Unit 6

General Principles and Processes of

Isolation of Elements
 Unit 6

General Principles and Processes

of Isolation of Elements
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.
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.

The history of civilisation is linked to the use of metals in antiquity in many

ways. Different periods of early human civilisations have been named after
metals. The skill of extraction of metals gave many metals and brought
about several changes in the human society. It gave weapons, tools,
ornaments, utensils, etc., and enriched the cultural life. The ‘Seven metals
of antiquity’, as they are sometimes called, are gold, copper, silver, lead,
tin, iron and mercury. Although modern metallurgy had exponential growth
after Industrial Revolution, it is interesting to note that many modern
concepts in metallurgy have their roots in ancient practices that pre-dated
the Industrial Revolution. For over 7000 years, India has had a rich tradition
of metallurgical skills.

The two important sources for the history of Indian metallurgy are
archaeological excavations and literary evidences. The first evidence of
metal in Indian subcontinent comes from Mehrgarh in Baluchistan, where a
small copper bead, dated to about 6000 BCE was found. It is however
thought to be native copper, which has not been extracted from the ore.
Spectrometric studies on copper ore samples obtained from the ancient
mine pits at Khetri in Rajasthan and on metal samples cut from
representative Harappan artefacts recovered from Mitathal in Haryana and
eight other sites distributed in Rajasthan, Gujarat, Madhya Pradesh and
Maharashtra prove that copper metallurgy in India dates back to the
Chalcolithic cultures in the subcontinent. Indian chalcolithic copper objects
were in all probability made indigenously. The ore for extraction of metal
for making the objects was obtained from chalcopyrite ore deposits in
Aravalli Hills. Collection of archaeological texts from copper-plates and
rock-inscriptions have been compiled and published by the Archaeological
Survey of India during the past century. Royal records were engraved on
copper plates (tamra-patra). Earliest known copper-plate has a Mauryan
record that mentions famine relief efforts. It has one of the very few pre-
Ashoka Brahmi inscriptions in India.

Harappans also used gold and silver, as well as their joint alloy electrum.
Variety of ornaments such as pendants, bangles, beads and rings have been
found in ceramic or bronze pots. Early gold and silver ornaments have been
found from Indus Valley sites such as Mohenjodaro (3000 BCE). These are
on display in the National Museum, New Delhi. India has the distinction of
having the deepest ancient gold mines in the world, in the Maski region of
Karnataka. Carbon dating places them in mid 1st millennium BCE.

Hymns of Rigveda give earliest indirect references to the alluvial placer

gold deposits in India. The river Sindhu was an important source of gold in
ancient times. It is interesting that the availability of alluvial placer gold in
the river Sindhu has been reported in modern times also. It has been
reported that there are great mines of gold in the region of Mansarovar and
in Thokjalyug even now. The Pali text, Anguttara Nikaya narrates the
process of the recovery of gold dust or particles from alluvial placer gold
deposits. Although evidence of gold refining is available in Vedic texts, it is
Kautilya’s Arthashastra, authored probably in 3rd or 4th century BCE,
during Mauryan era, which has much data on prevailing chemical practices
in a long section on mines and minerals including metal ores of gold, silver,
copper, lead, tin and iron. Kautilya describes a variety of gold called
rasviddha, which is naturally occurring gold solution. Kalidas also
mentioned about such solutions. It is astonishing how people recognised
such solutions.

The native gold has different colours depending upon the nature and
amount of impurity present in it. It is likely that the different colours of
native gold were a major driving force for the development of gold refining.

Recent excavations in central parts of Ganges Valley and Vindhya hills have
shown that iron was produced there possibly as early as in 1800 BCE. In the
recent excavations conducted by the Uttar Pradesh State Archaeological
Department, iron furnaces, artefacts, tuyers and layers of slag have been
found. Radiocarbon dating places them between BCE 1800 and 1000. The
results of excavation indicate that the knowledge of iron smelting and
manufacturing of iron artefacts was well known in Eastern Vindhyas and it
was in use in the Central Ganga Plains, at least from the early 2nd
millennium BCE. The quantity and types of iron artefacts and the level of
technical advancements indicate that working of iron would have been
introduced much earlier. The evidence indicates early use of iron in other
areas of the country, which proves that India was indeed an independent
centre for the development of the working of iron.

