SARASWATI VIDYA MANDIR

SR. SEC. SCHOOL,

kamlanagar,Agra

Investigatory project-
‘METALLURGY’

SESSION : 2019-20
SUBMITTED TO: SUBMITTED BY:
Mr. Ankush Agarwal vibhu chaturvedi
P.G.T.,HOD of chemistry XII-A 1
 CERTIFICATE
This is to certify that the Chemistry project titled
METALLURGY has been successfully completed
by VIBHU CHATURVEDI of class 12TH in the
partial fulfilment to the curriculum of CENTRAL
BOARD OF SECONDARY EDUCATION
[C.B.S.E.] leading to the award of board
examination in the session 2019-20.

……………………….
MR. ANKUSH AGARWAL
P.G.T. [ HEAD OF CHEMISTRY DEPT.]

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ACKNOWLEDGEMENT
we are thankful to our chemistry teacher ‘MR.
ANKUSH AGARWAL’ who helped and guided
me while making this project file. We would also
like to thank chemistry department of our school
‘SARASWATI VIDYA MANDIR SENIOR
SECONDARY SCHOOL’ who helped and gave
time for the completion of this project file.

- VIBHU CHATURVEDI

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 THEORY
1. Native State
The elements which have very low reactivity and are not attacked by oxygen or air, moisture, carbon
dioxide or other non-metals occur in the free state, called native state. For example, carbon,
sulphur, nitrogen, noble gases, metals like gold, silver, platinum, etc. occur in nature in the native
state. Therefore, these elements are also called native elements.
2. Combined State
The elements which are reactive and have a tendency to combine with oxygen or air, moisture,
carbon dioxide and non-metals like carbon, nitrogen, sulphur, phosphorus, arsenic, halogen, etc.
occur in the combined state. Therefore, these elements occur in the crust of the earth in the form
of their compounds. In the combined state the non-metals are usually found in the reduced form and
the metals in the oxidised form.
 Among the metals, only a few metals, such as silver, gold, platinum, etc. occur in native state.
 Non-metals such as carbon and sulphur also occur in native state as well as in combined state.
 Among metals, aluminium is the most abundant. It is the third most abundant element.
 Iron is the second most abundant metal in earth’s crust.
MINERALS AND ORES
The naturally occurring chemical substances in which metals occur in the earth’s crust are called
minerals. The mineral, from which the metal can be economically and conveniently extracted, is
called an ore.
Aluminium occurs in the earth’s crust in the form of two minerals, bauxite (Al2O3.2H2O) and clay
(Al2O3.2SiO2.2H2O). Out of these two, aluminium can be conveniently and economically extracted
from bauxite, while it has not been possible to extract aluminium from clay by some easy and cheap
method. Therefore, the ore of aluminium is bauxite though both bauxite and clay are minerals of
aluminium.
Similarly, the main minerals of copper are copper glance (Cu 2S), copper pyrites (CuFeS2), malachite
[CuCO3.Cu(OH)2], etc. but copper can he conveniently extracted from copper pyrites. Therefore, the
ore of copper is copper pyrites. Thus, it may he concluded that
 All the ores are minerals but all the minerals are not ores.
Metal Name Composition
Aluminium (Al) Cryolite Na3AIF6
Iron (Fe) Hematite Fe2O3
Magnetite Fe3O4
Capper (Cu) Copper glance Cu2S
Copper pyrites CuFeS2
Qo.1. In general, which metals do you expect to occur in native state in nature? Give examples.
Sol:- In general, the metals which lie below hydrogen in electrochemical series occur in native
State in nature because these are not attacked by oxygen, moisture and CO 2 present in the
atmosphere. Common examples are Cu. Ag, Au, Pt etc.
Qo.2. Why do metal sulphides occur mainly in rocks and metal halides occur mostly in lakes and seas.
Sol:- Metal sulphides are insoluble in water and therefore, they occur mostly in rocks. On the other
hand, metal halides are highly soluble in water. Therefore, they get dissolved in rain water and are,
carried to lakes and seas.
EXTRACTION OF METALS: METALLURGY
The process of extracting metals from their ores is called metallurgy. The ores are generally
contaminated with earthly or undesired materials (impurities). These are called gangue or matrix.
The process of metallurgy depends upon the nature of the ore and the impurities present in it.
Therefore, it is not possible to have a universal method. Common steps involved in the metallurgical
operations are:
1. Crushing and grinding of the ore 2. Concentration or benefaction of the ore
3. Extraction of crude metal from concentrated ore 4. Purification or refining of the metal.
1. Crushing and Grinding of the Ore
The ores occur in nature as huge lumps. They are broken to small pieces with the help of crushers
or grinders. These pieces are then reduced to fine powder with the help of a ball mill or stamp mill.
This process is called pulverisation.
2. Concentration or benefaction of the ore:- The process of removal of unwanted impurities
(gangue) from the ore is called ore concentration or ore dressing or ore benefaction.
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(i) Gravity separation or Levigation.
This method is based on the differences in the specific gravities of metallic ores and the gangue
particles. Therefore, this method is known as gravity separation. This method is frequently used
when the ore particles are heavier than the earthy or rocky gangue particles.
(ii) Magnetic separation
This is based on the differences in magnetic properties
of the ore components. If either ore or the gangue (one
of these two) is attracted by a magnet then ore can be
separated from the impurities with the help of magnetic
separation method. For example, the magnetic impurities
such as iron and manganese tungstates (FeWO 4,
MnWO4) present in tin stone (SnO2, non-magnetic) are
separated by this method.
(iii) Froth flotation
This method is based on the principle of difference in the
wetting properties of the ore and gangue particles with
water and oil. It is used for the extraction of those metals in which the ore particles are preferentially
wetted by oil and gangue by water. This method has been used for the concentration of sulphide
ores, such as galena (PbS), zinc blende (ZnS), copper pyrites (CuFeS 2), etc. The sulphide ore
particles are preferentially wetted by oil and gangue particles by water.
In this method, the powdered ore is mixed with water to form a suspension in a tank (Fig). To this
suspension small quantities of collectors and froth stabilizers are added. Collectors (e.g., pine oil,
eucalyptus oil, fatty acids, xanthates, etc.) enhance non-wettability of the mineral particles and froth
stabilizers (e.g., cresols, aniline) help in stabilization of the froth. The mineral ore particles become
wet by oil while the gangue (impurities) particles by water. The water is agitated by a rotating paddle
or by blowing air violently, when froth (or foam) is formed. During the process, the ore particles
which are preferentially wetted by the oil become lighter. The froth carries the lighter ore particles
along with it to the surface. The heavier impurities are left behind in water and these sink to the
bottom. Since the ore particles float with the froth at the surface, this process is called froth
floatation process.
Sometimes, depressants are used to
prevent certain types of particles from
forming the froth with air bubbles. For
example, sodium cyanide can be used as
a depressant in the separation of zinc
sulphide ore (ZnS) and lead sulphide ore
(PbS). Sodium cyanide forms a layer of
zinc complex, Na2[Zn(CN)4] on the surface
of ZnS and therefore prevents it from
forming the froth. Therefore, it acts as a
depressant.
(iv) Leaching: This is a chemical method of
concentration and is useful in case the ore
is soluble in a suitable solvent. In this
method, the powdered ore is treated with certain reagents in which the ore is soluble but the
impurities are not soluble. The impurities left undissolved are removed by filtration.
Leaching method is used for concentrating ores of aluminium, silver, gold etc. For example, the ore
of aluminium, bauxites-concentrated by this method.
Leaching is also used to concentrate silver and gold ores. The ore containing native metal (silver or
gold) is treated with a dilute solution (0.5%) of NaCN or KCN in the presence of atmospheric
oxygen. The metal dissolves in the solution as a complex.

