METALLURGY

Minerals: Naturally occurring chemical substance in which metal exist either in its free
state or in combined state is called mineral.

Ore: Mineral from which metal can be conventionally and economically extracted is
called ore & impurities associated with it is called gangue or matrix.

Sulphide Ores :
Galena : PbS Cinnabar : HgS
Zinc blend : ZnS Chalcopyrite : CuFeS2
Copper glance : Cu2S Fool’s Gold : FeS2

Oxide Ores:
Bauxite : Al2O3. 2H2O Hematite : Fe2O3
Limonite : Fe2O3. 3H2O Tin stone or Cassiterite : SnO2

Carbonate Ores :
Siderite : FeCO3 Calamine : ZnCO3
Malachite : Cu2CO3(OH)2 Dolomite : CaCO3.MgCO3. 2H2O
lime stone : CaCO3

Sulphate Ores :
Gypsum : CaSO4.2H2O Anglesite PbSO4
Glauber’s salt : Na2SO4. 10H2O Mohr’s salt: (NH4)2Fe(SO4)2.6H2O

Halide Ores :
Rock salt : NaCl Cryolite : Na3AlF6
Fluorspar : CaF2 Carnallite : KCl. MgCl2.6H2O

Nitrate Ores :
Chile Saltpetre : NaNO3 Indian Saltpetre : KNO3

Native Ores :
Those metals which are chemically less reactive. They occur in the earth crust in form
of free state (lumbs)
e.g : Cu, Ag, Au, Hg, Pd, Pt, Bi

The extraction of metal from its ore is completed in five steps

Step I : Pulverization : The crushing of ore to powdered state is called pulverization.

Step II : Concentration or Dressing or beneficent of ore
Step III : Conversion of Concentrated ore into oxide form
Step IV : Reduction of oxide to the metal
Step V: Purification or refining of crude metal :

Step I : Pulverization
The crushing of ore to powdered state is called pulverization This process in stamp mill
or ball mill

Step II : Concentration or Dressing or benefaction of Ore

(a) By Gravity separation : Ore particles are heavier than the gangue
particles. This is used for the separation of most of the gangue particles :

Cassiterite or Tinstone contains impurities of wulframite or wulframates of Fe & Mn.

Tin stone : SnO2→Diamagnetic

Wulframites or wulframates of
Fe & Mn : FeWO4,MnWO4⇒Paramagnetic
Ulframates of Fe & Mn from Tin stone by magnetic separator.

(c) By Froth Floatation Process : This method 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 gangue particles are prefrentially by water.

This is based on the physical phenomenon of adsorption.

Froth Stabilizers : They reduce surface tension of water e.g. cresols, amine.

Collector : Sodium or Potassium xanthates. It combines with sulphide ore & makes
them water replant so that its affinity towards pine oil increases (Adsorption tendency
increases)

KOH+EtOH→EtO–K++H2O

Depressant : KCN or NaCNZnS is found to be an impurity with the lead sulphide.

Therefore to separate out PbS from ZnS depressant KCN or NaCN added.
PbS+NaCN→ No complex formation due to very low Ksp of PbS.
ZnS+4NaCN→4Na++[Zn(CN)4]2–+S––
(water soluble)

Thus, ZnS becomes water soluble & it remains with gangue while PbS comes out with
the froth.

Activator : CuSO4
From galena (PbS.ZnS) ZnS is removed
ZnS+4NaCN⇌4Na++[Zn(CN)4]2–CuSO4−→−−−−[Cu(CN)4]3–+ZnS↓
+S−− (watersoluble)
(more stable)
& ZnS is taken out by froth floatation second time.

(ii) Chemical Method of Concentration

Leaching : It involves dissolution of metallic ore in a suitable reagent in which metallic

ore is soluble and impurities are insoluble.

Leaching of alumina from bauxite :

Al2O3(s)+2NaOH(aq)+3H2O(I)→2Na[Al(OH)4](aq)
Having F2O3as important leachant.The aluminate in solution is acidified by adding
acid and hydrated Al2O3 is
precipitated. 2Na[Al(OH)4](aq)+H+(aq)⇌Al(OH)3↓+H2O+Na+(aq).

(white ppt)

Hydrated alumina is filtered, dried and heated to give back pure Al2O3:

Al(OH)3↓→Al2O3(s)+3H2O(g)

white (pure)

Other examples
In the metallurgy of silver and gold, the respective metal/ore is leached with very
dilute solution of NaCN or KCN in the presence of air (for O2) from which the metal is
obtained by displacement reaction.

