ORES & METALLURGY

Commercially important ores of iron, copper, lead, magnesium, aluminium, tin and
silver. Carbon reduction process (iron and tin), Self reduction process (copper and lead),
Electrolytic reduction process (magnesium and aluminium), Cyanide process (silver and
gold).

CONTENTS INTRODUCTION
 Occurrence of metals Elements have been broadly divided into
 Metallurgy metals and non-metals on the basis of their
physical and chemical properties. Metals
 Extraction of iron
have generally low ionisation energies, low
 Extraction of Tin electron affitinities and low
 Extraction of copper electronegativities which are responsible
for their high electrical and thermal
 Extraction of lead
conductivities. high malleability and
 Extraction of magnesium ductility, metallic lustre and hardness Of
 Extraction of aluminium the 108 elements known at present, about
70 are metals. In the present chapter, we
 Extraction of silver
shall study the occurrence and general
 Extraction of gold methods used for the extraction of metals
from their ores.
 Chemistry : Ores & Metallurgy

1. OCCURRENCE OF METALS
Metals occur in nature sometimes free but mostly in the combined state. The earth’s crust is the
biggest source of metals Some soluble salts of metals arc also found in sea water.
Noble metals which have little or no affinity for oxygen and which resist the attack of water and
other chemical reagents, occur in the free, i.e. the native state. Thus, metals such as silver, gold and
platinum occur in nature in native state along with alluvial impurities such as clay arid sand.
Sometimes lumps of pure metals are also found, These are called nuggets.
The standard electrode potentials (i.e. rcduction potentials) of such metals are always positive which
means that the ions of such metals have a tendency to accept electrons and get reduced to the
corresponding metals, That is why these metals occur in metallic, i.e., native state.
The standard electrode potentials of active metals, on the other hand, are negative which means that
these metals have a tendency to get oxidised to their ions In other words, the ions of such metals are
reluctant to get reduced to the metallic state. That is why the active metals occur in nature in the
form of their compounds. i.e., in the combined state. These compounds are known as minerals.
The minerals from which metals can be conveniently and economically extracted are referred to as
Ores.
Active metals occur in the form of the following categories of ores.
Active metals occur in the form of the following categories of ores :
Sulphide ores. Metals such as iron, mercury, copper, etc., occur as their sulphides, e.g., iron pyrites
(FeS), galena (PbS), cinnabar (HgS), copper pyrites (CuFeS2) zinc blende (ZnS) etc.
Oxide ores. Metals such as iron, aluminium manganese, tin, zinc, etc. occur as their oxides, e.g.,
haematite (Fe2O3), bauxite (Al2O3.2H2O), pyrolusite (MnO2), cassiterite (SnO2) zincite (ZnO), etc.
Carbonate ores. The important carbonate ores are of magnesium, iron, copper, zinc and lead, e.g.,
magnesite (MgCO3), dolomite (CaCO3, MgCO3), siderite (FeCO3), malachite [Cu(OH)2CuCO3],
calamine (ZnCO3 ), etc.
Halide ores. Chloride ores are the most common among the halide ores. The chlorides of sodium,
potassium and magnesium are found in salt beds on the surface of the earth and in sea water.
Carnallite (KCI.MgCI2.6H2O), rock salt (NaCI) and horn silver (AgC1) are common examples of
chloride ores. Bromides and iodides of potassium and magnesium are present in small amounts in
sea water. The fluoride ores include fluospar (CaF2) and cryolite (AIF3.3NaF)
Sulphate ores. Many sulphide ores get converted into sulphates by atmospheric oxidation. The
common sulphate ores are barytes (BaSO4), anglesite (PbSO4), epsomite (MgSO4.7H2 O), anhydrite
(CaSO4 ), etc.
1. Native Ores: These ores contain metal in free state. For example: Silver, gold, platinum, mercury,
copper etc. Sometime lumps of pure metals are found known as nuggets.

Metals Minerals/Ores with their chemical formula

1. Copper (IB, coinage metal) a) Cuprite; Cu 2 O
b) Copper pyrites; CuFeS2 (as sulphides)
c) Copper glance; Cu 2S (as sulphides)
d) Malachite; CuCO 3 ; Cu(OH) 2
Chemistry : Ores and Metallurgy

d) Azurite 2CuCO 3 .Cu(OH) 2

2. Silver (IB, best reductive metal) a) Horn silver (chloroapyrite); AgCl (as halide)
b) Lunar Caustic; AgNO 3 (as nitrate)
c) Silver glance or argentite; Ag 2S (as sulphide)
d) Ruby silver or pyrogyrite; 3Ag 2S. Sb 2S3

3. Magnesium (II A, bridge metal) a) Carnalite; KCl, MgCl2 .6H 2 O (chloride)

b) Dolomite; MgCO 3 ; CaCO 3 (Carbonate)
c) Magnesite; MgCO 3 (carbonate)
d) Epsomite; MgSO 4 .7H 2 O (sulphate)
e) Kiesserite; MgSO 4 .7H 2 O (sulphate)
f) Asbestos; CaMg(SiO 3 ) 4
4. Zinc (II B, amphoteric metal) a) Zinc blende; ZnS (sulphide)
b) Zincite; ZnO (oxide)
c) Calamine; ZnCO 3 (carbonate)
d) Willemite; Zn 2SiO 4 (silicate)
5. Aluminium (III A, amphoteric metal) a) Bauxite; Al 2 O 3 .2H 2 O (oxide)
b) Corundum; Al2 O 3 (oxide)
c) Feldspar; KAlSi3O 6 (oxide)
d) Clay silicate; Al2 O3 .2SiO 2 .2H 2 O (oxide)
e) Cryolite; 2NaF. AlF3 (Na 3 AlF6 ) (halide ore)
f) Alum; K 2SO 4 .Al2 (SO 4 ) 3 .24H 2 O
g) Diaspore; Al 2 O 3 .H 2 O
h) Mica’ K 2 O.3Al 2 O 3 .6SiO 2 .2H 2 O
i) Lapis Lazuli (Sodium aluminium silicate with
sulphur)
6. Tin (IV A, amphoteric metal) a) Cassiterite or Tin stone; SnO 2
b) Stannite; Cu 2S.FeS.SnS2
 Chemistry : Ores & Metallurgy

