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Metallurgy
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
Step I : Pulverization
The crushing of ore to powdered state is called pulverization This process in stamp mill
or ball mill
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.
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
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.
(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
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
Ellingham diagram
M(s)+X2O2(g)Δ→M2Ox(s)
Δ G=Δ H–TΔS
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.
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.
Properties of slag
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
Cu2O+H2Δ→2Cu+H2O MoO3+3H2Δ→Mo+3H2O
SiCl4+2MgΔ→2MgCl2+Si
TiCl4+2Mg−→−−−−−−Δ1000−1150oCTi+2MgCl2
ZrCl4 +2MgΔ→Zr+2MgCl2
TiCl4+4NaΔ→Ti+4NaCl
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
Self reduction is responsible for acid rain than roasting because SO2 dissolves in air,
(3927cc CO2 in1000cc ofH2O)
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
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
On Passing electricity
At cathode : 2Na++2e–→Na
At Anode : 2Cl–→Cl2↑+2e–
In sol. Na++OH–→NaOH
In the reduction of molten metal salt, electrolysis is done. Such methods are based on
electrochemical principles which could be understood through the equation,
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.
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
This method is used for refining of those metal which have very low m.p. in comparison to
impurity present in them.
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)
2. By Chemical Methods
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
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.
3. By Electrolytic Refining
GOLD
Occurrence : Found mostly in free state in quartz veins called auriferous quartz.
4Au+8NaCN+2H2O+O2→4Na[Au(CN)2]+4NaOH
soluble air
2Na[Au(CN)2]+Zn→Na2[Zn(CN)2]+2Au↓
(Impure)
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.
The role of air is to oxidize Na2S so that reaction proceed in the forward direction.
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.
If alloy contains Au > 20%, then some Ag is added to it so as to reduce the % Au below 20.
2AgCl+2NaCN→2Na[Ag(CN)2]+2NaCl
soluble complex
2Na[Ag(CN)2]+Zn(dust)→2Ag+Na2[Zn(CN)4]
(iii) 2AgCl+Na2CO3−→−−Fuse2Ag+CO2+12O2+2NaCl
COPPER
Ores :
Reverberatory Furance
S+O2→SO2↑;4As+SO2→2As2O3↑;4Sd+3O2→2Sb2O3↑
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
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)
(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.
(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.
IRON
Ores : HaematiteFe2O3(Main ORE) ; Limonite Fe2O3.3H2O; Magnetite Fe3O4; Siderite
FeCO3; Iron pyritesFeS2
(2) Calcination following by roasting : The concentrated ore is roasted with excess air in
a reverberatory furnace. During roasting step, the following changes occur :
(Fe2O3ore + lime stone + coke) is smelted in blast furnace and following changes take
place.
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.
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.
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.
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 :
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)
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)
In this method 2 – 5% iron is also oxidised by air because hearth is open therefore this
method is discarded is modern age.
(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.
**(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.
(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
Calcination :
MnO2 gives explosive rxn. with Al therefore in this step it is converted into mixed
oxide Mn3O4.
ALUMINIUM
Ores :
Purification of Bauxite :
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.
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 :
Sea water contains 0.13% magnesium as chloride and sulphate. It involves following
steps.
Mg(OH)2+2HCl(aq)→MgCl2+2H2O(Neutralization reaction)
MgCl2.6H2O−→−−−−−Dry HCl(g)ΔMgCl2+6H2O
It is not made anhydrous by simple heating because it gets hydrolysed.
MgCl2.6H2O−→ΔMgO+5H2O+2HCl
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.