Unit 6

General Principles and Processes of Isolation of Elements

Thermodynamics illustrates why only a certain reducing element and a minimum specific temperature are suitable for reduction of a metal oxide to the metal in an extraction.

Objectives

After studying this Unit, you will be able to:

appreciate the contribution of Indian traditions in the metallurgical processes,

explain the terms minerals, ores, concentration, benefaction, calcination, roasting, refining, etc.;

understand the principles of oxidation and reduction as applied to the extraction procedures;

apply the thermodynamic concepts like that of Gibbs energy and entropy to the principles of extraction of Al, Cu, Zn and Fe;

explain why reduction of certain oxides like Cu2O is much easier than that of Fe2O3;

explain why CO is a favourable reducing agent at certain temperatures while coke is better in some other cases;

explain why specific reducing agents are used for the reduction purposes.

A few elements like carbon, sulphur, gold and noble gases, occur in free state while others in combined forms in the earth’s crust. The extraction and isolation of an element from its combined form involves various principles of chemistry. A particular element may occur in a variety of compounds. The process of metallurgy and isolation should be such that it is chemically feasible and commercially viable. Still, some general principles are common to all the extraction processes of metals. For obtaining a particular metal, first we look for minerals which are naturally occurring chemical substances in the earth’s crust obtainable by mining.
Out of many minerals in which a metal may be found, only a few are viable to be used as sources of that metal. Such minerals are known as ores. Rarely, an ore contains only a desired substance. It is usually contaminated with earthly or undesired materials known as gangue. The extraction and isolation of metals from ores involve the following major steps:
• Concentration of the ore,
• Isolation of the metal from its concentrated ore, and
• Purification of the metal.
The entire scientific and technological process used for isolation of the metal from its ores is known as metallurgy.

In the present Unit, first we shall describe various steps for effective concentration of ores. After that we shall discuss the principles of some of the common metallurgical processes. Those principles shall include the thermodynamic and electrochemical aspects involved in the effective reduction of the concentrated ore to the metal.

6.1 Occurrence of Metals

Elements vary in abundance. Among metals, aluminium is the most abundant. It is the third most abundant element in earth’s crust (8.3% approx. by weight). It is a major component of many igneous minerals including mica and clays. Many gemstones are impure forms of Al₂O₃ and the impurities range from Cr (in ‘ruby’) to Co (in ‘sapphire’). Iron is the second most abundant metal in the earth’s crust. It forms a variety of compounds and their various uses make it a very important element. It is one of the essential elements in biological systems as well

The principal ores of aluminium, iron, copper and zinc are given in Table 6.1.

Table 6.1: Principal Ores of Some Important Metals

For the purpose of extraction, bauxite is chosen for aluminium. For iron, usually the oxide ores which are abundant and do not produce polluting gases (like SO₂ that is produced in case iron pyrites) are taken. For copper and zinc, any of the listed ores (Table 6.1) may be used depending upon availability and other relevant factors. Before proceeding for concentration, ores are graded and crushed to reasonable size.

6.2 Concentration of Ores

Removal of the unwanted materials (e.g., sand, clays, etc.) from the ore is known as concentration, dressing or benefaction. Before proceeding for concentration, ores are graded and crushed to reasonable size. Concentration of ores involves several steps and selection of these steps depends upon the differences in physical properties of the compound of the metal present and that of the gangue. The type of the metal, the available facilities and the environmental factors are also taken into consideration. Some of the important procedures for concentration of ore are described below.

6.2.1 Hydraulic Washing

This is based on the difference between specific gravities of the ore and thegangue particles. It is therefore a type of gravity separation. In one such process, an upward stream of running water is used to wash the powdered ore. The lighter gangue particles are washed away and the heavier ore particles are left behind.

6.2.2 Magnetic Separation

This is based on differences in magnetic properties of the ore components. If either the ore or the gangue is attracted towards magnetic field, then the separation is carried out by this method. For example iron ores are attracted towards magnet, hence, non–magnetic impurities can be separted from them using magnetic separation. The powdered ore is dropped over a conveyer belt which moves over a magnetic roller (Fig.6.1) Magnetic substance remains attracted towards the belt and falls close to it.

Fig. 6.1: Magnetic separation (schematic)

6.2.3 Froth Floatation Method

This method is used for removing gangue from sulphide ores. In this process, a suspension of the powdered ore is made with water. Collectors and froth stabilisers are added to it. Collectors (e.g., pine oils, fatty acids, xanthates, etc.) enhance non-wettability of the mineral particles and froth stabilisers (e.g., cresols, aniline) stabilise the froth.

Fig. 6.2: Froth floatation process (schematic)

The mineral particles become wet by oils while the gangue particles by water. A rotating paddle agitates the mixture and draws air in it. As a result, froth is formed which carries the mineral particles. The froth is light and is skimmed off. It is then dried for recovery of the ore particles.

Sometimes, it is possible to separate two sulphide ores by adjusting proportion of oil to water or by using ‘depressants’. For example, in the case of an ore containing ZnS and PbS, the depressant used is NaCN. It selectively prevents ZnS from coming to the froth but allows PbS to come with the froth.