7. Lead (IV A, amphoteric metal) a) Galena; PbS

b) Cerussite; PbCO 3
c) Anglessite; PbSO 4
d) White lead; 2Pb(OH) 2 .PbCO 3
8. Iron (VIII, transition metal) a) Iron pyrite; FeS2
b) Siderite; FeCO3
c) Red haematite; Fe2 O3
d) Magnetite; Fe3O 4
e) Limonite or brown haematite; 2Fe2 O3 .3H 2 O

2. In combined state: Reactive metals are found in combined state in nature. Such metals are attacked
by O2, H2O, CO2 etc. Na, Mg, Ca, Fe, Cu, Zn Al, Pb etc, occur in combined state in nature. These
metals are not found in free state.
Minerals: The natural material in which the metal is found in nature is called mineral.
Ores: Those minerals from which the metal can be extracted conveniently, economically and in
large quantity are called ore.
Thus, all the ores are minerals but all the minerals are not ores.
Gangue or Matrix: Metallic ores are often found to contain non-metallic and rocky materials such
as sand, clay, quartz, feldspar, silicates, mica etc. These unwanted impurities are called gangue or
matrix. Gangue is a waste material present in the ore.
Flux : Ores contain some impurities which have high melting point. Flux is used to remove these
influsible impurities in the form of a fusible slag.
Infusible impurity + Flux = Fusible slag.
Slag has low melting point, it is lighter than the metal and is insoluble in molten metal. It floats over
the molten metal and is removed from the upper exit (tap hole) in the furnace. To remove the
infusible impurity ore is mixed with a flux and is then heated at high temperature. Flux are of two
types.
a) Acidic flux b) Basic flux
a) Acidic Flux: These are used to remove the basic impurity present in the roasted ore. For
example, in the metallurgy of copper to remove the basic impurity of FeO present an acidic flux
(SiO2) is used.
FeO  SiO 2 
 FeSiO3
Impurity flux slag
(ferrous silicate)

b) Basic flux: These are used to remove the acidic impurity present in the roasted ore. For
example, in the metallurgy of iron, to remove the acidic impurity of SiO2 present a basic flux
lime stone (CaCO3) is used.
CaCO3  SiO 2 
 CaSiO3  CO 2
flux impurity slag (calcium silicate)
Chemistry : Ores and Metallurgy

2. METALLURGY
The process of extracting metals from their ores is called metallurgy. The process of metallurgy
would necessarily depend upon the nature of the ore which is to be worked out for the extraction of
the metal. It is not possible to chalk out a universal scheme for the extraction of all metals since the
extraction of each metal involves individual procedure depending upon its nature and properties.
However, heavy metals such as copper, iron, zinc, lead, tin, etc., are extracted from their ores by the
conventional ‘Roasting and Smelting’ processes. The active metals such as alkali metals,
magnesium, calcium, aluminium, etc., are obtained by the electrolysis of their chlorides, oxides or
hydroxides in fused state and the noble metals such as gold and silver are obtained by the
amalgamation or the cyanide process.
Various Steps Involved in Metallurgical Processes. The various steps essentially involved in the
extraction of pure metals from their respective ores arc as follows:
1. Concentration of the Ore
Metallic ores are often found mixed with rocky material, e.g., quartz, felspar, mica and other
silicates. These impurities are known as gangue. Before the ore is subjected to metallurgical
process, it is necessary to remove these unwanted impurities mechanically. This operation is
known as concentration of the ore. The common methods of concentration are as follows.
a. Hand picking. Quite often, the ore is separated from the main stock in a sufficient degree
of purity by simply picking it by hand and then eliminating the adhering rocky material by
breaking with hammer.
b. Gravity separation. The ore can be concentrated by taking advantage of the differences in
the specific gravities of metallic ore and the earthy impurities. The ore, after grinding, is
agitated with water or washed with a running stream of water. The heavy ore settles down
rapidly while the lighter earthy material (gangue) is washed away. The two common
techniques of gravity separation are described below.
Hydraulic Classifier. Finely powdered ore is dropped into a conical reservoir, called
hydraulic classifier, from the top. A powerful stream of water is introduced from the
bottom of the reservoir. The gangue, being lighter, is carried away by water and the heavier
ore particles accumulate at the apex of the cone. The conical shape of the reservoir helps in
reducing the velocity of water and thus prevents the ore particles from being carried away
along with the stream of water.
Wilfley Table. Wilfley table is a wooden table having a slanting floor on which long
wooden strips called cleats or riffles are fixed. The powdered ore is suspended in a stream
of water and delivered at one end of the table which is then given a bumping motion. The
heavier ore particles are obstructed by the cleats while the lighter impurities pass over and
arc carried away by the stream of water. The ore particles which collect behind in the cleats
move to one side as a result of the motion of the table and are collected.
c. Magnetic separation. Ferromagnetic ores, as of iron, that are affected by a magnet, are
separated from the non-magnetic impurities by means of magnetic separators. A magnetic
separator consists of a leather belt moving over two rollers, one of which is magnetic. The
powdered ore is dropped on the belt at one end. At the other end, the magnetic portion of
the ore is attracted by the magnetic roller and falls nearer to the roller while the non-
magnetic impurities fall farther off.
d. Electrostatic separation. This method is based on the fact that the particles which are
good conductors of electricity become electrically charged as soon as they are brought into
an electrostatic field and are consequently repelled by the electrode carrying the like
charge. Lead sulphide and zinc sulphide ores which occur together in nature are separated
 Chemistry : Ores & Metallurgy

