General Principles of Metallurgy

A few elements like carbon, silver, gold and noble gases occur in free state, while
other elements generally occur in combined state in the earth’s crust. Most of the
metals occur as their minerals. For obtaining a particular metal, first we look for
its minerals; they are naturally occurring chemical substances in the earth’s crust
obtained by mining.
Ore: Out of many minerals in which a metal may be found, only a few minerals are
chemically and commercially viable to be used as sources for the extraction of
metals. Such minerals are known as Ores.
(The mineral which is most suitable to get the metal is known as an ore). All ores are
minerals but all minerals are not ores.
Gangue or Matrix: Ores usually contaminated with earthy materials and undesired
chemical compounds. These are collectively known as gangue or matrix.
Metallurgy: The branch of science which deals with the different methods of
extracting the metal from its natural sources and then converting them into
useful materials to the mankind is known as metallurgy.
Occurrence:
Metals occur mostly as their oxides, carbonates, sulphides, chlorides. Elements
vary in their natural 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 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.
The principal ores of aluminium, iron, copper and zinc have been given in the
table given below.
Metal Ores Composition
Bauxite Al2O3.2H2O
Al Cryolite Na3AlF6
Kaolinite [Al2(OH)4Si2O5]
Haematite Fe2O3
Magnetite Fe3O4
Fe
Siderite FeCO3
Iron pyrites FeS2
Malachite CuCO3.Cu(OH)2
Azurite 2CuCO3.Cu(OH)2
Cu Cuprite Cu2O
Copper glance Cu2S
Copper pyrites CuFeS2 Cu2S. Fe2S3
Zinc blende or sphalerite ZnS
Zn Calamine ZnCO3
Zincite ZnO

Principle of Extraction:
The minerals available in nature contain various types of impurities. Some
impurities are combined with the minerals either physically or chemically. So
depending on the nature of the impurities, different types of treatment of the ore
are adopted.
The extraction and isolation of metals from ores involves the following major steps:
A. Concentration of the ore,
B. Isolation of the metal from its concentrated ore, and
C. Purification of the metal.
A. Ore Concentration
“Removal of the unwanted materials (e.g., sand, clay, stones etc.,) from the ore
is known as Concentration, dressing or benefaction.
The impurities of certain types can be eliminated from the ore in the molten state
only. Most of the impurities in the ores do not melt easily at the temperature of
the normal industrial furnaces. Therefore, certain special substances are added to
the ore and the mixture is melted. The added substances facilitate the formation
of the molten ore by lowering the melting point.
“An outside substance added to the ore to lower its melting point, is known as
flux.”
“Flux combines with the gangue (i.e. impurities in the ore) chemically and
forms easily fusible products, called Slag.”
An acidic flux is used to remove basic impurity.
FeO + SiO2 → FeSiO3
Basic impurity Acidic Flux Fusible slag
A Basic Flux is used to remove acidic impurity
SiO2 + CaO → CaSiO3
Acidic impurity Basic flux Fusible slag
Since this entire process is costly, the gangue is removed first by other cheap
physical methods from the ores containing the large amount of gangue. This partial
purification of removing gangue from the ore is known as ore concentration.
Some of the common methods of ore dressing are described here.
(i) Hand picking:
In this method sand and small stones are removed. Lumps of the ore are broken to
small pieces. The sand and mud adhering to the ore are washed by a stream of
water. Then the pieces of the ore are dropped on a rotating roller belt and the
stones are weeded out.
Ex: The sand and stones, from the Haematite are removed by hand.
(ii) Hydraulic washing or Levigation
This is based on the differences in the 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.
Example: Cassiterite (SnO2) is concentrated by this method. Wilfley’s tables are
specially made tables for washing of ores.
(iii) Magnetic separation:
This is based on the differences in the magnetic properties of the ore and gangue.
If either the ore or the gangue is magnetic substance, then such separations are
carried out. In this process, the finely powdered ore is dropped on a belt moving
on two strong electromagnetic rollers. The magnetic and the non – magnetic
substances form two separate heaps.
Ex: Haematite and magnetite have magnetic ore particles where as cassiterite (Tin
stone) has wolframite as a magnetic impurity.

(iv) 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. To this froth Collectors and
stabilisers are added. 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.
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.

(v) Leaching:
This method is often used if the ore is soluble in some suitable solvent.
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) + 2 NaOH (aq) + 3H2O(l) → 2Na[Al(OH)4] (aq)
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)
Sodium silicate remains in the solution and the insoluble hydrated alumina is
filtered, dried and heated to 1470 K give pure Al2O3.
Al2O3.xH2O(s) → Al2O3(s) + xH2O (g)
(vi) Liquification:
This method is useful for such ores which contain fusible mineral particles and high
melting gangue. This method is used with stibnite, an antimony mineral. It is taken
in a fireclay pots with perforated bottom and heated to around 500 – 6000C. Only
the mineral part of the ore melts and flows out leaving the gangue behind.
B. Extraction of Crude Metal from Concentrated ore
To extract metal from concentrated ore, it must be converted into a form which is
suitable for reduction. Usually sulphide ores are converted to oxides before
reduction, because oxides are easier to reduce. Thus isolation of metals from
concentrated ore involves two major steps
(a) conversion of ore into oxide, and
(b) reduction of the oxide to metal.
(a) Conversion of ore into oxide
(i) Calcination: Calcination involves heating of the ore in the absence (or limited
supply) of air just below its fusion temperature. It removes the volatile matter
which escapes leaving behind the metal oxide.

