METALS AND METALLURGY

EXTRACTION OF SODIUM(DOWN'S PROCESS)

NaCl

Electrolyte
Temperature 6000C Molten mixture

33.3% NaCl + 66.7% CaCl 2

By product Cl2 gas

NaCl = Na+ + ClNa Cathode reaction : Na+ +e -e Anode reaction : Cl Cl Cl + Cl Cl2

Electrodes : Graphite anode Iron cathode

Collection: Sodium is removed from time to time with the help of proforated ladles made by Ni and kept under kerosene

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EXTRACTION OF SODIUM(CASTNER PROCESS)

NaOH

Electrolyte
Molten

NaOH at 3180C

By products: H2 at cathode O2 at anode

Electrode reaction NaOH = Na+ + OHcathode : Na+ + e = Na Anode : OH- -e = OH 4OH = 2H2O + O2

Electrodes cathode : steel anode : Nickel cylinder

Water produced at anode is again electrolysed and H at cathode and O2 at anode 2 evolves.

Collection: Sodium is removed from time to time with the help of proforated ladles made by Ni and kept under kerosene

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EXTRACTION OF CALCIUM BY ELECTROLYSIS

CaCl2
Temperature 7000C

Electrolyte
Molten mixture

CaCl2 + CaF2 (6:1 ratio)

By product : Cl2 gas

Electrode Recation : CaCl2 = Ca+2 + 2ClCathode : Ca+2 + 2e = Ca Anode : 2Cl- = Cl2

Electrodes : cathode: Fe rod anode : graphite

Calcium can not extracted by carbon reduction method because at higher temperature calcium reacts with carbon to form calcium carbide(CaC2)

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PREPARATION OF PURE ALUMINA(BAEYER'S PROCESS)
Finely powdered bauxite containing Fe2O3,TiO2,SiO2 as impurities Calcined(FeO Fe2O3) FeO if any

organic matters are removed Calcined ore Digested with 45% NaOH soln at 1500C under 80lb pressure filtered

Al2O3+2NaOH = 2NaAlO3 + H2O SiO2 + 2NaOH = Na2SiO2 + H2O Filtrate NaAlO2 + Na2SiO3 filtered Filtrate NaAlO2 + 2H2O = Al(OH)3 + NaOH

Residue Fe2O3,TiO2

diluted with water and cooled to 25-300C, Stirred with freshly prepared aluminium hydroxide(seeding agent) Precipitate Al(OH)3

Pure alumina Al2O3

wash with water heat 10000C

2Al(OH)3

Al2O3 + 3H2O

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EXTRACTION OF ALUMINIUM(ELECTROLYSIS PROCESS)
pure alumina

Electrolyte
Molten
Pure alumina + fused cryolite + fluorsper 20:60:20

Electrode reaction AlF3.3NaF = AlF3 + 3NaF AlF3 = Al+3 + 3Fcathode : Al+3 + 3e = Al Anode : 3F- -3e = 3F Al2O3 + 6F = 2AlF3 + 3[O] 6[O] = 3O 2

Electrodes cathode :carbon lined steel anode : graphite

oxygen liberated at anode attacks anode.In order to prevent that, some coke is added to electrolytic mixture.This coke reacts with O 2 to form CO 2

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PURIFICATION OF ALUMINIUM(HOOP'S PROCESS)
electrolytic cell
iron tank lined with carbon

Fitted with three liquids differing in specific gravity

Upper layer is pure fused Al acts as cathode Central layer is the molten mixture of the fluorides of Al,Ba and Na--- used as electrolyte Bottom layer is impure metal in fused state acts as anode

on passing current pure Al goes to the top layer from the central layer and an equivalent amount of metal from the bottom layer passes into central layer

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EXTRACTION OF COPPER(FROM COPPER PYRITES)
Copper pyrites, contains (3% Cu)- Cu2S, Fe2S3, silica sulphur, arsenic concentration by oil floatation process Concentrated ore, (25-30% Cu) Cu2S,Fe2S3,SiO2 Cu2S,Fe2S3 + O2 = Cu2S + 2FeS + SO2 Cu2S,Fe2S3 + 4O2 = Cu2S + 2FeO + 3SO2 2Cu2S + 3O2 = 2Cu2O + 2SO2 Cu2O + FeS = Cu2S + FeO Roasting in reverberatory furnace Roasted ore, Cu2S,FeS FeO,SiO2,little Cu2O 2FeS + 3O2 = 2FeO + 2SO2 FeO + SiO2 = FeSiO3 CaO + SiO2 = CaSiO3 Cu2O + FeS = Cu2S + FeO Matte : Cu2S + small amt of FeS self reduction: Bessemer converter Blister Copper 98% pure SO2 Blast Furnace Smelting : roasted ore + coke + silica + lime stone

By products : SO2,Ferrous silicate,anode slime

2Cu2S + 3O2 = 2Cu2O + 2SO2 2Cu2O + Cu2S = 6Cu + SO2 Cu2S + 2O2 = Cu2SO4 Cu2S + Cu2SO4= 4Cu + SO2