by this technique. The mixed ore, after grinding, is fed upon a roller in a thin layer and
subjected to the influence of an electrostatic field. Lead sulphide ore, being a good
conductor, gets charged immediately and is thrown away from the roller due to electrical
repulsion. The zinc sulphide ore which is a poor conductor is not charged and hence drops
vertically from the roller.
e. Froth flotation. This process is based on the principle of preferential Wetting of the solid
surface by liquids. Metallic sulphides, for instance, are wetted by certain oils, like pine oil,
but not by water.
The finely divided ore is put in water to which a small quantity of oil (e.g., pine oil) has
been added. The water is agitated violently with air (Fig. 1) when froth is formed at the air-
water interface. The ore which is preferentially wetted by the oil rises to the surface along
with the foam while the stony matter (gangue) which is preferentially wetted by water
remains in the water below the foam, as shown on the right of the figure. The foam
separates out and, in due course, settles down as shown on the left of the figure. This
process is known as froth flotation process.

Fig. Froth flotation process

f. Leaching. This is a chemical method for the concentration of ores. In this method, the
powdered ore is treated with some suitable reagent which may dissolve the ore but not the
impurities. The impurities are filtered off and the ore is recovered from the solution by
suitable chemical methods. For example, during the extraction of aluminium from bauxite
(A1203.2H20), the finely divided ore is treated with hot sodium hydroxide solution.
Alumina present in the ore dissolves forming soluble sodium metaaluminate but impurities
are left behind and are filtered off.
2. Calcination
Calcination is a process in which the ore is heated in a limited supply of air at a temperature
insufficient to melt it. During calcination, organic matter, volatile impurities and moisture
present in the ore are expelled and the remaining mass becomes porous. Calcination is also done
to remove water from hydrated oxide ores or carbon dioxide from a carbonate ore. For example,
when limestone is heated, carbon dioxide is given off and limestone is said to be calcined.
When bauxite is calcined, water is removed and anhydrous alumina is left. Similarly, iron ores
on calcination give anhydrous iron oxide. The various chemical changes are represented below:
CaCO3 — CaO + CO2
Al2O3.2H2O — A12O3 + 2H2 O
2Fe2O33H2O — 2Fe2O3 + 3H2O
Calcination is generally done in a reverberatory furnace. It renders the ore porous and easily
workable in subsequent stages.

3. Roasting
Chemistry : Ores and Metallurgy

Roasting is a wider term used to denote the process in which the ores (usually sulphide ores)
either alone or with the addition of other materials, arc subjected to the action of heat in the
presence of air, at temperatures well below their melting points, in order to bring about their
oxidation.
2ZnS + 3O2 — 2ZnO + 25O2
2PbS + 3O2 — 2PbO + 25O2
2CuS + 3O2 — 2Cu2O + 2SO2
Sometimes, during roasting, oxidation of sulphides takes place only upto sulphates. For
example,
ZnS + 2O2 — ZnSO4
PbS + 2O2 — PbSO4
During roasting the volatile impurities like sulphur, arsenic, phosphorus, etc., are removed in
the form of their volatile oxides which escape as gases through the chimney.
S + O2 — SO2
4As + 3O2 — 2As2O3
P4 + 5O2 — 2P2O5
Roasting is carried out either in a reverberatory furnace or in a blast furnace. In a reverberatory
furnace, the charge is placed on the hearth and heated by the flames deflected from its roof. The
reverberatory furnace is used in roasting the ores of copper, tin, lead, etc.
Blast furnace is a long vertical furnace (Fig. 3), made of steel plates, lined inside with fire
bricks. It is provided with an arrangement for blowing in air near the base, as shown in the
figure. It is also provided with a hole for removing the slag and a tapping hole for taking out the
metal.

A reverberatory furnace. A blast furnance

4. Reduction to Free Metal

Different methods are used for the reduction of the roasted or clacined ore to metallic state.
These methods depend upon the ease with which an ion can be reduced to the metal which, in
turn, depends upon the sign and the magnitudç of the standard electrode potential (E°) of the
metal ion. Ions which have positive or only slightly negative E°, ranging between 0 and –0.5 V,
 Chemistry : Ores & Metallurgy

