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Unit 6

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General Principles and Processes of Isolation of Element
(Concepts, Questions & Exceptions)

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Minerals: Naturally occurring chemical substances in the earth’s crust obtainable by mining.
Ores: Out of many minerals in which a metal may be found, only a few are viable to be used as

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sources of that metal. Such minerals are known as ores.

Gangue: Minerals is usually contaminated with earthly or undesired materials known as gangue

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Metallurgy: The entire scientific and technological process used for isolation of the metal from
its ores is known as metallurgy

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The extraction and isolation of metals from ores involve the following major steps:
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1. Concentration of the ore
2. Isolation of the metal from its concentrated ore
3. Purification of the metal
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A few elements like carbon, sulphur, gold and noble gases, occur in free state while others in
combined forms in the earth’s crust.
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Occurrence of Metals:
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1. Among metals, aluminium is the most abundant.

2. It is the third most abundant element in earth’s crust (8.3% approx. by weight).
3. It is a major component of mica and clays.
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4. Many gemstones are impure forms of Al� O� and the impurities range from Cr (in ‘ruby’)
to Co (in ‘sapphire’).
5. Iron is the second most abundant metal in the earth’s crust.
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Q. Which of the following is not an ore of Iron

(a) Haematite (b) Malachite (c) Siderite (d) Magnetite
 Concentration of Ores: Removal of the unwanted materials (e.g., sand, clays, etc.) from the
ore is known as concentration, dressing or benefaction. It involves several steps and selection of
these steps depends upon the differences in physical properties of the compound of the metal

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present and that of the gangue
1. Hydraulic Washing: This is based on the differences in gravities of the ore and the gangue

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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 ores are left behind

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2. Magnetic Separation: This is based on differences in magnetic properties of the ore
components.

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Q. Which of the ores can be
concentrated by magnetic

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separation method?

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3. Froth Floatation Method:

This method has been in use for sulphide ores. In
this process, a suspension of the powdered ore is
made with water. To it, collectors and froth
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stabilisers are added. Collectors (e. g., pine oils,

fatty acids, xanthates, etc.) enhance non-wettability
of the mineral particles and froth stabilisers (e. g.,
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cresols, aniline) stabilise the froth.

Sometimes, it is possible to separate two sulphide
ores by adjusting proportion of oil to water or by
using ‘depressants’. For example, in case of an ore
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containing ZnS and PbS, the depressant used is

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NaCN. It selectively prevents ZnS from coming to

the froth but allows PbS to come with the froth
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Q. Froth flotation process is based on

(a) Wetting properties of ore particle (b) Specific gravity of ore particles
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(c) Magnetic properties of ore particles (d) Electrical properties of ore particles

Q. What is the role of depressant in froth floatation process?

 Q. Iron pyrites ore is concentrated by
(a) Froth floatation (b) Electrolysis (c) Roasting (d) Magnetic separation

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4. Leaching: Leaching is often used if the ore is soluble in some suitable solvent.

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(a) Leaching of alumina from bauxite:
1. Bauxite, usually contain SiO� , iron oxides and titanium oxide (TiO� ) as impurities.
2. Treat the powdered ore with a concentrated solution of NaOH at 473-523 K and 35-36 bar

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pressure.
3. This way, Al� O� is leached out as sodium aluminate (and SiO� too as sodium silicate)

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leaving the impurities behind:

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The aluminate in solution is neutralised by passing CO� gas and hydrated Al� O� is precipitated.

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At this stage, the solution is seeded with freshly prepared samples of hydrated Al� O� which induces
the precipitation:
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The sodium silicate remains in the solution and hydrated alumina is filtered, dried and heated to
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give back pure Al� O�

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Leaching of Silver (Ag) and that of Gold (Au): In the metallurgy of silver and that of gold, the
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respective metal is leached with a dilute solution of NaCN or KCN in the presence of air from
which the metal is obtained later by replacement:
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Extraction of Crude Metal from Concentrated Ore:

(a) Conversion to oxide (b) Reduction of the oxide to metal.
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(a) Conversion to oxide

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(i) Calcination: Calcinaton involves heating when the volatile matter escapes leaving behind the
metal oxide:
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Q. Which of the following reactions is an example for calcination process ?