(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:

The SO2 produced is utilised for manufacturing H2SO4.

During extraction of copper, the sulphide ore of copper (CuFeS2) heated in
reverberatory furnace. The ore is mixed with silica and roasted. Most of the
FeS that is formed during the heating of CuFeS2, is converted into FeO. Iron
oxide (FeO) combines with silica to form iron silicate (FeSiO3), called slag.
Copper is produced in the form of copper matte which contains Cu2S and FeS.

(b) Reduction of the oxide to metal.

Some oxides and halide ores are reduced to obtain the metals. The commonly
used reducing agents in the metallurgy are
(i) Coke (ii) CO (iii) water gas (iv) H2 gas (v) Al – metal
The selection of the reductant depends on the chemical activity of the metal.
The following are some examples.
(a) Zinc and tin are obtained by reduction with coke

(b) Fe2O3 is reduced by CO to get Fe

(c) NiO is reduced by water gas

(d) Molybdenum and Tungsten oxides are reduced with H2

(e) Metals like Al, Mg or Ca are also used for the reduction. When Al is used as a
reducing agent, the process is referred as Goldschmidt’s Alumino Thermic process
or simply Gold Schmidt Thermite process. This reaction is highly exothermic.
These reactions require about 6000C. This is provided by the exothermic nature of
the reduction. During these reactions the temperatures increase up to 25000C to
30000C. So the metal is obtained in molten state.
C. Purification of the metal
Refining is an important stage in the metallurgy. Depending on the impurities
nature various refining methods are used
Electrolytic method – refining:
Zn, Cu, Ag, Au etc., impure metals are refined by this method. In this method, the
impure metal is used as anode and the pure metal is used as cathode. An acidified
solution of the metal salt or a molten metal salt is used as the electrolyte. On
passing electricity pure metal is deposited on the cathode. The impurities settle to
the bottom at the anode. This is known as anode mud.

Example: Cu is refined using an electrolytic method. Anode is of impure copper and

pure copper strip is taken as cathode. Acidified CuSO4 solution is used as an electrolyte.

During electrolysis, pure copper will be deposited on the cathode and impurities
from the blister copper deposit as anode mud. Zinc may also be refined in this way.
Assignment questions:
1. Write a note on ore dressing in metallurgy?
2. Write in brief about the methods of refining of metals
3. Describe magnetic separation method for concentration of an ore. Explain
with a suitable example
4. Write short notes on each of the following in connection with the metallurgy
a. Liquification
b. Oxidation
c. Reduction
5. Discuss froth floatation process
Example set:
1. Which one of the following is gangue?
a. Waste materials present in the ore to be removed during concentration
b. Waste materials left after concentration
c. Waste materials left after purification of the metal
d. All the above.
Solution: a)
2. Which of the following methods are used for the concentration of
Cassiterite?
a. Hand picking
b. Hydraulic washing
c. Magnetic separation
d. Forth flotation process
Solution: b)
Occurrence and Principles of extraction of Fe
A. Occurrence:
Iron is the second most abundant metal after Al and fourth most abundant
element in the earth’s crust. The earth’s core is believed to consist mainly of iron
and nickel, and the occurrence of iron meteorites suggests that it is abundant also
in the solar system. It mostly occurs in the combined state.
The major iron ores are given here under

Name of the mineral Formula

Haematite (Reddish brown coloured) Fe2O3
Magnetite (Magnetic oxide) Fe3O4
Limonite (Hydrated oxide) 2Fe2O3.3H2O
Siderite (Spathic iron ore) FeCO3
Iron pyrites FeS2
B. Principles of extraction of Fe:
The chemistry of iron can be studied under three sections depending upon the
type of iron required. The sections are
a. Manufacture of cast iron
b. Manufacture of wrought iron and
c. Manufacture of steel.
a. Manufacture of cast iron:
Iron is extracted from its oxides in a blast furnace. Manufacture of caste
iron involves several steps. The iron ore after subjected to concentration and
calcination/roasting it will be fed into the blast furnace along with coke and lime
stone. Blast furnace is an almost cylindrical furnace, lined inside with fire bricks.
The roasted iron ore (8 parts), desulphurised coke (4 parts) and lime stone
(1 part) are mixed in 8:4:1 parts by weight and fed in to blast furnace from its top.
Reduction of ore takes place in the blast furnace. Hot air is blown from the
bottom of the furnace. The oxygen in the air burns the coke and produces heat
and CO for reducing the iron oxide. The temperature range in the furnace is about
3000 - 20000c.
Various reactions take place in the blast furnace at different temperature
and different zones.
S. Temperature Name of Changes occurring in the Chemical reaction
No range zone zone
1 4000-7000C Zone of Spongy iron is formed iron Fe2O3 + 3C ⟶ 2Fe + 3CO
reduction oxide is reduced Fe2O3 + 3CO⟶ 2Fe + 3CO2
2 8000-10000C Zone of CO2 is reduced to CO. CO2 + C ⟶ 2CO -163kJ
slag Limestone decomposes to Δ
formation lime and CO2.Lime CaCO3 → CaO + CO2
combines with SiO2 to CaO + SiO2⟶ CaSiO3
form the slag, CaSiO3.
0 0
4 1200 -1300 C Zone of Coke burns to CO2. C + O2⟶ CO2 + heat
fusion Porous iron melts.
Any iron oxide remaining is FeO + C ⟶ Fe + CO
completely reduced to Fe.
4 Above Near the Molten iron collects in the
0
1400 C hearth bottom of the hearth. Slag
floats on iron molten.