4M(s)+8CN–(aq)+2H2O(aq)+O2(g)→4[M(CN)2]–(aq)+4OH–(aq)
(M = Ag Or Au)
2[M(CN)2]–(aq)+Zn(s)→[Zn(CN)4]2–(aq)+2M(s)↓

Step III : Conversion of Concentrated ore into oxide form : It is done either by
calcination or by roasting.

(i) Calcination

Calcination is carried out for carbonate, hydrated metal oxide & metal hydroxide
ores.
It is carried out in the absence of air i.e.,heating in absence of air.
Due to calcination ore becomes porous.
Volatile organic impurities get evaporated

eg. CaCO3(s)−→ΔCaO+CO2

CaCO3MgCO3.2H2O−→ΔCaO+MgO+2CO2↑+2H2O

2Al(OH)3−→ΔAl2O3+2H2O↑
Al2O3.2H2O−→ΔAl2O3+2H2O↑
Pb(OH)2.PbCO3−→Δ2PbO+CO2↑+H2O
FeCO3−→ΔFeO+CO2↑
FeO3.3H2O−→ΔFe2O3+2H2O↑
Cu(OH)2.CuCO3−→Δ2CuO+CO2↑+H2O Black powder

ZnCO3−→ΔZnO+CO2↑

(ii) Roasting

In the presence of air the sulphide are heated in free supply of air below m.p.
Impurities of sulphur, phosphorus, arsenic & antimony are converted into their
corresponding volatile oxide & thus get removed. Moisture & Water of crystallization
are also removed.

Example
(1) PbS+32O2Δ→PbO+SO2↑
PbS+2O2Δ→PbSO4

(2) ZnS+32O2Δ→ZnO+SO2↑(Utilised in manufacturing of H2SO4)

ZnS+2O2→ZnSO4

Step IV : Reduction of oxide to the metal

Reduction of Metal oxide / conc. ore into free metal .
This can be carried out

(i) chemical reduction

(ii) By self reduction or auto reduction or Air Reduction
(iii) Metal - displacement method
(iv) By electrolytic Reduction
(v) By amalgamation.

(i) & (ii) method are collectively known as Pyrometallurgy

e.g. Sn, Pb, Fe, Hg, Cu, B, Zn, (Based on Ellinghum diagram)
(iii) step is called hydrometallurgy — Cu, Ag, Au are extracted
(iv) step is called Electrometallurgy, Alkali, Alkaline earth metals & Al & base
electrolysis
(v) is used for Ag & Au

(i) Chemical Reduction

1.Smelting i.e.,carbon Reduction-Reduction of metal oxide by coke, coal & CO
Reduction of the metal oxide usually involves heating it with some other Substance
acting as a reducing agent, e.g., C or CO or even another metal. The reducing
agent (e.g., carbon) combines with the oxygen of the metal oxide.

MxOy+yC→xM+yCO

Some metal oxides get reduced easily while others are very difficult to be
reduced. To understand the variation in the temperature requirement for thermal
reductions and to predict which element will suit as the reducing agent for a given
metal oxide (MxOy), Gibbs energy interpretations are done, which is explained by
ellingham diagram.

∵Δ G=Δ H–TΔ S

If ΔH is greater than zero then reduction will be feasible on increasing temperature

i.e., |TΔ S|>|Δ H|

Ellingham diagram

M(s)+X2O2(g)Δ→M2Ox(s)

Δ G=Δ H–TΔS

∴ For forward reaction ΔS<0

(Ellingham diagram for formation of M2Ox)

ΔΔ

To extract metal from sulphide ore is carried out by firstly roasting it into metal
oxide & followed by its smelting. Metal sulphide or sulphide ore is not directly
smelted to metal.

2PbS+CΔ→2Pb+CS2(Thermodynamically Not feasible)

Pbs+32O2Δ→PbO+SO2↑PbO+CΔ→Pb+CO↑⎫⎭⎬⎪⎪⎪⎪⎪⎪Thermodynamically
feasible

Δ Gf of PbS = –21.9 kcal/mol

Δ Gf of CS2= +17.15 kcal/mol
Δ Gf of PbO = –45.1 kcal/mol
Δ Gf of SO2= –71.7 kcal/mol
Δ Gf of CO = – 32.8 kcal/mol

Flux

Additional substances which are used during metal extraction to remove acidic or
basic impurity are called flux depending upon nature of impurity flux are of two types.