are easily reduced even under mild conditions. Ions which have higher E°, ranging between –
0.5 to –1.5V (such as the ions of transition metal) are reduced by interaction with metals which
have more negative E° than those of the metal ions to be reduced. Highly electropositive metals
having E° more negative than 1.5 V (such as alkali and alkaline earth metals) can be obtained’
from their ions only under drastic reducing conditions.
A brief description of methods used for the reduction of various categories of ions is given
below.
a. Reduction by Displacement. This is the simplest method in which a metal is preciptiated
from the solution of its ions by the addition of another metal which is more electropositive.
For instance, the solution left after the extraction of zinc from ZnSO4 solution by
electrolysis contains traces of Cd2+ ions. Addition of a small amount of zinc which is more
electropositive than Cd, reduces Cd2+ ions to Cd metal.
Zn + CdSO4 — ZnSO4 + Cd
Some. copper sulphide ores which are poor in copper content are left to weather in rain and
air. This oxidises copper sulphide ore to CuSO4 which dissolves in ‘the rain water. The
addition of iron to this solution precipitates copper.
Fe + CuSO4 — FeSO4 + Cu
b. Reduction by Thermal Decomposition. Metals which are less electropositive than
hydrogen (i.e., metals with positive E°) either occur in free state or form compounds which
easily decompose on heating to yield the metal. For instance, Ag2O and HgO decompose
even on moderate heating (< 100°C) to give Ag and Hg, respectively.
c. Reduction by Carbon (Smelting). A large number of metal oxides can be reduced by
carbon at elevated temperatures (>1000°C). The thermodynamics of the reduction process
would be discussed shortly.
The roasted ore is mixed with a suitable quantity of carbon (coal or coke) and heated to a
high temperature above the melting point of the metal in a furnace. Carbon and carbon
monoxide (produced by the incomplete combustion of carbon) reduce the oxide to the free
metal. For example,
Fe2O3 + 3C — 2Fe + 3CO
Fe2O 3 + 3CO — 2Fe + 3CO2
PbO + C — Pb +CO
PbO + CO — Pb +CO2
During reduction, an additional substance called the flux, is added to the ore. It combines
with impurities to form easily fusible product known as slag.
Impurities + flux 
 fusible product
(present in the ores) Slag

Slag is not soluble in molten metal. Being lighter, it can be easily skimmed off from the
surface of the molten metal.
The choice of flux depends upon the impurities present in the ore. For example, if the ore
contains acidic impurities such as SiO2, P2O5, then basic fluxes like lime (CaO), magnesite
(MgCO3), haematite (Fe2O3), etc., are used.
SiO 2  CaO 
 CaSiO 3
Acidic impurity Basic flux Cal. silicate (slag)

On the other hand, if the ore contains basic impurities such as CaO, FeO, MgCO3, then
acidic fluxes like sand and borax are used.
Chemistry : Ores and Metallurgy

FeO  SiO2 
 FeSiO3
Basic impurity Acidic flux Iron silicate (slag)

Smelting is generally carried out in a reverberatory furnace (Fig. 2) or a blast furnace

(Fig. 3) in a controlled supply of air.

A vertical retort furnace for the smelting of zinc ores.

In the case of metals which are volatile in nature (for example, zinc), smelting cannot be
done in an open furnace. In such cases, reduction of the oxide ore is carried out in fire-clay
retorts. The vertical retort, which is now in common use, is shown in Fig. 4. Heating is
done by producer gas.
It is to be noted that reduction with carbon is practical only if the required temperature is
achieved conveniently which may not be so always.
Refining or Purification
After various metallurgical operations, the metal first obtained is usually impure. The impurities
largely consist of
(i) other metals produced by the simultaneous reduction of their respective oxides originally
present in the ore.
(ii) unreduced oxides and sulphides of the metals and
(iii) substances taken up in the furnace, e.g., residual slag, flux, etc.
The impure metal is, therefore, subjected to certain purifying processes which depend upon the
metal under treatment and the nature of the impurities to be removed. The usual refining processes
are:
a. Liquation process. This process is employed when the impurity is less fusible than the metal
itself. The impure metal is placed on the sloping hearth of a furnace and gently heated. The
metal melts and drains away leaving behind the infusible material on the hearth.
b. Distillation process. This process is employed for purification of volatile metals like mercury,
zinc and cadmium. The impure metal is heated in a retort and its vapours are condensed in a
 Chemistry : Ores & Metallurgy

receiver. While the pure metal distils over, the non-volatile impurities are left behind in the
retort.
c. Oxidation processes. Oxidation processes are employed for refining when impurities
consisting of other metals get oxidized more readily than the metal itself. The impure metal is
exposed in a molten state to the oxidizing influence of air in a suitable furnace. The oxides of
other metals which are formed are removed from the surface by skimming. Sometimes, the
oxide of the metal itself is added which provides the oxygen to the impurities. Thus, copper
oxide is added to impure molten copper to provide oxygen required for the oxidation of the
impurities.
d. Thermal decomposition of suitable compounds. In this method, the impure metal is converted
into some volatile compound which decomposes easily to yield the pure metal. Two examples
are given below.
(i) Mond’s Process. Impure nickel is treated with CO at 50°C when Ni(CO)4 gas is produced
which when heated to 250°C in a closed vessel decomposes to give CO and pure nickel.
CO is recycled to react with more of the impure nickel This process is known as Mond’s
process.
(ii) van Arkel-de-Boer Process. This method is used (or ultrapurification of Zr and Ti. The
impure metal is heated with iodine to give volatile MI4 (M = Ti, Zr). The iodide is then
heated electrically in a closed container when MI4 decomposes to give the metal which
deposits on the tungsten filament of the electric heater. The iodine liberated is recycled to
react with further quantity of the impure metal. The tungsten filament is then drilled out
leaving behind the hollow bar of pure titanium or zirconium, as the case may be.
e. Electrorefining. A large number of metals are refined electrolytically. The impure metal in the
form of blocks is made the anode of an electrolytic cell while the cathode is a thin plate of the
pure metal. A solution of a soluble salt of the metal is used as the electrolyte. On passing the
electric current, the pure metal dissolves from the anode and is deposited on the cathode. The
soluble impurities go into solution while the insoluble matter settles down at the bottom and is
called the anode mud.
f. Zone refining. This technique is employed for preparing extremely pure metals. This is based
on the principle that when the melt of an impure metal is allowed to cool, the pure metal
crystallizes out while the impurities remain in the melt. In this technique, the impure metal is
converted into a bar which is heated at one end with a moving circular heater. This end melts
and forms a molten zone. As the heater is moved slowly along the length of the rod, the pure
metal cystallizes out of the already melted zone while the impurities pass into the adjacent
newly melted zone. This process is carried out throughout the length of the rod. As a result, the
impurities are completely driven to one end of the rod which is cut off and discarded. The
process is carried out in an inert atmosphere to prevent oxidation of the metal.