The metal is obtained by replacement reaction as:

(where M = Au or Ag)
For example,
(i) For Ag2S (argentite), an ore of silver the reactions are:

Sodium sulphide, thus formed is oxidised to sodium sulphate by blowing air into the solution.
5
 This helps the reaction to occur in the forward direction.

The above solution after filtration and removing insoluble impurities is heated with zinc to get silver.

(ii) Gold is also extracted in a similar way.

This process is known as Mac Arthur Forest Cyanide Process.

3. Extraction of Crude Metal from Concentrated Ore
The process of working of he concentrated ore to extract metal depends upon the nature of the ore
as well as the nature of the impurities present in the ore. This involves oxidation and reduction
reactions.
(A) Conversion of the concentrated ore to its oxide form (Oxidation or de-electronation)
(i) Calcination: Calcination is a process of heating the ore strongly either in a limited supply of air or in
the absence of air. During calcination, the following changes take place
(i) Moisture is removed (ii) The volatile impurities are removed
(iii) The ore becomes porous (iv) water from hydrated oxides is removed
(v) Carbonates decompose to oxides.
(a) Zinc occurs as zinc carbonate in calamine (ZnCO3). The ore is calcined i.e., heated strongly in the
absence of air to convert it to zinc oxide. During calcination, carbon dioxide is expelled.

Similarly,

(b) Aluminium occurs as Al2O3.H2O in its bauxite ore. When the bauxite ore is calcined, water vapours
are expelled and anhydrous aluminium oxide is obtained.

(c) Water of hydration are removed from limonite (Fe 2O3.3H2O).

(ii) Roasting
Roasting is the process of heating the ore strongly in the presence of excess of air at a temperature
below the melting point of the metal. It is mainly employed in case of sulphide ores. As a result of
roasting, the moisture and volatile impurities are removed and the ore is converted to oxide. For
example, impurities of sulphur, arsenic and phosphorus are, removed as their volatile oxides,
SO2, As2O3, P2O5, respectively.

The ores of the metal are converted into their oxides. For example, the sulphide ore of the metal is
roasted to give oxide.