(i) Basic Flux : It is used to remove acidic impurity eg : CaO,

MgO, CaCO3, MgCO3FeCO_3 etc.
(ii)Acidic Flux : It is used to remove basic impurity eg
:SiO2, B2O3, P2O5, Na2B4O7. (Borax)

Smelting : Phenomenon of slag formation by combining flux with impurity is called

smelting.
Flux + Impurity →Slag (Smelting)
(Basic or acidic)

Properties of slag

(i) Slag has low melting point than metal.

(ii) Slag is lighter than metal therefore it floats over the molten metal and prevents
further oxidation of molten metal by air.
(iii) Slag immiscible with molten metal therefore it can be easily separated from
molten metal.

(b) Gold Schmidt Thermite Reduction

Thermite : Al powder
Cr2O3+2AlΔ→2Cr+Al2O3 (Δ Gf ( = –540 kJ/mole)△G3 = –827 kJ/mole)
B2O3+2AlΔ→2B+Al2O3
2Mn3O3+8AlΔ→9Mn+4Al2O3
Fe2O3+2AlΔ→2Fe+Al2O3

This method is used for reduction of those metal oxides which are highly stable if
they are reduced by coke it will occur at very high temperature & at this high
temperature the liberated metal will combine with the coke & carbide will be
formed hence Al powder i.e., thermite is used

(c) Reduction by Hydrogen

Because of inflammable nature of hydrogen its use as a reducing agent is very
restricted.

Cu2O+H2Δ→2Cu+H2O MoO3+3H2Δ→Mo+3H2O

Reduction by other metals

SiCl4+2MgΔ→2MgCl2+Si

Krollprocess used for extraction of Ti & Zr

TiCl4+2Mg−→−−−−−−Δ1000−1150oCTi+2MgCl2

ZrCl4 +2MgΔ→Zr+2MgCl2

I.M.I Process (Imperial Metal Industries)

TiCl4+4NaΔ→Ti+4NaCl

(ii) By Self reduction or Auto reduction or Air Reduction

This method is used for extraction of copper, lead, mercury i.e., it is used for the
extraction of metal from their sulphide ores.
In this method the sulphide ore is roasted in free supply of air to its metal oxide &
then air supply is cut off followed by heating by increasing temperature & metal is
extracted by self reduction.

PbS+32O2Δ→PbO+SO2↑

PbS+2O2Δ→PbSO4

Now air supply is cut off followed by heating

PbS(s)+2PbO(s)Δ→3Pb(l)+SO2

Self reduction is responsible for acid rain than roasting because SO2 dissolves in air,
(3927cc CO2 in1000cc ofH2O)

(iii) By Metal Displacement Method or By Hydrometalurgy :

In this method the concentrated ore is treated/ leached with specific chemical
reagent that converts the ore into water soluble salt. Now, on adding more
electropositive metal into the aqueous salt solution the metal (less electro positive)
is displaced

e.g. Extraction of Copper from Malacite :

Cu(OH)2CuCO3+H2SO4→2CuSO4+CO2↑+2H2O

or

Cu(OH)2.CuCO3Δ→2CuO4+CO2↑+HO2
CuO+H2SO4→CuSO4+H2O
H2SO4⇒leaching agent, it leached out Cu as CuSO4
Now, on adding more electropositive metal :
CuSO4+Fe→FeSO4+Cu↓ (Reducing agent)

∴ Eocu++/cu =+0.34
Eofe++/fe =_0.40

∴Eocell = 0.74 ⇒ △G<O

Iron is found to be an impurity in the copper ores hence if Zn is added to extract

copper, iron will also be displaced along with copper & that is why iron is used.
Both metals which extracted & by which we extracted are water insoluble

(iv) Electro Metallurgy

The metal is extracted by passing electricity into its fused salt or in aqueous solution.

Extraction of sodium :
⇒By electrolysis of Aq. NaCl solution :
NaCl(s)+x H2O⇌Na+(aq)+Cl–(aq)
H2O⇌H++OH–

On passing electricity
At cathode: 2H++2e–→H2↑
∴ EoH+/1/2h2=0;Δ G=−n FEO
EoNa+/Na=−2.7V;Δ G=−n FEo
∴ Na+ does not discharge at cathode

At anode :
2Cl−⟶Cl2↑+2e−
Eo1/2Cl2/Cl− =-1.36 Volt
Eo1/2O2/OH− = -0.44 V

In sol : Na+OH−→ NaOH

⇒ By electrolysis of fused NaCl :
NaCl(s) Δ −→−−−Na++Cl−
Motion state

On Passing electricity
At cathode : 2Na++2e–→Na
At Anode : 2Cl–→Cl2↑+2e–
In sol. Na++OH–→NaOH

Electrochemical Principles of Metallurgy

We have seen how principles of thermodynamics are applied to pyrometallurgy.