Blast furnace – Manufacture of cast iron

The iron obtained is from blast furnace is known as Pig iron, it contains about 4%
carbon and many impurities in smaller amount (e.g., S, P, Si, Mn). Cast iron is
prepared by re melting the pig iron with scrap iron and coke using hot air blast. It
contains slightly lower carbon content (about 3%).
b. Manufacture of wrought iron:
Wrought iron is the purest form of commercial iron (contains about 0.2 % C). It is
prepared from cast iron by oxidizing the impurities in a reverboratory furnace.
The furnace is given a basic lining of iron oxide. The impurities and the carbon
present in cast iron combine with the lining (Fe2O3). The impurities form a slag
and carbon is oxidized to CO and escapes. It burns with a blue flame. The flames
are known as “puddler’s candles”. Hence the process is known as puddling
process. Wrought iron is malleable, strong, ductile and resistant corrosion.

Carbon and various impurities present combine with lining and form slag.

3C + Fe2O3 ⟶ 2Fe + 3CO

3Mn + Fe2O3 ⟶ 2Fe + 3MnO

3Si + 2Fe2O3 ⟶ 4Fe + 3SiO2

MnO + SiO2 ⟶ MnSiO3 (Slag)

c. Manufacture of steel:
Steel contains a lower percentage of carbon and other impurities than the pig
iron. Hence by the purification of pig iron steel can be prepared.
Bessemer converter process:
The impurities in the pig iron are oxidized rapidly by steam of air or air and O2
mixture in Bessemer converter.
The Bessemer converter is a pear shaped furnace. It is constructed with steel. It is
lined with silica or lime depending on the proportions of impurities (P, Si, Mn and
C) present in the iron. It is mounted on trunnions so that it can be tilted as one
desires. Air is forced through the inlets at the bottom.
Carbon and various other impurities present combine with oxygen and form slag.

2Fe3C + O2 ⟶ 6Fe +2CO [C is present in Pig iron as Fe3C]

Si + O2 ⟶ SiO2
2Mn + O2 ⟶ 2MnO
2Fe + O2 ⟶ 2FeO
P4 + 5O2 ⟶ P4O10
MnO +SiO2 ⟶MnSiO3
FeO + SiO2 ⟶FeSiO3
6CaO + P4 O10 ⟶ 2 Ca3 (PO4)2

The basic slag containing Ca3 (PO4)2 is known as Thomas slag. It is used as
phosphate fertilizer. The CO burns with a blue flame. As soon as the CO is
completely burnt out, the Bessemer converter is tilted to take some more
substances in to it. In order to produce steel with desired properties, additives
such as spiegeleisen (a ferromaganese alloy of iron contains 15-20% Mn, small
amount of C and the rest iron) can be added to the molten steel once the
impurities have been removed.
Occurrence and principles of extraction of Cu
A. Occurrence:
Copper is a chemical element with symbol “Cu” comes from Latin word “cuprum”
and atomic number 29. It occurs in the combined state mostly. The important
minerals of copper are given below

Name of the mineral formula

Cuprite Cu2O
Chalcocite or copper glance Cu2S
Copper pyrite or chalcopyrite CuFeS2
Malachite green CuCO3.Cu(OH)2
Azurite blue 2CuCO3.Cu(OH)2

B. Extraction of copper from sulphide ore:

Copper pyrites is the main source of copper metal. From it copper metal is
obtained by smelting process. Following steps are involved in the extraction of
copper.
a. Concentration:
The finely crushed ore is concentrated by Froth-Floatation process. In this process
the finely crushed ore is suspended in water, a little amount of pine oil is added
and the mixture is vigorously agitated by current of air. The ore particles get
wetted by the oil and float as a froth which is skimmed off. The gangue sinks to
the bottom. The froth is separated and about 95% concentrated ore is obtained.
b. Roasting:
The concentrated ore is then roasted in a reverbaratory furnace in a current of
air. Sulphur is oxidized to SO2 and impurities of arsenic and antimony are removed
as volatile oxides. The following reaction takes place.
2CuFeS2 + O2  Cu 2S + 2FeS + SO2

Cuprous sulphide and ferrous sulphide are further oxidized (partially) into their oxides.
2Cu 2S + 3O 2  2Cu 2O  2SO 2
2FeS  3O 2  2FeO + 2SO 2

c. Smelting:
The roasted ore is mixed with coke and silica (SiO2) and is introduced in to a blast
furnace. The hot air blast converts FeO in to ferrous silicate (FeSiO3).
FeO + SiO 2  FeSiO3
Cu 2 O  FeS  Cu 2S + FeO