Both calcination and roasting are generally carried in a reverberatory furnace. In case of
roasting, the air holes are kept open while in case of calcination, the air holes are partially or
completely closed.
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(B) Conversion of the oxide of the metal to the metallic form (Reduction or electronation)
The metal oxides are usually reduced to free metals by using a suitable reducing agent such as
carbon, carbon monoxide or even another metal. The reduction process involves electron gain or
electronation. The process of extraction of metal by heating the metal oxide with a suitable reducing
agent is called thermal reduction or pyrometallurgy.
(i) Reduction with carbon and carbon monoxide. The oxides of metals like zinc, copper, tin, lead,
etc. can be reduced by using carbon as reducing agent. The process of extraction of metal by
reduction of its oxide with carbon (in the form of charcoal, coke or carbon monoxide) is called
smelting. In this process, the roasted ore is mixed with a suitable amount of carbon (coke or coal)
or carbon monoxide and heated to a high temperature above, the melting point of the metal in a
furnace. Carbon or carbon monoxide (produced by incomplete combustion of carbon) reduces the
oxide to free metal.

For example,

Cassiterite

The carbon reduction process is generally carried out in a blast furnace.

(ii) Reduction by hydrogen. Certain metal oxides are reduced by hydrogen. Because of the
inflammable nature of hydrogen, it is used in very few cases. For example, molybdenum and
tungsten oxides are reduced by current of hydrogen at higher temperature (1270-1470 K).

(iii) Reduction by aluminium. Many oxides, like Cr2O3, Mn3O4, etc. are not reduced easily by carbon or
CO. These metal oxides are reduced by strongly electropositive metals such as aluminium. The
process of reduction of a metal oxide to the metal with the help of aluminium powder is called
aluminothermy. For example,

The above reaction is highly exothermic and therefore, the metals are produced in the molten state.
The above process is also known as Goldschmidt thermite process.
Similarly, Fe2O3 can be reduced to metallic iron by aluminium

also called thermite welding.

(v) Reduction with water gas. Nickel oxide (NiO) is reduced to nickel by heating carefully in a tower at
600 K in which a current of water gas (CO + H 2) is passed. In this case both CO and H2 present in
water gas act as reducing agents.
NiO + CO  N2 + CO2
NiO + H2  N2 + H2O
(vi) Self reduction or Auto-reduction. Reduction can also be carried out by self reduction or
auto-reduction in which the anions associated with the metal help in the reduction. This is used for
the reduction of sulphide ores of Pb, Hg and Cu.

Copper is also obtained by reducing Cu 2S by partly converted Cu2O in this way during smelting.

Copper is also obtained by reducing Cu 2S by partly converted Cu2O in this way during smelting.

All roasting processes are carried out in reverberatory furnace.

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Some other Methods of Reduction
1. Reduction by precipitation (Hydro-metallurgy) or Displacement method: The process of
extraction of metals by dissolving the ore in a suitable chemical reagent and the precipitation of the
metal by more electropositive metal is called hydrometallurgy.

The solution is decanted off and made alkaline by adding NaOH and then treated with zinc or
aluminium to precipitate silver.

Gold is also precipitated from its complex salt solution in a similar way.

Metals such as Ti, Zr, Ta etc. are also obtained by reducing their complex salts with alkali metals or
Al.
II. Electrolytic Reduction:
Certain highly electropositive metals such as alkali metals of groups 1 and 2 alkaline earth metals
and aluminium, etc. are commonly extracted by the electrolysis of their fused salts. The process of
extraction of metals by electrolysis process is called electrometallurgy. For example, sodium is
extracted from fused sodium chloride by electrolysis as :

The sodium metal is liberated at cathode and collected.

4. Purification or refining of metals:-
The metal obtained by any of the above methods is usually impure and is known as crude metal.
Therefore, the crude metal is to be purified. The impurities may be in the form of
(i) Unreduced oxides of the metals (ii) non-metals like C, Si, P, As, S etc.
(iii) Foreign metals (iv) slag or flux.
The process of purifying the crude metal is called refining.
For obtaining metals of high purity, several techniques are used depending upon the differences in
the properties of the metal and the impurity.
Some of the common methods of refining are
1. Liquation
This method is used for refining the metals having low-
melting points, such as tin, lead, bismuth, etc. In this
method, the impure metal is placed on the sloping
hearth (Fig.) of the reverberatory furnace and is gently
heated in an inert atmosphere of carbon monoxide.
The metal melts and flows down leaving the non-
fusible impurities (called dross) on the hearth. The
pure metal is collected at the bottom of the sloping
hearth in a receiver.
2. Electrolytic refining
This is most general method for the refining of
metals and is based upon the phenomenon of
electrolysis. In this method, the impure metal is
made to act as anode. A strip of the same metal in
pure form is used as cathode. Both anode and
cathode are placed in a suitable electrolytic bath
containing soluble salt of the same metal. On passing current, metal ions from the electrolyte are
deposited at the cathode in the form of pure metal while equivalent amount of metal dissolves from
the anode into the electrolyte in the form of metal ions. The impurities fall down below the anode as
anode mud. The• reaction occurring at the electrodes are
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3. Zone refining
This method is used for
metals which are required
in very high purity. For
example, extremely pure
silicon, germanium, boron,
gallium and indium are
refined by this method.
This method is based on
the principle that the
impurities are more soluble
in the melt than in the solid
state of the metal.
Therefore, an impure metal. on solidification will deposit crystals of pure metal and the impurities will
remain behind in the molten part of the metal. In this method, the impure metal is cast into a thin
bar. A circular mobile heater is fixed at on end of the rod of impure metal. One zone of the bar is
meIted by a circular mobile heater in the atmosphere of an inert gas like argon. At the heated zone,
the metal melts (Fig.). As the heater moves slowly, the impurities also move into the adjacent
molten part. In this way, the impurities are made to move into one end which is finally cut off and
discarded. The molten metal present at the colder region solidifies in the mean time since it is away
from the heater. Thus, we get completely pure metal by this method. This method is specially useful
for producing semiconductors of very high purity. Germanium, for example, purified by this method
contains impurities only upto 7-10 ppm.
4. Vapour phase refining
This Method is based on the fact that certain metals are converted to their volatile compounds while
the impurities are not affected during compound formation. The compound formed decomposes on
heating to give pure metal. Thus, the two requirements are
(i) The metal should form a volatile compound with an available reagent.
(ii) The volatile compound should be easily decomposable so that the metal can be easily
recovered.
For example, nickel is refined by this technique and the method is known as Mond process. In this
method, nickel is heated in a steam of carbon monoxide to form volatile nickel carbonyl Ni(CO) 4.
The carbonyl vapours when subjected to still higher temperature (450—470 K) undergoes thermal
decomposition giving pure nickel.

