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CHAPTER GENERAL PRINCIPLES AND PROCESSES
00 OF ISOLATION OF ELEMENTS
At present there are 118 known chemical elements. 78% of the elements known
so far are metals. A few elements like C, S, Au and noble gases occur in free state while
others in compound form in the earths crust. Elements with atomic number above 94
are prepared by bombardment reactions.
Abundance of elements in the earth’s crust:
O Si Al Fe Ca Na K Mg Ti H.............
Mode of occurance of metals
Unreactive metals are usually found in the native (free) form. They are placed below
hydrogen in the activity series. Reactive metals are always found in the combined form
(Minerals and Ores). They are placed above hydrogen in the activity series.
Minerals : - The compounds of metals occur in nature are called minerals
Ores : - The minerals from which metals can be conveniently and economically ex-
tracted are called ores. While all ores are minerals but all minerals are not ores.
Ores may be devided into the following types.
Oxides
Haematite (Fe2O3) Magnetite (Fe3O4), Limonite (Fe2O33H2O)
Bauxite (Al2O32H2O), Corundum (Al2O3) Diaspore (Al2O3H2O)
Cuprite or Ruby copper (Cu2O), cassiterite or Tinstone (SnO2)
Zincite (ZnO), Pyrolusite (MnO2), Rutile (TiO2), Illmenite (FeO.TiO2)
Sulphides
Iron pyrites (FeS2), Copper pyrites (CuFeS2)
Copper glance (Cu2S), Zinc blende or Sphalerite (ZnS)
Galena (PbS), Cinnabar (HgS), Silver glance (Ag2S)
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Carbonates
Magnesite (MgCO3), Dolomite (CaCO3.MgCO3) Siderite (FeCO3)
Malachite [(CuCO3 Cu(OH)2] Azurite [2CuCO3 .Cu (OH)2], Calamine (ZnCO3)
Halides
Common salt or Rock salt (NaCl), Sylvine (KCl) Carnallite (KCl.MgCl26H2O), Cryolite
(Na3AlF6) Fluospar (CaF2), Horn silver (AgCl).
Sulphates
Gypsum (CaSO4.2H2O) Epsom salt MgSO4 ,7H 2O Barytes BaSO4 , Anglesite
PbSO4
Silicates
Asbestos CaMg3 SiO3 4 , Talc Mg 2 Si 2 O5 2 Mg OH 2 , Willemite Zn 2SiO 4 ,
Feldspar KAlSi3O8 Mica K2O 3Al2O3 6SiO2 2H2O , Kaolinite Al2O3 2SiO2 2H 2O
Phosphates
Phosphorite Ca 3 PO 4 2
Monazite sand (Orthophosphates of Lanthanides)
Metallurgy : The earthy impurities present in metal compounds are known as ganue or
matrix.
The entire scientific and technological process used for isolation of the metal from its
ores is known as metallurgy.
Different steps involved in metallurgy are
(i) Concentration or dressing of ore
(ii) Isolation of the metal from its concentrated ore
(iii) Purification or refining of the metal.
Physical methods of ore dressing
1. Levigation or gravity separation
This is based on the differences in gravities of the ore and the gangue particles. In one
such process, an upward stream of running water is used to wash the powdered ore.
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The lighter gangue particles are washed away and the hearies ore are left behind.
Wilfley table and hydraulic classifier are used in gravity separation
Carbonate and oxide ores are concentrated by this method Ex: SnO2, Fe2O3, FeO.Cr2O3
etc.
2. Froth flotation process :
Sulphide ores are concentrated by this method. It is based on different welting tenden-
cies of ores and gangue. This method is effective when surface of ore particles is hy-
drophobic while those of gangue particles hydrophilic. The function of different sub-
stances added here are as follows.
a) Frothers - Make froth Ex. Pine oil, Eucalyptus oil, fatty acids etc.
b) Stabilizers - Stabilizes froth formed Ex: Aniline, Cresols etc.
c) Collectors - Surface of collectors adsorb ore particles over it so that the oil
wettability of ore particles is improved
Ex.Ethyl xanthate, potassium ethyl xanthate etc.
Sometimes this method can be used for the separation of two sulphide ores using
depresents and activators.
Depresents : Substances which will reduce foaming capacity of a substance. Ex. NaCN,
KCN, Na2CO3 etc. Ore containing Zns and Pbs can be separated using the depresent
NaCN. It prevents ZnS from coming to froth.