The Innovative Washerwoman

One can do wonders if he or she has a scientific temperament and is attentive to observations. A washerwoman had an innovative mind too. While washing a miner’s overalls, she noticed that sand and similar dirt fell to the bottom of the washtub. What was peculiar, the copper bearing compounds that had come to the clothes from the mines, were caught in the soapsuds and so they came to the top. One of her clients, Mrs. Carrie Everson was a chemist. The washerwoman told her experience to Mrs. Everson. The latter thought that the idea could be used for separating copper compounds from rocky and earth materials on large scale. This way an invention came up. At that time only those ores were used for extraction of copper, which contained large amounts of the metal. Invention of the Froth Floatation Method made copper mining profitable even from the low-grade ores. World production of copper soared and the metal became cheaper.

6.2.4 Leaching

Leaching is often used if the ore is soluble in some suitable solvent. Following examples illustrate the procedure:

(a) Leaching of alumina from bauxite

Bauxite is the principal ore of aluminium. It usually contains SiO2, iron oxides and titanium oxide (TiO2) as impurities. Concentration is carried out by heating the powdered ore with a concentrated solution of NaOH at 473 – 523 K and 35 – 36 bar pressure. This process is called digestion. This way, Al2O3 is extracted out as sodium aluminate. The impurity, SiO2 too dissolves forming sodium silicate. Other impurities are left behind.

Al2O3(s) + 2NaOH(aq) + 3H2O(l) → 2Na[Al(OH)4](aq) (6.1)

The sodium aluminate present in solution is neutralised by passing CO2 gas and hydrated Al2O3 is precipitated. At this stage, small amount of freshly prepared sample of hydrated Al2O3 is added to the solution. This is called seeding. It induces the precipitation.

2Na[Al(OH)4](aq) + CO2(g) → Al2O3.xH2O(s) + 2NaHCO3 (aq) (6.2)

Sodium silicate remains in the solution and hydrated alumina is filtered, dried and heated to give back pure Al2O3.

Al2O3.xH2O(s) Al2O3(s) + xH2O(g) (6.3)

(b) Other examples

In the metallurgy of silver and gold, the respective metal is leached with a dilute solution of NaCN or KCN in the presence of air, which supplies O2. The metal is obtained later by replacement reaction.

4M(s) + 8CN–(aq)+ 2H2O(aq) + O2(g) → 4[M(CN)2]– (aq) + 4OH–(aq) (M= Ag or Au) (6.4)

2[M(CN)2]- (aq) + Zn (s) → [Zn(CN)4]2- (aq) +2M (s) (6.5)

Intext Questions

6.1 Which of the ores mentioned in Table 6.1 can be concentrated by magnetic separation method?

6.2 What is the significance of leaching in the extraction of aluminium?

6.3 Extraction of Crude Metal from Concentrated Ore

The concentrated ore must be converted into a form which is suitable for reduction. Usually the sulphide ore is converted to oxide before reduction because oxides are easier to reduce. Thus isolation of metals from concentrated ore involves two major steps viz.,

(a) conversion to oxide, and

(b) reduction of the oxide to metal.

(a) Conversion to oxide

(i) Calcination: Calcinaton involves heating. It removes the volatile matter which escapes leaving behind the metal oxide:

Fe2O3.xH2O(s) Fe2O3 (s) + xH2O(g) (6.6)

ZnCO3 (s) ZnO(s) + CO2(g) (6.7)

CaCO3.MgCO3(s) CaO(s) + MgO(s ) + 2CO2(g) (6.8)

(ii) Roasting: In roasting, the ore is heated in a regular supply of air in a furnace at a temperature below the melting point of the metal. Some of the reactions involving sulphide ores are:

2ZnS + 3O2 → 2ZnO + 2SO2 (6.9)

2PbS + 3O2 → 2PbO + 2SO2 (6.10)

2Cu2S + 3O2 → 2Cu2O + 2SO2 (6.11)

Fig. 6.3: A section of a modern reverberatory furnace

The sulphide ores of copper are heated in reverberatory furnace [Fig. 6.3]. If the ore contains iron, it is mixed with silica before heating. Iron oxide ‘slags of ’* as iron silicate and copper is produced in the form of copper matte which contains Cu2S and FeS.

FeO + SiO2 → FeSiO3 (slag) (6.12)

The SO2 produced is utilised for manufacturing H2SO4 .

* During metallurgy, ‘flux’ is added which combines with ‘gangue’ to form ‘slag’. Slag separates more easily from the ore than the gangue. This way, removal of gangue becomes easier.

(b) Reduction of oxide to the metal

Reduction of the metal oxide usually involves heating it with some other substance acting as a reducing agent (C or CO or even another metal). The reducing agent (e.g., carbon) combines with the oxygen of the metal oxide.

MxOy + yC → xM + y CO (6.13)

Some metal oxides get reduced easily while others are very difficult to be reduced (reduction means electron gain or electronation). In any case, heating is required. To understand the
variation in the temperature requirement for thermal reductions (pyrometallurgy) and to predict which element will suit as the reducing agent for a given metal oxide (MxOy), Gibbs energy interpretations are made.