The product of the blast furnace consists mostly of Cu2S and a little of ferrous
sulphide. This product is known as “copper matte (matte)”. It is collected from the
outlet at the bottom of the furnace.
d. Bessemerization process:
Copper metal is extracted from molten matte through bessemerization. The
matte is mixed with SiO2 and introduced in to Bessemer converter. The hot air is
passed through the tuyeres into molten matte. Blast of air converts Cu2S partly
into Cu2O which reacts with remaining Cu2S to give molten copper.
2Cu 2S + 3O2  2Cu 2 O  2SO 2
2Cu 2 O  Cu 2S  6Cu + SO 2

The copper so obtained is called "Blister copper" (98% pure) because, as it

solidifies, SO2 escapes out producing blisters on its surface.
e. Refining of copper:
Blister copper is refined by electrolysis. Blocks of blister copper (impure copper)
are used as anodes and thin sheets of pure copper act as cathodes. The cathode
plates are coated with graphite in order to remove deposited copper. The
electrolyte is copper sulphate (CuSO4) mixed with a little amount of H2SO4 to
increase the electrical conductivity. Optimum potential difference is 1.3 volt for
this electrolytic process. During electrolysis, pure copper is deposited on the
cathode plates and impurities which are soluble fall to the bottom of the cell as
anode mud.
anode: Cu  Cu +2 +2e-
cathode: Cu +2 +2e-  Cu
This electrically refined copper is 100% pure.

Uses:
It is used as thermal conductor, an electrical conductor, a building material and a
constitute of various metal alloys.
Process of molten electrolysis of Al
(a) Occurrence:
In the earth’s crust, aluminium is the most abundant (8.3% by weight) metallic
element and the third most abundant of all elements (after oxygen and silicon).
It is never found in the elemental state.
The important minerals of Al are given below.
Name of the mineral Formula
Corundum Al2O3
Diaspore Al2O3.H2O
Bauxite Al2O3.2H2O
Gibbsite Al2O3.3H2O
Cryolite Na3AlF6
(b) Extraction:
For the purpose of extraction of Al, Bauxite is the important source. From bauxite
Al is obtained by electrolysis. For this purpose pure bauxite is necessary. The
following steps are used in extraction of aluminum.
(i) Purification of Bauxite
(ii) Electrolytic reduction of alumina
(iii) Refining of aluminium

(i) Purification of Bauxite:

Bauxite containing iron oxide as major impurity is known as red bauxite; it can be
purified either by Baeyer’s process or by Hall’s process. Whereas bauxite
containing silica as major impurity is known as white bauxite and is purified by
Serpek’s process.
1. Baeyer’s Process:
Crushed bauxite is treated with moderately concentrated sodium hydroxide
solution under pressure (about 35 atm) at 423 K for a few hours in a furnace
called autoclave. Alumina reacts with NaOH and forms sodium meta aluminate
which dissolves in H2O and the impurities are left behind and are removed by
filtration.
Al2O3.2H2O(s) + 2 NaOH → 2 NaAlO2 (aq) + 3 H2O (l)
The filtered sodium meta aluminate is diluted with water, then hydrated
aluminum oxide is precipitated as aluminum hydroxide.
2 NaAlO2 (aq) + 4H2O → 2 NaOH + Al2O3.3H2O (Hydrated Alumina)
or
2 Al (OH)3 (Aluminum hydroxide)
The precipitate thus obtained is calcined at about 10500C; the aluminum hydroxide
decomposes to give anhydrous alumina, giving of water vapour in the process.
12000 𝐶
2 Al (OH) 3 (s) → Al2O3 (s) + 3 H2O (g) ↑
2. Hall’s Process:
In Hall’s process when red bauxite is treated with sodium carbonate, aluminum
oxide converts into soluble sodium meta aluminate which can be extracted with
H2O and the impurities (Fe2O3 or silica) are left behind.
Al2O3.2H2O + Na2CO3 → 2 NaAlO2 + CO2 + 2 H2O
The extracted sodium meta aluminate is separated by filtration, then the solution
is saturated with CO2 at 323-333K. Aluminium hydroxide is precipitated as a
result of hydrolysis of sodium meta aluminate.
323 𝐾
2 NaAlO2 (aq) + 3 H2O (l) + CO2 (g ) → 2 Al (OH)3 (s) + Na2CO3 (aq)
The aluminium hydroxide obtained in this process on heating at 10500C gives
anhydrous Alumina.
10500 𝐶
2 Al (OH) 3 → Al2O3 + 3 H2O

3. Serpek’s process:
(This method is used for the purification of bauxite which contains SiO2 as the
main impurity.)
In this process, most of the silica of the bauxite is volatilized. Powdered bauxite
and coke are mixed and heated in an atmosphere of nitrogen at 18000c.
Aluminium nitride is formed. SiO2 is reduced to Si and it escapes as vapour.
18000 𝐶
Al2O3 + 3 C + N2 → 2 AlN + 3 CO
Aluminium nitride is hydrolysed to give aluminium hydroxide.
2 AlN + 3 H2O → 2 Al (OH)3 + NH3
The Aluminium hydroxide thus obtained is heated to about 10500c. The
Aluminium hydroxide decomposes to give anhydrous Alumina.
10500 𝑐
2 Al (OH) 3 → Al2O3 + 3 H2O

(ii) Electrolytic reduction of Alumina: (Hall-Heroult Process)

