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Metallurgy
Ore and mineral:
The mining material by which the extraction of metal can be done economically are called
ores while which are uneconomical for the extraction of metal are called minerals. E.g.
CuFeS2 is an ore of copper while it is an mineral of copper.
Ores May Be Divided Into Five Groups
(I) Native ores: These ores contain the metal in free state e.g. silver, gold etc.
(II) Oxide ores: These ores consist of oxides of metal.
Ore of Ore Ore name Trick
Fe2O3 Haematite Hema
Fe Fe3O4 (FeO.Fe2O3 ) Magnetite mange
Fe2O3 .3H2O Limonite limozene car
Al2O3 Corundum
caddu
Al2O3 .H2O Diaspore
Al
Al2O3 .2H2O Bauxite
banega
Al2O3 .3H2O Gibbsite
Cr FeO.Cr2O3 Chromite
Cu Cu2O Cuprite
Mn MnO2 Pyrolusite
Sn SnO2 Cessiterite
Zn ZnO Zincite
(III)Sulphides ores: These ores consist of sulphides of metals like copper, lead, mercury
etc. Examples are copper pyrites (CuFeS2), Galena (PbS), Cinnabar (HgS) etc.
Ore of ore Trick Ore name Trick
Hg HgS Haan Cinnebar baar mein
baithkar
Zn ZnS Ji Zinc Blende blenderspride ke
Cu Cu2S Cukoo Copper glance glass
of
Chalcocite
CuFeS2 ka Copper pyrite pe
or
Chalcopyrite
Ag Ag 2S aaj Silver glance glass
Pb PbS placement Galena gale mein
ho gaya
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(iv)Halide ores: These ores consist of fluoride of chloride of metals.
Ore of Ore Ore name Trick
Mg KCl.MgCl2 .6H2O Carnalite Car ki
Ag AgCl Horn silver Horn se
Al Na3 AlF6 Cryolite Kaan
Ca CaF2 Fluorspar Faad diya
(V) Carbonate ore:
Ore of Ore Ore name Trick
Mg MgCO3 Magnesite Mummy
CaCO3 Limestone Laayi
Ca
CaCO3 .MgCO3 Dolomite Do
Zn ZnCO3 Calamine Char
CuCO3 .Cu(OH)2 Malachite Masaledaar
Cu
CuCO3 .2Cu(OH)2 Azurite Aaloo
Pb PbCO3 Cerussite Ke
Fe FeCO3 Siderite Samose
Metallurgy: The process of extracting metals from their ores is called metallurgy.
Ore in
Enriched Pure
mining mineral metallurgical purification
mine Ore
enrichment
operation
Metal
Ore Metal
Processes of metallurgy:
(1) Crushing/grinding of the ore
(2) Concentration/enrichment of ore
(3) Extraction of metal from enriched ore
(4) Purification or refining of metal
(1) CRUSHING/GRINDING OF THE ORE:
Crushing: Crushing is done by Grinding: Grinding is done by using
crushers like jaw crusher, gyratory grinding mills like ball mill, rod mill etc.
crusher etc.
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(2) CONCENTRATION OR ENRICHMENT OF THE ORE
The removal of unwanted earthy and silicious impurities (i.e. gangue) from the ore is called
concentration or enrichment of ores.
The finely ground ore is concentrated by the following methods:
I. Hydraulic washing or Levigation or Gravity separation: The process by which lighter
earthy particles are freed from the heavier ore particles by washing with water is called
levigation. For this purpose, the ore is either agitated with water or washed with an upward
stream of running water. The lighter impurities are washed away while heavier ore
particles settle down.
This method is used when the ore particles are heavier than the earthy or rocky gangue or
vice versa particles.
II. Electromagnetic separation: This method of concentration is employed when either
the ore or the impurities associated with it are magnetic in nature.