6.4 Thermodynamic Principles of Metallurgy

Some basic concepts of thermodynamics help us in understanding the theory of metallurgical transformations. Gibbs energy is the most significant term. To understand the variation in the temperature required for thermal reductions and to predict which element will suit as the reducing agent for a given metal oxide (MxOy), Gibbs energy interpretations are made. The criterion for the feasibility of a thermal reduction is that at a given temperture Gibbs energy change of the reaction must be negative. The change in Gibbs energy, ∆G for any process at any specified temperature, is described by the equation:

∆G = ∆H – T∆S (6.14)

where, ∆H is the enthalpy change and ∆S is the entropy change for the process.For any reaction, this change could also be explained through the equation:

$∆ G^{⊝} = - RTlnK$ (6.15)

where, K is the equilibrium constant of the ‘reactant – product’ system at the temperature, T. A negative ΔG implies a +ve K in equation 6.15. And this can happen only when reaction proceeds towards products. From these facts we can make the following conclusions:

1. When the value of ∆G is negative in equation 6.14, only then the reaction will proceed. If ΔS is positive, on increasing the temperature (T), the value of TΔS would increase (ΔH < TΔS) and then ΔG will become –ve

2. If reactants and products of two reactions are put together in a system and the net ΔG of the two possible reactions is –ve, the overall reaction will occur. So the process of interpretation involves coupling of the two reactions, getting the sum of their ΔG and looking for its magnitude and sign. Such coupling is easily understood through Gibbs energy (Δ $G^{⊝}$ ) vs T plots for formation of the oxides (Fig. 6.4)

Ellingham Diagram

The graphical representation of Gibbs energy was first used by H.J.T.Ellingham. This provides a sound basis for considering the choice of reducing agent in the reduction of oxides. This is known as Ellingham Diagram. Such diagrams help us in predicting the feasibility of thermal reduction of an ore. The criterion of feasibility is that at a given temperature, Gibbs energy of the reaction must be negative.
(a) Ellingham diagram normally consists of plots of $∆_{f} G^{⊝}$ vs T for formation of oxides
of elements i.e., for the reaction,
2xM(s) + O₂(g) → 2M_xO(s)
In this reaction, the gaseous amount (hence molecular randomness) is decreasing from left to right due to the consumption of gases leading to a –ve value of ΔS which changes the sign of the second term in equation (6.14). Subsequently ΔG shifts towards higher side despite rising T (normally, ΔG decreases i.e., goes to lower side with increasing temperature). The result is +ve slope in the curve for most of the reactions shown above for formation of M_xO(s).
(b) Each plot is a straight line except when some change in phase (s→liq or liq→g)
takes place. The temperature at which such change occurs, is indicated by an
increase in the slope on +ve side (e.g., in the Zn, ZnO plot, the melting is indicated
by an abrupt change in the curve).
(c) There is a point in a curve below which ΔG is negative (So M_xO is stable). Above
this point, M_xO will decompose on its own.
(d) In an Ellingham diagram, the plots of $∆ G^{⊝}$ for oxidation (and therefore reduction
of the corresponding species) of common metals and some reducing agents are given. The values of $∆_{f} G^{⊝}$ , etc.(for formation of oxides) at different temperatures are depicted which make the interpretation easy.
(e) Similar diagrams are also constructed for sulfides and halides and it becomes clear why reductions of M_xS is difficult. There, the $∆_{f} G^{⊝}$ of M_xS is not compensated

Limitations of Ellingham Diagram

1. The graph simply indicates whether a reaction is possible or not, i.e., the tendency of reduction with a reducing agent is indicated. This is so because it is based only on the thermodynamic concepts. It does not explain the kinetics of the reduction process. It cannot answer questions like how fast reduction can proceed? However, it explains why the reactions are sluggish when every species is in solid state and smooth when the ore melts down. It is interesting to note here that ∆H (enthalpy change) and the ∆S (entropy change) values for any chemical reaction remain nearly constant even on varying temperature. So the only dominant variable in equation(6.14) becomes T. However, ∆S depends much on the physical state of the compound. Since entropy depends on disorder or randomness in the system, it will increase if a compound melts (s→ l) or vapourises (l→ g) since molecular randomness increases on changing the phase from solid to liquid or from liquid to gas.

2. The interpretation of ∆rGƟ is based on K (∆GƟ = – RT lnK). Thus it is presumed that the reactants and products are in equilibrium:

MxO + Ared l xM + AredO

This is not always true because the reactant/product may be solid. [However it explains how the reactions are sluggish when every species is in solid state and smooth when the ore melts down.It is interestng to note here that ΔH (enthalpy change) and the ΔS (entropy change) values for any chemical reaction remain nearly constant even on varying temperature. So the only dominant variable in equation(6.14) becomes T. However, ΔS depends much on the physical state of the compound. Since entropy depends on disorder or randomness in the system, it will increase if a compound melts (s→l) or vapourises (l→g) since molecular randomness increases on changing the phase from solid to liquid or from liquid to gas].

