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The process of extraction of metal from its ores in profitable manner.
Process of metallurgy involves –
(Conversion of the concentrated ore into its oxide form):
Ex. 2Fe2O3.3H2O → 2Fe2O3 + 3H2O
CaCO3 → CaO + CO2
(ii) Roasting (Conversion of the concentrated ore into its oxide form): Employed for sulphide ores
a. Reduction by carbon (smelting)
The oxides of less electropositive metals like Pb, Zn, Fe, Sn, Cu etc. are reduced by strongly heating with coal or coke. Reduction of the oxide with carbon at high temperature is known as smelting.
b. Reduction by aluminium (Alumino-Thermic reduction)
c. Reduction by heating in air (Auto-reduction)
d. Electrolytic reduction (Electro-metallurgy)
(i) Employed for highly electropositive metals such as Na, K, Ca, Mg, A1 etc.
(ii) These metals are extracted by the electrolysis of their oxides, hydroxides or chlorides in fused state
on fusion: NaCl ⇌ Na+ + Cl– (ions become mobile)
at cathode: Na+ + e– → Na
at anode: Cl– → Cl + e–
Cl + Cl → Cl2
e. Hydrometallurgy (Reduction by precipitation)
Process in which more electropositive metals displace less electropositive metals from salt solution. Silver sulphide dissolved in sodium cyanide which forms a soluble complex, then silver is precipitated by the addition of zinc powder.
Ag2S + 4 NaCN → 2 Na [Ag (CN)2] + Na2S(sodium dicyanoargentate (I))
2 Na [Ag (CN)2] + Zn → Na2 [Zn (CN)4] + 2 Ag ↓
3. Refining or purification:
2. Distillation process:
3. Oxidation process
Employed for refining of highly electro positive metals like Al, Cu, Ag, Zn, Sn, Pb, Cr and Ni.
Electrolytic refining of copper:
5. Van-Arkel process:
6. Zone refining:
7. Mond’s process:
Nickel is purified by using CO gas. This involves the formation of nickel tetracarbonyl.
Haematite – Fe2O3 (chief); Limonite – 2Fe2O3.3H2O ; Siderite – FeCO3;
Magnetite – Fe3O4, Pyrite – FeS2.
(i) Roasting: FeO changes to Fe2O3 to prevent the loss of iron during smelting.
4FeO + O2 → 2Fe2O3
(ii) Smelting: In reduction zone:
At 400° C
3Fe2O3 + CO → 2Fe3O4 + CO2↑
Fe3O4 + CO → 3FeO + CO2 ↑
FeO + CO → Fe + CO2↑
Ca CO3 → CaO + CO2↑
In central zone:
Fe + 2CO → CO2 + C + Fe
(900 – 1200°C) Fe acts as catalyst here and ‘C’ so formed is dissolved in Fe.
CaO (flux) + SiO2(impurity) → CaSiO3(slag)
In fusion zone:
CO2 + C → 2CO, ΔH = + ve
(1100- 1200°C) melting of iron takes place
In combustion zone:
C + O2 → 2CO, ΔH = – ve
(d) Pig Iron: C 3.1 – 4.5%, small amounts of Si, S, P ; hard and brittle, obtained from blast furnace
(e) Wrought Iron: C 0.15 – 0.28%, purest form ; malleable, fibrous
(f) Steel: C 0.15 – 1.5%, strength is high.
Copper pyrites CuFeS2 (chief) ; cuprite or ruby copper Cu2O ; copper glance Cu2S; malachite Cu (OH)2 . CuCO3 ; Azurite Cu (OH)2 . 2CuCO3.
2CuFeS2 + O2 → Cu2S + 2FeS + SO2
2FeS + 3O2 → 2FeO + 2SO2
2Cu2S + 3O2 → 2Cu2O + 2SO2
Cu2O + FeS → Cu2S + FeO
FeO + SiO2 → FeSiO3
(iii) Bessemerisation :
2FeS + 3O2 → 2FeO + 2SO2
FeO + SiO2 → FeSiO3
2Cu2S + 3O2 → 2CuO + 2SO2
Cu2S + 2Cu2O → 6Cu2+ + SO2 (self reduction)
(iv) Poling: Molten Cu is stirred with poles of green wood to reduce any copper oxide in Cu.
(v) Electrolytic refining: Anode-impure Cu; cathode – pure Cu; electrolyte CuSO4 + H2SO4.
(i) Purification of Bauxite:
If Fe2O3 is major impuirity – Red bauxite
– ore is roasted to convert ferrous oxide to ferric oxide
– NaAlO2 + 2H2O → NaOH + Al(OH)3
(ii) Electrolysis of fused Alumina.
Cathode : Iron-tank lined with carbon bricks carbon rods
Anode : carbon rods
Electrolyte : Molten [Al2O3 (5%) Na3AlF6 (85%) + CaF2(5%) + AlF3(5%)] O2 is liberated at anode and A1 collects at the bottom.
(iii) Reactions : Na3AlF6 → 3NaF + AlF3
AlF3 ⇌ Al3+ + 3F–
At anode : Al2O3 + 6F– → 2Al F3 + 3/2 O2 + 6e–
At cathode : 2Al3+ + 6e– → 2Al
(iv) Electrolytic refining (Floope’s process), three layers process.
Cathode : Carbon electrodes
Anode : Fe tank lined with
Bottom layer : Impure aluminium consists of Cu, Si etc in molten state.
Middle layer : molten mixture of Fluorides of Na, Ba, Al and Al2O3
Top layer : pure molten aluminium.
On passing the current, Al is deposited at cathode from the middle layer and an equivalent amount of Al from the bottom layer moves into the middle layer leaving behind the impurities.
(a) Ores : Silver glance or argentite Ag2S, Ruby silver Ag2S. Sb2 S3, Horn silver AgCl.
(b) Process : Cyanidation or Mac-Arthur-Forrest process
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