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

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.

(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.

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.

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.

(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) 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.

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) In the concentrated ore, the metal exists in positive oxidation state and hence it is to be reduced to its elemental state.
(ii) From the principles of thermodynamics; that the reduction of oxide is easier when compared to reduction of other compounds of metal and hence, before reduction, the are is first converted into the oxide of metal of interest.

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.