3. EXTRACTION OF IRON
Iron is usually extracted from the haematite.
Concentration of the ore
1. Dressing of the ores: The iron ores are first broken into small pieces 3-5 cm in size.
2. Roasting: During roasting S, As, P are oxidized to the respective oxides.
S + O2  SO2 
4As + 3O2  2As2 O3 
Chemistry : Ores and Metallurgy

FeCO3 decomposes as,

FeCO3 FeO + CO2 
Fe2O3.3H2O loses water
Fe2O3. 3H2O  Fe2 O3 + 3H2O
Fe3O4 is decomposed to ferrous oxide and ferric oxides.
Fe3O4  FeO + Fe2 O3
Ferrous oxide reacts with silica to forms ferrous silicate at high temperature.
FeO + SiO2 FeSiO3
But the conversion of FeO into Fe2O3 will prevent the formation of FeSiO3. Thus the mass of
the ore becomes porous casting the increase in the effective surface area.
3. Smelting in the Blast furnace: Blast furnace is a shaft furnace made of steel plate of 20-30 m
with 4 – 6 m diameter. Concentrated ore after calcinations is reduced with carbon i.e. smelted
in the blast furnace.
Reactions taking place in the blast furnace are
i) Zone of combustion :
C + O2  CO2
(Coke)
CO2 + C  2CO ; H = +ve (Newmann’s inversion reaction)
ii) Zone of reduction: The following reduction reactions are called indirect reduction, which is
done by CO, which is unstable at higher temperature (See Ellingham diagram).
Fe2O3 + 3CO  2Fe + 3CO2
FeO + CO  Fe + CO2
iii) Zone of slag formation :
CaCO3  CaO + CO2
(lime stone)
CaO + SiO2  CaSiO3 ;
Fusible slag
iv) Zone of fusion (lower part of furnace):
 Chemistry : Ores & Metallurgy

Orange

Cup and cone

arrangement Waste gases
200-250ºC
400ºC Refractory bricks
600ºC
700ºC
800-1000ºC
1300ºC Hot air
1600ºC
Tuteres

Molten
slag
Molten metal

Molten iron is heavier from molten slag. The two liquid are periodically tapped off. The molten iron
tapped off from the furnace is solidified into blocks.
Preparation of Wrought Iron: This is done by heating cast iron with haematite (Fe2O3) which
oxidizes C to CO, S to SO2, Si to SiO2, P to P4O10 and Mn to MnO
Fe2O3 + 3C  2Fe + 3CO
Where CO and SO2 escape, manganous oxides (MnO) and Silica (SiO2) combine to form slag.
MnO + SiO2  MnSiO3
Similarly phosphorus pentoxide combines with haematite to form ferric phosphate slag.
2Fe2O3 + P4O10  4FePO4
Bosh: The diameter of the furnace gradually increases from the top down wards. Widest part of the
furnace is called Bosh. At above 2m, tubes are there through which hot air blast is blown into the
furnace.
Hearth: Below the bosh this region exists. (1) slag notch is at higher height and (2) tap hole for
metal passage at lower position from the bottom. At the top of the furnace the hopper is there which
is cup and cone arrangement. Through this charge is introduced till the charge bed in the furnace is
4/5th of the furnace. Hot air at 700ºC is forced into the furnace through the tubes. The thermal
gradient inside exists from 1800ºC (hearth) to 400ºC-900ºC in the upper region. Near both the
reactions temperature varies from 1200º-1300º.
Chemical reactions which have taken place are:
1. At 1200ºC near the tuyeres,
C + O2  CO2 ; CO2 + C  2CO
2. Above bosh 600º - 900ºC, ferric oxide is partially reduced by CO as
Fe2O3 + 3CO 2Fe + 3CO2
900ºC
3. CaCO3   CaO + CO2
1000 1300ºC
2CO   CO2 + C
Chemistry : Ores and Metallurgy

Fe2O3 + 3C  2Fe + 3CO

CaO + SiO2  CaSiO3 (slag)
4. The reaction at 1500ºC, MnO2 is reduced to
MnO2 + 2C  Mn + 2CO
Ca3(PO4 )2  3 CaO + P2O5
CaO + SiO2  CaSiO3
2P2O5 + 10C  P4 + 10CO
5. Collection of Cast Iron : Metal is cast into ingots for further refining like steel making.
Wrought Iron: Minimum % of carbon is 0.1 to 0.25% and other impurities like S, P, Mn, Si less
than 0.3%.
Manufacturing process : Cast iron is taken in pudding furnace and melted by hot blast of air. The
chemical reactions, which occur are
S + O2  SO2 ; 3S + 2Fe2O3  4Fe + 3SO2
3Si + 2Fe2O3  4Fe + 3SiO2
3Mn + Fe2 O3  2Fe + 3MnO
MnO + SiO2  MnSiO3
3C + Fe2O3  2Fe + 3CO
4P + 5O2  2P2O5 ; Fe2 O3 + P2O5  2FePO4 (slag)
The impurities are removed from iron, the melting point of the metal rises and it becomes a semi
solid mass. Metal taken out from the furnace in the form of balls with the help of the rubbles. The
balls are then beaten under hammer to separate out of the slag. The product formed, is thus called
wrought iron.
Some Important Alloy