The reducing agent forms its oxide when the metal oxide is reduced. The role of reducing agent is to provide ΔGV negative and large enough to make the sum of ΔGV of the two reactions (oxidation of the reducing agent and reduction of the metal oxide) negative. As we know, during reduction, the oxide of a metal decomposes:

M_{x} O (s) \to x M (s o l i d o r l i q) + \frac{1}{2} O_{2} (g)

(6.16)

The reducing agent takes away the oxygen. Equation 6.16 can be visualised as reverse of the oxidation of the metal. And then, the

∆_{f} G^{⊝}

value is written in the usual way:

x M (s o r l) + \frac{1}{2} O_{2} (g) \to M_{x} O (s) [∆ {G^{⊝}}_{(M, M_{x} O)}]

(6.17)

If reduction is being carried out through equation 6.16, the oxidation of the reducing agent (e.g., C or CO) will be there:

C (s) + \frac{1}{2} O_{2} (g) \to C O (g) [∆ G_{(C, C O)}]

(6.18)

C O (g) + \frac{1}{2} O_{2} (g) \to C O_{2} (g) [∆ G_{(C o, C O_{2})}]

(6.19)

If carbon is taken, there may also be complete oxidation of the element to

{CO}_{2} :

\frac{1}{2} C (s) + \frac{1}{2} O_{2} (g) \to \frac{1}{2} C O_{2} (g) [\frac{1}{2} ∆ G_{(C, C O_{2})}]

(6.20)

On subtracting equation 6.17 [it means adding its negative or the reverse form as in equation 6.16] from one of the three equations, we get:

M_{x} O (s) + C (s) \to xM (s or l) + CO (g)

(6.21)

M_{x} O (s) + CO (g) \to xM (s or l) + {CO}_{2} (g)

(6.22)

M_{x} O (s) + \frac{1}{2} C (s) \to xM (s or l) + \frac{1}{2} {CO}_{2} (g)

(6.23)

The reactions describe the actual reduction of the metal oxide, MxO, that we want to accomplish. The ∆rGƟ values for these reactions in general, can be obtained from the corresponding ∆f GƟ values of oxides.

As we have seen, heating (i.e., increasing T) favours a negative value of ∆rGƟ. Therefore, the temperature is chosen such that the sum of ∆rGƟ in the two combined redox processes is negative. In ∆rGƟ vs T plots (Ellingham diagram, Fig. 6.4), this is indicated by the point of intersection of the two curves, i.e, the curve for the formation of MxO and that for the formation of the oxide of the reducing substance. After that point, the ∆rGƟ value becomes more negative for the combined process making the reduction of MxO possible. The difference in the two ∆rGƟ values after that point determines whether reduction of the oxide of the element of the upper line is feasible by the element of which oxide formation is represented by the lower line. If the difference is large, the reduction is easier.

Example 6.1

Suggest a condition under which magnesium could reduce alumina.

Solution

The two equations are:

(a) Al + O2 → Al2O3 (b) 2Mg +O2 → 2MgO

At the point of intersection of the Al2O3 and MgO curves (marked “A” in diagram 6.4), the ∆rG0 becomes ZERO for the reaction:

Al2O3 +2Mg → 2MgO +Al

Below that point magnesium can reduce alumina.

Example 6.2

Although thermodynamically feasible, in practice, magnesium metal is not used for the reduction of alumina in the metallurgy of aluminium. Why ?

Solution

Temperatures below the point of intersection of Al2O3 and MgO curves, magnesium can reduce alumina. But the process will be uneconomical.

Example 6.3

Why is the reduction of a metal oxide easier if the metal formed is in liquid state at the temperature of reduction?

Solution

The entropy is higher if the metal is in liquid state than when it is in solid state. The value of entropy change (∆S) of the reduction process is more on positive side when the metal formed is in liquid state and the metal oxide being reduced is in solid state. Thus the value of ∆rGƟ becomes more on negative side and the reduction becomes easier.

6.4.1 Applications

(a) Extraction of iron from its oxides

Oxide ores of iron, after concentration through calcination/roasting (to remove water, to decompose carbonates and to oxidise sulphides) are mixed with limestone and coke and fed into a Blast furnace from its top. Here, the oxide is reduced to the metal. Thermodynamics helps us to understand how coke reduces the oxide and why this furnace is chosen. One of the main reduction steps in this process is:

FeO(s) + C(s) → Fe(s/l) + CO (g) (6.24)

It can be seen as a couple of two simpler reactions. In one, the reduction of FeO is taking place and in the other, C is being oxidised to CO:

FeO (s) \to Fe (s) + \frac{1}{2} O_{2} (g) [∆ G_{(FeO, Fe)}]

(6.25)

C (s) + \frac{1}{2} O_{2} (g) \to CO (g) [∆ G_{(C, CO)}]

(6.26)

When both the reactions take place to yield the equation (6.24), the net Gibbs energy change becomes:

∆ G_{(C, CO)} + ∆ G_{(FeO, Fe)} = ∆_{r} G

(6.27)

Naturally, the resultant reaction will take place when the right hand side in equation 6.27 is negative. In ΔG₀ vs T plot representing reaction 6.25, the plot goes upward and that representing the change C→CO (C,CO) goes downward. At temperatures above 1073K (approx.), the C,CO line comes below the Fe,FeO line [ΔG (C, CO) < ΔG(Fe, FeO)]. So in this range, coke will be reducing the FeO and will itself be oxidised to CO. In a similar way the reduction of Fe₃O₄ and Fe₂O₃ at relatively lower temperatures by CO can be explained on the basis of lower lying points of intersection of their curves with the CO, CO2 curve in Fig. 6.4.