In the metallurgy of aluminium, purified Al2O3 obtained from bauxite is mixed

with Na3AlF6 and CaF2, which lowers the melting point of the mix and also
increases conductivity. The fused matrix is electrolysed. Electrolysis is carried out
in an iron or steel tank. The steel tank is lined inside with the graphite (carbon)
that acts as cathode. Anode consists of a number of carbon or copper rods
suspended from the top of the electrolytic cell. The anodes are immersed partially
into the electrolyte. The electrolyte consists of a fused mixture of alumina,
cryolite and fluorspar. The surface of the electrolyte is covers with powdered
coke. This prevents the oxidation of the metal formed in electrolysis.
The following reactions takes place in the electrolytic cell.
Na3AlF6 → 3 NaF + AlF3
(Cryolite)
4 AlF3 → 4 Al+3 + 12 F- (ionization)

Aluminium ions move towards the cathode (i.e. carbon lining) and they are
discharged. Aluminium metal is formed. Fluoride ions are discharged to give
fluorine at the anode.
At cathode: 4 Al+3 + 12e- → 4 Al
At anode: 12 F- → 12F + 12e-
2 Al2O3 + 12 F → 4 AlF3 + 3O2
C + O2 → CO2
Aluminium produced at the cathode, sinks to the bottom of the cell. It is removed
from time to time through tapping hole. Fluorine formed at the anode reacts with
alumina and displaces the oxygen to form aluminium fluoride. Oxygen which is
evolved at the anode reacts with the carbon of anode produces CO and CO2 which
corrodes the anode. For this reason electrodes have to be frequently replaced.
Alumina is added at intervals. In this process, 99% pure aluminium is obtained.

(iii) Refining of Aluminium:

Aluminium obtained by the electrolytic reduction contains impurities like Si, Cu,
etc. it is further purified by Hoope’s electrolytic method.
The electrolytic cell used for refining of aluminium consists of an iron tank lined
inside with carbon. It contains three layers of fused masses. These layers differ in
their specific gravities. The upper layer is of pure aluminium. A number of
graphite rods acts as cathode. They are suspended from the top into the upper
layer. The middle layer consists of a fused mixture of fluorides of sodium, barium
and aluminium. This layer acts as an electrolyte. The bottom layer contains
impure aluminium. The carbon lining of the tank acts as anode. To increase the
density of fused impure Al layer copper and silicon are added.

On passing current Aluminium ions from the middle layer, are discharged at the
cathode layer (upper layer). Pure Al is deposited in the upper layer. At the same
time an equivalent amount of aluminium passes into the middle layer from the
bottom layer. 99.89% Al is obtained in this process.
Uses of Iron, Copper, Aluminium and Zinc

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 for cutting tools
and crushing machines, and stainless steel for cycles, automobiles, utensils, pens,
etc.

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).

Aluminium foils are used as wrappers for chocolates. 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.

Zinc is used for galvanising iron. It is also used in large quantities in batteries,
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%). Zinc dust is used as a reducing agent in the
manufacture of dye-stuffs, paints, etc.
Polymers
Introduction:
The word polymer has been derived from Greek (Poly = many; mer = unit or part).
Polymers are macro – sized molecules of relatively high molecular masses, some of which find
extensive use in our daily life.
Structurally, they are characterized by linear chains or a cross – linked network.
Common examples of materials made up of polymers are plastic dishes, cups, non - stick pans,
automobile tyres, packing bags, rain coats, television and computer cabinets, flooring materials
and materials for biomedical and surgical operations.
Some Important Terms:
Polymer:
Polymer is a macromolecule having higher molecular mass formed by a repeated combination
of small molecules called monomers.
Monomers:
Monomers are simple molecules, which combine with each other to form polymers. Monomers
are also called building blocks of polymers. For example ethylene, vinyl chloride, etc.
Polymerization:
The repeated addition of similar or dissimilar simple units to form a giant molecule is known as
polymerization. In the process monomers are transformed into polymers.
Classification of polymers:

S. Basis of Nature of polymers Common examples Some simple structures

NO classification (3) (if any) (4) (5)
(1) (2)
1. Source of a. Natural polymers Proteins, Cellulose,
polymer Starch and rubber
(Occurrence) etc

b. Semisynthetic Cellulose acetate

polymers (rayon); cellulose
nitrate

c. Synthetic polymers Polyethylene, PVC,

nylon, terylene
2. Structure of a. Linear polymer High density
polymers Polythene, PVC
b. Branched polymer Low density
polythene

c. Cross linked or Bakelite; melamine

network polymers

3. Type of a. Condensation Nylon – 6, 6

polymerization polymers

Bakelite

Terylene

b. Addition polymers Polythene

Neoprene;

PVC

Polypropylene,
Buna-S, Buna-N,
polyvinyl
pyrrolidone (PVP)

4. Thermal a. Thermoplastic Polyethylene,

behavior polymers Polystyrene, PVC,
Nylon

b. Thermosetting Bakelite,
polymers Urea-formaldehyde
resins, polysiloxanes
5. Polarity a. Cationic Polystyrene;
polymerization
polymers Polyvinyl ethers,
poly isobutene
Buna type synthetic
rubbers

b. Anionic polymerization Polyacrylonitrile

polymers

Poly isoprene

6. Molecular forces a. Elastomers Buna – N

(These are rubber- like
solids with elastic
properties)
Buna – S

Neoprene

b. Fibres Polyamides:
(Fibres are the thread Nylon 6, 6
forming solids which
possess high tensile
Polyesters:
strength and high
Terylene (or) dacron
modulus.)