Similar principles are effective in the reductions of metal ions in solution or molten
state. Here they are reduced by electrolysis or by adding some reducing element.

In the reduction of molten metal salt, electrolysis is done. Such methods are based on
electrochemical principles which could be understood through the equation,

ΔG° = –nE°F ………………… (16)

Here n is the number of electrons and E° is the electrode potential of the redox couple
formed in the system. More reactive metals have large negative values of the
electrode potential. So their reduction is difficult. If the difference of two E° values
corresponds to a positive E° and consequently negative ΔG° in equation (16), then
the less reactive metal will come out of the solution and the more reactive metal will
go to the solution, e.g.,

Cu2+(aq)+Fe(s)→Cu(s)+Fe2+(aq)

In simple electrolysis, the Mn+ ions are discharged at negative electrodes (cathodes)
and deposited there. Precautions are taken considering the reactivity of the metal
produced and suitable materials are used as electrodes. Sometimes a flux is added
for making the molten mass more conducting.

Step V: Purification or refining of crude metal

1. By physical Methods

1. liquation
2. Distillation
 3. Zone refining
2. By Chemical Methods

1. Oxidation
2. Poling
3. Vapour Phase Refining
3. By Electrolytic Refining

1. By Physical Method

1.1. Liquation Method

This method is used for refining of those metal which have very low m.p. in comparison to
impurity present in them.

e.g. →Sn, Pb, Hg, Bi, Zn

1.2. Distillation Method :

It is used for refining of those metals which are volatile & hence it is used for refining of
Zn, Cd, Hg (i.e., is of filled d orbital metal)

1.3. Zone Refining (Si, Ge, Pb, B, Ga)

Concept : Impurities are more soluble in the melt than in the solid state. (Fractional
crystallization)

2. By Chemical Methods

2.1. Oxidation : (Fe, Sn, Pb)

eg. Pig iron : M.P. 1080

**Impurities : **C, P, Mn, Si

P4+5O2→P4O10 −→−CaO Ca3(PO4)2

Si+O2→SiO2(acidic)

Mn+12O2→MnO(Basic)

MnO+SiO2→MnSiO3+Heat
Slag

C+12O2→CO

This method is used for the refining of metals in which impurities are more oxidisable than
metal itself.

When impurities oxidise they are converted into either volatile oxides or non volatile oxides
Non-volatile oxides are removed either by slag formation or by removing their skum
Oxidation is known by various names : bassemerization (Fe), Cupellation (Ag), Softening
(Pb) or Puddling (for iron), tossing (for iron)

2.2. Polling

When along with impurities the metal to be refine is also oxidized part then this
method is used. In this method the molten impure metal is steared with green wood
log, The hydrocarbons released from the log reduce metal oxide into metal while
impurity oxides are not reduced. This method is used for refining of Cu & Tin. In both
metals during poling iron get oxidised into FeO which in turn is oxidised
into Fe2O3while in case of Sn, SnO2 is reduced to tin (Sn) & in case of Cu copper (I)
oxide i.e., cuprous oxide is reduced to Cu,

Cu2O→Cu

2.3. Vapour Phase Refining :

Impure metal is allowed to react with a suitable reagent such that a volatile unstable
compound is formed & then the compound is decomposed to pure free metal when
it is subjected to heat.

Mond’s Process used for refining of Ni

Ni+4Cu 50oC−→−− Ni(CO)4 230oC−→−−− Ni+CO↑impure volatile

unstable pure

3. By Electrolytic Refining

Anode : Impure metal

cathode : Pure metal

Electrolyte : Aq. salt sol. of metal/fused metal salt + Acid

Anode Mud : Metals which are less electropositive than the metal to be refined.
In electrolyte : More electropositive metals are found.
eg. in Cu : Ag, Au, Fe, Zn

GOLD
Occurrence : Found mostly in free state in quartz veins called auriferous quartz.

Extraction of gold from native ore :

(A) Crushing and concentration : The gold ore is crushed, powdered finely and
concentrated by washing with water.

(B) Treatment with 0.25–1% sodium cyanide or potassium cyanide solution)

Extraction of Au, from Native ore by Mac-Arthur forrest cyanide process.

4Au+8NaCN+2H2O+O2→4Na[Au(CN)2]+4NaOH
soluble air
2Na[Au(CN)2]+Zn→Na2[Zn(CN)2]+2Au↓
(Impure)

Impure Au is purified by Electrolytic refining method or by amalgamation.