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(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:

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reverberatory furnace. If the ore
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contains iron, it is mixed with silica
before heating. Iron oxide ‘slags’ as iron
silicate and copper is produced in the
form of copper matte which contains
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Cu� S and FeS.

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(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
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reducing agent (e.g., carbon) combines with the oxygen of the metal oxide

Thermodynamic Principles of Metallurgy:

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Gibbs energy is the most significant term here. The change in Gibbs energy, ΔG for any process
at any specified temperature, is described by the equation:
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A negative ΔG implies a +ve K. And this can happen only when reaction proceeds towards
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products. From these facts we can make the following conclusions:

 1. When the value of ΔG is negative, 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.

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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

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looking for its magnitude and sign. Such coupling is easily understood through Gibbs
energy (∆G� ) vs T plots for formation of the oxides

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Ellingham Diagram: Ellingham Diagram 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

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reaction must be negative

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(a) Ellingham diagram normally consists of plots of ∆� G� vs T for formation of oxides of elements
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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
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term in equation. Subsequently ΔG shifts towards higher side despite rising T (normally, ΔG
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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� O (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

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(c) There is a point in a curve below which ΔG is negative (So M� O is stable). Above this point,
M� O will decompose on its own.
(d) In an Ellingham diagram, the plots of ∆G� for oxidation of common metals and some reducing

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agents are given. The values of ∆� 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

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reductions of M� S is difficult. There, the ∆� G� of M� S is not compensated.

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

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Q. Is it true that under certain conditions, Mg can reduce Al� O� and Al can reduce MgO? What
are those conditions?
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Q. Out of C and CO, which is a better reducing agent at 673 K ?
Q. The value of ∆� G� for formation of Cr� O� is -540 kJmol�� .and that of Al� O� is -827kJmol�� .
Is the reduction of Cr� O� possible with Al ?
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Limitations of Ellingham Diagram

1. It does not say about the kinetics of the reduction process (Cannot answer questions like how
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fast it could be ?).

2. The interpretation of ∆G� is based on K (∆G� = – RT lnK). Thus it is presumed that the reactants
and products are in equilibrium. This is not always true because the reactant/product may be solid.
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(a) Extraction of iron from its oxides: Blast furnace

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Oxide ores of iron, are mixed with limestone and coke and fed into a Blast furnace from its top.
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Here, the oxide is reduced to the metal.

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Thermodynamics helps us to understand how coke reduces the oxide and why this furnace is
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chosen.
It can be seen as a couple of two simpler reactions.
 …………1

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…………2

……………3

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When both the reactions take place to yield the equation (3), the net Gibbs energy change becomes

……………4

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Naturally, the resultant reaction will take place when the right hand side in equation (4) is negative.
In ∆G� vs T plot representing reaction (1), the plot goes upward and that representing the change

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C→CO, (C,CO) goes downward.
At temperatures above 1073K (approx.), the C,CO line comes below the Fe, FeO line [ΔG (C, CO)

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< ΔG (Fe, FeO)]. So in this range, coke will be reducing the FeO and will itself be oxidised to CO.

