and flows out leaving behind the less the bottom, the preheated air comes in contact with the falling
fusible impurities of Cu, Fe, W etc. The liquid Sn is then coke and combustion of coke into CO2 takes place.
strirred with poles of green wood to reduce SnO2 (Impurity) C + O  CO2 H = – 393.5 kJ
to Sn. CO2 produced in the combustion zone rises up and meets
(ii) Electrolytic refining : with more coke in fusion zone and gets reduced to CO.
Anode : Impure Sn CO2 + C  2CO H = + 163.0 kJ
Cathode : Pure Sn
Electrolyte : SnSO4 + H2SO4

6. Iron : Charge

Ores : Haematite Fe2O3(Main ORE) ; Limonite Fe2O3.3H2O

; Magnetite Fe3O4 ; Siderite FeCO3 ; Iron pyrites FeS2
Cup and cone
Extraction of Iron from ore haematite : arrangement
200-250°C Waste gases
Crushing and concentration : The oxide ore is first crushed 400°C
in jaw crushers and then is broken in small pieces. Haematite
500°C Retractory
(non-magentic) is washed with running water to remove
700°C bocks
earthy and siliceous impurities by levigation.
800-1000°C
Hot air
Calcination following by roasting : 1300°C

The concentrated ore is roasted with excess air in a 1800°C Tuyeres

reverberatory furnace. During roasting step, the following
changes occur : Molten
slag Molten metal

(a) If FeCO3 is present as impurity, it gets decomposed into Blast furnace

FeO which is oxidised by air to Fe2O3. (ii) Reduction zone (250 - 700°C)
FeCO3  
 FeO + CO2 (calcination) Near the top of the furnace (reduction zone), the
siderite temperature varies from 250-700°C. Here the oxide ore
4FeO + O2 (air) 

 2Fe2O3 (Roasting) (Fe2O3) is reduced to spongy iron with the help of uprising
In this way, formation of FeSiO3 slag is prevented during vapours of CO produced in the zone of fusion.
melting, and following reaction does not occur. Fe2O3 + 3CO 
400 700C
 2Fe + 3CO2
SiO2 + FeO  FeSiO3 (slag) Actually above Reduction, takes in 3 steps :
(b) The impurities of S, As are also removed as their volatile 3Fe2O3 + CO  2Fe3O4 + CO2 
oxides Fe3O4 + CO  3FeO + CO2 
S + O2 SO2 FeO + CO  Fe + CO2 
4As + 3O2  2As2O3, (Spongy iron)
The entire mass becomes porous and hence the
Any Fe 2O 3 which escapes from reduction in
reduction of Fe2O3 to spongy iron becomes easy at later stage.
reduction zone is reduced in fusion zone.
Reduction in blast furnace.
(Fe2O3 ore + lime stone + coke) is smelted in blast furnace
and following changes take place.

: info@motion.ac.in, url : www.motion.ac.in, : 1800-212-1799

99, 8003899588
 Metallurgy | 13

(iii) Slag formation zone (700-1000°C) Manufacturing of wrought from cast Iron :
In the middle of the furnace (slag formation zone) where the Wrought iron is mannfactured from puddling furnace having
temperature varies from 700-1000°C, lime stone (CaCO3) inner lining of haematite (Fe2O3) oxidant for impurities
present in the change decomposes into CaO and CO2. present in cast iron.

CaCO3 
 CaO + CO2
1000 C
Mn + Fe2O3  MnO + 2 Fe

CaO combines with the impurity of SiO2 and forms a fusible (O.A.) (basic)
slag of CaSiO3. Thus CaO acts as a basic flux. Si + Fe2O3  SiO2 + 2 Fe
CaO(basic flux) + SiO2 (acidic impurity)  CaSiO3(slag) (O.A.) (basic)
Slag is lighter than the molten iron. It moves down and floats MnO + SiO2  MnSiO3 + (slag)
over molten iron. This region where slag is fromed is called (O.A.) (basic)
slag formation zone.
S + Fe2O3  SO2 + 2 Fe
C + Fe2O3  3CO + 2 Fe
(iv) Fusion Zone (1000 - 1500°C)
Since the reduction of CO2to CO is an endothermic reaction 3P4 + 10Fe2O3  6P2O5 + 20Fe

(Heat is required), temperature is decreased to about 1500°C. P2O5 + Fe2O3  2FePO4(slag)

Fe2O3 is reduced to Fe which might not have been reduced
in the reduction zone. Manufacturing of steel from cast from :
Fe2O3 + 3C  2Fe + 3CO (i) Bassemerisation (already discussed)
Impurities are also reduced and get mixed up with spngy (ii) Open-Hearth process (Siemen Marthin’s
Iron. process)
MnO2 + 2C  Mn + 2CO
(iii) Electrical furnace process
2P2O5 + 10C  P4 + 10CO
SO2 + C  S + 2CO
Open hearth process (siemen Mortin’s
SiO2 + 2C  Si + 2CO
process)
Spongy iron produced in the reduction zone melts here and
Mn + Fe2O3  MnO + 2 Fe
gets impured in called pig iron, while slag being lighter floats
(O.A.) (basic)
over and thus prevents oxidation of Fe by blast of hot air.