Iron smelting and the use of iron was especially established in South Indian
megalithic cultures. The forging of wrought iron seems to have been at peak
in India in the Ist millennium CE. Greek accounts report the manufacture of
steel in India by crucible process. In this process, iron, charcoal and glass
were mixed together in a crucible and heated until the iron melted and
absorbed the carbon. India was a major innovator in the production of
advanced quality steel. Indian steel was called ‘the Wonder Material of the
Orient’. A Roman historian, Quintus Curtius, records that one of the gifts
Porus of Taxila (326 BCE) gave to Alexander the Great was some two-and-
a-half tons of Wootz steel. Wootz steel is primarily iron containing a high
proportion of carbon (1.0 – 1.9%). Wootz is the English version of the word
‘ukku’ which is used for steel in Karnataka and Andhra Pradesh. Literary
accounts suggest that Indian Wootz steel from southern part of the Indian
subcontinent was exported to Europe, China and Arab world. It became
prominent in the Middle East where it was named as Damasus Steel.
Michael Faraday tried to duplicate this steel by alloying iron with a variety
of metals, including noble metals, but failed.

When iron ore is reduced in solid state by using charcoal, porous iron
blocks are formed. Therefore, reduced iron blocks are also called sponge
iron blocks. Any useful product can be obtained from this material only
after removing the porosity by hot forging. The iron so obtained is termed
as wrought iron. An exciting example of wrought iron produced in ancient
India is the world famous Iron Pillar. It was erected in its present position in
Delhi in 5th century CE. The Sanskrit inscription engraved on it suggests
that it was brought here from elsewhere during the Gupta Period. The
average composition (weight%) of the components present in the wrought
iron of the pillar, besides iron, are 0.15% C, 0.05% Si, 0.05% Mn, 0.25% P,
0.005% Ni, 0.03% Cu and 0.02% N. The most significant aspect of the
pillar is that there is no sign of corrosion inspite of the fact that it has been
exposed to the atmosphere for about 1,600 years.

Radiocarbon dating of charcoal from iron slag revealed evidence of

continuous smelting in Khasi Hills of Meghalaya. The slag layer, which is
dated to 353 BCE – CE 128, indicates that Khasi Hill region is the earliest
iron smelting site studied in the entire region of North East India. The
remnants of former iron-ore excavation and iron manufacturing are visible
even now in the landscape of Khasi Hills. British naturalists who visited
Meghalaya in early 19th century described the iron industry that had
developed in the upper part of the Khasi Hills.

There is archaeological evidence of zinc production in Rajasthan mines at

Zawar from the 6th or 5th BCE. India was the first country to master zinc
distillation. Due to low boiling point, zinc tends to vapourise while its ore is
smelted. Pure zinc could be produced after a sophisticated ‘downward’
distillation technique in which the vapour was condensed in a lower
container. This technique was also applied to mercury. Indian metallurgists
were masters in this technique. This has been described in Sanskrit texts of
14th century.

Indians had knowledge about mercury. They used it for medicinal purpose.
Development of mining and metallurgy declined during the British colonial
era. By the 19th century, once flourished mines of Rajasthan were mostly
abandoned and became almost extinct. In 1947 when India got
independence, European literature on science had already found its way
slowly into the country. Thus, in post independence era, the Government of
India initiated the process of nation building through the establishment of
various institutes of science and technology. In the following sections, we
will learn about the modern methods of extraction of elements.

6.1 OCCURRENCE OF METALS

A few elements like carbon, sulphur, gold and noble gases, occur in free
state while others are found in combined forms in the earth’s crust.
Elements vary in abundance. Among metals, aluminium is the most
abundant. In fact, 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. For example, gems ‘ruby’ and ‘sapphire’ have Cr and Co
respectively as impurity. 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.

For obtaining a particular metal, first we look for minerals which are
naturally occurring chemical substances in the earth’s crust and are obtained
through mining. Out of many minerals in which a metal may be found, only
a few are viable to be used as source of that metal. Such minerals are
known as ores.
The principal ores of aluminium, iron, copper and zinc are given in Table
6.1.
Table 6.1: Principal Ores of Some Important Metals
A particular element may occur in a variety of compounds. The process of
isolation of element from its compound should be such that it is chemically
feasible and commercially viable.