Activators : Substances promotes foaming tendency. Ex. CuSO4. A mixture of galena
(Pbs) and sphalerite (znS) can be effectively separated by this method. A coating of
CuS is formed over ZnS and improve its floating characteristics.
3. Magnetic separation
When either ore or gangue is ferromagnetic, this method is employed.
Ex. Mixture of Wolframite (FeO.WO3 - Magnetic) and cassiterite (SnO2) - non mag-
netic). Some other ferromanetic ores are chromite ore (FeO.Cr2O3) Magnetite (Fe3O4),
Pyrolusite (MnO2), Illmenite, Rutile etc.
4. Electrostatic separation
The difference in electrical conductivities of ore and gangue is made use. Ex. Mixture of
Pbs and ZnS, Pbs is charged immediately in an electrostatic field and is thrown away
from the roller from ZnS which is not charged and hence drops vertically from the roller.
5. Liquation
Ores having low m.p than gangue are concentrated by this method
Ex. Stibnite (Sb2S3) ore of antimony
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Chemical methods of ore concentration
Leaching
Difference in the solubilities of ore and gangue in a given solvent is made use.
Ex. Extraction of pure alumina (Al2O3) from bauxite. Bauxite contains SiO2, FeO, TiO2
etc as impurities.
(i) Baeyer’s method Powdered bauxite is treated with a concentrated solution of NaOH
at 473 - 523 K and 35 - 36 bar pressure. Al2O3 is leached out as sodium aluminate,
leaving the impurities behind.
2Na Al OH 4 aqu
Al2O3 2NaH 3H 2O
The aluminate in solution is neutralised by passing CO2 gas and hydrated alumina is
precipitated 2Na Al OH 4 aqu 2CO2 g
Al2O3 xH 2O S 2NaHCO3
The sodium silicate remains in the solution and hydrated alumina is filtered , dried and
ignited to give back pure alumina
1470 K
Al 2O3 xH 2O
Al2 O3 x H 2 O
(ii) Hall’s process: Used for red bauxite containing Fe2O3 as major impurity
Fuse
Al 2 O 3 2H 2 O Na 2 CO 3
2NaAlO 2 CO 2 2H 2 O
2Al OH 3 Na 2 CO3
2NaAlO 2 3H 2 O CO 2
2Al OH 3
1473 K
Al2 O3 3H 2O
(iii) Serpeck’s process
For white bauxite containing silica as major impurity
2100K
Al2O3 2H 2 O 3C N 2 2AlN 3CO 2H 2O
Electric furnace
Al OH 3 NH 3
AlN 3H 2 O
SiO 2 2CO
2CO 2 Si
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Silicon volatilise at the temperature
2Al OH 3 Al2O3 3H2O
1473k
In the metallurgy of silver and gold, the respective metal is leached with a dilute solution
of NaCN or KCN in the presence of air (For O2) from which the metal is obtained later
by replacement reaction.
Extraction of crude metal from concentrated ore
The concentrated ore must be converted into a form which is suitable for reduction.
Usually the sulphide ore is converted to oxide before reduction. Oxides are easier to
reduce. Thus isolation of metals from concentrated ore involves two major steps.
a) conversion to oxide
b) reduction of the oxide to metal
Conversion to oxide
(i) Calcination : It involves strong heating of the ore, in the absence of air below its m.p
in a reverberatory furnace. Oxygen is not used up in this process. H 2 O / CO 2 or both
are getting removed and the product becomes process. Applied to carbonates, hy-
droxides and hydrated oxides.
CaCO3 MgCO3 S
CaO S MgO S 2CO 2 g
2Al OH 3
Al2O3 3H 2 O
Al 2O3 2H 2O
Al2O3 2H 2O
(ii) Roasting: Is the process of strong heating in excess of air below m.p in a reverbera-
tory furnace. Oxygen is used up in this process. Mainly applied to sulphide ores since
G of is very high. The impurities like organic matter, sulphur and Arsenic are removed
by roasting in the form of their volatile oxides ie CO 2 H 2O , SO 2 and As 2O3 respec-
tively.
