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Ores and Metallurgy

 Metals like Au, Ag, Cu, Pt occur in nature in the free state
The S.R.Ps of such metals are always positive; while the S.R.Ps of active metals are
negative.
Au+3  Au, E = +1.5 Zn+2  Zn, E = –0.76
Ag  Ag, E = +0.80
+ Al+3  Al, E = –1.66
 Naturally occurring sources of metals like oxides, carbonates, silicates, sulphides etc.,
are called minerals
 A mineral from which a metal can be extracted profitably is called an ore.
 An ore is a mineral but a mineral may not be an ore

Element Ores
Cu Copper Pyrites: CuFeS2 (Chalcopyrites)  metallic lustre, more copper
coloured.
Malachite: Cu (OH)2. CuCO3 →basic copper carbonate, green in colour.
Copper glance / chalcocite: Cu2S  dark grey
Cuprite: Cu2O→ ruby red coloured
Turauoise: Cu Al6(PO4)4 (OH)8 .4H2O  popular gemstone because of blue
color.
Zn Zinc blende (Europe) / Sphaelerite (USA) : ZnS
Smithsonite (USA) / Calamine (Europe) : ZnCO3
Hemimorphite : Zn4(OH)2 Si2O7 H2O
Zincite: ZnO
Ag Argentite or silner glance: Ag2S
Horn silver : AgCl
pyrargyrite / ruby silver: 3 Ag2S. Sb2S3
Sn Cassiterite / tinstone: SnO2
Pb Galena: PbS
Cerussite: PbCO3
Anglerite: PbSO4
Fe Haematite: Fe2O3
Magnetite: Fe3O4
Limonite: Fe2O3.3H2O
Siderite: FeCO3
Iron pyrites: FeS2

METALLURGY
The metallurgy of a metal involves three main operations:
(1) Concentration or dressing
(2) Reduction
(3) Purification or refining
(1) First operation – Concentration or dressing of ores: The undersired impurities present in
ores are called Gangue or Matrix. The removal of these impurities from the ores is known as
concentration. The concentration is done by physical as well as chemical methods.

PHYSICAL METHODS
(a) Gravity separation: Generally, oxide and carbonate ores are concentrated by this method. For
example, tin ore (cassiterite) and iron ore (haematite) are concentrated by gravity method.
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(b) Electromagnetic separation: When one component either the ore or impurity is magnetic in
nature, this method can be used for separation. For example, wolframite (FeWO4) a magnetic
ore, is separated from the non-magnetic ore, cassiterite SnO2, by this method.
(c) Froth floatation process: This method is used for the concentration of sulphide ores. The method
is based on the preferential wetting properties with the frothing agent and water. With this
method, it is possible to concentrate the dense ores such as galena and zinc blende.

CHEMICAL METHODS

(a) Calcination: It involves heating of the ore below its fusion temperature in absence of air.It
removes moisture and carbon dioxide.
Example: Al2O3 . 2H2O  Al2O3 + 2H2O
2Fe2O3 . 3H2O  2Fe2O3 + 6H2O
Ca CO3  CaO + CO2
CuCO3 . Cu(OH)2  2CuO + CO2 + H2O
Calcination makes the ore porous. The step is generally performed in reverberatory furnace.

(b) Roasting: It is also heating of the ore either alone or with some other material usually in presence
of air below its fusion temperature. Roasting is generally done in a reverberatory furnace or in
a blast furnace. In roasting definite chemical changes like oxidation, chlorination, ets., take
place while in calcinations there occurs only expulsion of organic matter, water, carbon
dioxide, etc., i.e., it does not involve any major chemical change.