Sl. No. Name Composition

1. Stainless steel Fe, Cr, Ni
2. Invar Fe, Ni
3. Alnico Fe, Al, Ni, Co
4. Brass Cu, Zn
5. Bronze Cu, Zn, Sn
6. Gun metal Cu, Sn
7. Bell Metal Cu, Sn
8. German Silver Cu, Zn, Ni
9. Solder, pewter Pb, Sn
10. Babbitt metal Sn, Sb, Cu
 Chemistry : Ores & Metallurgy

4. EXTRACTION OF TIN
The chief ore of tin is cassiterite or tin stone, SnO2. It also contains silica and wolframite iron
(tungstate, FeWO4), iron pyrites and arsenical pyrites and sometimes copper pyrites. The ore is
concentrated, and then smelted to give crude tin which is finally refined).
Roasting : The impure tin stone is roasted in current of hot air in an inclined revolving tube-furnace,
when arsenic and sulphur are expelled as volatile oxides; most of the iron is converted to the
magnetic oxide, Fe3O4 and copper forms oxide and sulphate
Smelting : The black tin is mixed with one-fifth of its weight of crushed anthracite coal and some
lime and fluorspar to act as a flux and smelted at 1200º-1300ºC in a reverberatory furnace when the
tin oxide is reduced to the metal. The molten tin and slag form two layers and are run out separately
SnO2 + 2C  Sn + 2CO
The liquid tin is cast into ingots or else refined to a higher purity.
A good amount of tin goes into the slag, because of the amphoteric nature of tin dioxide, the slag
may contain 10 to 25% tin. Tin is recovered from the slag by smelting it at a much higher
temperature with carbon, flux and some scrap iron to decompose the tin oxide.
SnSiO3 CaO  Sn + CaSiO3 + CO
SnSiO3 + Fe  Sn + FeSiO3 ; SnO2 + 2C  Sn + 2CO
Refining :
i) The crude tin is refined by liquation or sweating i.e. by heating the ingots on the slopping hearth
of a reverberatory furnace, when the easily fusible tin (melting point 232ºC) melts and runs
away leaving behind a dross of an alloy of tin with iron, copper, tungsten and arsenic Bismuth
and Lead because of their low melting points go with tin and remain in the sweated tin.
ii) The liquated tin is further treated by poling, i.e. the liquid tin stirred with poles of green wood
so that a large surface is exposed to the air, when the remaining impurities are oxidized and
separated as scum on the surface and are skimmed off. The tin so obtained is of over 99%
purity. The scum and dross contain much tin and are worked up by smelting.

5. EXTRACTION OF COPPER
Copper glance or Chalcocite : Cu2S
Chalcopyrites (copper pyrites) : Cu2S.Fe2S3
Cuprite : Cu2O
Malachite : [CuCO3.Cu(OH)2]
Azurite : [2CuCO3.Cu(OH)2]
Extraction of Metallic Copper :
1. Concentration of the ore by froth floatation process: Copper pyrites contains only
2-3% of copper. The rest of the ore contains iron ore, silica, silicious materials, sulphur, arsenic
etc. as impurities. Froth flotation by Xanthate and pine oil. The froth is collected and dried
when concentrated ore is obtained which contains 25-30% of Cu.
2. Roasting
2CuFeS2 + O2  Cu2S + 2FeS + SO2
2CuFeS2 + 4O2  Cu2S + 2FeO + 3SO2 
2Cu2S + 3O2  2Cu2O + 2SO2
Chemistry : Ores and Metallurgy

Cu2O + FeS  Cu2 S + FeO

3. Smelting of the roasted ore in blast furnace : material required
a) Roasted ore
b) Lime stone
c) Coke (used as fuel)
d) Silica (used as flux)
e) Lime stone (used to remove excess silica)
Reactions occurring given as follows
2FeS + 3O2  2FeO + 2SO2
Cu2O + FeS  Cu2 S + FeO
FeO + SiO2  FeSiO3 (removed as slag)
CaO + SiO2  CaSiO3 (removal as slag)
4. Self reduction in Bessemer Converter
Reactions involved are,
2FeS + 3O2  2FeO + 2SO2
FeO + SiO2  FeSiO3 (Slag)
2Cu2S + 3O2  Cu2O + 2SO2 
When approximately 2/3 of the cuprous sulphide is oxidized, the blast of air is stopped. The
produced Cu2O and Cu2S are reduced by the rest of cuprous sulphide to produce metallic copper
with the evolution of SO2.
Cu2S + 2Cu2O  6Cu + SO2 
Cu2SO4 + Cu2S  4Cu + 2SO2
As the molten cools, it gives off the dissolved off SO2. The SO2 gas escaping in the form of
bubbles, leaves the surface of the metal with full of cavities which gives the metal is blistered
appearance. This is why the metal thus obtained is by blister copper.
5. Refining
Electrorefining
Anode : Impure copper obtained above
Cathode : Pure copper
Electrolyte : 15% CuSO4 solution + 5% H2SO4
When electric current is passed through the electrolyte, the anodes gradually dissolve and pure
copper is deposited on the cathodes which gradually grow in size. The impurities like Fe, Zn, Ni
etc., dissolved in the solution as sulphates while gold, silver, platinum settle down below the
anode as anode mud.
Reaction coming are as follows
CuSO4 Cu+2+ + SO4–2
At anode : Cu  Cu+2 + 2e
At cathode : Cu+2 + 2e  Cu
 Chemistry : Ores & Metallurgy

6. EXTRACTION OF LEAD
Lead is mainly extracted from galena. After the concentration of the ore by froth flotation process,
the ore is roasted in a reverberatory furnace for about six hours at a moderate temperature in a
current of air. Part of galena is converted into lead oxide and lead sulphate. After this, the supply of
air is stopped and small quantities of carbon, quicklime and cheap iron ore are added along with
increase of temperature. At this stage, unreacted sulphide reacts with the lead oxide and sulphate
giving metallic lead :
PbS + 2PbO  3Pb + 2SO2
PbS + PbSO4  2Pb + 2SO2
The obtained lead contains impurities such as Cu, Ag, Bi, Sb and Sn. Silver is removed by Parke’s
process where molten zinc is added to molten impure lead. The former is immiscible with the latter.
Silver is more soluble in molten zinc than in molten lead. Zinc-silver alloy solidifies earlier then
molten lead and thus can be separated. After this, crude lead is refined electrolytically (Electrolyte;
lead silicoflyuoride, PbSiF6 and hydrofluosilicic acid, H2SiF6 with a little gelatin, anode; crude lead
and cathode; pure lead).