Roasting is of four different types.
a) Oxidising : S O 2
SO 2
P4 5O 2
2P2O5
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2ZnS 3O 2
2ZnO 2SO 2
2Cu 2S 3O 2
2Cu 2O 2SO 2
b) Partial oxidising (sulphating)
PbS 2O 2
PbSO 4
ZnS 2O 2
2nSO 4
c) Reducing (self reduction)
It is applied to ores of Hg, Cu, Pb etc
2Pbs 3O 2
2PbO 2SO 2
PbS 2PbO
3Pb SO 2
d) Chloradised roasting
TiC 4Cl 2
TiCl4 CCl4
Aq 2S 2NaCl
2AgCl Na 2S
Slagging or smelting
None fusible impurities are removed by this method
The concentrated ore is melted by heating with an external substance called flux so that
it will combine with the gangue to form an easily fusible material called slag.
Flux gangue
slag
If the impurity is acidic SiO 2 - basic flux (CaO, MnO) is used
If the gangue is basic (MnO, FeO) - acid flux (SiO2, P2O5) is used
Smelling is the process of extraction of a metal from its roasted / calcined ore by heat-
ing it with powdered Coke in presence of a flux.
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Reduction of oxide to the metal
Reduction of the metal oxide usually involves heating it with some other substance act-
ing as a reducing agent (C, CO, H2, metals like Na, Mg, Al etc can be used)
The reducing agent combines with the oxygen of the metal oxide.
ZnO C
Zn CO
Fe 2 O3 3CO
2Fe 3CO 2
WO3 3H 2
W 3H 2O
ICI process
TiCl4 4Na
Ti 4NaCl
Atmosphereof Ar
Kroll process
TiCl4 2Mg
Ti 2MgCl2
12731423 K
Alumino thermite process
The metal oxides having very high m.p’s can be reduced by thermite reduction method
using aluminimum powder. Ex. Oxides of Cr, Mn, Ti, Mo, Fe, etc
Cr2 O3 s 2Al s
2Cr Al2O3 s
Fe 2 O3 s 2Al s
2Fe Al2 O3 s
These reactions are highly exothermic hence the metal is obtained in the molten form.
The thermite mixture contains the oxide and Al powder in the ratio 3 : 1. The ignition
mixture contains Mg powder and an oxidising agent likes BaO2 / KClO3
Thermal decomposition :Some of the metal oxides are thermally unstable and thermal
decomposition gives the metal.
573 K 673 K
Ex. Ag 2O 2Ag ½O 2 ; HgO Hg ½O 2
Thermodynamic Principles of Metallurgy
For a spontaneous reaction, the free energy change G must be negative
ie, G H TS
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Consider a reaction such as the formation of an oxide from a metal
2xM s O2 g
2M x O s
Dioxygen is used up in this reaction. Gases have a higher entropy than liquids or solids.
In this reaction S decreases and hence S is negative. Thus if the temperature is raised
then TS becomes more ve . Thus the free energy change increases with an increase
of temperature.
The free energy changes that occur when one gram molecule of a common reactant (in
this case O2) is used may be plotted graphically against temperature for a number of
reactions of metals to their oxides. These graphs are called Ellingham diagram (for
oxides). Similar diagrams can be plotted for sulphides and halides. The Ellingham dia-
gram for oxides shows several important features.
1) The graph for metal to metal oxide all slope upwards because the free energy change
increases with an increase of temperature.
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2) All the free energy changes follow a straight line unless the material melt or vaporise,
when there is a large change in entropy associated with the change of state, which
changes the slope of the line.
Ex. Hg - HgO line changes slope at 629 K when Hg boils similarly Mg - MgO line changes
slope at 1393 k when Mg boils.
3) When the temperature is raised, a point will be reached where the graph crosses the
G 0 line. Below this temperature the free energy of formation of the oxide is nega-
tive, so the oxide is stable. Above this temperature, the G of formation of the oxide ie
+ve, the oxide becomes unstable and should decompose into the metal and dioxygen.
In practice the metals Ag, Au and Hg can be easily extracted by thermal decomposition
of their oxides.
4) Any metal will reduce the oxide of other metals which lie above it in the Ellingham
diagram because the free energy will become more –ve by an amount equal to the
difference between the two graphs at that particular temperature. Thus Al reduces ox-
ides of Fe, Cr, Ti in the well known thermite reduction, but Al will not reduce MgO at a
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temperature below 1773 K.
In case of carbon combining with oxygen, two reactions are possible
C s O g
CO 2 g ; C s ½O 2 g
CO g
In the first reaction the volume of CO2 produced is the same as the volume of O2 used.