c. Thermoplastic polymers Polythene;

These are capable of
soften on heating and
Polyvinyl chloride;
harden on cooling

Polystyrene
d. Thermosetting Bakelite
polymers
On heating these polymers
undergo extensive cross
linking in moulds and Urea – HCHO
become infusible resins
afterwards

7. Organic and a. Organic polymers Leather; cellulose; (C6H10O5)n

inorganic Rayon
substances
b. Inorganic polymers Glass, silicone
rubbers etc

General Methods of Polymerization (Types of polymerization reactions)

There are two broad types of polymerisation reactions.
a. Condensation polymerization or Step Growth polymerisation
b. Addition polymerization or Chain Growth polymerisation
a. Condensation polymerization or Step Growth polymerisation:
A polymerisation reaction in which bifunctional or polyfunctional monomers undergo
intermolecular condensation with continuous elimination of byproducts, such as H 2O, HCI, NH3,
etc., is called condensation polymerisation.
Examples: Nylon-6,6, Nylon 6 (Polyamides), Terylene or dacron (Polyester), Bakelite etc.
Nylon - 6,6 is prepared by condensation polymerisation of hexamethylenediamine with adipic
acid under high pressure and temperature.

b. Addition polymerization or Chain Growth polymerisation:

A polymerization reaction in which monomers containing one or more double bonds are added
to each other without the elimination of any byproducts is called addition polymerization.
Examples: Polythene, Polypropene, Polyvinyl Chloride (PVC), Polytetrafluoroethene (Teflon),
Polyacrylonitrile, etc.
Ethene undergoes polymerization to form polythene
n H 2C CH2 H 2C CH2
n
Ethene Polyethene

The empirical formula of the monomer and polymer are the same.
Homopolymers and copolymers
The addition polymers formed by the polymerization of a single monomeric species are known as
homopolymers. e.g., Polythene, Polypropene, Polyvinyl Chloride (PVC), Polytetrafluoroethene
(Teflon), Polyacrylonitrile, etc.

For example, polythene prepared from polymerisation of ethene

n H 2C CH2 H 2C CH2
n
Ethene Polyethene

Addition polymers formed by the polymerisation of a two different monomeric species are
called as copolymers. e.g., Buna-S, Buna-N etc.

For example, Buna-S is copolymer obtained by the polymerisation of 1,3 Butadiene and Styrene.

Addition polymerization takes place through the formation of either free radicals or ionic species.
a. Free Radical mechanism and
b. Ionic Addition Polymerization.

a. Free-radical mechanism of polymerization:

Free-radical polymerisation is initiated by organic peroxide or other reagents. These reagents
decompose to give free radicals.
Benzoyl or t – Butyl peroxide is common initiators, used.
Following steps are involved.
i. Chain initiation: Organic peroxides undergo homolytic fission to form free radicals.

Free radical adds to the monomer (i.e. an alkene) molecule to form a new free radical.
ii. Chain propagation: The free radical formed attacks another alkene molecule and the
process continues in building a long chain.

iii. Chain termination: The chain reaction comes to halt when two free radicals (either chains
or monomer units) combine.

Free radical polymerisation can also be initiated by a mixture of ferrous sulphate and hydrogen
peroxide (FeSO4 + H2O2).

b. Ionic Addition Polymerization:

Vinylic monomers can undergo addition polymerization through the formation of ionic
intermediates instead of free radicals. Here the initiator is an ion, and not a free radical. Ionic
polymerization may be:
a. Cationic addition polymerization
b. Anionic addition polymerization
a. Cationic addition polymerization mechanism:
Cationic polymerisation is initiated by use of acids such as H2SO4, HF or BF3 in H2O.
The following steps are involved:
i. Chain initiation: The acid gives proton.

H2SO4 H+ HSO4–

HF H+ + F–

BF3 + H2O H+ + BF3 (OH)–

The proton adds to the carbon atom of the double bond of the monomer (alkene) to form a
carbonium ion.

ii. Chain propagation: The carbonium ion combines with another molecule of alkene to form a
new carbonium ion and the process continues to form a long chain.
iii. Chain termination: The chain may be halted by combination with negative ion or loss of a proton.

b. Anionic Addition Polymerization:

An anionic initiator will generate a carbanion as an intermediate and thus the polymerization is
of anionic addition type. Here the active centre of the propagating species is negatively
charged. Hence it occurs easily with monomers containing electron withdrawing groups such as
phenyl, nitrile etc., which are able to stabilize the propagating species.

i. Chain initiation: Initiation can be brought about by reagents such as n-butyl lithium or
potassium amide. In the initiation step, the base adds to a double bond to form a carbanion.

ii. Chain propagation: In the chain propagation, this carbanion adds to the double bond of
another monomer and the process repeats to form a long chain.

iii. Chain termination: The chain reaction can be terminated by addition of an acid.