(C) Electrolytic refining method :

Anode : Impure Au
Cathode : Pure Au
Electrolyte : 4% AuCl3solution acidified with 10% HCl

Purple of Cassius :
It is of colloidal gold solution :

2AuCl3+3SnCl2→2Au+3SnCl4
(Very dil.)
The gold thus precipitated is absorbed by Sn(OH)4 formed by hydrolysis of

SnCl4SnCl4+4H2O→Sn(OH)4+4HCl

This form of gold is purple in colour named after its discoverer, Cassius.

SILVER
Ores :
(i) Silver glance or argentiteAg2S(main ore)
(ii) Ruby silver or pyrargyrite 3Ag2S.Sb2S3
(iii) Horn silver or chlorargyrite AgCl.

Extraction of silver from silver glance

(A) Crushing and concentration : The ore is crushed, powdered and concentrated
by froth flotation process.

(B) Extraction of Ag by Mac-Arthur forest cyanide process : (Treatment with 0.4-0.7%

sodium cyanide solution)

The role of air is to oxidize Na2S so that reaction proceed in the forward direction.

Impure Ag is purified by Electrolytic refining method or by amalgamation.

(C) Electrolytic refining :

Anode : Impure Ag
Cathode : Pure Ag
Electrolyte : AgNO3(aq) + HNO3.

Silver from (commercial lead) argentiferous lead by Parke’s process :

Desilverisation of Lead :

Lead extracted from galena (PbS) contains impurities of Cu, Ag, Bi, As, Fe Zn, Sn, etc.
and is called commercial lead or argentiferrous lead. This contains Ag upto 2% which
is extracted by parks process. Commercial lead is mixed with a large quantity of Zn
and the mixture is melted, where Zn-Ag alloy is formed and Pb remains in the molten
state. The alloy is strongly heated where Zn is distilled of leaving Ag. This silver contains
some Pb impurity which is removed by cupellation process. Impure Ag is melted in a
cupel (a boat shaped dish made of bone ash) by passing Hot blast of air. Pb is
oxidized to PbO (litherge) which is either absorbed by cupel or carried away by blast
of air leaving pure Ag.

Separation of silver from gold (Parting with conc. H2SO4)

Alloy (Au < 20%) is boiled with conc. H2SO4 where Ag is dissolved as Ag2SO4 and Au
remains as spongy mass.

Ag2SO4+Zn→2Ag+ZnSO4(Metal displacement reaction)

(sparingly soluble solution)

If alloy contains Au > 20%, then some Ag is added to it so as to reduce the % Au below 20.

Silver from silver coin or silver ornaments

(Ag+Cu)−→−−−−−−dis. in HNO3Ag+(aq.)+Cu2+(aq.)+3NO−3(aq.)−→−−−dil.HClAgCl↓+Cu2
+(aq.)+3NO−3(aq.)

Recovery of Ag from AgCl :

(i) By treating with KCN solution :

2AgCl+2NaCN→2Na[Ag(CN)2]+2NaCl
soluble complex
2Na[Ag(CN)2]+Zn(dust)→2Ag+Na2[Zn(CN)4]

(ii) Boiling with caustic soda and glucose.

2AgCl+2NaOH→Ag2O+2NaCl+H2O−→−−−−C6H12O62Ag+C6H12O7(Gluconic Acid)

(iii) 2AgCl+Na2CO3−→−−Fuse2Ag+CO2+12O2+2NaCl

COPPER
Ores :

 Copper pyrites or Chalcopyrites CuFeS2 (main ore)

 Cuprite or ruby copper Cu2O
 Malachite CuCO3Cu(OH)2 (green)
 Azurite 2CuCO3.Cu(OH)2 (Blue)
 Copper glance Cu2S,
 Bornite (peacock ore) Cu5FeS4.

Extraction of copper from copper pyrites

(A) Crushing and concentration : Ore is first crushed and then powdered finely and
powdered ore is concentrated by froth floatation process.
(B) Roasting : Concentrated ore along with SiO2 is heated in excess of air in a
reverberatory furnace.
(Cu2S+FeS+FeS2)2CuFeS2+O2→Cu2S+2FeS+SO2↑
2FeS+3O2→2FeO+2SO2↑ (Major oxidation)2Cu2S+3O2→2Cu2O+2SO2↑(Minor
oxidation)Cu2O+FeS→Cu2S+FeO



Reverberatory Furance

S+O2→SO2↑;4As+SO2→2As2O3↑;4Sd+3O2→2Sb2O3↑

(C) Slag formation :