So the change in entropy is very small and G hardly changes with temperature. Thus
the graph of G against T is almost horizontal.
The second reaction produces two volumes of CO for every one volume of O2 used.
Thus S is +ve and hence G becomes increasingly –ve as T increases. Conse-
quently the line on the Ellingham diagram slops down words. The two lines of
C CO 2 and C CO cross at about 983 K Below this temperature, the reaction to
form CO2 is energetically more favourable, but above 983 K the formation of CO is
prefered. Below 983 K, CO is a more effective reducing agent than carbon. Above 983
K, carbon is a better reducing agent than CO.
Carbon is extensively used to reduce iron oxide in the extruction of iron, but it may also
be used to reduce any of the other oxides above it on the Ellingham diagram. Since the
G line slops downwords it will eventually cross and lie below all the other graphs for
metal / metal oxide. Thus in principle carbon could be used to reduce any metal oxide if
a sufficiently high temperature were used.
Limitations of Ellingham diagram.
(i) It does not say about kinetics of reduction process
(ii) It does not tell us about activation temerature
(iii) It cannot predct reversibility of reduction reaction at certain temperature
(iv) It does not say about possibility of reaction between metal formed and reducer
used at high temperature.
Extraction of some metals
1. Extraction of Iron from its oxides
Oxide ores of iron, after concentration through calcination / roasting are mixed with lime
stone and coke and fed into a blast furnace from is top. Blast furnace is a tall tower
about 100 feet height, 25 ft diameter at wider part, lined inside with fire clay bricks. In
the furnace the oxide is reduced to the metal. One on the main reduction steps in this
process is
FeO s
Fe s / Co g _____ 1
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It can be seen as a couple of two simpler reaction. In one, the reduction of FeO is taking
place and in the other, C is being oxidised to CO
FeO s
Fe s ½O 2 g G FeO, Fe ___ 2
C s ½O2 g
CO g G C, CO ___ 3
When both the reactions take place to yield the equation (1), the net Gibb’s energy
change becomes
G C, CO G FeO, Fe r G _____ 4
Naturally the resultant reaction will take place when the right hand side in equation (4) is
negative.
In G o Vs T plot representing reaction (2) the line goes upword and that representing
the change C
CO goes down word. At temperature above 1073 K (approximately),
the C CO line come below the Fe FeO line G C, CO G Fe, FeO so in
this range, coke will be reducing the FeO and will it self be oxidised to CO. In a similar
way the reduction of Fe3O4 and Fe2O3 at relatively lower temperature by CO can be
explained on the basis of lower lying points of interseciton of their curves with the CO,
CO2 curve in the figure.
In the blast furnace, reduction of iron oxide takes place in different temperature ranges.
Hot air is blown from the bottom of the furnace and coke is burnt to give temperature
upto about 2200 K in the lower portion. The CO and heat move to upper part of the
furnace. In the upper part, the temperature is lower and the iron oxides
Fe2O3 and Fe3O4 coming from the top are reduced in steps to FeO. Thus the reduc-
tion reactions taking place in the lower temperature range and in the higher tempera-
ture range, depends on the points of corresponding intersections in the r G o Vs T
plots. These reactions can be summarised as follows.
(i) Zone of reduction - In the upper part of the furnace the temperature is between 500 -
900K. Here the ores are reduced to Fe by CO
573673K
3Fe 2O3 s CO g
2Fe3O 4 s CO 2 g
773873 K
Fe3O 4 s 4CO g
3Fe s 4CO 2 g
773873 K
Fe 2 O3 s CO g
2FeO s CO 2 g
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In the middle part of the furnace, the temperature is between 900 - 1500 K. At tempera-
ture above 1073 K, reduction of FeO formed in the upper part of the furnace occurs.
1073 K
FeO s C s Fe s / CO g
Further, direct reduciton of iron ores (ie haematite, magnetite etc), left unreduced around
873 K, to iron by carbon occurs above 1073 K
1073 K
Fe 2 O3 s 3C s 2Fe s / e 3CO g
(ii) Zone of slag formation :
In the middle portion of the furnace the temperature is around 1123 K. In this region lime
stone decomposes to form CaO, CO2. CaO acts as flux and combines with silica (im-
purity) to form fusible CaSiO3 slag.
