PHOENIX OF METALS

METALLURGY
 OCCURRENCE OF THE METALS
• Most metals come from minerals.
• A mineral is a naturally occurring substance with a range
of chemical composition.
• An ore is a mineral deposit concentrated enough to
allow economical recovery of a desired metal.
• Metals exist in various forms
• In the Earth’s surface
• As ions in seawater
• In the ocean floor
• The chief ores in the order of economic importance are:
(i) Oxides (ii) sulphides (iii) carbonates (iv) sulphates (v)
halides and (vi) silicates.
• (a) 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.
• (b) Combined Ores:
These ores contain metal in combination with oxygen or
sulphur or halides etc.
Sr. No. Metals Ores
1. Iron Iron pyrite; FeS2 (as sulphide) , Siderite; FeCO3 (as carbonate), Red

haematite; Fe2O3 (as oxide), Magnetite; Fe3O4 (as oxide), `

Limonite or brown haematite; 2Fe2O3.3H2O (as oxide)

2. Copper Cuprite; Cu2O (as oxide), Copper pyrites; CuFeS2 (as sulphides),

Copper glance; Cu2S (as sulphides), Malachite; CuCO3.Cu(OH)2

, Azurite; 2CuCO3.Cu(OH)2

3. Lead Galena; PbS (as sulphide), Cerussite; PbCO3 (as carbonate) ,

Anglessite; PbSO4 (as sulphate), White lead; 2Pb(OH)2.PbCO3

(as carbonate)
Sr. No. Metals Ores
4. Aluminium Bauxite; Al2O3.2H2O (as oxide), Corundum; Al2O3 (as oxide), Feldspar; KAlSi3O6 (as
oxide), Clay silicate; Al2O3.2SiO2.2H2O (as oxide), Cryolite; 3NaF.AlF3(Na3AlF6) (as
halide), Alum; K2SO4.Al2(SO4)3.24H2O (as sulphate), Diaspore; Al2O3.H2O (as oxide),
Mica; K2O.3Al2O3.6SiO2.2H2O (as oxide)

5. Zinc Zinc blende; ZnS (as sulphide) or sphalerite, Zincite; ZnO (as oxide), Smithsonite,
ZnCO3 (as carbonate) , Hemimorphite or Calamine, Zn2SiO4.H2O (as silicate)

6. Silver Horn silver (chlorapatite); AgCl (as halide), Lunar caustic; AgNO3 (as nitrate), Silver
glance or argentite; Ag2S (as sulphide), Ruby silver or pyrogyrite; 3Ag2S.Sb2S3
METALS AND THEIR MINERALS
Shining & Mining
 CONCENTRATION OF ORES
It is also called ore dressing, the aim is to increase the
amount of metal in each tone of ore. The ore is crushed then
ground and concentrated, the following methods may be
used:
• Gravity concentration
• Froth Flotation
• Magnetic separation
 GRAVITY CONCENTRATION

• Some ores are heavier than the waste. The ore

is shaken by a jolting box, or similar, while wet.

• Particles will separate into layers depending

on weight, the metal may be removed as a
layer.
 FROTH FLOTATION
• The fine particles of ore are swirled around in large tanks with air blown in
and flotation agents added. The particles attach to the bubbles and float to
the surface where the froth is skimmed off.
 MAGNETIC SEPERATION
• In the seperation of ores that have magnetic
properties, the ore is ground and passed over
a rotating drum.
• The drum has a magnet inside it which holds
the magnetic ore particles as the waste falls
outside the screen.
• The ore held on the drum can be released or
scraped off.
 CHEMICAL METHODS FOR
CONCENTRATION OF ORES

Leaching:
It involves the treatment of the ore with a
suitable reagent as to make it soluble while
impurities remain insoluble. The ore is recovered
from the solution by suitable chemical method.
e.g. bauxite ore contains ferric oxide, titanium
oxide and silica as impurities.
 LEACHING OF BAUXITE
Al2O3 2H2O+2NaOH 2NaAlO2 + 3H2O