Roasted ore mixed with sand and strongly heated in furnace.
FeO+SiO2→FeSiO3
slag flux
Upper layer containing slag is removed and lower layer contains mostlyCu2S (98%) with
little amount of FeS(2%) is called**matte.**
(D) Bessemerisation : (Self – reduction)
2FeS+3O2−→Δ2FeO+2SO2
FeO+SiO2−→−fuseFeSio3(slag)
2Cu2S+3O2−→Δ2Cu2O+2SO2(partial roasting)
(limited air)

Impure copper obtained has blister appearances and therefore called blister copper.
(E) Poling : Molten Cu is stirred with poles of green wood to reduce any copper oxide
impurity into Cu.
(F) Electrolytic refining :
Anode - impure Cu ;
Cathode - Pure Cu ;
Electrolyte CuSO4+H2SO4.
The more electropositive impurities like Zn, Fe, Ni etc. get dissolved in solution and less
positive impurities like Ag, Au collect below anode as anode mud.

LEAD
Ores : Galena PbS (Main ore) ; Anglesite PbSO4; CerussitePbCO3

Extraction of lead from galena :

**(i) Crushing and concentration :**The ore is crushed, grinded finely and
concentrated by froth floatation process.

(ii) Roasting: In reverberatory furnace, limited supply of air is passed at moderate

temperature.

PbS+2O2−→ΔPbSO4;2PbS+3O2−→Δ2PbO+2SO2

(iii)Self reduction : Air supply is cut off and the temperature is increased to melt the
change in reverberatory furnace.

PbSR.A.+2PbO−→−−−−Δhigh temp3Pbimpure+SO2

PbSR.A.+PbSO4−→−−−−Δhigh temp2Pbimpure+2SO2

SiO2+CaO(flux)−→−fuseCaSiO3(slag)

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.

(iv)Electrolytic refining :
Anode - Impure Pb
Cathode - Pure Pb
Electrolyte -PbSiF6+H2SiF6+ gelatine

TIN

Ores : Cassiterite or Tin stoneSnO2 (Main ore) - It contains impurities of pyrites of Cu and Fe
and magnetic impurity of wolframite which is a mixture ofFeWO4+MnWO4.
This mineral is also called black tin to distinguish it from the metal Sn which is also called
white tin.

Extraction of Sn from cassiterite

(i) Crushing and concentration
The ore is crushed and washed with a stream of runing water to remove lighter silicious
impurities followed by magnetic separation method to remove the magnetic impurity
of Wolframite.

(ii) Roasting
Concentrated ore is heated in presence of air, and volatile impurities (S asSO2, As
asAs2O3and Sb asSb2O3) are removed. The impurities of pyrites of Cu and Fe are
converted into their respective oxides and sulphates.

(iii) Washing
Sulphates of copper and iron are dissolved in water. The ore thus obtained contains
60–70% SnO2 and is called as black tin.

(iv)Carbon reduction
The black tin is mixed with anthracite coal and heated to about 1300°C. If SiO2 is
present as impurity then CaO is added as flux.

Refining
(i) Liquidation and poling :
Impure Sn is melted on the sloping hearth where Sn(m.pt. 232°C) is first melt and flows out
leaving behind the less fusible impurities of Cu, Fe, W etc. The liquid Sn is then strirred with
poles of green wood to reduceSnO2(Impurity) to Sn.

(ii) Electrolytic refining :

Anode : Impure Sn
Cathode : Pure
Sn Electrolyte :SnSO4+H2SO4

IRON
Ores : HaematiteFe2O3(Main ORE) ; Limonite Fe2O3.3H2O; Magnetite Fe3O4; Siderite
FeCO3; Iron pyritesFeS2

Extraction of Iron from ore hematite :

(1) Crushing and concentration : The oxide ore is first crushed in jaw crushers and then
is broken in small pieces. Hematite (non-magnetic) is washed with running water to
remove earthy and siliceous impurities by levitation.

(2) Calcination following by roasting : The concentrated ore is roasted with excess air in
a reverberatory furnace. During roasting step, the following changes occur :

 If FeCO3is present as impurity, it gets decomposed into FeOwhich is oxidized by air

to Fe2O3.
FeCO3−→ΔFeO+CO2(calcination)
siderite
4FeO+O2(air)→2Fe2O3(Roasting)
In this way, formation of FeSiO3 slag is prevented during melting, and following
reaction does not occur.
SiO2+FeO→FeSiO3(slag)
 The impurities of S,As are also removed as their volatile oxides
S+O2→SO2↑
4As+3O2→2As2O3↑,
The entire mass becomes porous and hence the reduction of Fe2O3 to spongy iron
becomes easy at later stage.