CaCO3 s
1123 k
CaO s CO 2 g H 179.9 k J
1123 k
CaO s SiO 2 s
C aSiO3 s
slag
(iii) Zone of heat absorption. This is the lower part of the furnace and the temperature here
is between 1423 - 1673 K. As CO2 and heat produced at the bottom moves up it meets
the descending charge. The coke present in the charge reduce CO2 to CO
CO 2 g C s
2CO g : H 163.2 K J
Since this reaction is endothermic the temperature falls to 1423 K.
(iv) Zone of combustion : Near the bottom, coke burns to form CO2
C s O 2 g
CO 2 g ; G 393.3 K J
Since the reaction is exothermic the temperature here rises to around 2200 K.
(v) Zone of fusion : In the lower part of the furnace, temperature is between 1423 - 1673 K.
In this region, spongy iron melts and dissolves some C, S, P, Se, Mn etc. CaSio3 slag
also melts in this region. Molten slag and molten iron from two separate layers which
are periodically tapped off.
Commercial forms of Iron
(a) Pig Iron : The iron obtained from blast furnace contains about 4% carbon and many
impurities in traces like S, P, Si, Mn etc. This is known as pig iron and cast into variety
of shapes M.P 1473 K.
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Cast iron is different from pig iron and is made by melting pig iron with scrap iron and
coke using hot air blast. Carbon content is about 3%. It is extremely hard and brittle.
(b) Wrought iron malleable iron : It is the puerst form of iron, contains 0.2 to 0.5% carbon
and traces of P and Si. M.P 1673 K prepared from cast iron by oxidising impurities. in
a reverberatory furnace (called puddling furnace) lined with haematite. Haematite
oxidises C to CO, S to SO2, Si to SiO2, P to P4O10 and Mn to MnO. CO and SO2 escape
whereas MnO and SiO2 combine to form slag.
Wrought iron is resistant to rusting and corrosion due to the presence of MnSiO3 and
FePO4 slags.
(c) Steel : Carbon content is about 0.1 to 1.5% it is made by removing most of the carbon
and other impurities from pig iron either as gases or converted into slag. Then required
quantities of different elements are added to impart different properties to steel. The
addition of mixture of C and Mn into produced steel is known as spiegeleisen.
2. Extraction of copper from cuprous oxide (Cu2O)
In the graph of G o VS T for formation of oxides, the Cu2O line is almost at the top. So
it is quite easy to reduce oxide ores of copper directly to the metal by heating with coke
(both the lines of C, CO and C, CO2 are at much lower positions in the graph particularly
after 500 - 600 K)
The sulphide ores are roasted /smelted to give oxides 2Cu 2S 3O 2
2Cu 2O 2SO 2 .
The oxide then be easily reduced to metallic copper using coke.
Cu 2 O C
2Cu CO
In actual process, the roasted ore is mixed with silica and heated strongly in a blast
furnace. In the furnace iron oxide slags out as iron silicate and copper is produced in
the form of copper matter. It contains Cu2S and FeS
2CuFeS2 O 2
Cu 2S 2FeS SO 2
2FeS 3O 2
2FeO 2SO 2
FeO SiO 2
FeSiO3
Copper matter is than changed into silica lined Bessemer converter. Some silica is
also added and hot air blast is blown to convert the remaining FeS to FeO and Cu2S/
Cu2O to metallic copper
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Following reacitons takes place.
2FeS 3O 2
2FeO 2SO 2
FeO SiO 2
FeSiO3
2Cu 2S 3O 2
2Cu 2O 2SO 2
2Cu 2O Cu 2S
6Cu SO 2
The solidified copper obtained has blistered appearance due to the evolution of SO2
and is called blister copper. It is about 99% pure.
Extraction of Zinc from ZnO
The reduction of ZnO is done using coke. The temperature in this case is higher than
that in cse of copper. All this three curves representing the oxidation of carbon
C, CO; C, CO2 ; CO, CO2 lie above the oxidation curve of Zn till the boiling point of
Zinc (1180 K) is reached. Above 1270 K, f G for the reduction of ZnO by carbon is
negative and hence ZnO is easily reduced by coke above 1270 K. For the purpose of
heating, the oxide is made into bricketts with coke and clay.
Coke, 1673 k
ZnO C
Zn CO
The metal is distilled off and collected by rapid chilling. Zinc obtained is called ‘spelter’.