Bauxite ore Sodium

aluminate

Al(OH)3 + NaOH NaAlO2+2H2O

Aluminum
hydroxide

Al(OH)3 ⎯⎯⎯→
Heat Al2O3 + 3H2O
LEACHING OF ARGENTITE
ROASTING
REACTIONS INVOLVING ROASTING

2PbS + 3O2 ⎯→ 2PbO + 2SO2

PbS + 2O2 ⎯→ PbSO4
2ZnS + 3O2 ⎯→ 2ZnO + 2SO2
ZnS + 2O2 ⎯→ ZnSO4
CuS + 2O2 ⎯→ CuSO4
2Cu2S + 3O2 ⎯→ 2Cu2O + 2SO2
 EXTRACTION OF CRUDE METAL FROM
CONCENTRATED ORE
• In this section we will be looking at the following
processes to convert concentrated ore into crude
metal. They are as follows:
• SMELTING :
• The process of extracting metal from its fused (molten)
state is called smelting.
• A less electropositive metal ore of Pb, Zn, Fe etc. are
treated with powerful reducing agent such as C, H2, CO
etc. depending upon the nature of metal and its oxide
the following processes can be used.
 SMELTING

• Reduction by another metal (aluminium)

• Self−reduction process
• Reduction of oxides with hydrogen/ Carbon and its oxides
 CARBON REDUCTION PROCES
• Carbon, the cheapest available reducing agent usually in the form of coke
is employed in the extraction of the lead, zinc, iron and tin etc.
• ZnO + C ⎯→ Zn + CO
• ZnO + CO ⎯→ Zn + CO2
• PbO + C ⎯→ Pb + CO
• PbO + CO ⎯→ Pb + CO2
• Fe2O3 + 3C ⎯→ 2Fe + 3CO
• Fe2O3 + 3CO ⎯→ 2Fe + 3CO2
• MnO2 + 2C ⎯→ Mn + 2CO
• Mn2O3 + 3C ⎯→ 2Mn + 3CO
•
 SnO + C ⎯→ Sn + CO
SnO + CO ⎯→ Sn + CO2

During reduction, additional substance called flux is also added to the ore. It
combines with impurities to form easily fusible product known as slag.
Impurities + Flux ⎯→ Fusible product (slag)
Flux is a substance that is added to the ore during smelting (a) to decrease the
melting point (b) to make the ore conducting and (c) to remove all the
impurities (basic and acidic).
The nature of the flux depends upon the nature of impurity to be removed. An
acidic flux (e.g. sand i.e. SiO2) is used to remove basic impurities (e.g. metallic
oxides like FeO) while basic flux (e.g. CaO) is used to remove acidic impurities
(e.g. sand).
 FeO + SiO2 ⎯→ FeSiO3 (fusible slag)
Impurity acidic flux
SiO2 + CaO ⎯→ CaSiO3 (fusible slag)
Impurity basic flux
Alumina is a bad conductor of electricity but when cryolite
(flux) is added, it becomes a good conductor and the melting
point is decreased. Hence, CaF2, KF, cryolite etc are neutral
flux.
 REDUCTION BY ANOTHER METAL
(ALUMINIUM)
If the temperature needed for carbon to reduce an oxide is too high then for
economic or practical purposes, the reduction may be effected by
another highly electropositive metal such as aluminium, which liberates
a large amount of energy (1675 kJ mol–1) on oxidation to Al2O3. This
process of reduction of a metal oxide to metal with the help of
aluminium powder is called aluminothermy or Goldschmidt
Aluminothermic Process or Thermite process.
 • This process is employed in the case of those metals,
which have very high melting points and are to be
extracted from their oxides.
3Mn3O4 + 8Al ⎯→ 9Mn + 4Al2O3
• 3MnO2 + 4Al ⎯→ 3Mn + 2Al2O3
• B2O3 + 2Al ⎯→ 2B + Al2O3
• Cr2O3 + 2Al ⎯→ 2Cr + Al2O3
 SELF−REDUCTION PROCESS

• The cations of the less electropositive metals

like Pb, Hg, Sb and Cu may be reduced
without the use of any additional reducing
agent. Elevated temperatures and anion or
anions associated with the metal may bring
about this change.
• Cu2S + 2Cu2O ⎯→ SO2 + 6Cu (self reduction reaction)

2HgS + 3O2 ⎯→ 2HgO + 2SO2

2HgO + HgS ⎯→ 3Hg + SO2 (selfreduction reaction)

2PbS + 3O2 ⎯→ 2PbO + 2SO2

PbS + 2PbO ⎯→ 3Pb + SO2 (self reduction reaction)