(3) Reduction in blast furnace.

(Fe2O3ore + lime stone + coke) is smelted in blast furnace and following changes take
place.

(i) Combustion Zone (155 - 1700°C)

A blast of dry preheated air is blown into the furnace from near the bottom of the
furnace. Near the bottom, the preheated air comes in contact with the falling coke and
combustion of coke intoCO2takes place.

C+O→CO2 ΔH= – 393.5 kJ

CO2produced in the combustion zone rises up and meets with more coke in fusion zone
and gets reduced to CO.
CO2+C→2CO ΔH=+163.0kJ

(ii) Reduction zone (250 - 700°C)

Near the top of the furnace (reduction zone), the temperature varies from 250-700°C.
Here the oxide ore (Fe2O3) is reduced to spongy iron with the help of uprising vapours of
CO produced in the zone of fusion.
Fe2O3+3CO −→−−−−−400−700oC 2Fe+3CO2
Actually above Reduction, takes in 3 steps :

3Fe2O3+CO→2Fe3O4+CO2↑
Fe3O4+CO→3FeO+CO2↑
FeO+CO→Fe+CO2↑
(Spongy iron)

Any Fe2O3 which escapes from reduction in reduction zone is reduced in fusion zone.

(iii) Slag formation zone (700-1000°C)

In the middle of the furnace (slag formation zone) where the temperature varies from 700-
1000°C, lime stone (CaCO3) present in the change decomposes into CaO and CO2.

CaCO3−→−−−1000∘CΔCaO+CO2

CaO combines with the impurity of SiO2 and forms a fusible slag of CaSiO3. Thus CaO acts
as a basic flux.
CaO(basic flux) +SiO2 (acidic impurity) →CaSiO3(slag)
Slag is lighter than the molten iron. It moves down and floats over molten iron. This region
where slag is fromed is called slag formation zone.

(iv) Fusion Zone (1000 - 1500°C)

Since the reduction of CO2 to CO is an endothermic reaction (Heat is required),

temperature is decreased to about 1500°C. Fe2O3 is reduced to Fe which might not have
been reduced in the reduction zone.

Fe2O3+3C→2Fe+3CO

Impurities are also reduced and get mixed up with spngy Iron.

MnO2+2C→Mn+2CO
2P2O5+10C→P4+10CO
SO2+2C→S+2CO
SiO2+2C→Si+2CO
Types of Iron :

1. Cast iron (2% to 5% carbon & other impurity)

2. Steel (0.5% to 2% carbon & other impurity)
3. Wrought iron ( < 0.5% carbon & other impurity)

Manufacturing of wrought from cast Iron :

Wrought iron is manufactured from puddling furnace having inner lining of haematite
(Fe2O3) oxidant for impurities present in cast iron.
Mn+Fe2O3→MnO+2Fe
(basic) (O.A.)
Si+Fe2O3→SiO2+2Fe
(basic) (O.A.)
MnO+SiO2→MnSiO3 + (slag)
(basic) (O.A.)
S+Fe2O3→SO2↑+2Fe
C+Fe2O3→3CO+2Fe
3P4+10Fe2O3→6P2O5+20Fe
P2O5+Fe2O3→2FePO4(slag)

Manufacturing of steel from cast from :

(i) Bassemerization (already discussed)
(ii) Open-Hearth process (Siemens Martin’s process) (iii) Electrical furnace process

Open hearth process (siemen Martin’s process)

Mn+Fe2O3→MnO+2Fe
(basic) (O.A.)
Si+Fe2O3→SiO2+2Fe
(Acidic) (O.A.)
MnO+SiO2→MnSiO3 + (slag)
(basic) (O.A.)
S+Fe2O3→SO2↑+Fe
(O.A.)
C+Fe2O3→3CO↑+2Fe
3P4+10Fe2O3→6P2O5+20Fe
P2O5+3CaO→Ca3(PO4)2(Thomas slag)

After adding requried amount of spiegeleisen steel is formed.

In this method 2 – 5% iron is also oxidised by air because hearth is open therefore this
method is discarded is modern age.

In modern age steel is manufactured by electrical furnace process or by L.D. process. In

electrical furnace process heating effect is produced by passing electricity and all
chemical reaction are similar to open-hearth process.
Heating Treatment of Steel
(i) Annealing : Process of heating steel upto redness and then cooling it slowly is called
annealing, In this way steel becomes soft, malleable and elastic.