Fig. 6.4: Gibbs energy (∆rGƟ) vs T plots (schematic) for the formation of some oxides per mole of oxygen consumed (Ellingham diagram)

In the Blast furnace, reduction of iron oxides takes place in different temperature ranges. Hot air is blown from the bottom of the furnace and coke is burnt to give temperature upto about 2200K in the lower portion itself. The burning of coke therefore supplies most of the heat required in the process. The CO and heat moves to upper part of the furnace. In upper part, the temperature is lower and the iron oxides (Fe2O3 and Fe3O4) coming from the top are reduced in steps to FeO. Thus, the reduction reactions taking place in the lower temperature
range and in the higher temperature range, depend on the points of corresponding intersections in the ΔrG0 vs T plots. These reactions can be summarised as follows:

At 500 – 800 K (lower temperature range in the blast furnace),

Fe2O3 is first reduced to Fe3O4 and then to FeO

3 Fe2O3 + CO → 2 Fe3O4 + CO2 (6.28)

Fe3O4 + 4 CO → 3Fe + 4 CO2 (6.29)

Fe2O3 + CO → 2FeO + CO2 (6.30)

At 900 – 1500 K (higher temperature range in the blast furnace):

C + CO2 → 2 CO (6.31)

FeO + CO → Fe + CO2 (6.32)

Fig. 6.5: Blast furnace

Limestone is also decomposed to CaO which removes silicate impurity of the ore as slag. The slag is in molten state and separates out from iron.

The iron obtained from Blast furnace contains about 4% carbon and many impurities in smaller amount (e.g., S, P, Si, Mn). This is known as pig iron and cast into variety of shapes. Cast iron is different from pig iron and is made by melting pig iron with scrap iron and coke using hot air blast. It has slightly lower carbon content (about 3%) and is extremely hard and brittle.

Further Reductions

Wrought iron or malleable iron is the purest form of commercial iron and is prepared from cast iron by oxidising impurities in a reverberatory furnace lined with haematite. The haematite oxidises carbon to carbon monoxide:

Fe2O3 + 3 C → 2 Fe + 3 CO (6.31)

Limestone is added as a flux and sulphur, silicon and phosphorus are oxidised and passed into the slag. The metal is removed and freed from the slag by passing through rollers.

(b) Extraction of copper from cuprous oxide [copper(I) oxide]

In the graph of ∆rGƟ vs T for the formation of oxides (Fig. 6.4), the Cu2O line is almost at the top. So it is quite easy to reduce oxide ores of copper directly to the metal by heating with coke. The lines (C, CO) and (C, CO2) are at much lower positions in the graph particularly after 500 – 600K. However, many of the ores are sulphides and some may also contain iron. The sulphide ores are roasted/smelted to give oxides:

2Cu2S + 3O2 → 2Cu2O + 2SO2 (6.32)

The oxide can then be easily reduced to metallic copper using coke:

Cu2O + C → 2 Cu + CO (6.33)

In actual process, the ore is heated in a reverberatory furnace after mixing with silica. In the furnace, iron oxide ‘slags of’ as iron slicate is formed. Copper is produced in the form of copper matte. This contains Cu2S and FeS.

FeO + SiO2 → FeSiO3 (Slag) (6.34)

Copper matte is then charged into silica lined convertor. Some silica is also added and hot air blast is blown to convert the remaining FeS, FeO and Cu2S/Cu2O to the metallic copper. Following reactions take place:

2FeS + 3O2 → 2FeO + 2SO2 (6.35)

FeO + SiO2 → FeSiO3 (6.36)

2Cu2S + 3O2 → 2Cu2O + 2SO2 (6.37)

2Cu2O + Cu2S → 6Cu + SO2 (6.38)

The solidified copper obtained has blistered appearance due to the evolution of SO2 and so it is called blister copper.

(c) Extraction of zinc from zinc oxide

The reduction of zinc oxide is done using coke. The temperature in this case is higher than that in the case of copper. For the purpose of heating, the oxide is made into brickettes with coke and clay.

ZnO + C Zn + CO (6.39)

The metal is distilled off and collected by rapid chilling.

Intext Questions

6.3 The reaction,

Cr2O3+2Al → Al2O3+2Cr (∆GƟ= – 421kJ)

is thermodynamically feasible as is apparent from the Gibbs energy value. Why does it not take place at room temperature?