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 of iron pyrites) are taken. For
copper and zinc, any of the ores listed in Table 6.1 may be used depending
upon the availability and other relevant factors.

The entire scientific and technological process used for isolation of the
metal from its ore is known as metallurgy. The extraction and isolation of
an element from its combined form involves various principles of
chemistry. Still, some general principles are common to all the extraction
processes of metals.
An ore rarely 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 involves the following major steps:

• Concentration of the ore,

• Isolation of the metal from its concentrated ore, and
• Purification of the metal.
In the following Sections, we shall first describe the various steps for
effective concentration of ores. After that principles of some of the common
metallurgical processes will be discussed. Those principles will include the
thermodynamic and electrochemical aspects involved in the effective
reduction of the concentrated ore to the metal.

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 the
gangue 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)

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.

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) + 2CO2(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)

(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
To extract metal from concentrated ore, it must be converted to a form
which is suitable for reduction to metal. Usually sulphide ores are 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 (6.12)
(slag)
The SO2 produced is utilised for manufacturing H2SO4 .

(b) Reduction of oxide to the metal

Reduction of the metal oxide usually involves heating it with a reducing
agent, for example 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 by the metal ion). In any case,
heating is required.

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.
When the value of ∆G is negative in equation 6.14, only then the reaction
will proceed. ∆G can become negative in the following situations:
1. If ∆S is positive, on increasing the temperature (T), the value of T∆S
increases so that ∆H < T∆S. In this situation ∆G will become negative on
increasing temperature.
2. If coupling of the two reactions, i.e. reduction and oxidation, results in
negative value of ∆G for overall reaction, the final reaction becomes
feasible. Such coupling is easily understood through Gibbs energy (∆rGV)
vs T plots for the formation of the oxides (Fig. 6.4). These plots are drawn
for free energy changes that occur when one gram mole of oxygen is
consumed.
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.
 Fig. 6.4: Gibbs energy (∆rG0) vs T plots (schematic) for the formation of
some oxides per mole of oxygen consumed (Ellingham diagram)

As we know, during reduction, the oxide of a metal decomposes and the

reducing agent takes away the oxygen. The role of reducing agent is to
provide ∆rGV negative and large enough to make the sum of ∆rGVof the
two reactions, i.e, oxidation of the reducing agent and reduction of the
metal oxide negative.

MxO(s) → xM (solid or liq) + O2 (g) (6.15)

If reduction is carried out by carbon the oxidation of the reducing agent
(i.e., C) will be there:

(6.16)
There may also be complete oxidation of carbon to CO2.

(6.17)
On coupling (combing) reaction 6.15 and 6.16 we get:
MxO(s) + C(s) → xM(s or l) + CO(g) (6.18)
On coupling reaction 6.15 and 6.17 we have

MxO(s) + C(s) → xM(s or l) + CO2(g) (6.19)

Similarly, if carbon monoxide is reducing agent, reactions 6.15 and 6.20
given below need to be coupled.

CO(g) + O2(g) → CO2(g) (6.20)

Over all reaction will be as follows:
MxO(s) + CO(g) → xM(s or l) + CO2(g) (6.21)

Ellingham Diagram

(a) Ellingham diagram normally consists of plots of ∆fGV vs T for the formation of oxides of

common metals and reducing agents i.e., for the reaction given below.

2xM(s) + O2(g) → 2MxO(s)

In this reaction, gas is consumed in the formation of oxide hence, molecular randomness

decreases in the formation of oxide which leades to a negative value of ∆S as a result sign

of T∆S term in equation (6.14) becomes positive. Subsequently ∆fGV shifts towards higher
side despite rising T. The result is positive slope in the curve for most of the reactions for the

formation of MxO(s).

(b) Each plot is a straight line and slopes upwards except when some change in phase

(s→ l or l→ g) takes place. The temperature at which such change occurs, is indicated by an

increase in the slope on positive side (e.g., in the Zn, ZnO plot, the melting is indicated by an

abrupt change in the curve) [Fig. 6.4].