For example,
Ore Magnetic Non magnetic
substance
chromite FeO.Cr2O3 = FeCr2O4 silicious gangue
magnetite Fe3O4 silicious gangue
pyrolusite MnO2 silicious gangue
TiO2 SnO2
Wolframite (Fe,Mn)WO4 SnO2
III. Froth floatation. This method is used for the concentration of sulphide ores such as
zinc blende (ZnS), copper pyrites ( CuFeS2 ), galena (PbS) etc.
This method is based upon the fact that the sulphide ore is preferentially wetted by oils while
that of gangue is preferentially wetted by water.
The ore is crushed into a fine powder and mixed with water to form a suspension in a tank
.To this suspension are added collectors (e.g. pine oil, xanthates, i.e., ethyl xanthate and
potassium ethyl xanthate, and fatty acids) which enhance the net wettability of the ore
particles and froth stabilizers (e.g., cresols and aniline) which stabilise froth.
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Procedure: The suspension is violently agitated by the rotating paddle which draws in air
causing frothing.During this process, the ore particles which are preferentially wetted by
the oil become lighter and thus rise to the surface along with the froth while the gangue
particles which are preferentially wetted by water become heavier and thus settle down at
the bottom of the tank. The froth is skimmed off. It is allowed to collapse and finally dried
to get the concentrated ore.
Ore containing two sulphides:
If the mineral to be concentrated consists of sulphides of two metals, then additional
reagents called froth depressants are used to prevent one type of sulphide ore particles
from forming the froth with air bubbles. For example, sodium cyanide is used as a
depressant to separate lead sulphide (PbS) ore from zinc sulphide (ZnS) ore. NaCN forms a
zinc complex, Na[Zn(CN)4 ] on the surface of ZnS thereby preventing it from the formation
of froth, under these conditions, only PbS forms a froth and hence separated from ZnS ore.
4NaCN + ZnS ⎯⎯
→ Na[Zn(CN)4 ] + NaS
Sod. tetracyanozincate(II)
Substance examples Comment
added
collectors pine oil, xanthates, i.e., ethyl Create froth
xanthate and potassium ethyl
xanthate, and fatty acids
froth stabilizers cresols and aniline stabilise froth
froth NaCN Prevent one sulphide to
depressants form froth
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VI. Leaching. This process consists in treating the powdered ore with a suitable reagent
(such as acids, bases or other chemicals) which can selectively dissolve the ore but not the
impurities.
(a) Leaching of bauxite. Pure alumina ( Al2O3 ) is obtained from the bauxite ore by Baeyer's
process. The bauxite ore usually contains impurities of iron oxide (Fe2O3), silica (SiO) and
titanium oxide (TiO2). The powdered ore is heated with a concentrated (45%) solution of
NaOH at 473–523 K and 35–36 bar pressure. Under these conditions, alumina ( Al2O3
dissolves forming sodium meta–aluminate and silica (SiO2) as sodium silicate, leaving
behind the impurities
473−523K
Al2O3(s) + 2NaOH(aq) + 3H2O(l) ⎯⎯⎯⎯ → 2Na[Al(OH)4 ](aq)
Alumina Sod. meta −aluminate
473−523K
SiO2(s) + 2NaOH(aq) ⎯⎯⎯⎯ → Na2SiO3(aq) + H2O(l)
Silica Sod. silicate
The resulting solution is filtered (to remove undissolved impurities), cooled and its pH
adjusted downward either by dilution or by neutralization with CO, when aluminium
hydroxide gets precipitated. Thereafter, the solution is seeded with freshly prepared
samples of hydrated alumina when hydrated alumina gets precipitated leaving sodium
silicate in the solution.
2Na[Al(OH)4 ](aq) + 2CO2(g) ⎯⎯
→ Al2O3 .xH2O(s) +2NaHCO3(aq)
Sod. meta −aluminate
Hydrated alumina, obtained as above, is filtered, washed and finally heated to about 1473
K to get pere alumina (Al2O3).