(ii) Quenching : Process of heating steel upto redness and then cooling it suddenly by
plundging in into oil or water is called quenching. In this way steel become hard and
brittle.

(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

(i) Case – Hardening : Process of forming hard coating of 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.

ZINC

Ores : Zinc blende ZnS (main ore), Zincite (ZnO), Calamine, ZnCO3.

Extraction of zinc from zinc blende :

(A) Crushing and concentration :
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−→Δ2ZnO+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 −→−−−−−−−−1100oC−1400oC Zn↑+CO

vapour (R.A.)
Vapours of zinc are collected by rapid cooling to get zinc spelter (Impure Zn). Impure Zn is
purified either by electrolytic refining method **or by **distillation.

(D) Electrolytic refining :

Anode : Cathode : Electrolyte :
Impure Zn Aluminium
Electrode ZnSO4(aq)+H2SO4

Extraction of Cr From FeCr2O4 (FeO.Cr2O3) Chromite Ore

Concentration Step : Chromite ore is concentrated by gravity separation method to
remove light impurities followed by magnetic separation method to remove non-
magnetic impurities.

Chemical Method to Separate Cr2O3

Al-reduction method : (Goldsmith alumino thermite process)

Cr2O33 part+Al(R.A.)1 part Thermite mixture−→−−−−−−−

−−Mg Ribbon+BaO2 ΔIgnition MixtureAl2O3+2Cr(Molt
enimpuremetal)↓+ Heat
Impure Cr is purified by electrolytic refining method.
Anode : Impure chromium
Cathode : Hg-electrode
Electrolyte : CrCl3 + HCl
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 900oC−→−−− Mn3O4(MnO+Mn2O3)+O2↑

Al-reduction method : (Goldsmith alumino thermite process)

Mn3O43 part+2Al(R.A.)1 part Thermite mixture−→−

−−−−−−−−Mg Ribbon+BaO2 ΔIgnition Mixture4Al2O3+
9MnImpuremetal)↓+ Heat

Impure Mn is purified by electrolytic refining method.

Anode : Impure Mn
Cathode : Hg-electrode
Electrolyte : MnSO4+H2SO4

ALUMINIUM
Ores :

(i) Bauxite Al2O3.2H2O (main ore) ; Diaspore Al2O3.H2O ; Corundum Al2O3

(ii) Mica K2O.3Al2O3.6SiO2.2H2O; Kaolin Al2O3.2SiO2.2H2O
(iii) CryoliteNa3AIF6
(ii)
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
AlF3→Al+3+3F–
At cathode Al+3+3e–→Al
At anode 3F–→3F+3e–
Al2O3+6F→2AIF3+32O2↑
C+12O2→CO2
CO+12O2→CO2

Anodes are periodically changed as they are consumed by oxygen liberated at anode.

Electrolytic refining (Hoppe’s Method)

Iron box lined with carbon, contains the three molten layers.
Bottom layer : Impure Al as anode
Middle layer : (Na3AlF6+BaF2) Molten electrolyte
Tope layer : molten pure Al as cathode.

On passing the current aluminium is deposited at cathode from the middle layer and an
equivalent amount is taken from anode (bottom layer) leaving behind the impurities. In
this way aluminium obtained is 99.98% pure.

MAGNESIUM

Ores :

Carnallite MgCl2.KCl6H2O (main ore) ; Epsom MgSo4.7H2Omagnesite MgCO3 ;

Kiesserite MgSO4.H2O ; Dolomite MgCO3.CaCO3;
Kainite K2SO4.MgSO4.MgCl2.6H2O(Mg is also found in Talc, sabestos and
chlorophyll)

Sea water contains 0.13% magnesium as chloride and 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)

(b) Preparation of hexahydrated magnesium chloride :

Mg(OH)2+2HCl(aq)→MgCl2+2H2O(Neutralization reaction)

The solution on concentration and crystallization gives the crystals of MgCl2.6H2O

(c) Preparation of anhydrous magnesium chloride :

MgCl2.6H2O−→−−−−−Dry HCl(g)ΔMgCl2+6H2O
 It is not made anhydrous by simple heating because it gets hydrolysed.

MgCl2.6H2O−→ΔMgO+5H2O+2HCl

(d) Electrolysis of fused anhydrous MgCl2

Magnesium chloride obtained by any of the above methods is fused and mixed with
sodium chloride and calcium chloride in the temperature range of 972 – 1023K. The
molten mixture is electrolysed. Magne- sium is liberated at the carhode (iron pot) and
chlorine is evolved at graphite anode.