(c) When temperature is raised, a point is reached in the curve where it crosses ∆rGV=0 line.

Below this temperature, ∆rGV for the formation of oxide is negative so MxO is stable. Above

this point, free energy of formation of oxide is positive. The oxide, MxO will decompose on its

own.

(d) Similar diagrams are constructed for sulfides and halides also. From them it becomes clear

that why reduction of MxS is difficult.

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 ∆rGV is based on K (∆GV = – 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. In commercial processes

reactants and products are in contact for a short time.

The reactions 6.18 and 6.21 describe the actual reduction of the metal
oxide, MxO, that we want to accomplish. The ∆rG0 values for these
reactions in general, can be obtained from the corresponding
∆f G0 values of oxides.
As we have seen, heating (i.e., increasing T) favours a negative value of
∆rG0. Therefore, the temperature is chosen such that the sum of ∆rG0 in the
two combined redox processes is negative. In ∆rG0 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 ∆rG0 value
becomes more negative for the combined process making the reduction of
MxO possible. The difference in the two ∆rG0 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 aluminain 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 ∆rGV becomes more on negative side and the reduction becomes easier.

(a) Extraction of iron from its oxides

After concentration, mixture of oxide ores of iron (Fe2O3, Fe3O4) is
subjected to calcination/roasting to remove water, to decompose
carbonates and to oxidise sulphides. After that these are mixed with
limestone and coke and fed into a Blast furnace from its top, in which the
oxide is reduced to the metal. In the Blast furnace, [Fig. 6.5] reduction of
iron oxides takes place at different temperature ranges. A blast of hot air is
blown from the bottom of the furnace by burning coke in the lower portion
to give temperature upto about 2200K. The burning of coke, therefore,
supplies most of the heat required in the process. The CO and heat move to
the 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. 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 (6.22)
Fe3O4 + 4 CO → 3Fe + 4 CO2 (6.23)
Fe2O3 + CO → 2FeO + CO2 (6.24)
 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.
At 900 – 1500 K (higher temperature range in the blast furnace):
C + CO2 → 2 CO (6.25)
FeO + CO → Fe + CO2 (6.26)
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
involves reaction 6.27 given below.
FeO(s) + C(s) → Fe(s/l) + CO (g) (6.27)
This reaction can be seen as a reaction in which two simpler reactions have
coupled. In one the reduction of FeO is taking place and in the other, C is
being oxidised to CO:

FeO(s) → Fe(s) + O2(g) (6.28)

C(s) + O2 (g) → CO (g) (6.29)

When both the reactions take place to yield the equation (6.27), the net
Gibbs energy change becomes:
∆rG0 (C, CO) + ∆rG0 (FeO, Fe) = ∆rG0 (6.30)
Naturally, the resultant reaction will take place when the right hand side in
equation 6.30 is negative. In ∆rG0 vs T plot representing the change Fe→
FeO in Fig. 6.6 goes upward and that representing the change C→ CO
(C,CO) goes downward. They cross each other at about 1073K. At
temperatures above 1073K (approx.), the C, CO line is below the Fe, FeO
line < . So above 1073 K in the range of temprature
900–1500 K coke will reduce FeO and will itself be oxidised to CO. Let us
try to understand this through Fig. 6.6 (approximate values of ∆rG0 are

given). At about 1673K (1400oC) ∆rG0 value for the reaction:

2FeO→ 2Fe+O2 is +341 kJmol-1 because it is reverse of Fe→ FeO change

and for the reaction
2C+O2→ 2CO ∆rG0 is -447 kJmol-1. If we calculate ∆rG0 value for overall

reaction (6.27 the value will be -53 kJmol-1). Therefore, reaction 6.27
becomes feasible. In a similar way the reduction of Fe3O4 and Fe2O3 by CO
at relatively lower temperatures can be explained on the basis of lower
lying points of intersection of their curves with the CO, CO2 curve.
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.
It can be moulded 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.
Fig. 6.6: Gibbs energy Vs T plot (schematic) for the formation of oxides of
iron and carbon (Ellingham diagram)

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 ∆rG0 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 (6.34)
(Slag)
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 (∆rG0= – 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,
∆G0 = – nE0F (6.40)
here n is the number of electrons and E0 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 E0 values corresponds to a positive E0 and
consequently negative ∆G0 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.
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)

Fig. 6.7: Electrolytic cell for the extraction of aluminium

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 ∆G0 for this reaction is + 422 kJ. When it is converted to E0 (using ∆G0
= – nE0F), we get E0 = – 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

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.
 Fig. 6.8: Zone refining process
(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

You have learnt about chromatographic technique of purification of
substances in Class XI (Unit–12).
Column chromatography 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.
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.

