The choice of method will depend on the nature of the ore, type of impurity and environmental factors

The preliminary step in metallurgical process is removal of the impurities. This removal process is known as concentration of ore.

Copper, Silver, Gold and Platinum

It is essential to design an eco friendly metallurgical process that would minimize waste, maximize energy efficiency. Such advances in metallurgy is vital for the economic and technical progress in the current era.

Metallurgy relates to the science and technology of metals. The various steps involved in the extraction of metals form their ores as well as refining of crude metals are collectively know as metallurgy.

(i) The extraction of metals from their oxides can be carried out by using different reducing agents.
(ii) Consider the following reaction
\(\frac{2}{\mathrm{y}} \mathrm{M}_{\mathrm{x}} \mathrm{O}_{\mathrm{y}(\mathrm{s})} \rightarrow \frac{2 \mathrm{x}}{\mathrm{y}} \mathrm{M}_{(s)}+\mathrm{O}_{ 2(\mathrm{~g})}\)            (1)
(iii) The above reduction may be carried out with carbon. In this case the reducing agent carbon may be oxidized to either CO or CO₂
\(\mathrm{C}+\mathrm{O}_{2} \rightarrow \mathrm{CO}_{2(\mathrm{~g})}  \)                  (2)
\(2 \mathrm{C}+\mathrm{O}_{2} \rightarrow 2 \mathrm{CO}_{(\mathrm{g})} \)                (3)
(iv) If CO is used as a reducing agent
\(2 \mathrm{CO}+\mathrm{O}_{2} \rightarrow 2 \mathrm{CO}_{2(\mathrm{~g})}\)           (4)
(v) A suitable reducing agent is selected based on the thermodynamics considerations.
(vi) We know that for a spontaneous reaction, the change in free energy (\(\triangle\)G) should be negative.
(vii) Therefore, thermodynamically, the reduction of metal oxide with a given reducing agent can occur if the free energy change for the coupled reaction is negative.
(viii) Hence, the reducing agent is selected in such a way that it provides a large negative \(\triangle\)G value for the coupled reaction.

i) Silica is an acidic flux which is mixed with Copper pyrites ore and is heated in a reverberatory furnace. The ferrous oxide formed from the ore is basic in nature and it combines with silica to form ferrous silicate. It is removed as slag.
\(\mathrm{FeO}_{(s)}+\mathrm{SiO}_{2(s)} \overset { \Delta }{ \longrightarrow } \mathrm{FeSiO}_{3(s)}\\ gangue \quad flux \quad \quad slag\)
ii) Aluminium oxide does not dissolve in water, but it dissolves in molten cryolite. This is an aluminium compound with a lower melting point than aluminium oxide. The use of cryolite reduces some of the energy costs involved in extracting aluminium.
\(\mathrm{Al}_{2} \mathrm{O}_{3} \overset { \Delta }{ \longrightarrow } 2 \mathrm{Al}^{3+}+3 \mathrm{O}^{2-}\)
iii) Van-Arkel method is based on the thermal decomposition of metal compounds which lead to the formation of pure metals. Zirconium can be purified by using this method. Zirconium metal is heated with iodine at a temperature of 550 K to form zirconium tetraiodide. (ZrI₄). The impurities are left behind
\(\mathrm{Zr}_{(\mathrm{s})}+2 \mathrm{I}_{2(\mathrm{~s})} \frac{550 \mathrm{~K}}{\mathrm{D}} \mathrm{ZrI}_{\text {t(vapour })}\)
The volatile (ZrI₄) on further heating around 1800 K, it gives pure zirconium.
\(\mathrm{ZrI}_{4 \text { (vapour) }} \frac{1800 \mathrm{~K}}{\mathrm{D}} \mathrm{Zr}_{(\mathrm{s})}+2 \mathrm{I}_{2} \)    
iv) In the extraction of lead from galena (PbS) by froth flotation process, if ZnS is present as impurity, Sodium cyanide is added to depresses the flotation property of ZnS. It forms a complex. Na₂[Zn(CN)₄] on the surface of zinc sulphide.

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
\({ 4Al }^{ 3+ }_{(melt)}+{ 6O }^{ 2- }_{(melt)}+{ 3C }_{ (s) }\longrightarrow { 4Al }_{ (l) }+{ 3CO }_{ 2(g) }\)

Ellingham diagram for the formation of ZnO and CO₂ intersects around 1200 K. Above this temperature ZnO lies above Carbon which indicates Carbon is the better reducing agent CO is more effective reducing agent only below 983 K.