5. Van Arkel Method

This method is similar to above method and used for getting ultra pure metals. In this method, the
metal is converted to a volatile unstable compound (e.g., iodide) taking care that the impurities are
not affected during compound formation. The compound thus obtained is decomposed to get the
pure metal, This method is used for the purification of metals like titanium and zirconium.

Qo:- How does sodium cyanide act as depressant in preventing ZnS from forming the froth?
Sol:- Solution: Sodium cyanide combines with ZnS to form a complex Na 2[Zn(CN)4] on the surface of ZnS
and therefore, it prevents it from forming the froth.

Qo:- What is flux ? How is it useful?

Sol: Flux is a substance which combines with gangue (impurities) present in roasted ore to form easily
fusible material called slag.
Flux + Gangue ------ Slag
Thus, flux helps to remove impurities from the roasted or calcined ore.

9
ALUMINIUM
Occurrence: Aluminium is a third most abundant element forming 8.3% of the earth's crust. It is a
constituent of clay, slate and many types of silicate rocks. It is found only in the combined state,
the important minerals are :
(i) Oxides:-
(a) Corundum, ruby, sapphire, emerald, Al 2O3. (b) Diaspore, Al2O3.H2O.
(c) Gibbsite, Al2O3.3H2O. (d) Bauxite, Al2O3.2H2O,
it is the chief ore of Aluminium from which extraction of Aluminium is made. It is usually
associated with varying amounts of ferric oxide and silica.
(ii) Fluoride: Cryolite, Na3AlF6. It is the second important ore of Aluminium.
(iii) Basic sulphate: Alunite or Alum stone, K 2SO4 .Al2(SO4)3.4Al(OH)3
(iv) Basic phosphate: Turquoise, AlPO4.Al(OH)3.H2O.
It is usually blue coloured due to presence of copper phosphate.
(v) Silicates: Felspar, KAlSi3O8, kaolin, porcelain, mica, china Clay, slate, etc., Al 2O3:2SiO2H2O.
Extraction: Aluminium is mainly isolated from bauxite ore which is generally contaminated with ferric
oxide and silica. The removal of ferric oxide and silica from bauxite ore is essential before it is
subjected to electrolysis because it is rather difficult to remove iron and silicon from Aluminium
metal, the presence of these elements makes the Aluminium metal brittle and liable to corrosion.
Thus, the extraction of Aluminium from bauxite ore involves the following three steps.
(i) Purification of bauxite ore, i.e., removal of ferric oxide and silica.
(ii) Electrolytic reduction of Al 2O3.
(iii) Electrolytic purification of Aluminum.
Refining of Aluminium by Hoope's electrolytic method:
Aluminium is further purified by Hoope's process. The electrolytic cell consists of an iron box lined
inside with carbon. The cell consists of three layers which differ in specific gravities. The upper
layer is of pure Aluminium which acts as cathode. The middle layer consists of a mixture of the
fluorides of Al, Ba and' Na. The lowest layer consists of impure Aluminium which acts as anode.
The middle layer works as electrolyte
The graphite rods dipped in pure Aluminium and Cu-Al Alloy rod at the bottom in the impure
Aluminum work as conductors. On electrolysis, Aluminium is deposited at cathode from the
middle layer and an equivalent amount of Aluminium is taken up by the middle layer from the
bottom layer (impure Aluminium). Therefore, Aluminium is transferred form bottom to the top layer
through middle layer while the impurities are left behind. Aluminium thus obtained is 99.98% pure.
Physical Properties :
(a) Aluminium is a bluish white lustre metal. The lustre is destroyed on long expo sure to air due
to formation of a thin film of oxide on the surface.
(b) The density of Aluminium is 2.7 g mL –1 (light metal). It is malleable and ductile.
(c) It is a good conductor of heat and electricity.
(d) It melts at 660°C and boils at 1800°C.
(e) It can be welded and cast but difficult to solder.
Purification or bauxite ore : The following methods are used for purifying the bauxite ore.
(a) Baeyer's process : This process is mainly applied to bauxite ore containing ferric oxide as chief
impurity. The colour or such ore is usually red and hence called red bauxite.
The powdered ore is first roasted at a low temperature as to convert any ferrous oxide, if present,
into ferric oxide. It is then digested with a concentrated solution of sodium hydroxyl: (density 1.45
9 ML–1) in an autoclave under pressure at 150°C for several hours. The Aluminium oxide
dissolves in caustic soda forming soluble sodium meta Aluminate (NaAlO 2) while ferric oxide and
silica remain insoluble and settle down. These are removed by filtration.