6.4 Is it true that under certain conditions, Mg can reduce Al2O3 and Al can reduce MgO? What are those conditions?

6.5 Electrochemical Principles of Metallurgy

We have seen how principles of thermodyamics are applied to pyrometallurgy. Similar principles are effective in the reductions of metal ions in solution or molten state. Here they are reduced by electrolysis or by adding some reducing element.

In the reduction of a molten metal salt, electrolysis is done. Such methods are based on electrochemical principles which could be understood through the equation,

∆GƟ = – nEƟF (6.40)

here n isthe number of electrons and EƟ is the electrode potential of the redox couple formed in the system. More reactive metals have large negative values of the electrode potential. So their reduction is difficult. If the difference of two EƟ values corresponds to a positive EƟ and consequently negative ∆GƟ in equation 6.40, then the less reactive metal will come out of the solution and the more reactive metal will go into the solution, e.g.,

Cu2+ (aq) + Fe(s) → Cu(s) + Fe2+ (aq) (6.41)

In simple electrolysis, the Mn+ ions are discharged at negative electrodes (cathodes) and deposited there. Precautions are taken considering the reactivity of the metal produced and suitable materials are used as electrodes. Sometimes a flux is added for making the molten mass more conducting.

Aluminium

In the metallurgy of aluminium, purified Al2O3 is mixed with Na3AlF6 or CaF2 which lowers the melting point of the mixture and brings conductivity. The fused matrix is electrolysed. Steel vessel with lining of carbon acts as cathode and graphite anode is used. The overall reaction may be written as:

2Al2O3 + 3C → 4Al + 3CO2 (6.42)

This process of electrolysis is widely known as Hall-Heroult process.

Fig. 6.7: Electrolytic cell for the extraction of aluminium

Thus electrolysis of the molten mass is carried out in an electrolytic cell using carbon electrodes. The oxygen liberated at anode reacts with the carbon of anode producing CO and CO2. This way for each kg of aluminium produced, about 0.5 kg of carbon anode is burnt away. The electrolytic reactions are:

Cathode: Al3+ (melt) + 3e– → Al(l) (6.43)

Anode: C(s) + O2– (melt) → CO(g) + 2e– (6.44)

C(s) + 2O2– (melt) → CO2 (g) + 4e– (6.45)

Copper from Low Grade Ores and Scraps

Copper is extracted by hydrometallurgy from low grade ores. It is leached out using acid or bacteria. The solution containing Cu2+ is treated with scrap iron or H2 (equations 6.40; 6.46).

Cu2+(aq) + H2(g) → Cu(s) + 2H+ (aq) (6.46)

Example 6.4

At a site, low grade copper ores are available and zinc and iron scraps are also available. Which of the two scraps would be more suitable for reducing the leached copper ore and why?

Solution

Zinc being above iron in the electrochemical series (more reactive metal is zinc), the reduction will be faster in case zinc scraps are used. But zinc is costlier metal than iron so using iron scraps will be advisable and advantageous.

6.6 Oxidation Reduction

Besides reductions, some extractions are based on oxidation particularly for non-metals. A very common example of extraction based on oxidation is the extraction of chlorine from brine (chlorine is abundant in sea water as common salt) .

2Cl–(aq) + 2H2O(l) → 2OH–(aq) + H2(g) + Cl2(g) (6.47)

The ∆GƟ for this reaction is + 422 kJ. When it is converted to EƟ (using ∆GƟ = – nEƟF), we get EƟ = – 2.2 V. Naturally, it will require an external emf that is greater than 2.2 V. But the electrolysis requires an excess potential to overcome some other hindering reactions (Unit–3, Section 3.5.1). Thus, Cl2 is obtained by electrolysis giving out H2 and aqueous NaOH as by-products. Electrolysis of molten NaCl is also carried out. But in that case, Na metal is produced and not NaOH.

As studied earlier, extraction of gold and silver involves leaching the metal with CN–. This is also an oxidation reaction (Ag → Ag+ or Au → Au+). The metal is later recovered by displacement method.

4Au(s) + 8CN–(aq) + 2H2O(aq) + O2(g) → 4[Au(CN)2]–(aq) + 4OH–(aq) (6.48)

2[Au(CN)2]–(aq) + Zn(s) → 2Au(s) + [Zn(CN)4]2– (aq) (6.49)

In this reaction zinc acts as a reducing agent.

6.7 Refining

A metal extracted by any method is usually contaminated with some impurity. For obtaining metals of high purity, several techniques are used depending upon the differences in properties of the metal and the impurity. Some of them are listed below.

(a) Distillation (b) Liquation

(c) Electrolysis (d) Zone refining

(e) Vapour phase refining (f) Chromatographic methods

These are described in detail here.

(a) Distillation

This is very useful for low boiling metals like zinc and mercury. The impure metal is evaporated to obtain the pure metal as distillate.

(b) Liquation

In this method a low melting metal like tin can be made to flow on a sloping surface. In this way it is separated from higher melting impurities.