This method is commonly used to concentrate sulphide ores such as galena (PbS), zinc blende (ZnS) etc.
In this method, the metallic ore particles which are preferentially wetted by oil can be separated from gangue.

In this extraction, a basic flux, quick lime (CaO) is used, since the silica gangue present in the ore is acidic in nature. The quick lime combines with it to form calcium silicate (slag).
CaO_(s) + Sio_2(s) ⟶ CaSio_3(s)
Flux       Gangue    Slag

(i) Concentration of the ore
(ii) Extraction of crude metal
(iii) Refining of crude metal

(i) The impure nickel is heated in a stream of carbon monoxide at around 350 K.
(ii) The nickel reacts with the CO to form a highly volatile nickel tetracarbonyl.
(iii) The solid impurities are left behind 
\({ Ni }_{ (s) }+4{ CO }_{ (g) }\longrightarrow { Ni(CO) }_{ 4(g) }\)
(iv) On heating the nickel tetracarbonyl around 460 K, the complex decomposes to give pure metal.
\({ Ni(CO) }_{ 4(g) }\longrightarrow { Ni }_{ (s) }+{ 4CO }_{ (g) }\)

(i) Magnetic separation is applicable to ferromagnetic ores and it is based on the difference in the magnetic properties of the ore and the impurities.
(ii) For example tin stone can be separated from the wolframite impurities which is magnetic.
(iii) Similarly, ores such as chromite, pyrolusite having magnetic property can be removed from the non magnetic siliceous impurities.
(iv) The crushed ore is poured on to an electromagnetic separator consisting of a belt moving over two rollers of which one is magnetic.
(v) The magnetic part of the ore is attracted towards the magnet and falls as a heap close to the magnetic region while the nonmagnetic part falls away from it as shown in the figure.

(i) Froth flotation method is commonly used to concentrate sulphide ores such as galena (PbS), zinc blende (ZnS) etc.
(ii) In this method, the metallic ore particles which are preferentially wetted by oil can be separated from gangue.
(iii) In this method, the crushed ore is suspended in water and mixed with frothing agent such as pine oil, eucalyptus oil etc.
(iv) A small quantity of sodium ethyl xanthate which acts as a collector is also added.
(v) A froth is generated by blowing air through this mixture.
(vi) The collector molecules attach to the ore particle and make them water repellent.
(vii) As a result, ore particles, wetted by the oil, rise to the surface along with the froth.
(viii) The froth is skimmed off and dried to recover the concentrated ore.
(ix) The gangue particles that are preferentially wetted by water settle at the bottom.

(i) Ellingham diagram is constructed based only on thermodynamic considerations. It gives information about the thermodynamic feasibility of a reaction. It does not tell anything about the rate of the reaction. More over, it does not give any idea about the possibility of other reactions that might be taking place.
(ii) The interpretation of \(\triangle\)G is based on the assumption that the reactants are in equilibrium with the product which is not always true.

1. The crude metal is refined by electrolysis. It is carried out in an electrolytic cell
Anode : Impure metal to be refined with dilute acid.
Cathode : Thin strips of pure metal
Electrolyte : Aqueous solution of the salts of the metal with dilute acid.
2. The metal dissolves from the anode, pass into the solution.
3. At the same amount of metal ions from the solution will be deposited at the cathode.
4. During electrolysis, the less electropositive impurities in the anode, settle down at the bottom and are removed as anode mud.
Example: Electrolytic refining of silver.
Cathode: Pure silver
Anode: lmpure silver rods
Electrolyte: Acidified aqueous solution of silver nitrate
5. When a current is passed through the electrodes the following reactions will take place
(a) Reaction at anode: \({ Ag }_{ (s) }\longrightarrow { Ag }^{ + }_{ (aq) }+{ 1e }^{ - }\)
(b) Reaction at cathode: \({ Ag }^{ + }_{ (aq) }+{ 1e }^{ - }\longrightarrow { Ag }_{ (s) }\)
6. During electrolysis, at anode silver loses electrons and form silver ions and the silver ions migrate towards the cathode and get discharged and deposited on the cathode.
7. Copper, Zinc etc can also be refined by this process.

a) i) Ellingham diagram for the formation of Al₂O₃ and MgO intersects around 1500^oC. Above this temp Mg lies above the Aluminium line. Hence only above 1500^oC 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.

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.

(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) + SiO_2(s) → CaSiO_3(s)
Flux     + gangue → Slag

c) Assertion is true, but reason is false

d) Both assertion and reason are false

d) Both (A) and (R) are false

b) Both (A) and (R) are true and (R) is not the correct explanation of (A).

a) Both (A) and (R) are true and (R) is the correct explanation of (A)