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 Al2O3.2H2O+2NaOH  2NaAlO 2 + 3H2O
Sodium meta Aluminate
(soluble)
The sodium meta Aluminate solution is agitated with freshly precipitated Al(OH) 3 for 36 hours
when sodium metal Aluminate undergoes hydrolysis with the formation of Al(OH) 3 precipitate.
NaAlO 2 + 2H2O  NaOH + Al(OH)3
Precipitate
The precipitate is washed and dried..
The solution of NaOH is concentrated and used again
(b) Hall's process:
Bauxite is fused with sodium carbonate. Al 2O3 combines with sodium carbonate forming sodium
meta Aluminate. The fused mass is extracted with water where Fe 2O3 and SiO 2 remain as
insoluble in the residue. Al2O3 + Na2CO3  2NaAlO 2 + CO2
The solution containing sodium meta Aluminate is warmed to 50-60°C and carbon dioxide is
Circulated through it. Al(OH)3 separates out as precipitate.
2NaAlO2 + CO2 + 3H2O  2Al(OH)3 + Na2CO3
The precipitate is filtered, washed and dried. The solution of Na 2CO3 is concentrated and used
again.
(c) Serpeck's process: This process is used when silica is present in considerable amounts in
bauxite ore. The ore is mixed with coke and heated at 1800°C in presence of nitrogen, where AlN
(Aluminium nitride) is formed Al2O3 + 3C + N2  2AlN + 3CO
Silica is reduced to silicon which volatilises off at this temperature. SiO2+2C  Si + 2CO
AlN is hydrolysed with water into Aluminium hydroxide.
This process has one distinct advantage that ammonia is obtained as a valuable by product.
Calcinations or Aluminium hydroxide:
The Aluminium hydroxide precipitate obtained in the above processes is calcined at 1500°C in a
rotary kiln to obtain pure Alumina (Al 2O3). 2Al(OH)3  1500
 Al2O3 + 3H2O
Electrolytic reduction of pure Alumina :
The electrolysis of pure Alumina faces two
difficulties: (i) Pure Alumina is a bad conductor of
electricity, (ii) The fusion temperature of pure
Alumina is about 2000°C and at this temperature
when the electrolysis is carried of fused mass, the
metal formed vapourises as the boiling point of
Aluminium is 1800°C. The above difficulties are
overcome by using a mixture containing Alumina,
cryolite (Na3AlF6) and fiuorspar (CaF 2) in the ratio of 20 : 24 : 20. The fusion temperature of this
mixture is 900°C and it is a good conductor of electricity. The electrolysis is carried out in an iron
box lined inside with gas carbon which acts
as cathode. The anode consists of carbon
rods which dip in the fused mixture or the
electrolyte from above. The fused electrolyte
is covered with a layer of coke (Fig.). The
current passed through the cell serves two
purposes (i) heating of the electrolyte-The
temperature of the cell is automatically
maintained at 900-950°C, (ii) electrolysis. On
Fig.
passing current, Aluminium is discharged at
cathode. Aluminium being heavier than
11
electrolyte sinks to the bottom and is tapped out periodically from tapping hole. Oxygen is
liberated at anode. It attacks carbon rods forming CO and CO 2. The process is continuous. When
the concentration of the electrolyte decreases, the resistance of the cell increases. This is
indicated by the glowing of a lamp placed in parallel. At this stage more of Alumina is added. The
exact mechanism of the electrolysis is not yet known. Two concepts have been proposed.
Refining of Aluminium by Hoope's electrolytic method: Aluminium is further purified by Hoope's
process. The electrolytic cell consists of an iron box lined inside with carbon. The cell consists of
three layers which differ in specific gravities. The upper layer is of pure Aluminium which acts as
cathode. The middle layer consists of a mixture of the fluorides of Al, Ba and' Na. The lowest layer
consists of impure Aluminium which acts as anode. The middle layer works as electrolyte. The
graphite rods dipped in pure Aluminium and Cu-Al Alloy rod at the bottom in the impure Aluminum
work as conductors. On electrolysis, Aluminium is deposited at cathode from the middle layer and
an equivalent amount of Aluminium is taken up by the middle layer from the bottom layer (impure
Aluminium). Therefore, Aluminium is transferred form bottom to the top layer through middle layer
while the impurities are left behind. Aluminium thus obtained is 99.98% pure.