Si + Fe2O3  SiO2 + 2 Fe
Types of Iron :
(O.A.) (Acidic)
1. Cast iron (2% to 5% carbon & other impurity)
2. Steel (0.5% to 2% carbon & other impurity)
MnO + SiO2  MnSiO3 + (slag)
3. Wrought iron (< 0.5% carbon & other impurity)
(O.A.) (basic)
S + Fe2O3  SO2 + Fe
(O.A.)
C + Fe2O3  3CO  + 2Fe
3P4 + 10Fe2O3  6P2O5 + 20Fe
P2O5 + 3CaO  Ca3(PO4)2 (Thomas slag)

Corporate Office : Motion Education Pvt. Ltd., 394 - Rajeev Gandhi Nagar, Kota
14 | Metallurgy

(iii) Tempering : Process of heating quenched steel much

below redness and then colling it slowly is called tempering.
In this steel becomes neither so hard nor so brittle.

Surface Treatment of steel :

Open hearth furnace for the manufacture steel from (i) Case – Hardening : Process of forming hard coating of
cast iron iron carbide over mild steel by heating it with charcoal is
called case – hardening.
(ii) Nitriding : Process of forming hard coating of iron nitride
by heating steel with ammonia gas is called nitriding.

After adding requried amount of spiegeleisen steel is formed. 7. Zinc :

In this method 2 – 5% iron is also oxidised by air because Ores : Zinc blende ZnS (main ore), Zincite (ZnO), Calamine,
hearth is open therefore this method is discarded is modern ZnCO3.
age. Extraction of zinc from zinc blende :

(A) Crushing and concentration :

In modern age steel is manufactured by electrical furnace
process or by L.D. process. In electrical fumace process
heating effect is produced by passing electricity and all
chemical reaction are similar to open-hearth process.
The ore is crushed and concentrated by froth floatation
process.
(B) Roasting :
The concentrated ore is roasted in presence of excess of air

2ZnS + 3O2 2ZnO + 2SO2

ZnS + 2O2 ZnSO4

2ZnSO4 2ZnO + 2SO2 + O2

ZnSO4 decomposed at higher temperature

(C) Carbon Reduction (Balgian process) :

Roasted ore is heated with coke in a vertical fire clay retort.
ZnO + C Zn  + CO
Heating Treatment of STEEL
(R.A.) vapour
(i) Annealing : Process of heating steel upto redness and Vapours of zinc are collected by rapid cooling to get zinc
then cooling it slowly is called annealing, In this way steel spelter (Impure Zn).
becomes soft, malleable and elastic. Impure Zn is purified either by electrolytic refining method
or by distillation.
(ii) Quenching : Process of heating steel upto redness and
then cooling it suddenly by plundging in into oil or water is (D) Electrolytic refining :
called quenching. In this way steel become hard and brittle. Anode : Impure Zn
Cathode : Aluminium Electrode
Electrolyte : ZnSO4(aq) + H2SO4
: info@motion.ac.in, url : www.motion.ac.in, : 1800-212-1799
99, 8003899588
 Metallurgy | 15

* Extraction of Cr From FeCr2O4(FeO.Cr2O3) Chromite ORE :

Conc. Step : Chromite ore is concentrated by gravity sep. Method to remove light impurites followed by magnetic sep.
method to remove non-magnetic impurities.
Chemical Method to Separate Cr2O3 :
fuse
4FeO.Cr2O3 + 7O2 (air) + 8 Na2CO3/16NaOH 
lim e
 2Fe
e2O3 + 8Na2CrO4 + 8CO2/8H2O

2Na+ (aq) + Cr2O72–(aq) + SO42– (aq) 2Na+(aq) + CrO42– (aq)

(Orange Solution) yellow solution

Carbon red.
Na2Cr2O7.2H2O 
method
 NaCrO2 
H2 O
 Cr(OH)3
(orange crystal) (green ppt)

Cr2O3 (green solid)

Al-reduction method : (Goldsmith alumino thermite process)


Cr2O3  Al(R.A.) 
Mg Ribbon  BaO2
 Al2 O3  2Cr   Heat

3part 1part ? ? ? ? ? ? ? ??
? (Molten
? ? ? ? ??? ? ? ? ? ? lgnition Mixture Impure
Thermite Mixture metal)

Impure Cr is purified by electrolytic refining method.