6.8 USES OF ALUMINIUM, COPPER, , ZINC AND IRON

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 ∆G0 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.

A Summary of the Occurrence and Extraction of some Metals is

Presented in the following Table
EXERCISES
6.1 Copper can be extracted by hydrometallurgy but not zinc. Explain.
6.2 What is the role of depressant in froth floatation process?
6.3 Why is the extraction of copper from pyrites more difficult than that
from its oxide ore through reduction?
6.4 Explain: (i) Zone refining (ii) Column chromatography.
6.5 Out of C and CO, which is a better reducing agent at 673 K ?
6.6 Name the common elements present in the anode mud in electrolytic
refining of copper. Why are they so present ?
6.7 Write down the reactions taking place in different zones in the blast
furnace during the extraction of iron.
6.8 Write chemical reactions taking place in the extraction of zinc from zinc
blende.
6.9 State the role of silica in the metallurgy of copper.
6.10 Which method of refining may be more suitable if element is obtained
in minute quantity?
6.11 Which method of refining will you suggest for an element in which
impurities present have chemical properties close to the properties of that
elements?
6.12 Describe a method for refining nickel.
6.13 How can you separate alumina from silica in a bauxite ore associated
with silica? Give equations, if any.
6.14 Giving examples, differentiate between ‘roasting’ and ‘calcination’.
6.15 How is ‘cast iron’ different from ‘pig iron”?
6.16 Differentiate between “minerals” and “ores”.
6.17 Why copper matte is put in silica lined converter?
6.18 What is the role of cryolite in the metallurgy of aluminium?
6.19 How is leaching carried out in case of low grade copper ores?
6.20 Why is zinc not extracted from zinc oxide through reduction using
CO?
6.21 The value of ∆fG0 for formation of Cr2 O3 is – 540 kJmol−1and that of
Al2 O3 is – 827 kJmol−1. Is the reduction of Cr2 O3 possible with Al ?
6.22 Out of C and CO, which is a better reducing agent for ZnO ?
6.23 The choice of a reducing agent in a particular case depends on
thermodynamic factor. How far do you agree with this statement? Support
your opinion with two examples.
6.24 Name the processes from which chlorine is obtained as a by-product.
What will happen if an aqueous solution of NaCl is subjected to
electrolysis?
6.25 What is the role of graphite rod in the electrometallurgy of aluminium?
6.26 Outline the principles of refining of metals by the following methods:
(i) Zone refining
(ii) Electrolytic refining
(iii) Vapour phase refining
6.27 Predict conditions under which Al might be expected to reduce MgO.
(Hint: See Intext question 6.4)
Answers to Some Intext Questions
6.1 Ores in which one of the components (either the impurity or the actual
ore) is magnetic can be concentrated, e.g., ores containing iron (haematite,
magnetite, siderite and iron pyrites).
6.2 Leaching is significant as it helps in removing the impurities like SiO2,
Fe2O3, etc. from the bauxite ore.
6.3 Certain amount of activation energy is essential even for such reactions
which are thermodynamically feasible, therefore heating is required.
6.4 Yes, below 1350°C Mg can reduce Al2O3 and above 1350°C, Al can
reduce MgO. This can be inferred from ∆GV Vs T plots (Fig. 6.4).
 Table of Contents
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
Froth Floatation Method
Leaching
6.3 Extraction of Crude Metal from Concentrated Ore
6.4 Thermodynamic Principles of Metallurgy
6.5 Electrochemical Principles of Metallurgy
6.6 Oxidation Reduction
6.7 Refining
6.8 Uses of Aluminium, Copper, , Zinc and Iron
Summary
Exercises