12
 COPPER
Occurrence:
Copper constitutes only 0.0001 percent of the earth's crust. Its deposits, however, are
concentrated. Copper is found in nature in the following forms.
1. Native state: Copper is found in the metallic condition in large quantities near lake
Superior in U.S.A.; in the Ural mountains (Russia) and Sweden.
2. Combined state: The principal ores of copper are sulphides, oxides and basic carbonates.
Sulphide ores
(i) Chalcopyrities or copper pyrites. CuFeS 2 (ii) Chalcocite or copper glance, Cu 2S
(iii) Cuprite (red); Cu2O
Extraction
Dry process for the extraction of copper: Copper is extracted mainly from copper pyrites by dry
process or smelting process. The process of extraction of copper from copper pyrites involves the
following steps:
(i) Concentration of the ore: The concentration of the sulphide ores is done by froth floatation
process. The ores are powdered and sieved and then thrown into tanks of water to which pine oil
and potassium xanthate have been added. A strong stream of air is passed which agitates the
whole mass. Froth is produced which carries Along the particles of the ore to the surface of the
liquid while the impurities settle to the bottom of the tank . Though froth is continuously separated.
This is the concentrated ore.
(ii) Roasting: The concentrated ore is heated strongly in a current of air on the hearth of the
reverberate furnace (Fig.). During roasting the following changes take place.
(a) Free sulphur is oxidised and removed as sulphur dioxide.

(b) The arsenic and antimony present in the ore are removed as volatile oxides.

(c) The pyrite is converted into cuprous sulphide and ferrous sulphide with evolution of sulphur
dioxide.

(d) The sulphides of copper and iron are partially oxidised.

2FeS  3O 2 
 2FeO  2SO 2
2Cu 2S+3O2 
 2Cu2O + 2SO 2
Smelting :
The roasted ore is mixed with coke and silica and transferred to a small blast furnace. The mixture
is heated in the presence of excess of air.
(a) The cuprous oxide reacts with ferrous sulphide. FeS + Cu 2O  FeO + Cu2S
[Iron has greater affinity for oxygen than copper. The copper oxide formed reacts with unchanged
iron sulphide to form iron oxide and reproduce copper sulphide. So it is difficult to oxidise cuprous
sulphide until whole of the iron sulphide is oxidised]
(b) Most of the iron sulphide is oxidised to ferrous oxide :
2FeS + 3O2  2FeO + 2SO2
(c) Ferrous oxide combines with silica and forms ferrous silicate. By this reaction most of the iron
is removed as slag
FeO + SiO 2  FeSiO3
Ferrous silicate (slag)
13
 The lowest point of the furnace consists of a shallow hearth in which the molten mass collects
which is known as 'Matte'. The matte contains mostly cuprous sulphide with a little iron sulphide.
(d) Bessemerisatlon: The matte obtained from smelting is transferred to a Bessemer converter.
Some sand (silica)
is added and a blast of air is blown through the molten
mass. The bessemer converter is usually a pear shaped
steel vessel lined with magnesite and quartz. It is fitted
with air-blast layers and mounted in such a way that it
can be tilted in the desired direction (Fig.). The following
reactions occur in the bessemer converter. Remaining
ferrous sulphide gets oxidised.
2FeS + 3O2  2FeO + 2SO 2
FeO + SiO 2  FeSiO 3
(Slag)
The blast of air is continued for Almost another two hours. Excess of silica is absorbed by basic
lining of the converter and part of cuprous sulphide is oxidised which combines with remaining
cuprous sulphide to form free copper metal.
2Cu2S + 3O2  2Cu2O + 2SO2
Cu2S + 2Cu2O  6Cu + SO2
This presents an example of auto-reduction.
The molten copper is poured off and allowed to cool. During cooling, the dissolved sulphur
dioxide comes out and large blisters are formed on the surface. Hence, the metal formed is given
the name 'blaster copper'. Blister copper consists 98% copper and 2% impurities.
(v) Refining: Blister copper is subjected to refining by either of the following two methods.
(a) Refining by poling: The blister copper is melted on the hearth of a reverberatory furnace and
stirred with poles of green wood in the presence of air. Arsenic, antimony, zinc and sulphur, if
present are converted into their volatile oxides while iron, lead and nickel are oxidised to their
oxides which come to the surface in the form of scum and are removed. If any cuprous oxide is
formed due to the oxidation of copper, is reduced back to copper by hydrocarbons (methane, etc.)
which are produced by the decomposition of green wood. This process produces copper of about
99.5% purity and is known as tough pitch copper.
(b) Electrolytic refining: Copper is usually refined
electrolytically.
Anode used: Impure copper rod.
Cathode used: Pure copper plate.
Electrolyte used: A solution containing 15% of
CuSO4 along with 5% of H2SO4

Electrolytic copper has a purity of 99.96-99.99%.