1473K
Al2O3 .xH2O(s) ⎯⎯⎯ → Al2O3(s) + xH2O(g)
(b) Leaching of silver and gold ores (Mac Arthur Forest cyanide process)
In this process, the finely powdered argentite or the native silver or gold is treated with a
dilute solution (0.5 %) of sodium or potassium cyanide while a current of air is con
indicusly passed. As a result, silver and gold get oxidised which then combine with CN−
ions forming their respective soluble conplex cyanides while the impurities remain
unaffected which are filtered off. Thus:
4M + 8CN− + 2H2O + O2 ⎯⎯
→ 4[M(CN)2 ]− + 4OH−
Soluble complex
(i) For silver, 4Ag + 8NaCN + 2H2O + O2 ⎯⎯
→ 4Na[Ag(CN)2 ] + 4NaOH
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If instead of native silver ore, silver glance or argentite (Ag2S) is used for leaching of silver,
the initial reaction forming the solubie silver complex is reversible. However, the current
of air used oxidises largely Na2S (formed in the reaction) to Na2SO4 thereby pushing the
equilibrium in the forward direction.
Ag2S + 4NaCN 2Na[Ag(CN)2 ] + Na2S
Sod. dicyanoargentate(I)
(Soluble complex)
4Na2S + 2H2O + 5O2(air) ⎯⎯
→ 2Na2SO4 + 4NaOH + 2S
(ii) For gold: 4Au + 8KCN + 2H2O + O2 ⎯⎯
→ 4K[Au(CN)2 ] + 4KOH
(soluble complex)
(3) EXTRACTION OF METAL FROM ENRICHED ORE
(a) Calcination and Roasting:
Calcination is a process in which the ore is heated, generally in absence of air or very
limited supply of air at a temperature below their melting points .The changes that carried
out in calcination are
(I) water is expelled out from a hydrated oxide
Al2O3 .2H2O ⎯⎯
→ Al2O3 + 2H2O
(II) Carbon dioxide from a carbonate ore. e.g.
PbCO3 ⎯→
⎯ PbO + CO2
ZnCO3 ⎯→
⎯ ZnO + CO2
CaCO3 ⎯⎯
→ CaO + CO2
(II) If the ore was concentrated by gravity separation then it contains moisture,
calcination removes it.
(IV) some impurities are removed as their oxides:
S8 + 8O2 ⎯⎯
→ 8SO2
P8 + 5O2 ⎯⎯
→ P4O10
Roasting is a process in which the ore (usually sulfide ore) alone or mixed with other
materials is heated usually in presence of air, at temperature below their melting points.
The changes that carried out in roasting are
2ZnS + 3O2 ⎯⎯
→ 2ZnO + 2SO2
CuS + 2O2 ⎯⎯
→ CuSO4
2CuFeS2 + 4O2 ⎯⎯
→ Cu2S + 2FeO + 3SO2
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Calcination proceeds only with expulsion of some small molecules like water, CO 2, SO2 etc.
without any chemical change while during roasting definite chemical changes like
oxidation, chlorination takes place. Calcination and roasting are generally carried out in
reverberatory furnace.
Flux
Gangues are generally substance that melts at high temperature, but when it mixed with
flux it form a low temperature fusible slag. i.e.
Gangue + Flux ⎯⎯
→ Slag
Fluxes are of the following two types:
(I)Acidic fluxes like silica, borax etc. These are used when the gangue is basic such as
lime or other metallic oxides like MnO, FeO, etc. The chemical reaction which takes place
in removing a basic gangue is as follows:
Ex, slag formation in the metallurgy of copper:
FeO + SiO2 ⎯⎯
→ FeSiO3
gangue flux slag
(ii) Basic fluxes like CaO, lime stone (CaCO3), magnesite (MgCO3), dolomite (CaCO3.MgCO3)
etc. These fluxes are used when the gangue is acidic like silica, P4O10 etc. For example
SiO2 + MgCO3 ⎯⎯
→ MgSiO3 + CO2
gangue flux slag
(b) Reduction to free metal
The calcined or roasted ore is then reduced to the metallic state in either of the following
ways.