 REDUCTION OF OXIDES WITH
HYDROGEN/ CARBON AND ITS OXIDES

• Molybdenum and tungsten are obtained by reducing their oxides by

hydrogen at elevated temperatures.
Co3O4 + 4H2 ⎯→ 3Co + 4H2O
GeO2 + 2H2 ⎯→ Ge + 2H2O
2NH4[MoO4] + 7H2 ⎯→ 2Mo + 8H2O + 2NH3
2NH4[WO4] + 7H2 ⎯→ 2W + 8H2O + 2NH3

• This method is not widely used because many metals react with hydrogen at
elevated temperature, forming hydrides. There is also a risk of explosion from
hydrogen and oxygen present in the air.
 THERMODYNAMICS OF
REDUCTION
• 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 ArG negative and large enough to
make the sum of ArG of the two reactions, i.e, oxidation of the
reducing agent and reduction of the metal oxide negative.
 REFINING OR PURIFICATION

• The metals obtained by the application of above

reduction methods from the concentration ores are
usually impure.
• Some purifying process known as refining in
order to remove undesired impurities. Various
processes for this are
 LIQUATION PROCESS

• The process is based on the difference in

fusibility of the metals and impurities.
When impurities are less fusible than metal
itself, this process is used. The impure
metal such as Bi, Sn, Pb, Hg etc. is placed
on the sloping hearth of the furnace and
gently heated. The metal melts and flow
down.
 CUPELLATION

• Cupellation is a process used to separate noble metals such as gold or silver

from base metals such as lead. In this process, an alloy consisting of both
noble and base metals is placed in a crucible. This mixture is then melted
and allowed to freeze. When solidified, a button consisting of precious
metals and lead can be removed from the slag of metal oxides and other
materials. After cooling, the metals are placed in a special pot made of
bone ash or clay called a cupel. Under high heat, lead turns to litharge, a
lead oxide, which is absorbed by the cupel or lost to the atmosphere. At the
end of the cupellation process, a button of pure gold and silver remains in
the bottom of the cupel.
 VAN ARKEL PROCESS

This method is used for obtaining ultrapure metals. The impure metal is converted into
volatile compounds which is then decomposed electrically to get pure metal. Ti, Zr,
Hf, Si etc. are purified by this method.

ImpureMetal +I2 → Metal Iodide vapour ⎯⎯⎯⎯⎯⎯

Heating
Tunstun Filament
→ PureMetal +I2
Z MOND’S PROCESS

Ni is purified by this process. Impure Nickel is treated with CO

at 330-350 K, when volatile nickel carbonyl is formed. The
carbonyl is subjected to 450-470 K, when it decomposes giving
pure nickel.
ImpureNickel + CO ⎯⎯⎯⎯
330-350 K
→ Ni(CO)4 ⎯⎯⎯⎯
450-470 K
→ Ni + 4CO
 ZONE REFINING

• The small scale production of high-purity metals using the

principle that an impure solid melts will deposit pure crystals
on solidifying.
• This method is used for purification of
germanium, gallium, silicon etc which are
generally used as semiconductor.
 BASSEMERISATION

• This is a process in the metallurgy of copper.

• It involves the reduction of molten matte (mixture of cuprous and ferrous
sulphide) obtained after smelting of copper pyrites ore in a Bessemer
converter.
• The following reactions takes place in the converter.
• i) Air oxidizes iron sulphide to iron oxide and SO2
• 2FeS + 3O2 ⎯→ 2FeO + 2SO2
• ii) Sand reacts with iron oxide to form iron silicate
• 2FeO + SiO2 ⎯→ FeSiO3 (Slag)
 iii) cuprous oxide.
2Cu2S + 3O2 ⎯→ 2Cu2O + 2SO2
iv) The cuprous oxide so formed reacts immediately with
remaining cuprous sulphide to form metallic copper.
After the iron has been removed, hot blast of air
converts a part of cuprous sulphide to
2Cu2O + Cu2S ⎯→ 6Cu + SO2

• the reaction is exothermic, the heat liberated maintains the crude copper in
the molten state.
• The completion of the reaction is indicated by the appearance of green
flame produced by the vaporization of copper.
 FURNACE
REVERBERATORY
The sulphide ores of copper are
heated in reverberatory furnace.

If the ore contains iron, it is mixed

with silica before heating. Iron oxide
‘slags’as iron silicate and copper is
produced in the form of copper
matte which contains Cu2S and
FeS.
BLAST FURNACE
METALLURGY OF COPPER
METALLURGY OF SILVER
OTHER METALS METALLURGY WE
CAN REFER NCERT