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SILVER
Silver is found in nature in two forms.
1. Native state: It occurs in the metallic condition usually associated with copper, gold and platinum
metals.
2. Combined state: The important ores of silver are:
(a) In the form or sulphide:
Argentite or silver glance, Ag 2S
(b) In the from of halide : Chlorargyrite or Horn silver, AgCl.
(I) Extraction or silver from argentite ore (Cyanide process): Cyanide process is the modern process
for the extraction of silver. The process is also called as Mac-Arthur and Forest process. It is
based on two points.
(i) Silver compounds (or even free silver) dissolve in sodium cyanide solution forming a complex salt,
Na[Ag(CN)2], in presence of air.
(ii) Silver is precipitated from this complex salt by the addition of zinc.
The process involves the following steps:
(i) Concentration or the ore: Concentration of the ore is done by froth floatation process. The
ore is crushed and taken in a take filled with water to which pine oil and potassium xanthenes
have been added. The whole mixture is agitated by passing a strong stream of air. The ore
particles come to the surface Along with froth while siliceous impurities settle to the bottom.
(ii) Cyanidation: The concentrated ore is ground to a very fine powder in ball mill. The finely
powdered ore is treated with dilute solution (0.4 to 0.6%) of sodium cyanide and a current of air
is blown through the whole mass. The Silver present in the ore dissolves in the solution slowly
to form sodium argento cyanide.
Ag 2S + 4NaCN  2 Na[Ag(CN)2]+ Na 2S
The above reaction is reversible. The air which is blown in serves an important function in
removing sodium saphead from the equilibrium mixture and causing the reaction to proceed in
the desired direction.
4Na2S + 5O2 + 2H2O  2Na2SO4 + 4NaOH + 2S.
The soluble sodium argent cyanide is removed by titration.
[Metallic silver and silver chloride (Horn silver) also dissolve in sodium cyanide solution.
4Ag + 8NaCN + 2H2O + O2 (air)  Na[Ag(CN)2] + 4NaOH
Or
AgCl + 2NaCN  Na[Ag(CN)2]+ NaCl

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(iii) Recovery of silver: Silver is precipitated from the solution by addition of zinc powder in a finely
divided condition. Silver is precipitated as a dark amorphous mass, while zinc goes into the
complex.
2Na[Ag(CN)2] + Zn  Na 2[Zn(CN)4] + 2Ag
[Zinc is more electropositive than silver]
The precipitated silver is removed by filtration. Dried and fused with potassium nitrate in a
crucible in furnace. The impurities are oxidized and rise as a scum on the surface Liquid silver
on cooling appears as compact mass.
(iv) Refining: The main impurities are of lead copper and gold. These are removed by following
method.
Electrolytic process: The impure silver is made as anode and pure silver plate as cathode. The
electrolytic solution is of silver nitrate containing 10% nitric acid. On passing electric current silver
ions start depositing on cathode and equivalent amount from anode comes into solution. In this way
silver is transferred from anode to cathode. Copper goes into solution as copper nitrate while gold
collects below the anode as anodic mud.

To get Silver from Silver coins or Silver Ornaments (Cu-Ag Alloy):

Silver coin or silver ornament is a Cu-silver alloy. Silver can be obtained from this alloy by dissolving
it in HNO3 when a solution containing mixture of Cu(NO3)2 and AgNO3 is obtained.

The excess of HNO3 is removed by boiling and the solution is treated with dil. HCl when a white ppt.
of AgCl is obtained while CuCl2 remains in solution.

Silver can be obtained from silver chloride by any of the following methods:
(a) AgCl is treated with KCN solution when potassium argento cyanide, K[Ag(CN) 2] soluble complex is
obtained.
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 The solution containing K[Ag(CN)2] is treated with zinc so that Ag gets precipitated (black ppt.).

(b) The precipitate of AgCl is reduced by Zn/H2SO4.

Passivity of Iron:- When a piece of iron is dipped in conc. HNO 3, a reaction takes place which stops after
sometime completely. This iron now cannot displace hydrogen from dilute acids and cannot displace
copper from CuSO4 solution. The iron in this form is said to be passive and this process is called
passivity of iron. The loss of chemical activity of iron is called passivity. It is due to the formation of
an extremely thin film (invisible) of oxide on the surface of iron. Passive iron can be made active by
scratching or heating in a. reducing atmosphere of H 2 or CO or by dissolving out in iodine solution.
The passivity of iron is important in preventing corrosion of iron.
Heat Treatment of Steel
(i) The hardness and elasticity of steel can be changed by heating the steel at different temperatures
and then allowing it to cool. For example,
(a) Annealing: It is a process of heating steel to bright redness and then cooling it very slowly to make
the steel soft and ductile. As a result, the steel becomes soft and ductile.
(b) Quenching: It is a process of heating steel to bright redness and then cooling it suddenly by
plunging it in water or oil to have extremely hard and brittle steel. It has very low elasticity.
(c) Tempering: It is a process of heating the quenched steel to a temperature much below redness and
cooling it slowly. Such a steel is neither so hard nor so brittle. During the process of tempering, a
thin film of oxide is formed on the surface of steel. The colour of oxide film depends on the
temperature at which the quenched steel is heated.