(a) Smelting: The oxides of less electropositive metals like Pb, Zn, Fe, Cu, Sn etc are reduced
by strongly heating them with coke or coal. Reduction of oxide with carbon at high
temperature is known as smelting. Blast furnace is used in reduction of iron oxides while
reverberatory furnace in used in the reduction of tin oxide.
(b) Electrolytic reduction: Highly electropositive metals like Na, K, Al, Mg etc. are
extracted by electrolysis of their oxides, hydroxides or chlorides in fused state and the
metal is liberated at cathode. For example aluminum is obtained by electrolysis of alumina
mixed with cryolite which acts as an electrolyte. Oxides of highly electropositive metals
can't be reduced with carbon because such metals react with carbon to form carbide at high
temperature.
(c) Reduction by aluminium (alumino–thermite process): Certain oxides like Cr2O3,
V2O5, Mn3O4 are not satisfactory reduced by carbon. In such cases, Al is used as a reducing
agent. Alumino thermite reaction:
4Al + 3O2 ⎯⎯
→ 2Al2O3 + large amount of heat
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Cr2O3 + 2Al ⎯⎯
→ Al2O3 + 2Cr
3V2O5 + 10Al ⎯⎯
→5Al2O3 + 6V
Apart from this, reduction can also take place by precipitation and air. The former is
known as hydrometallurgy and the latter is auto reduction.
(d) Hydrometallurgy: The processing of ore of metal in their aqueous solution is known
hydrometallurgy.
→[Zn(CN)4 ]2− + 2Au
2[Au(CN)2 ]− + Zn(aq) ⎯⎯
(4) PURIFICATION OR REFINING OF METAL
All above processes of reduction give metals which are not totally pure. But in some cases
we need metals of nearly cent percent purity. That may be achieved in either of the
following ways depending on the metal.
(I) Oxidation process (Bessemerisation, cupellation, poling)
(a) Bessemerisation:The blowing of air through the molten pig iron introduces oxygen
into the melt which results in oxidation, removing impurities found in the pig iron, such
as silicon, manganese, and carbon in the form of oxides. These oxides either escape as gas
or form a solid slag.
(b) Cupellation: Cupellation is a refining
rocess in metallurgy,where ores or alloyed metals are treated under very high
temperatures and have controlled operations to separate noble metals,
like gold and silver, from base metals like lead, copper, zinc, arsenic, antimony or bismuth,
present in the ore. The process is based on the principle that precious metals do
not oxidise or react chemically, unlike the base metals; so when they are heated at high
temperatures, the precious metals remain apart and the others react forming slags or
other compounds.
Ag(s) + 2Pb(s) + O2(g) ⎯⎯
→ 2PbO + Ag(l)
(c) Poling: Poling is a metallurgical method which is generally employed in the
purification of copper and tin.
For Copper:
The impure metal, usually in the form of molten blister copper, is placed in an furnace for
two stages of refining.
First stage: In the first stage, sulphur and iron sulphide are removed by gently blowing
air through the molten metal to form iron oxides and sulfur dioxide. The iron oxides is
removed as it floats over the copper and the gaseous sulfur dioxide exits the furnace via
the off–gas system.
Second stage: Once the first oxidation stage is complete, the second stage
(reduction or poling) begins. This involves using a reducing agent, normally natural
gas or diesel (but ammonia, liquid petroleum gas, and naphtha can also be used), to react
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with the oxygen in the copper oxide to form copper metal. In the past, freshly cut
("green") trees were used as wooden poles. The sap in these poles acted as the reducing
agent. It was the use of these poles gave rise to the term "poling."