Types:
(i) Oxidising roasting: This type of roasting is generally applied in ores of lead, zinc, nickel, copper,
etc.
S + O2  SO2
4As + 3O2  2As2O3
2ZnS + 3O2  2ZnO + 2SO2
2PbS + 3O2  2PbO + 2SO2
2Cu2S + 3O2  2Cu2O + 2SO2
(ii) Partial oxidizing or Sulphating roasting: In this type,a part of sulphide ore is oxidized to
sulphate and the rest is converted into oxide.
2PbS + 3O2  2PbO + 2SO2
PbS + 2O2  PbSO4

(iii) Chlorinating roasting: This type of roasting is done in the case of silver ore. The ore, argentite is
mixed with common salt and the mixture is heated in the presence of air.
Ag2S + 2NaCl  2AgCl + Na2S

(c) Leaching: It involves the treatment of the ore with a suitable reagent as to make it soluble while
impurities remain insoluble. For example, bauxite ore contains ferric oxide, titanium oxide and
silica as impurities. When the powdered ore is digested with an aqueous solution of sodium
hydroxide at about 150C under pressure, the alumina (Al2O3) dissolves forming soluble
sodium meta-aluminate while ferric oxide (Fe2O3), TiO2 and silica remain as insoluble part.
Al2O3 + 2NaOH  2Na AlO2 + H2O
Pure alumina is recovered from the filtrate.
NaAlO2 + 2H2O  Al(OH)3 + NaOH
2Al (OH)3 
Ignited
(autoclave)
 Al2O3 + 3H2O
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Gold and silver are also extracted from their native ores by leaching (Mac – Arthur Forrest
cyanide process). Both silver and gold particles dissolve in dilute solution of sodium cyanide
is presence of oxygen of the air forming complex cyanides.
4Ag + 8NaCN + 2H2O + O2  4NaAg(CN)2 + 4NaOH
Sod. argentocyanide

4Au + 8NaCN + 2H2O + O2  4NaAu(CN)2 + 4NaOH

Sod. aurocyanide

Ag or Au is recovered from the solution by the addition of electropositive metal like zinc.
2NaAg(CN)2 + Zn  Na2Zn (CN)4 + 2ag 
2NaAu(CN)2 + Zn  Na2 Zn(CN)4 + 2Au 
Soluble complex

2. SECOND OPERATION – Reduction to free metal:

(a) Smelting: This involves the reduction of the ore to the molten metal at a high temperature. For the
extraction of less electropositive metals such as Pb, Zn, Fe, Sn, etc., powerful reducing
agents such as C, H2, CO, water gas, Na, K, Mg, Al may be used.
WO3 + 3H2  W + 3H2O
CuO + CO  Cu + CO2
BeCl2 + 2Na  Be + 2NaCl
CaI2 + 2K  Ca + 2KI
TiCl4 + 4Na  Ti + 4NaCl
TiCl4 + 2Mg  Ti + 2MgCl2
Cr2O3 + 2Al  2Cr + Al2O3
PbO + C  Pb + CO
(i) Carbon reduction process: Oxides of less electropositive metals are strongly heated with coal or
coke
PbO + C  Pb + CO
PbO + CO  Pb + CO2
Similarly, Fe2O3 + 3C  2Fe + 3CO
Fe2O3 + 3CO  2Fe + 3CO2
SnO2 + 2C  Sn + 2CO
The ores, even after concentration, contain some gangue. To remove gangue, certain
substances are mixed with concentrated ore which combine with gangue to form fusible
material which is not soluble in molten metal. The substances used are called fluxes and the
fusible material formed during reduction process is called slag. Slag is usually lighter and
floats on the surface of the molten metal.
(ii) Reduction by aluminium (Gold-schmidt aluminothermic process):
A mixture of concentrated oxide ore and aluminium powder, commonly called as thermite, is
taken in a steel crucible placed in a bed of sand. The reaction is started by the use of an
iginition mixture containing magnesium powder and barium peroxide.
Cr2O3 + 2Al  2Cr + Al2O3
3Mn3O4 + 8Al  9Mn + 4Al2O3
(b) Self reduction process: This process is also called autoreduction process or air reduction
process. The sulphide ores of less electropositive metals like Hg, Pb, Cu, etc., are heated in
air as to convert part of the ore into oxide or sulphate which then reacts with the remaining
sulphide ore to give the metal and sulphur dioxide.
2Hg + 3O2  2HgO + 2SO2 Extraction of Hg
2HgO + HgS  3Hg + SO2 from cinnabar ore
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2Cu2S + 3O2  2Cu2O + 2SO2 Extraction of Cu

