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Published on: 28/06/2019
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1.
Using the Ellingham diagram,
(A) Predict the conditions under which
(i) Aluminium might be expected to reduce magnesia.
(ii) Magnesium could reduce alumina.
(B) it is possible to reduce Fe2O3 by coke at a temperature around 1200K
2.
Explain zone refining process with an example.
3.
Give the basic requirement for vapour phase refining.
4.
Explain the electrometallurgy of aluminium.
5.
Explain alkali leaching in the extraction of aluminum.
6.
What is meant by ammonia leaching?
7.
What is cyanide leaching? Give an example
8.
Explain the following terms with suitable examples.
(i) Gangue
(ii) slag
1.
a) i) Ellingham diagram for the formation of Al2O3 and MgO intersects around 1500oC. Above this temp Mg lies above the Aluminium line. Hence only above 1500oC Aluminium might be excepted to reduce magnesia.
ii) Ellingham diagram for the formation of MgO lies below the formation of Al2O3. Hence MgO is more stable than Al2O3. Hence Magnesium could reduce Alumina.
1. Below 983K, formation of CO line lies below many of the metal oxide formation in Ellingham diagram, hence CO is more effective reducing agent than Carbon.
2. But above this temperature Carbon lies below other metal oxides.
b) Around 1200K Carbon lies below the formation of Fe2O3. Hence it is possible to reduce Fe2O3 by coke at 1200K.
2.
Zone refining :
1. Zone refining method is based on the principles of fractional crystallisation.
2. When an impure metal is melted and allowed to solidify, the impurities will prefer to be in the molten region. In this process the impure metal is taken in the form of a rod.
3. One end of the rod is heated using a mobile induction heater which results in melting of the metal on that portion of the rod.
4. When the heater is slowly moved to the other end the pure metal crystallises while the impurities will move on to the adjacent molten zone.
5. As the heater moves further away, the molten zone containing impurities also moves along with it.
6. The process is repeated several times by moving the heater in the same direction again and again to get pure metal.
7. This process is carried out in an inert gas atmosphere to prevent the oxidation of metals.
8. Elements such as germanium (Ge), silicon (Si) and galium (Ga) that are used as semiconductor are refined using this process.
3.
In this method, the metal is treated with a suitable reagent which can form a volatile compound with the metal.
Then the volatile compound is decomposed to give the pure metal.
4.
1. This process is called as Hall-Heroult process.
Cathode: In this method, electrolysis is carried out in an iron tank lined with carbon which acts as the cathode.
Anode: The carbon blocks immersed in the electrolyte acts as a anode.
Eletrolyte: A 20% solution of alumina, obtained from the bauxite ore is mixed with molten Cryolite and is taken in the electrolysis chamber.
2. About 10% calcium chloride is also added to the solution.
3. Here Calcium chloride helps to lower the melting point of the mixture.
Temperature: The fused mixture is maintained at a temperature of above 1270 K.
4. The chemical reactions involved in this process as follows
(a) Ionisaiton of alumina: \({ A }l_{ 2 }{ O }_{ 3 }\longrightarrow { 2Al }^{ 3+ }+{ 3O }^{ 2- }\)
(b) Reaction at cathode: \(2{ Al }^{ 3+ }_{(melt)}+{ 6e }^{ - }\longrightarrow { Al }_{ (l) }\)
(c) Reaction at anode: \(6{ O }^{2-}_{(melt)}\longrightarrow { 3O }_{ 2 }+{ 12e }^{ - }\)
5. Since carbon acts as anode the following reaction also takes place
(a) \({ C }_{ (s) }+{ O }^{ 2- }_{(melt)}\longrightarrow CO+{ 2e }^{ - }\)
(b) \({ C }_{ (s) }+{ 2O }^{ 2- }_{(melt)}\longrightarrow { CO }_{ 2 }+{ 4e }^{ - }\)
6. Due to the above two reactions, anodes are slowly consumed during the electrolysis.
7. The pure aluminium is formed at the cathode. The net electrolysis reaction can be written as
\({ 4Al }^{ 3+ }_{(melt)}+{ 6O }^{ 2- }_{(melt)}+{ 3C }_{ (s) }\longrightarrow { 4Al }_{ (l) }+{ 3CO }_{ 2(g) }\)
5.
(i) In this method, the ore is treated with aqueous alkali to form a soluble complex.
(ii) Bauxite, an important ore of aluminum is heated with a solution of sodium hydroxide or sodium carbonate in the temperature range 470 - 520 K at 35 atm to form soluble sodium meta-aluminate leaving behind the impurities, iron oxide and titanium oxide.
\({ Al }_{ 2 }{ O }_{ 3(s) }+2NaO{ H }_{ (aq) }+3{ H }_{ 2 }{ O }_{ (l) }\longrightarrow 2Na[Al({ OH })_{ 4 }]_{ (aq) }\)
(iii) The hot solution is decanted, cooled, and diluted. This solution is neutralised by passing CO2 gas, to the form hydrated Al2O3 precipitate
\(2Na\left[ Al\left( OH \right) _{ 4 } \right] _{ (aq) }+{ CO }_{ 2(g) }\longrightarrow { Al }_{ 2 }{ { O }_{ 3 }.x{ H }_{ 2 }O_{ (s) }+2NaHCO_{ 3(aq) } }\)
(iii) The precipitate is filtered off and heated around 1670 K to get pure alumina Al2O3
6.
When a crushed ore containing nickel, copper and cobalt is treated with aqueous ammonia under suitable pressure, ammonia selectively leaches these metals by forming their soluble complexes viz. [Ni(NH3)6]2+, [Cu(NH3)4]2+, and [Co(NH3)5H2O]3+ respectively from the ore leaving behind the gangue, iron(III) oxides/ hydroxides and aluminosilicate.
7.
(i) The crushed ore of gold is leached with aerated dilute solution of sodium cyanide.
(ii) Gold is converted into a soluble cyanide complex.
(iii) The gangue, aluminosilicate remains insoluble
\({ 4Au }_{ (s) }+{ 8CN }_{ (aq) }^{ - }+{ O }_{ 2(g) }+2{ H }_{ 2 }{ O }_{ (l) }\longrightarrow 4\left[ Au(CN)_{ 2 } \right] +_{ (aq) }^{ - }+{ 4OH }_{ (aq) }^{ - }\)
8.
(i) Gangue: The ores are associated with nonmetallic impurities, rocky materials and siliceous matter which are collectively known as gangue.
Eg: SiO2 is the gangue present in the iron ore (Fe2O3)
(ii) Slag: In the smelting process, a flux combines with Silica gangue forming slag.
CaO(s) + SiO2(s) → CaSiO3(s)
Flux + gangue → Slag
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