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In a similar way the reduction of Fe� O� and Fe� O� at relatively lower temperatures by CO can be
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explained on the basis of lower lying points of intersection of their curves with the CO, CO� curve.
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At 900 -1500 K (higher temperature range in the blast furnace):

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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.
 Limestone is added as a flux and sulphur, silicon and phosphorus are oxidised and passed into the
slag

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In the Blast furnace, reduction of iron

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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

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portion itself.
The burning of coke therefore supplies most

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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

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the iron oxides (Fe� O� and Fe� O� ) coming

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Thus, the reduction reactions taking place in
the lower temperature range and in the
higher temperature range.
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Pig 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: Cast iron is different from pig iron and is made by melting pig iron with scrap iron and
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coke using hot air blast. It has slightly lower carbon content (about 3%) and is extremely hard and
brittle.
Wrought iron or malleable iron: It is the purest form of commercial iron and is prepared from
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cast iron by oxidising impurities in a reverberatory furnace lined with haematite. This haematite
oxidises carbon to carbon monoxide:
Q. The following reactions take place in the blast furnace in the preparation of impure iron. Identify
the reaction pertaining to the formation of the slag.
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Q. Cast iron is
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(a) Made by melting pig iron with scrap iron and coke using hot air blast
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(b) Having slightly lower carbon content (about 3%) as compared to pig iron
(c) Extremely hard and brittle (d) All of the above statements are true
 (b) Extraction of copper from cuprous oxide [copper (I) oxide]: In the graph of ∆� G� vs T for
formation of oxides, the Cu� O 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 (both the lines of C, CO and C, CO� are at much

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lower positions in the graph particularly after 500-600K). However most of the ores are sulphide
and some may also contain iron. The sulphide ores are roasted/smelted to give oxides:

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

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In actual process, the ore is heated in a reverberatory furnace after mixing with silica. In the

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furnace, iron oxide ‘slags of’ as iron silicate and copper is produced in the form of copper matte.
This contains Cu� S and FeS

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

Q. Why copper matte is put in silica lined converter?
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(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 case of copper. For the purpose of heating, the oxide
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is made into brickettes with coke and clay. The metal is distilled off and collected by rapid chilling

Q. Why is zinc not extracted from zinc oxide through reduction using CO?
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Q. Out of C and CO, which is a better reducing agent for ZnO ?

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Electrochemical Principles of Metallurgy:

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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
 More reactive metals have large negative values of the electrode potential. So their reduction is
difficult. If the difference of two E � values corresponds to a positive E � and consequently negative
∆G� , then the less reactive metal will come out of the solution and the more reactive metal will go

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to the solution

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In simple electrolysis, the M �� ions are discharged at negative electrodes (cathodes) and deposited
there.

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Q. Why is the extraction of copper from pyrites more difficult than that from its oxide ore through
reduction?

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Extraction of Aluminium: By Hall-Heroult process

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purified Al� O� is mixed with
Na� AlF� or CaF� which lowers the
melting point of the mix and brings
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conductivity. The fused matrix is
electrolysed.
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Q. What is the role of cryolite in the metallurgy of aluminium?

Q. What is the role of graphite rod in the electrometallurgy of aluminium?
Q. In the extraction of aluminium by Hall-Heroult process, purified Al� O� is mixed with CaF� to
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(i) Lower the melting point of Al� O� (iii) Reduce Al�� into Al(s).
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(ii) Increase the conductivity of molten mixture. (iv) Acts as catalyst.

(a) (i) and (ii) (b) (i), (ii) and (iii) (c) (iii) and (iv) (d) (ii), (iii) and (iv)
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Copper from low grade ores and scraps copper is extracted by hydrometallurgy from low grade
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ores. It is leached out using acid or bacteria. The solution containing Cu�� is treated with scrap
iron or H�
 Q. Copper can be extracted by hydrometallurgy but not zinc. Explain.