7. EXTRACTION OF MAGNESIUM
Extraction of magnesium: Magnesium is commonly obtained by the electrolysis of fused
magnesium chloride containing a little (25%) sodium chloride and sodium fluoride at 700ºC in an
air-tight iron pot which itself serves as the cathode, the anode being a graphite rod which dips into
the electrolyte. The anode is surrounded by a perforated porcelain tube for the exit of chlorine. The
electrolysis is carried out in the atmosphere of coal gas so as to prevent the attack of atmospheric
oxygen and nitrogen on magnesium. Molten magnesium being lighter then the electrolyte, it floats
over the fused electrolyte and is withdrawn.
Graphite anode

Cl2
Porcelain hoood

Inert gas Inert gas (coal gas)

Iron cathode
Mg
Molten electrolyte
Iron cell

In Dow process, magnesium is recovered from seawater as magnesium chloride which is then
electrolysed using cell described in above figure.
Dow’s Sea Water Process: Sea water contains 0.13% Mg2+ ions.
Mg2+ (seawater) + Ca(OH)2 (from oyster shells)  Mg(OH)2 + CaCl2
CO2

(calcined dolomite )
 MgCl22H2 O
Chemistry : Ores and Metallurgy

spraydrying dry HCl

MgCl2.2H2O   MgCl2.1.5H2O heat
 MgCl2
Dow’s Natural Brine Process:
heat dil. HCl
MgCO3CaCO3  MgO.CaO   CaCl2(aq)+MgCl2 (aq)
(dolomite) (calcined dolomite)
CO2

(calcined dolomite )
 MgCl2(aq)+CaCO3

The reaction is : CaCl2.MgCl2(aq) + MgO.CaO + 2CO2  2MgCl2 (aq) + 2CaCO3

Electrolysis: Anhydrous carnallite (KCl.MgCl2.6H2O) may also be employed as the starting
material of magnesium chloride. The cathode may be a layer of molten lead on the floor of the cell
and anode may be graphite rods which are suspended above the molten lead. Magnesium liberated at
the cathode dissolves in molten lead. The alloy of lead-magnesium is subjected to electrolysis to
obtain pure magnesium (electrolyte : fused carnallite, anode-lead-magnesium alloy and cathode-steel
rods).
8. EXTRACTION OF ALUMINIUM
Important ores of aluminium
Bauxite Al2O3.2H2O
Cryolite Na3AlF6
Feldspar K2O.Al2O3.6SiO2 or KAlSi3O8
Mica K2O.3Al2O3.6SiO2.2H2O
Corundum Al2O3
Alumstone or Alunite K2SO4.Al2(SO4)3.4Al(OH)3
Aluminium is mainly extracted from bauxite ore.
Purification of Bauxite: By Bayer’s process commercially it is being carried out (for red bauxite
not for the white bauxite).
Flow sheet of Baeyer’s process for the preparation of pure Al2 O3.

Finely powdered bauxite

containing Fe2O3, TiO2.SiO2 as
impurities
Calcination (FeO  Fe2O3)
Organic matters are removed

Calcined ore (Digested with 45%, NaOH with at

150C under 80 lb pr. Filtered)

Residue Filtrate
(Fe2O3, TiO2) (NaAlO2 + Na2SiO3)
Freshly prepared Al(OH)3 Seeding agent filtered

Precipitate Filtrate
(Al(OH)3 (NaOH, Na2SiO3)
1000C

Al2O3 Pure
Alumina
 Chemistry : Ores & Metallurgy

Hall’s process: Crude bauxite at 1100ºC reacts with Na2CO3, Na2SiO3, NaFeO2, NaAlO2 are
formed.
Al2O3 + Na2CO3  2NaAlO2 + CO2 
Fe2O3 + Na2CO3  2NaFeO2 + CO2 
SiO2 + Na2CO3  Na2SiO3 + CO2 
Then at 50º-60ºC CO2 is passed through NaAlO2 solution and produces thereby Al(OH)3
2NaAlO2 + CO2 + 3H2O  2Al(OH)3 + Na2CO3
100ºC
 Al2O3 + 3H2O
2Al(OH)3 
Serpeck’s Process: Bauxite containing high percentage of silica can be purified by Serpeck’s
process. In this process finely powered bauxite is mixed with coke and the mixture is heated to
1800ºC in a current of nitrogen. The AIN thus obtained is reacted with hot and dilute NaOH,
produced NaAlO2 and excess AIN is hydrolysed and Al(OH)3 is formed.
Al2O3 + 3C + N2  3AlN + 3CO
SiO2 + 2C  Si + 2CO
AlN + NaOH  NaAlO2 + NH3
NaAlO2 2H2O  Al(OH)3 + NaOH
AlN + 3H2O  Al(OH)3 + NH3
1100ºC
2Al(OH)3   Al2O3 + 3H2O
(cryolite)
Electrolytic reduction of Al2O3: Pure alumina melts at about 2000ºC and is a bad conductor of
electricity. If fused cryolite AlF3.3NaF and CaF2 (Fluorspar) is added the mixture melts at 900ºC and
Al2O3 becomes a good conductor of electricity. Metallic Al is liberated at the cathode.
Electrolysis of molten mixture
Cathode : Carbon
Anode : Graphite rods
Electrolyte : 60 parts cryolite + 20 parts fluorspar + 20 parts pure Al2O3
Temperature : 900ºC
Reaction
According to the 1st theory of the following reaction occurs
Al2O3 2Al+3 + 3O–2
At cathode : 2Al+3 + 6e  2Al
At anode : 3O–2  3O2e
As cryolite has greater electrochemical stability it does not dissociate. It only increases the
dissociation of Al2O3
But the second theory states that, cryolite undergoes electrolytic dissociation first then Al+3 goes to
the cathode, produced F2 at anode then reacts with Al2O3 produces AlF3.
AlF3.3NaF Al+3 + 3Na+ + 6F–
At cathode : Al+3 + 3e  Al
At anode : 6F– 3F2 + 6e
Al2O3 + 6F2  4AlF3 + 3O2 
Chemistry : Ores and Metallurgy