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Electrochemical principles of metallurgy
In the reduction of a metal salt solution, electrolysis is done. It is based on the electro-
chemical principle
G o nFE o
Where n is the number of electrons and Eo is the electrode potential of the redox couple
formed in the system. More reactive metals have large –ve values of the electrode
potential. So their reduction is difficult. If the difference of two Eo values corresponds to
a +ve Eo and consequently –ve Go in the above equation then the less reactive metal will
come out of the solution and the more reactive metal will go into the solution.
Ex: Cu 2 aqu Fe s
Cu s Fe 2 aqu
In simple electrolysis, the Mn+ ions are discharge at –ve electrodes (cathodes) and
deposited there.
4. Extraction of Aluminium from Alumina (Hall - Heroult process)
Purified alumina Al2O3 is mixed with cryolite Na 3AlF6 and fluorspar (CaF2) which
lowers the m.p of the mix and brings conductivity. The fused mass is taken in a steel
tank lined inside with carbon which acts as the cathode. A series of graphite rods in-
serted into the mix serves as the anode. A powdered coke layer is maintained at the top
to prevent oxidation and loss of heat due to radiation. The temperature is maintained
around 1173 K. The oxygen liberated at anode reacts with the carbon of the anode
producing CO and CO2. For each Kg of Al produced, about 0.5 kg of carbon anodes is
burnt away. The carbon anodes are replaced periodically.
The electrode reactions are
Cathode : Al3 melt 3e
Al
Anode : C s O 2 melt
CO g 2e
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C s 2O 2 melt
CO 2 g 4e
Copper from low grade ores and scraps
Copper is extracted by hydrometallurgy from low grade ores. The ore is leached out
using acid or bacteria. The solution containing Cu2+ is treated with scrap iron or H2
Cu 2 aqu Fe s
Cu s Fe 2 aqu
Cu 2 aqu H 2 g
Cu s 2H aqu
Extraction of non metals and metals by oxidation
(i) Isolation of chlorine : Chlorine is extracted from brine by oxidation method using elec-
trolysis.
2Cl aqu 2H 2 O
2OH aqu H 2 g Cl2 g
The G o for the reaction , G o nFE o is +422 K J
The minimum potential difference E° for oxidation can be calculated as follows
422 1000 J 2 96500 E
E o 2.2 V
However due to overvoltage (bubble voltage) actual electrolysis requires an external
emf slightly greater than 2.2 V.
(Liberation of gases requires some extra voltage than the theoretical value of standard
electrode potential. This extra voltage required is called over voltage or bubble voltage)
During electrolysis Cl2 is liberated at the anode, H2 at cathode while NaOH is obtained
in the solution
(ii) Extraction of Au and Hg [Hydrometallurgy or Mac. Arthur - Forrest cyanide process]
These metals are extracted by hydrometallurgy by leaching the ore with cyanide ions.
This process is also an oxidation reaction as Au and Ag are first oxidised to Au+ and
Ag+ ions which then combine with CN– ions to form their respective soluble complexes.
The metal is later recovered by displacement method.
4Au s 8CN aqu 2H 2 O O 2 g
4 Au CN 2 aqu 4OH aqu
2
2 Au CN 2 aqu Zn s
2Au s Zn CN 4 aqu
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In this reaction Zn act as reducing agent
Refining of metals
(a) Distillation : Used for the refining of low boiling metals like Zn, Cd and Hg. The impure
metal is evaporated to get the pure metal as distillate.
(b) Liquation : Used for the refining of low melting metals like Sn, Pb, Bi. The impure metal
is melted on the sloping surface of a furnace. In this way it is separated from high melt-
ing impuritis.
(c) Pyrometallurgical oxidation process : This method is commonly used for metals like
Fe, Cu, Ag etc to remove impurities like C, P, Si, S etc.
(i) Poling : This method is employed when the impure metal contains impurities of its
own oxide. Ex. Cu2O in blister Cu and SnO2 in impure tin. The molten impure metal is
stirred with green wood poles. The gaseous hydrocarbons liberated reduces any oxide
present in the metal.
4Cu 2O CH4
8Cu CO2 2H 2O
(ii) Cupellation : Used for removing volatile impurities like lead present in Au & Ag.
Impure metal is heated in small dishes called Cupels made of bone ash. Pb will get
removed as volatile PbO.