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Oxidation Reduction:
Besides reductions, some extractions are based on oxidation particularly for non-metals. A very

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common example of extraction based on oxidation is the extraction of chlorine from brine
(chlorine is abundant in sea water as common salt)

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As studied earlier, extraction of gold and silver involves leaching the metal with CN � . This is also

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an oxidation reaction (Ag →Au� or Au → Au� ). The metal is later recovered by displacement

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method.
In this reaction zinc acts as a reducing agent

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Q. The silver complex ion formed during cyanide process is
a) Na� [Ag(CN)] b) Na[Ag(CN)] c) Na� [Ag(CN)� ] d) Na[Ag(CN)� ]
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Refining: For obtaining metals of high purity, several techniques are used depending upon the
differences in properties of the metal and the impurity.
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a) Distillation
b) Liquation
c) Electrolysis
d) Zone refining
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e) Vapour phase refining

f) Chromatographic methods
(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.
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(b) Liquation: In this method a low melting metal like Tin (Sn) can be made to flow on a sloping
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surface. In this way it is separated from higher melting impurities

Q. Liquation process is used for refining
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(a) Bismuth (b) Lead (c) Tin (d) All

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(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.
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Copper is refined using an electrolytic
method. Anodes are of impure copper and

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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

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anode to the cathode:

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Zinc may also be refined this way.

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Q. Name the common elements present in the anode mud in electrolytic refining of copper. Why
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are they so present ?
Q. During the process of electrolytic refining of copper, some metals present as impurity settle as
‘anode mud’. These are
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(a) Fe and Ni (b) Ag and Au (c) Pb and Zn (d) Sn and Ag
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(d) Zone refining: This method is based on the principle that the impurities are more soluble in
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the melt than in the solid state of the metal. A circular mobile heater is fixed at one end of a rod of
the impure metal
This method is very useful for producing semiconductor and other metals of very high purity, e.g.,
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germanium, silicon, boron, gallium and indium

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Q. The process of zone refining is used in the purification of

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(a) Si (b) Al (c) Ag (d) Cu

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Q. Method used for obtaining highly pure silicon which is used as a semiconductor material, is
(a) Oxidation (b) Electrochemical (c) Crystallization (d) Zone refining
 (e) Vapour phase refining: In this method, the metal is converted into its volatile compound and
collected elsewhere. It is then decomposed to give pure metal.

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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.

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1) Mond Process for Refining Nickel: In this process, nickel is heated in a stream of carbon
monoxide forming a volatile complex, nickel tetracarbonyl:

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2) 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.

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Q. Which of the following pairs of metals is purified by van Arkel method ?
(a) Ga and In (b) Zr and Ti (c) Ag and Au (d) Ni and Fe
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Q. Monds process is used for
(a) Ni (b) Al (c) Fe (d) Cu
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Chromatographic methods: It is described in GOC

Uses of some important metals:
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Uses of Aluminium:
1. Aluminium foils are used as wrappers for chocolates.
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2. The fine dust of the metal is used in paints and lacquers.

3. Aluminium, being highly reactive, is also used in the extraction of chromium and
manganese from their oxides.
4. Wires of aluminium are used as electricity conductors.
5. Alloys containing aluminium, being light, are very useful.
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Uses of Copper:
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1. Copper is used for making wires used in electrical industry and for water and steam pipes.
2. It is also used in several alloys that are rather tougher than the metal itself, e.g., brass (with
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zinc), bronze (with tin) and coinage alloy (with nickel).

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 Uses of Zinc:
1. It is also used in large quantities in batteries,

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

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Uses of iron:
1. Cast iron is used for casting stoves, railway sleepers, gutter pipes, toys, etc.

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2. It is used in the manufacture of wrought iron and steel.
3. Wrought iron is used in making anchors, wires, bolts, chains and agricultural implements.

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4. Steel finds a number of uses.

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5. Alloy steel is obtained when other metals are added to it.
6. Nickel steel is used for making cables, automobiles and aeroplane parts, pendulum,
measuring tapes, chrome steel for cutting tools and crushing machines, and stainless steel

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for cycles, automobiles, utensils, pens, etc.

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Q. Which of the following metal is used in the manufacture of dye-stuffs and paints?
(a) Copper (b) Zinc (c) Aluminium (d) Magnesium
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 Note: Do all Intex Questions, Back Exercise Questions, Solved Examples

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