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PURIFICATION OF COPPER(POLING PROCESS)
Blister Copper + 2-3% Fe, sulphur, arsenic Air is passed reverberatory furnace lined with silica

Blister copper is melted Fe and S oxidised to FeO and SO2, and As to volatile oxide FeO combined with silica Ferrous silicate floates on molten copper containing some Cu2O Cu2O removal : powdered coke is sprinkled on molten mass and then it is stirred with greenwood poles

99.5% pure Copper

Green poles of wood produces reducing gases which reduce the cuprous oxide to metallic copper

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EXTRACTION OF ZINC (FROM ZINC BLENDE)
Zinc blende ZnS + gangue

Crushing and grinding Powdered Zinc blende Roasting reactions 2ZnS + 3O2 = 2ZnO + 2SO 2 ZnS + 2O2 = ZnSO4 2ZnSO4 = 2ZnO + 2SO 2 + O2 Concentration by oil floatation method : water+ pyne oil + sod. xanthate + acid-blowing air Concentrated ore Roasting(i) controlled current of air (ii) Temp : 850-9000C Roasted ore (ZnO) + non volatile matters ZnO + C = Zn + CO ZnO + CO = Zn + CO 2 Carbon reduction Roasted ore + excess of coke temp : 14000C Spelter Zn impurites-Pb,Cd, Fe Electro refining Pure Zn thermal refining temp : 9200C distillate Zn + Cd Fractional dist 7670C Pure Zn(99.9%)

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EXTRACTION OF CAST IRON(FLOW CHART)
Iron ores (i)Magnetite(Fe3O4) (ii)Haematite(Fe2O3) (iii)Brown Haematite (Fe2O3.3H2O) (iv)Siderite(FeCO3) Broken into pieces,screened and washed with water to remove silicious materials

S+ O2 = SO2 4As + 3O2 = 2As2O3 FeCO3 = FeO + CO2 Fe2O3.3H2O = Fe2O3 + 3H2O reactn Fe3O4 = FeO + Fe2O3 4FeO + O2 = 2Fe2O3

Roastng : Coke is mixed with ores and the mixture is heated in excess of air

By products : slag: calcium and aluminium silicate Blust furnace gas : N2,CO,CO2,H2, hydrocarbon, C2N2

Roasted ore contains Fe2O3 and SiO2 At 12000C : C+ O2 = CO2 CO2+ C = 2CO At 6000C -9000C : Fe2O3 + 3CO = 2Fe + 3CO2 At 9000C : CaCO3 = CaO + CO2 CO2 + C = 2CO At 10000C-13000C : 2CO = C + CO2 Fe2O3 + 3C = 2Fe + 3CO CaO + SiO2 = CaSiO3(slag) At 15000C : MnO2 + 2C = Mn + 2CO Ca3(PO4)2 + 3SiO2=3CaSiO3 + P2O5 2P2O5 + 10C = P4 + 10CO SiO2 + C = Si + 2CO slag cast iron reactions Smelting of charge in blust furnace at high temperature Charge is: Fe2O3 : Coke : lime stone 8 : 4 : 1 Smelting : in the blust furnace Fe2O3 is reduced by coke and CO and slag is formed by the action of lime on silica

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EXTRACTION OF STEEL FROM CAST IRON
ACID BESSEMER PROCESS
Cast iron containing Mn,Si,MnO,S,C molten iron is fed into conveter and hot air (700 0C) under high pressure passed into molten iron Mn and Si oxidised to give MnO2 and silica which combine together to form manganous silicate

2Mn + O2 = 2MnO2 Si + O2 = SiO2 MnO + SiO2 = MnSiO3 S+O2 = SO2 4Fe + 3O2 = 2Fe2O3 Fe2O3 + C = Fe + 3CO 2C + O2 = 2CO

+
S oxidised to SO2 ,Fe to Fe2O3 which reduced by C to form Fe, C to CO

calculated amt of spiegeleisen (alloy of Fe,Mn and C) is added FeO + Mn = MnO + Fe FeO + C = Fe + CO Mn and C removes dissolved oxygen and reduce FeO to Fe

METALS AND METALLURGY

EXTRACTION OF STEEL FROM CAST IRON BASIC BESSEMER PROCESS
Molten cast iron + some CaO hot air uner pressure is passed Cast iron containing Si,P,S etc molten iron is fed into conveter which is lined inside with manesia (MgO) or lime(CaO) Mn and Si oxidised to give MnO2 and silica which combine together to form manganous silicate

2Mn + O2 = 2MnO2 Si + O2 = SiO2 MnO + SiO2 = MnSiO3 S+O2 = SO2 2C + O2 = 2CO 4P + 5O2 = 2P2O5 4CaO + P2O5 = Ca3(PO4)2.CaO thomas slag FeO + Mn = MnO + Fe FeO + C = Fe + CO

+
S oxidised to SO2 ,C to CO, P to P2O5 calculated amt of spiegeleisen is added to molten iron Mn and C removes dissolved oxygen and reduce FeO to Fe