(d) Electrolytic refining : Widely used in the refining of Au, Ag, Al, Pb, Cu, Zn etc. Crude
metal used as anode and a strip of pure metal used as cathode. A soluble salt of the
same metal acts as the electrolyte. Highly electro +ve metals like Fe, Zn etc. go into
solution while less electro +ve metals like Au, pt etc remain as anode mud.
In case of blister copper the electrode reactions are
At anode Cu 2 aqu 2e
: Cu s
At cathode : Cu 2 aqu 2e
Cu s
Impurities from the blister copper deposit as anode mud contains Sb, Se, Te, Ag, Au, pt
etc.
Refining of Al - Hoop’s process : The refining cell consists of three fused layers of differnt
densities. The bottom layer consists of impure Al mixed with Cu melt and forms the
anode. The middle layer consistsf of a mixture of cryolite and BaF2. The upper layer is
of pure Al which serves as the cathode.
On electrolysis, Al ions from the middle layer pass into the upper layer and discharged
at the cathode as pure Al metal. At the same time, an equivalent amount of Al from the
bottom layer goes into solution in the middle layer while the impurities remain below.
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(e) Thermal decomposition methods
(i) Mond’s process or carbonyl process for Nickel.
Impure Ni is heated in a stream of CO forming a volatile complex (nickel tetracarbonyl)
which is subjected to higher temperature so that it is decomposed giving the pure metal.
330350k
Ni CO 4
470k
Ni 4CO Ni 4CO
Impure Nickel tetracarbonyl pure
(ii) Van Arkel - de Boer process:
Metals like Ti, Zr, Hf, Si, Th, U etc are refined by this method. This method is very useful
for removing all the oxygen and nitrogen present in the form of impurity in metals. The
crude metal is heated in an evacuated vessel with iodine. The metal iodide being more
covalent, volatilises.
Zr 2I2
ZrI4
Impure
The metal iodide is decomposed on a tungsten filament, electrically heated to about
1800 K. The pure metal is thus deposited on the filament.
Zr I 4
Zr 2I 2
(f) Zone refining or fractional crystallisation
Used to get metals of very high purity Si, Ga, Ge, B, In etc used are semiconductores
are refined in this way. This method is based on the principle that the impurities are
more soluble in the melt than in the solid state of the metal. The impure metal in the form
of a rod is heated at one end with a circular heater. As the heater moved forward, the
pure metal crystallises out of the melt while the impurities pass on into the adjacent
molten zone. The process is repeated several times, so the impurites pass into one
end. This end is cut off. The diameter of the rod d is small enough to give a uniform melt.
(g) Chromatographic method
Commonly used for the separation of lanthanides. This method is very useful for purifi-
cation of elements which are available in minute quantities and the impurities are not
very different in chemical properties from the element to be purified.
The method is based on the principle that different components of a mixture are differ-
ently adsorbed on an adsorbent. The mixture to be separated is put in a liquid or gas-
eous medium (mobile phase) which is moved through the adsorbent (stationary phase).
Different components are adsorbed at different levels of the column. Later the adsorbed
components are eluted by using suitable solvents.
In column chromatography a paste of Al2O3 is prepared in a glass tube and the moving
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Brilliant STUDY CENTRE REPEATERS BOTANY -2020
medium containing a solution of the components is in liquid form.
There are other chromatographic methods like paper chromatography thin layer chro-
matography gas chromatography etc.
ALLOYS
Alloy % composion Applicatore
Magnelium Al - 98%, Mg-2% Chemical balance
Aircraft parts, boat
Al-95%, Cu-4%, Mg-0.5%,
Duralumin machinary
Mn-0.5%
Aluminium bronze Al-10%, Cu-90% coins, utensils
Al - 20%, Ni-20%,
Alnico Permanent magnets
Co-10%, Steel - 50%
Brass Cu - 60%, Zn -40% utensils
Bronze Cu-88-96%, Sn-4-12% Utensils, coins, statues
Cu-25-30%, Zn-25-30%,
German silver Flower vases, ornaments
Ni-40-50%
Invar Fe-64%, Ni -36% Metre scale, pendulum rods
Constantan Cu - 60%, Ni-40% Electrical apparatus
Ni-60-70%, Cu(25-30%)
Aeroplane and Marine
Monel metal Small amount of Fe, Traces
application
of Mn, Si, C
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