Cu2S + 2Cu2O  6Cu + SO2 from copper glance
2PbS + 3O2  2PbO + 2SO2 Extraction of lead
2PbO + PbS  3Pb + SO2 from galena ore

(c) Electrolytic reduction: The oxides of the highly electropositive metals like Na, K, Mg, Ca, Al, etc.,
cannot be reduced easily with carbon at moderate temperatures. For reduction, a very high
temperature is required at which the metal may combine with carbon to form a carbide. These
metals are thus extracted by the electrolysis of their oxides, hydroxides or chlorides in fused
state. Sodium is obtained by the electrolysis of fused mixture of NaCl and CaCl2 (Down’s
process) or by electrolysis of fused sodium hydroxide (Castner’s process). Aluminium is
obtained by the electrolysis of alumina mixed with cryolite.

(d) Hydrometallurgy: This process is based on the fact that more electropositive metal can displace
less electropositive metal from its salt solution.

(i) Extraction of copper: Malachite ore is first roasted.

CuCO3 . Cu(OH)2  2CuO + H2O + CO2
Copper oxide obtained is dissolved in sulphuric acid.
CuO + H2SO4  CuSO4 + H2O
(Soluble)

CuSO4 + Fe  Cu FeSO4

ppt. Soluble

(ii) Extraction of silver: The ore is dissolved in sodium cyanide solution.

Ag2S + 4NaCN  2NaAg(CN)2 + Na2S
By the addition of zinc turnings, Ag is precipitated
2NaAg(CN)2 + Zn  Na2 Zn(CN)4  2Ag
Soluble ppt.

3. Third operation – Refining or Purification:

(a) Liquation Process: This process based on the difference in fusibility of the metal and impurities.
When the impurities are less fusible than the metal itself, this process is employed. This
method is used to purify the metals like Bi, Sn, Pb, Hg, etc.,
(b) Distillation: This process is used for those metals which are easily volatile. This is used for the
purification of Zn, Cd, Hg, etc.
(c) Electrolytic refining of metals: Copper, silver, gold, aluminium, lead, etc., are purified by this
method. The impure metal is made anode while a thin sheet of pure metal acts as a cathode.
The electrolytic solution consists of generally an aqueous solution of a salt or a complex of
the metal. On passing the current pure metal is deposited on cathode.
(i) Purification of copper: Impuremetal – Anode, Thin sheets of copper – Cathode. Electrolyte – An
aqueous solution of copper sulphate containing H2SO4.
(ii) Purification of silver: Impure metal – Anode, A thin sheet of pure silver – Cathode. Electrolyte –
An aqueous solution of AgNO3 containing HNO3.
(iii) Purification of lead: Impure metal – Anode, A sheet of pure lead – Cathode. Electrolyte – A
solution of lead silico fluoride PbSiF6 containing 8–10% of H2SiF6.
(d) Special Methods:
(i) Mond’s process: Nickel is purified by this method. Impure nickel is treated with carbon monoxide
at 60–80C when volatile compound, nickel carbonyl, is formed. Nickel carbonyl decomposes
at 180C to form pure nickel and carbon monoxide which can again be used.
(ii) Van Arkel process: This method is generally applied for obtaining ultrapure metals. Ti, Zr, Hf, Si,
etc., have been refined by this method.
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Impure metal + I2  Metal iodide 

Heating
Tungsten
 Metal I2
Vapours Pure
filament

Ti(s) + 2I2(g) 523K

 TiI4 (g)
TiI4(g) 
1700K
 Ti + 2I2(g)

(iii) Zone refining or Fractional crystallization: Elements such as Si, Ge, Ga, etc., which are used
as semiconductors are refined by this method. The method is based on the difference in
solubility of impurities in molten and solid state of the metal.

N.B: Parke’s process: This process involves the extraction of silver from argentiferrous lead, i.e.,
lead containing silver as impurity. This method is based on solubility of Ag in molten Zn. When
argentiferrous lead is stirred with molten Zn, Ag passes into Zn layer and lead forms a separate layer.
The layers are separated and Zn layer is subjected to distillation. Zn being more volatile distills off
leaving behind Ag.