(c) Electrolytic refining

In this method, the impure metal is made to act as anode. A strip of the same metal in pure form is used as cathode. They are put in a suitable electrolytic bath containing soluble salt of the same metal. The more basic metal remains in the solution and the less basic ones go to the anode mud. This process is also explained using the concept of electrode potential, over potential, and Gibbs energy which you have seen in previous sections. The reactions are:

Anode: M → Mn+ + ne–

Cathode: Mn+ + ne– → M (6.50)

Copper is refined using an electrolytic method. Anodes are of impure copper and pure copper strips are taken as cathode. The electrolyte is acidified solution of copper sulphate and the net result of electrolysis is the transfer of copper in pure form from the anode to the cathode:

Anode: Cu → Cu2+ + 2 e–

Cathode: Cu2+ + 2e– → Cu (6.51)

Impurities from the blister copper deposit as anode mud which contains antimony, selenium, tellurium, silver, gold and platinum; recovery of these elements may meet the cost of refining. Zinc may also be refined this way.

(d) Zone refining

Fig. 6.8: Zone refining process

This method is based on the principle that the impurities are more soluble in the melt than in the solid state of the metal. A mobile heater surrounding the rod of impure metal is fixed at its one end (Fig. 6.8). The molten zone moves along with the heater which is moved forward. As the heater moves forward, the pure metal crystallises out of the melt left behind and the impurities pass on into the adjacent new molten zone created by movement of heaters. The process is repeated several times and the heater is moved in the same direction again and again. Impurities get concentrated at one end. This end is cut off. This method is very useful for producing semiconductor and other metals of very high purity, e.g., germanium, silicon, boron, gallium and indium.

(e) Vapour phase refining

In this method, the metal is converted into its volatile compound which is collected and decomposed to give pure metal. So, the two requirements are:

(i) the metal should form a volatile compound with an available reagent,

(ii) the volatile compound should be easily decomposable, so that the recovery is easy.

Following examples will illustrate this technique.

Mond Process for Refining Nickel: In this process, nickel is heated in a stream of carbon monoxide forming a volatile complex named as nickel tetracarbonyl. This compex is decomposed at higher temperature to obtain pure metal.

Ni + 4CO Ni(CO)4 (6.52)

Ni(CO)4 Ni + 4CO (6.53)

van Arkel Method for Refining Zirconium or Titanium: This method is very useful for removing all the oxygen and nitrogen present in the form of impurity in certain metals like Zr and Ti. The crude metal is heated in an evacuated vessel with iodine. The metal iodide being more covalent, volatilises:

Zr + 2I2 → ZrI4 (6.54)

The metal iodide is decomposed on a tungsten filament, electrically heated to about 1800K. The pure metal deposits on the filament.

ZrI4 → Zr + 2I2 (6.55)

(f) Chromatographic methods

This method is based on the principle that different components of a mixture are differently adsorbed on an adsorbent. The mixture is put in a liquid or gaseous medium which is moved through the adsorbent.Different components are adsorbed at different levels on the column.
Later the adsorbed components are removed (eluted) by using suitable solvents (eluant). Depending upon the physical state of the moving medium and the adsorbent material and also on the process of passage of the moving medium, the chromatographic method* is given the name. In one such method the column of Al2O3 is prepared in a glass tube and the moving medium containing a solution of the components is in liquid form. This is an example of column chromatography. This is very useful for purification of the elements which are available in minute quantities and the impurities are not very different in chemical properties from the element to be purified. There are several chromatographic techniques such as paper chromatography, column chromatography, gas chromatography, etc. Procedures followed in column chromatography have been depicted in Fig. 6.8.

Fig. 6.8: Schematic diagrams showing column chromatography

Looking it the other way, chromatography in general, involves a mobile phase and a stationary phase. The sample or sample extract is dissolved in a mobile phase. The mobile phase may be a gas, a liquid or a supercritical fluid. The stationary phase is immobile and immiscible (like the Al2O3 column in the example of column chromatography above). The mobile phase is then forced through the stationary phase. The mobile phase and the stationary phase are chosen such that components of the sample have different solubilities in the two phases. A component which is quite soluble in the stationary phase takes longer
time to travel through it than a component which is not very soluble in the stationary phase but very soluble in the mobile phase. Thus sample components are separated from each other as they travel through the stationary phase. Depending upon the two phases and the way sample is inserted/injected, the chromatographic technique is named. These methods have been described in detail in Unit 12 of Class XI text book (12.8.5).

6.8 Uses of Aluminium, Copper, Zinc and Iron

Aluminium foils are used as wrappers for food materials. The fine dust of the metal is used in paints and lacquers. Aluminium, being highly reactive, is also used in the extraction of chromium and manganese from their oxides. Wires of aluminium are used as electricity conductors. Alloys containing aluminium, being light, are very useful.

Copper is used for making wires used in electrical industry and for water and steam pipes. It is also used in several alloys that are rather tougher than the metal itself, e.g., brass (with zinc), bronze (with tin) and coinage alloy (with nickel).

Zinc is used for galvanising iron. It is also used in large quantities in batteries. It is constituent of many alloys, e.g., brass, (Cu 60%, Zn 40%) and german silver (Cu 25-30%, Zn 25-30%, Ni 40–50%). Zinc dust is used as a reducing agent in the manufacture of dye-stuffs, paints, etc.