Anode : Impure chromium
Cathode : Hg-electrode
Electrolyte : CrCl3 + HCl

Distillation
Hg – Cr
(alloy)

* Extraction of Mn from MnO2 (Pyrolusite) :

Pyrolusite is concentrated by gravity separation method followed by magnetic separation method to remove
non-magnetic impurity.

Calcination :
MnO2 gives explosive rxn. with Al therefore in this step it is converted into mixed oxide Mn3O4.
3MnO2 
900C
 Mn3O4(MnO + Mn2O3) + O2

Corporate Office : Motion Education Pvt. Ltd., 394 - Rajeev Gandhi Nagar, Kota
16 | Metallurgy

Al-reduction method :
(Goldsmith alumino thermite process) Distillation
Hg – Cr
(alloy)

Mn3 O 4  2Al(R.A.) 
Mg Ribbon  BaO2
 4 Al2 O3  9Mn  Heat

3part 1part ? ? ? ? ? ? ? ?? (Im pure
? ? ? ? ??? ? ? ? ? ?
Thermite Mixture
lgnition Mixture metal) 8. Aluminium :
Ores :
Impure Mn is purified by electrolytic refining method.
(i) Bauxite Al2O3.2H2O (main ORE) ; Diaspore Al2O3.H2O
Anode : Impure Mn
; Corundum Al2O3
Cathode : Hg-electrode
(ii) Mica K 2O.3Al 2 O 3.6SiO 2.2H 2 O ; Kaolin
Electrolyte : MnSO4 + H2SO4
Al2O3.2SiO2.2H2O
(iii) Cryolite Na3AIF6

Extraction of Al from Bauxite :

Purification of Bauxite :

Electrolysis of pure fused Al2O3 (Hall -

Heroult method)

Cathode - iron tank lined with graphite

Anode - Carbon rods dipped in molten electrolyte
Electrolyte - molten (20% Al2O3 + 60% Cryolite + 20% CaF2)
Temp  1100°C
Cryolite lowers the melting point of mixture and makes the
molten mix conducting.
Na3AlF6 3NaF +AlF3
+3 –
AlF3  Al + 3F Anodes are periodically changed as they are consumed by
At cathode Al+3 + 3e– Al oxygen liberated at anode.
– –
At anode 3F  3F + 3e

3 Electrolytic refining (Hoppe’s Method)

Al2O3 + 6F  2AIF3 + O
2 2
Iron box lined with carbon, contains the three molten layers.
1 Bottom layer : Impure Al as anode
C+ O  CO
2 2
1
CO + O  CO2
2 2
: info@motion.ac.in, url : www.motion.ac.in, : 1800-212-1799
99, 8003899588
 Metallurgy | 17

Middle layer : (Na3AlF6 + BaF2) Molten electrolyte (c) Preparation of anhydrous magnesium chloride :
Tope layer : molten pure Al as cathode. MgCl2.6H2O 

 MgCl2 + 6H2O
Dry HCl ( g)
On passing the current aluminium is deposited at
* It is not made anhydrous by simple heating because it gets
cathode from the middle layer and an equivalent amount is
hydrolysed.
taken from andoe (bottom layer) levaing behind the impurites.
MgCl2.6H2O 

 MgO + 5H2O + 2HCl
In this way aluminium obtained is 99.98% pure.

(d) Electrolysis of fused anhydrouns MgCl2 :

9. Magnesium : (Dow’s process)
Magnesium chloride obtained by any of the above methods
Ores :
is fused and mixed with sodium chloride and calcium chloride
Carnallite MgCl 2.KCl 6H 2 O (main ore) ; Epsom
in the temperature range of 972 – 1023K. The molten mixture
MgSo4.7H2O magnesite MgCO3 ; Kiesserite MgSO4. H2O ;
is electrolysed. Magnesium is liberated at the carhode (iron
Dolomite MgCO 3. CaCO 3 ; Kainite K2SO 4. MgSO 4 .
pot) and chlorine is evolved at graphite anode.
MgCl 2.6H2O (Mg is also found in Talc, sabestos and
chlorophyll) MgCl2 Mg2+ + 2Cl–

At cathode : Mg2+ + 2e–  Mg(99% pure) ;

Sea water contains 0.13% magnesium as chloride and
At anode : 2Cl–  Cl2 + 2e–
sulphate. It involves following steps.
(a) Precipitation of magnesium as magnesium
hydroxide by slaked lime :
MgCl2 + Ca(OH)2  Mg(OH)2  + CaCl2 (ppt. reaction)
Porcelain
hood
(b) Preparation of hexahydrated magnesium chloride:
Mg(OH)2 + 2HCl(aq)  MgCl2 + 2H2O (Neutralisation Inert gas
(Coal gas) Inert gas
reaction)
The solution on concentration and crystallisation gives the
magnealum
crystals of MgCl2.6H2O

Molten Electrolyte

Iron cell

Corporate Office : Motion Education Pvt. Ltd., 394 - Rajeev Gandhi Nagar, Kota