(ii) Surface Treatment: The surface treatment of the steel involves the following two processes:
(a) Case Hardening: It is the process of producing a thin coating of hardend steel on the surface of
mild steel. This is done by heating the mild steel with charcoal and then plunging into oil which
produces a thin coating of hardened steel on the surface. Such a steel becomes resistant to wear
and tear.
(b) Nitriding: It is the process of producing a hard coating of iron nitride on the surface of steel. Steel
on heating in an atmosphere of dry ammonia at 500—600 °C for about 3 to 4 days forms a hard
coating of iron nitride on the surface. This makes the steel extremely hard and resistant to corrosion.
Comparison of Cast Iron, Wrought Iron and Steel

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 METALLURGY OF IRON
The important ores of iron are:
(i) Haematite Fe2O3 (red oxide of iron) (ii) Limonite, Fe2O3. 2H2O (hydrated oxide of iron)
(iii) Magnetite, Fe3O4 (magnetic oxide of iron (iv) Siderite, FeCO 3 (v) Iron pyrites, FeS2
Iron is extracted as cast iron (contains carbon content about 2 .5 to 4 .5 %) from Haematite ore. It
involves following steps
1. Concentration: The ore is crushed into small pieces and is concentrated by gravity separation
process in which it is washed with water to remove lighter impurities like sand and clay.
2. Calcination: Now the concentrated ore is heated strongly in presence of limited supply of air in
reverberatory furnace and the following changes take place
(i) Moisture is removed.
(ii) Impurities of sulphur, phosphorus and arsenic are removed in the form of volatile oxides

(iii) Ferrous oxide is oxidised to Ferric oxide

In case of siderite ore, it is converted into ferric oxide.

(iv) The ore becomes porous and further process become convenient.
3. Smelting : The calcined ore is reduced with carbon in a blast furnace which is made up of steel and
lined inside with fire bricks. This is provided with cup and cone arrangement at the top and tuyeres,
tapping hole and slag hole at the base.
The charge consists of 8 parts of calcined ore and 4 parts of coke with 1 part of limestone. It is
introduced from the top through cup and cone arrangement and blast of hot air (1000 K) is blown
into the furnace through tuyerer. Coke acts reducing agent whereas lime acts as a flux. Different
reactions take place at the various zones of the blast furnace.
(a) Combustion zone:- This is the lowest zone in which coke burns to produce a temperature
of 1775 K - 2000 K and forms CO2 which rises upward to combine with coke to give CO.

(b) Slag formation zone:- It is the middle part of the furnace maintained at the temp. of 1075 K
— 1475 K.

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 (c) Reduction zone:- This is the upper part of the furnace having the temperature of 523 K-975 K

The iron formed in this zone is called the sponge iron.

(d) Fusion zone:- The region above combustion zone is called fusion zone. In this lone, the
temperature varies from 1423 —1673 K. The sponge iron fr9m the slag formation zone, melts and
dissolves some C, S, P, Si, Mn etc. Any unreduced iron oxide is reduced by coke in this zone. Slag
(CaSiO3) also melts in this region. Both the molten slag and the molten iron come down into hearth
where they form two separate layers. The molten slag being lighter forms the upper layer while
molten iron from the lower layer. The upper layer of slag prevents the molten metal from oxidation.
Both the layers are taken out separately through their separate tapping holes. The iron obtained
above is pig iron containing 4% carbon along with S, Si, P and Mn. Pig iron is converted into cast
iron by remelting pig iron with scrap iron and coke using hot air blast. It contains about 3% of
carbon.
METALLURGY OF ZINC
Important ores
(i) Zinc blende ZnS (ii) Calamine ZnCO3 (iii) Zincite ZnO
(iv) Franklinite ZnO, Fe2O3 (v) Willemite Zn2SiO4 (vi) Spinel ZnAl2O4
The principal ore of Zinc is zinc blende.
Extraction
1. Concentration : The ore is crushed and finely powdered. This form is concentrated by froth
floatation process.
2. Roasting: The concentrated ore is heated in presence of excess of air at about 1200 K so that zinc
sulphide is converted into zinc oxide.

Calamine requires only calcination.

3. Reduction: Zinc oxide is reduced to zinc by heating it with coke at 1673 K in vertical fire clay
retorts. 1673 K

The vapours of zinc are collected and condensed.

4. Refining: The impure metal is refined by electrolytic method. In this process, he impure zinc is
made anode while pure zinc is made the cathode. The electrolyte used is zinc sulphate containing
little amount of dilute sulphuric acid. On passing the electric current, pure zinc is obtained at the
cathode.

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BIBLIOGRPHY
 Ncert book of chemistry class 12th

 www.youtube.com/edushop

 www.davidupadhyay9758.wixsite.com

 Wikipedia.com

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