(II) Electro–refining: In this method, the impure metal is converted into a block which
forms the anode while cathode is a rod or plate of pure metal. These electrodes are
suspended in an electrolyte which is the solution of a soluble salt of the metal usually a
double salt of the metal. When electric current is passed, metal ions from the electrolyte are
deposited at the cathode in the form of pure metal while an equivalent amount of metal
dissolves from the anode and goes into the electrolyte solution as metal ion. The soluble
impurities present in the crude metal anode go into the solution while the insoluble
impurities settle down below the anode as anode mud.
Impure Cu=Cu+ Impurities (Ag, Au, Fe, Zn, Pb etc)
(III) Vapour phase refining
(a)Van–Arkel Method: In this method, the metal is converted into its volatile compound
such as iodide leaving behind the impurities. The compound thus formed is decomposed to
get the pure metal. Metals like Ti, Zr, Hf, V, Th etc. are purified by this method.
300 C 1400 C
Ti(s) + 2I2(s) ⎯⎯⎯ → TiI4(g) ⎯⎯⎯→ 2I2(g) + Ti(s)
Pure
(b) Mond process: Used for the purification of Ni.
100 C 200 C
Ni(s) + 4CO ⎯⎯⎯ → Ni(CO)4 ⎯⎯⎯ → Ni + 4CO
(IV) Zone refining or Fractional crystallization: This method is employed for preparing
extremely pure metals. This method is based upon the principle that when a molten impure
metal is allowed to cool, the pure metal crystallizes leaving behind the impurities in the
melt or impurities are more soluble in molten state than solid state. Semiconductors like
silicon, germenium and gallium are purified by this method.
Metallurgy of Iron:
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Alloys
An alloy is a combination of metals or of a metal and another element. Alloys are used in a
wide variety of applications. In some cases, a combination of metals may reduce the
overall cost of the material while preserving important properties.
Alloy of aluminium:
Alloy Composition Important Uses
properties
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1. Aluminium Al 95%, Cu 5% Light strong alloy Coins, utensils,
bronze with golden jewellery, picture
lustre, resistant frames, etc.
to corrosion
2. Magnalium Al 95% Mg 5% Light, tough and Light
strong instruments,
balance beams,
pressure cookers,
etc
3. Duralumin Al 95% Cu 4% Light, tough, Making
Mg 0.5% Mn ductile, resistant aeroplanes, .
0.5% to corrosive automobile parts,
action pressure cookers,
etc.
Alloy of copper:
Alloy Composition Uses
1. Brass Cu 60%, Zn 40% For making utensils,
condenser tubes, wires parts
of machinery, etc.
2. Bronze Cu 80%, Zn 10%, Sn 10%. For making cooking utensils,
statues, coins etc,
3. German silver Cu 25–30%, Zn 25–30%, For making silver wires,
Ni 40–50% resistance wires,
Alloy of Iron:
Alloy Composition Important Uses
properties
11
1. Stainless Fe 73%, Cr 18%, Resistant to cycles,
steel Ni 8% and carbon– corrosion automobiles,
1% pens,
2. Nickel steel Fe 96–98%, Ni 2–4% Resistant to For making
corrosion hard cables, –
and elastic automobiles and
aeroplane parts.
3. Chrome Fe 96–98%, Cr 2–4% High tensile For making axles,
steel strength ball .. bearings,
cutting tools and
crushing
machines.
4. Invar Fe 64%, Ni 36% Practically 'no For making
coefficient of watches, meter
expansion i scales,
penduluin rods,
etc.
5. Alnico Fe 60%, Al 12%, Ni Highly magnetic For making
20%, Co 8% permanent
magnets
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EXTRACTION OF ALUMINIUM
Aluminium Ore Al2O3 .2H2O
(Bauxite)
REFINING OF BAUXITE
Bayer’s Process:
roasted
Bauxite Ore ⎯⎯⎯→ to convert FeO to Fe2O3
150 C
Roasted Ore + NaOH solution ⎯⎯⎯→ NaAlO2
Hydrolysis in presence
⎯⎯⎯⎯⎯⎯⎯⎯
of little Al(OH)
→ Al(OH)3 +NaOH
3
ppt.
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