The formation of polystyrene from styrene in the presence of potassium amide is another
example of this type of polymerization.
Difference between Addition and Condensation polymers:
Addition polymers Condensation polymers
Formed by addition reaction. No elimination Formed by condensation process with
takes place. elimination of small molecules like H2O.
Molecular mass is a whole number multiple Molecular mass is not whole number
of the monomer units. multiple of the monomer units.
Generally involves identical monomer unit. Generally involves more than one different
monomer unit.
Monomers are unsaturated molecules. Monomer units must have two active
functional groups.
Generally chain growth polymers. Generally step growth polymers.

Preparation of some important addition polymers

Polytetrafluoroethene (Teflon)
Teflon is prepared by heating tetrafluoroethene with free radical or persulphate catalyst at high
pressures. It is chemically inert and resistant to attack by corrosive reagents. It is used in
making oil seals and gaskets and also non-stick surface coated utensils.
Catalyst
n CF2 CF2 F2C CF2
High pressure n
Tertafluoroethene Teflon

Polyacrylonitrile
Acrylonitrile undergoes addition polymerisation in presence of peroxide catalyst to give
Polyacrylonitrile.
CN
Peroxide catalyst
n CH2 CHCN H2C CH
n
Acrylonitrile Polyacrylonitrile

Some important condensation polymers

1. Polyamides: These polymers possessing amide linkages are important examples of synthetic
fibres and are termed as nylons. The general method of preparation consists of the
condensation polymerisation of diamines with dicarboxylic acids or condensation of amino
acids or their lactams.
Preparation of Nylon 6,6: It is prepared by the condensation polymerisation of
hexamethylenediamine with adipic acid under high pressure and at high temperature.
2. Polyesters: These are the polycondensation products of dicarboxylic acids and diols.
Preparation of Terylene or dacron: Dacron or terylene is the best example of polyesters. It is
prepared by heating a mixture of ethylene glycol and terephthalic acid at 420 to 460 K in the
presence of zinc acetate-antimony trioxide catalyst. Dacron fibre (terylene) is grease resistant
and is used in blending with cotton and wool fibres and also as glass reinforcing materials in
safety helmets, etc.

3. Phenol - formaldehyde polymers

Phenol - formaldehyde polymers are the oldest synthetic polymers. These are obtained by the
condensation reaction of phenol with formaldehyde in the presence of either an acid or a base
catalyst. The reaction starts with the initial formation of o-and/or p-hydroxymethylphenol
derivatives, which further condense to form compounds having rings joined to each other
through-CH2 groups. The initial product could be a linear product - Novolac used in paints.

Novolac on heating with formaldehyde undergoes cross linking to form an infusible solid mass
called bakelite. It is thermosetting polymer which cannot be reused or remoulded. Thus,
bakelite is formed by cross linking of linear chains of the polymer novolac. Bakelite is used for
making combs, phonograph records, electrical switches and handles of various utensils.
Polymers-II
Rubber:

Rubbers are polymers which undergo high degree of elongation when subjected to an external
force, but readily regain their original position when external force is removed. This property of
rubbers is called elasticity. Rubber is also called as elastomer. Rubber is of two types.

a. Natural rubber
b. Synthetic rubber

a. Natural rubber: It prepared from the rubber latex which is a colloidal dispersion of rubber in
water. This latex is obtained from the bark of the rubber tree. The latex is coagulated with
acetic acid or formic acid. The coagulated mass is then squeezed.
The raw natural rubber is a soft gummy and sticky mass. It is insoluble in water, dil. acids and
alkalies but soluble in benzene, chloroform, ether, petrol and carbon disulphide. It absorbs a
large amount of water. It has low elasticity and tensile strength.
Destructive distillation of natural rubber gives mainly isoprene (2-methyl butadiene).
(So it can be concluded that isoprene is a monomer of natural rubber. The number of
isoprene units varies from 11,000 to 20,000, in rubber which are linked together in a chain.)
Natural rubber is considered as a linear polymer of isoprene (2-methyl-1,3-butadiene ) and
it also called as cis -1,4-polyisoprene.

The cis-polyisoprene molecule consists of various chains held together by weak van der
Waals interactions and has a coiled structure. Thus, it stretches like a spring and exhibits
elastic properties.
Polyisoperene can also be synthesized by the industrial polymerisation of isoprene. Which is
called as synthetic Polyisoprene.

CH3 CH3
Polymerisation
n CH2 C CH CH2 CH2 C CH CH2
n
Isoprene Polyisoprene
Vulcanization of rubber:
The process of heating natural rubber with sulphur to improve its properties is called
vulcanization. Vulcanization was introduced by Charles Goodyear.
Natural rubber becomes soft at high temperature (>335 K) and brittle at low temperatures
(<283 K) and shows high water absorption capacity. It is soluble in nonpolar solvents and is
non-resistant to attack by oxidising agents. It has low elasticity and tensile strength. It has
low resistance to abrasion.
To improve upon these physical properties, a process of vulcanisation is carried out. This
process consists of heating a mixture of raw rubber with sulphur and an appropriate additive
at a temperature range between 373 K to 415 K. On vulcanisation, sulphur forms cross links
at the reactive sites of double bonds and at the allylic –CH2 present in the alpha position to
double bonds. As results the rubber gets stiffened.
The extent of stiffness depends upon the amount of sulphur used. In the manufacture of tyre
rubber, 5% of sulphur is used as a crosslinking agent and for making battery case rubber 30%
of sulphur is used.
The probable structures of vulcanised rubber molecules are shown below:

The differences between the natural rubber and vulcanized rubber are briefly listed in the table
that forms.
Differences between Natural Rubber and Vulcanised Rubber:
Natural rubber Vulcanized rubber
a. Natural rubber is soft and sticky Vulcanized rubber is hard and non-sticky.
b. It has low tensile strength. It has high tensile strength.
c. It has low elasticity. It has high elasticity.
d. It can be used over a narrow range of It can be used over a wide range of temperature
temperature (from 10° to 60°C). (– 40° to 100°C).
e. It has low resistance to wear and tear. It has high resistance to wear and tear.
f. It is soluble in solvents like ether, It is insoluble in all the common solvents.
carbon, tetrachloride, petrol, etc.
b. Synthetic rubber: The synthetic rubber is obtained by polymerising certain organic
compounds which may have properties similar to that of rubber. Most of these contain
carbon-carbon double bonds and are derived from butadiene.
Synthetic rubbers are either homopolymers of 1, 3 - butadiene derivatives or copolymers of
1, 3 -butadiene or its derivatives with another unsaturated monomer.
Some important examples are Neoprene, Styrene rubber (Buna-S) Nitrile rubber (Buna-N),
Thiokol, silicones, polyurethane rubber etc.
Preparation of Synthetic Rubbers
1. Neoprene
Neoprene or polychloroprene is prepared by the free radical polymerisation of chloroprene.
It has superior resistance to vegetable and mineral oils. It is used for making conveyor belts,
gaskets, mouse pads and hoses.

Cl Cl
Polymerisation
n CH2 C CH CH2 CH2 C CH CH2
n
Chloroprene Neoprene

2. Buna – N (Nitrile Rubber)

Buna-N is prepared by the copolymerisation of 1, 3 - butadiene and acrylonitrile in the
presence of a peroxide catalyst.
It is resistant to the action of petrol, lubricating oil and organic solvents. It is used in making
oil seals, tank lining, etc.

3. Buna – S (Styrene rubber)

Buna-S is probably the most important type of synthetic rubber, which is prepared by the
copolymerisation of 1, 3 - butadiene and styrene.
It is quite tough and is a good substitute for natural rubber. It is used for the manufacture of
motor tyres, floor tiles, footwear components, cable insulation, etc.
Molecular masses of polymers:

Polymer properties are closely related to their molecular mass, size and structure. The
growth of the polymer chain during their synthesis is dependent upon the availability of the
monomers in the reaction mixture. Thus, the polymer sample contains chains of varying
lengths and hence its molecular mass is always expressed as an average.

The molecular mass of a polymer can be expressed in two ways.

̅ n)
1. Number average molecular mass (𝑀
̅ 𝑤)
2. Weight average molecular mass (𝑀

1. Number average molecular mass (MN): If N1, N2, N3 ….. are the number of molecules with
molecular masses M1, M2, M3 …… respectively, then the number average molecular mass is

̅ n = [N1M1 + N2M2 + N3M3 +...]/[N1 + N2 + N3...]

𝑀

̅ n = ΣNiMi/ΣNi
This may be expressed as: 𝑀

Where Ni is the number of molecules of the ith type with molecular mass Mi.

2. Weight average molecular mass (MW): If m1, m2, m3 …. are the masses of the species with
molecular masses M1, M2, M3… respectively, then the weight average molecular mass is

̅ 𝑤 = [m1M1 + m2M2 + m3M3 ...]/[m1 + m2 + m3 +...] or = ΣmiMi/Σmi

𝑀

But mi = NiMi, so that MW = ΣNiMi2/ΣNiMi

Where Ni is the number of molecules of mass Mi.

Polymers of Commercial Importance: Some commercially important polymers along with their
structures and uses are given below in the table.

Biodegradable Polymers

Most of the polymers are quite resistant to the environmental degradation processes and
are thus responsible for the accumulation of polymeric solid waste materials. These solid
wastes cause acute environmental problems and remain undegraded for quite a long time.
In view of the general awareness and concern for the problems created by the polymeric
solid wastes, certain new biodegradable synthetic polymers have been designed and
developed. These polymers contain functional groups similar to the functional groups
present in biopolymers.
Aliphatic polyesters are one of the important classes of biodegradable polymers. Some
important examples are given below:
1. Poly (β-hydroxybutyrate-co-β-hydroxy valerate) (PHBV)
It is prepared by the copolymerisation of 3-hydroxybutanoic acid and 3-hydroxypentanoic
acid. PHBV is used in speciality packaging, orthopaedic devices and in controlled release of
drugs. PHBV undergoes bacterial degradation in the environment.

2. Nylon 2–nylon 6
It is an alternating polyamide copolymer of glycine (H2N–CH2– COOH) and amino caproic acid
[H2N (CH2)5 COOH] and is biodegradable.
O O

NH CH2 C NH CH2 5 C
n

Review questions:

Example set:
1. Natural rubber is a polymer of
a. CH2 = CH – CH = CH2
b. CH2 = CH2

Solution: d)
2. The commonly used vulcanizing agent is
a. Sulphur
b. Graphite
c. Carbon black
d. CO2
Solution: a)