Refining of aluminium: The aluminium metal obtained by the electrolysis of fused almina is about
99.5% pure. It can be further refined by Hoope’s electrolytic process.

9. EXTRACTION OF SILVER
Occurrence: It occurs in free state. The chief and important ore of silver is silver glance (Ag2S),
which is present as such or is associated with galena, PbS.
Cyanide Process (Mac Arthur Forest) Process: The finally powdered ore after being concentrated
by froth floatation process is treated with dilute (0.7%) NaCN solution and a current of air is blown
into it. The silver present in the ore dissolves forming a complex soluble argentocyanide.
Ag2S + 2NaCN  2AgCN + Na2S
AgCN + NaCN  Na[Ag(CN)2]
–––––––––––––––––––––––––––––––––––––
Ag2S + 4NaCN  2Na[Ag(CN)2 ] + Na2 S
or Ag2S + 4CN  2[Ag(CN)2]–1 + S–2
The reaction is reversible and in order to prevent backward reaction it is essential to remove sodium
sulphide from the sphere of action. The oxygen of the air converts sodium sulphide into sodium
sulphate and free sulphur and thus makes the above reaction irreversible.
Na2S + 5O2 + 2H2O  Na2SO4 + 4NaOH + 2S
In case the ore is silver chloride then, too, it goes into solution forming sodium argtentocyanide.
AgCl + 2NaCN  Na[Ag(CN)2] + NaCl
or AgCl + 2CN–  [Ag(CN)2]– + Cl–
The solution of sodium argentocyanide, obtained as above, is treated with finally powdered zinc.
Zinc being more electropositive than silver displaces it from the solution. A black precipitate of
silver is thus obtained.
2Na[Ag(CN)2] + Zn  Na2 [Zn(CN4] + 2Ag
The precipitated silver is mixed with potassium nitrate and fused when the impurities are oxidized
and removed as a scum from the surface of molten metal. On cooling a compact shining mass of
silver is formed.
This is the best method of extracting silver from its ore especially when the % of silver is low.
Refining of Silver: Silver so obtained is purified by electrolytic process. It consists of
Cathode : Pure Ag
Anode : Impure Ag
Electrolyte : AgNO3 solution containing 1% HNO3
On passing electric current pure silver is deposited on cathode while the same amount dissolves out
from anode. The more electro positive metals like copper and zinc remain in solution while less
electro positive gold comes down as anode mud.
Reaction : AgNO3 Ag+ + NO3–
Ag+ + e–  Ag(Cathode)
 Chemistry : Ores & Metallurgy

10. EXTRACTION OF GOLD

Occurrence: Gold occurs in free and combined state.
i) Native state: It is generally found in free state because it is a noble metal. The two important
sources are
a) Quartz veins: In this state, the fine particles of gold along with silver and platinum remain
embedded.
b) Alluvial sands: This is present in those rivers, which passes over auriferous rocks.
ii) Combined sands: Its compounds in nature are few. Bismuth qurite AuBi, Calaverite Au Te2.
Extraction: Gold is extracted from quartz veins and alluvial sands by the following methods :
i) Amalgamation process
ii) Cyanide process
iii) Chlorination process
Cyanide process (Mac Arthur Forrests): This is very good process for the removal of traces of
gold from tailings of amalgamation process or from even poorer ores. It is based on the fact that gold
dissolves in dilute solution (0.3%) of sodium cyanide in presence of atmosphere oxygen with the
formation of complex cyanide.
4Au + 8NaCN + 2H2 O + O2  4Na[Au(CN)2 + 4NaOH
Sod. aurocyanide
or 4Au + 8CN– + 2H2O + O2  4[Au(CN)2]– + 4OH–
The molten matte is finally transferred to Bessemer converter. A blast of sand and air is blown in the
converter through tuyeres which are situated a little above the bottom. This causes removal of S and
As oxides and ferrous oxide as slag. At the same time Cu2S is oxidized mostly into Cu2 O and partly
into CuO and CuSO4. All these reaction with Cu2S giving copper. The reactions are
ii) 2Cu2S + 3O2  2Cu2O + 2SO2 
2Cu2S + 5O2  2CuSO4 + 2CuO
2Cu2O + Cu2S  6Cu + SO2 
CuSO4 + Cu2S  3Cu + 2SO2 
Cu2S + 2 CuO  4Cu + SO2 
Finally, copper may be refined electrolytically (electrolyte; copper sulphate: anode; impure copper
and cathode; pure copper).