Cast iron, which is the most important form of iron, is used for casting stoves, railway sleepers, gutter pipes , toys, etc. It is used in the manufacture of wrought iron and steel. Wrought iron is used in making anchors, wires, bolts, chains and agricultural implements. Steel finds a number of uses. Alloy steel is obtained when other metals are added to it. Nickel steel is used for making cables, automobiles and aeroplane parts, pendulum, measuring tapes. Chrome steel is used for cutting tools and crushing machines, and stainless steel is used for cycles, automobiles, utensils, pens, etc.

Summary

Although modern metallurgy had exponential growth after Industrial Revolution, many modern concepts in metallurgy have their roots in ancient practices that predated the Industrial Revolution. For over 7000 years, India has had high tradition of metallurigical skills. Ancient Indian metallurgists have made major contributions which deserve their place in metallurgical history of the world. In the case of zinc and high–carbon steel, ancient India contributed significantly for the developemnt of base for the modern metallurgical advancements which induced metallurgical study leading to Industrial Revolution.

Metals are required for a variety of purposes. For this, we need their extraction from the minerals in which they are present and from which their extraction is commercially feasible.These minerals are known as ores. Ores of the metal are associated with many impurities. Removal of these impurities to certain extent is achieved in concentration steps. The concentrated ore is then treated chemically for obtaining the metal. Usually the metal compounds (e.g., oxides, sulphides) are reduced to the metal. The reducing agents used are carbon, CO or even some metals. In these reduction processes, the thermodynamic and electrochemical concepts are given due consideration. The metal oxide reacts with a reducing agent; the oxide is reduced to the metal and the reducing agent is oxidised. In the two reactions, the net Gibbs energy change is negative, which becomes more negative on raising the temperature. Conversion of the physical states from solid to liquid or to gas, and formation of gaseous states favours decrease in the Gibbs energy for the entire system. This concept is graphically displayed in plots of ∆GƟ vs T (Ellingham diagram) for such oxidation/reduction reactions at different temperatures. The concept of electrode potential is useful in the isolation of metals (e.g., Al, Ag, Au) where the sum of the two redox couples is positive so that the Gibbs energy change is negative. The metals obtained by usual methods still contain minor impurities. Getting pure metals requires refining. Refining process depends upon the differences in properties of the metal and the impurities. Extraction of aluminium is usually carried out from its bauxite ore by leaching it with NaOH. Sodium aluminate, thus formed, is separated and then neutralised to give back the hydrated oxide, which is then electrolysed using cryolite as a flux. Extraction of iron is done by reduction of its oxide ore in blast furnace. Copper is extracted by smelting and heating in a reverberatory furnace. Extraction of zinc from zinc oxides is done using coke. Several methods are employed in refining the metal. Metals, in general, are very widely used and have contributed significantly in the development of a variety of industries.

Exercises

6.1 Copper can be extracted by hydrometallurgy but not zinc. Explain.

Column I	Column II
A. Pendulum	1. Chrome steel
B. Malachite	2. Nickel Steel
C. Calamine	3. Na₃AlF₆
D. Cryolite	4. CuCO₃. Cu (OH)₂
	5. ZnCO₃

Column I	Column II
A. Coloured Bands	1. Zone refining
B. Impure metal to volatile complex	2. Fractional distillation
C. Purification of Ge and Si	3. Mond’s process
D. Purification of mercury	4. Chromatography
	5. Liquation

Column I	Column II
A. Cyanide process	1. Ultrapure Ge
B. Froth floatation process	2. Dressing of ZnS
C. Electrolytic reduction	3. Extraction of Al
D. Zone refining	4. Extraction of Au
	5. Purification of Ni

Column I	Column II
A. Sapphire	1. Al₂O₃
B. Sphalerite	2. NaCN
C. Depressant	3. Co
D. Corundum	4. ZnS
	5. Fe₂O₃

Column I	Column II
A. Blisterred Cu	1. Aluminium
B. Blast furnace	2. $2 {Cu}_{2} O + {Cu}_{2} S \to 6 Cu + {SO}_{2}$
C. Reverberatory furnace	3. Iron
D. Hall-Heroult process	4. $FeO + {SiO}_{2} \to {FeSiO}_{3}$
	5. $2 {Cu}_{2} S + 30_{2} \to 2 {Cu}_{2} O + 2 {SO}_{2}$

NCERT Ebook - General Principles and Processes of Isolation of Elements (OLD NCERT)

Unit 6

General Principles and Processes of Isolation of Elements

Objectives

6.1 Occurrence of Metals

6.2 Concentration of Ores

6.2.1 Hydraulic Washing

6.2.2 Magnetic Separation

6.2.3 Froth Floatation Method

6.2.4 Leaching

6.3 Extraction of Crude Metal from Concentrated Ore

6.4 Thermodynamic Principles of Metallurgy

6.4.1 Applications

6.5 Electrochemical Principles of Metallurgy

6.6 Oxidation Reduction

6.7 Refining

6.8 Uses of Aluminium, Copper, Zinc and Iron

Summary

Exercises

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