Namma Kalvi

UNIT – 1 METALLURGY
Answer the following questions
1. What is the difference between minerals and ores?

Minerals Ores

Naturally occuring substances obtained by Minerals that contain high percentage of

mining which contain the metals in free metal from which it can be extracted
state or conveniently
in the form of compounds like oxides, and economically are called ores.
sulphides etc. are called minerals.

All minerals are not ores All ores are minerals

Ex : Clay – Mineral of aluminium Ex : Bauxite –Ore of aluminium

2. What are the various steps involved in extraction of pure metals from their ores?
i)Concentration of the ore.
ii) Extraction of the crude metal.
iii) Refining of the crude metal.

3. What is the role of Limestone in the extraction of Iron from its oxide Fe2O3?
The silica gangue present in the ore is acidic in nature, the limestone a basic flux combines
with it to form calcium silicate (slag).

CaO (s) + SiO2 (s) CaSiO3 (s)

Flux Gangue slag

4.Which type of ores can be concentrated by froth floatation method? Give two
examples for such ores.
Sulphide ores can be concentrated by froth floatation method.
E.x : Galena (PbS), Zinc blende (ZnS)

5. Out of coke and CO, which is better reducing agent for the reduction of ZnO? why?
• Above 1073 K , Gibb’s free energy for formation of C2 from C is less than that of
Gibb’s free energy for formation of ZnO .Therefore C can easily reduce ZnO to Zn
• On the other hand Gibb’s free energy for formation of CO2 from C is higher than that
of Gibb’s free energy of formation of ZnO . Therefore CO cannot reduce ZnO

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6. Describe a method for refining nickel.

Impure nickel is heated in a stream of carbon monoxide at around 350K. Nickel reacts with
CO to form a highly volatile nickel tetracarbonyl. The solid impurities are left behind.
Ni(s) + 4CO(g) NiCO4(g)
On heating nickel tetra carbonyl around 460K, the complex decomposes to give pure nickel.
Ni(CO)4(g) Ni(S) + 4CO(g)

7. Explain zone refining process with an example

➢ The principle used in this process is fractional crystallisation.
➢ When an impure metal is melted and allowed to solidify, the impurities will prefer to
remain in the molten region. i.e impurities are more soluble in the melt than in the
solid state metal.
➢ In this process the impure metal is taken in the form of a rod. One end of the rod is
heated using a mobile induction heater, melting the metal on that portion of the rod.
➢ When the heater is slowly moved to the other end pure metal crystallises while
impurities will move on to the adjacent molten zone formed due to the movement of
the heater.
➢ As the heater moves further away, the molten zone containing impurities also moves
along with it.
➢ This process is repeated several times by moving the heater in the same direction
again and again to achieve the desired purity level.
➢ This process is carried out in an inert gas atmosphere to prevent the oxidation of
metals.
➢ Germanium, Silicon and gallium which are used as semiconductor are refined by this
process.

8. A) Predict the conditions under which

i) Aluminium might be expected to reduce magnesia.
ii) Magnesium could reduce alumina.
B) Carbon monoxide is more effective reducing agent than carbon below 983K but,
above
this temperature, the reverse is true - Explain.
c) It is possible to reduce Fe2O3 by coke at a temperature around 1200K

A) i) Ellingham diagram for the formation of Al2O3 and MgO intersects around 1600K.
Above this temperature aluminium line lies below the magnesium line. Hence we can use
aluminium to reduce magnesia above 1600K.

ii) In Ellingham diagram below 1600K magnesium line lies below aluminium line. Hence
below 1600K magnesium can reduce alumina.

B) The two lines for C →CO2 and C →CO cross at about 983K. Below this temperature the
reaction to form CO2 is energetically more favourable hence CO is more effective reducing

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agent than carbon below 983K. But above 983K the formation of CO is preferred, hence
carbon is more effective reducing agent than CO above this temperature.

C) In Ellingham diagram above 1000K carbon line lies below the iron line. Hence it is
possible
to reduce Fe2O3 by coke at a temperature around 1200K.

9. Give the uses of zinc.

➢ Metallic zinc is used in galvanisation to protect iron and steel structures from rusting
and corrosion.
➢ Zinc is used to produce die - castings in the automobile, electrical and hardware
industries.
➢ Zinc oxide is used in the manufacture of paints, rubber, cosmetics, pharmaceuticals,
plastics, inks, batteries, textiles and electrical equipment.
➢ Zinc sulphide is used in making luminous paints, fluorescent lights and x - ray
screens.
➢ Brass an alloy of zinc which is highly resistant to corrosion is used in water valves
and communication equipment.

10. Explain the electrometallurgy of aluminium.

Hall - Herold Process
Cathode : Iron tanked lined with carbon
Anode : Carbon blocks
Electrolyte : 20% solution of alumina obtained from bauxite + Molten Cryolite + 10%
calcium chloride (lowers the melting point of the mixture)
Temperature: Above 1270K
Ionisation of Alumina : Al2O3 2Al3+ + 3O2-
Reaction at cathode : Al3+ (melt) + 3e- Al(l)
2- -
Reaction at anode : 2O (melt) O2 + 4e
Since carbon acts as anode the following reaction also takes place on it.
C(s) + O2 - (melt) CO + 2e -
C(s) + 2O2 -(melt) CO2 + 4e -
During electrolysis anodes are slowly consumed due to the above two reactions. Pure
aluminium is formed at the cathode and settles at the bottom.
Net electrolysis reaction is
4Al3+ (melt) + 6O2- (melt) + 3C(s) 4Al(l) + 3CO2(g)

11.Explain the following terms with suitable examples. i) Gangue ii) Slag
i) Gangue :
The non metallic impurities, rocky materials and siliceous matter present in the ores are
called gangue.
E.x : SiO2 is the gangue present in the iron ore Fe2O3.
ii) Slag :

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Slag is a fusible chemical substance formed by the reaction of gangue with a flux.
CaO (s) + SiO2 (s) CaSiO3 (s)
Flux Gangue slag

12.Give the basic requirement for vapour phase refining.

• The metal should form a volatile compound , when treated with a suitable reagent
• Then the volatile compound should decomposed to give the pure metal.

13. Describe the role of the following in the process mentioned.

i) Silica in the extraction of copper.
ii) Cryolite in the extraction of aluminium.
iii) Iodine in the refining of Zirconium.
iv) Sodium cyanide in froth floatation.
i) In the extraction of copper silica acts as an acidic flux to remove FeO as slag FeSiO3.
FeO(s) + SiO2(s) FeSiO3(s)
Flux Slag
ii) Cryolite serves as an added impurity and lowers the melting point of the
electrolyte.

iii) First Iodine forms a Volatile tetraiodide with impure metal, which decomposes to give
pure metal. Impure zirconium metal is heated in an evacuated vessel with iodine to form the
volatile zirconium tetraiodide (ZrI4). The impurities are left behind, as they do not react
with iodine.

iv) Sodium cyanide acts as a depressing agent in froth floatation process. When a sulphide
ore of a metal of interest contains other metal sulphides the depressing agent sodium
cyanide selectively prevent other metal sulphides from coming to the froth.

14. Explain the principle of electrolytic refining with an example.

Crude metal is refined by electrolysis carried out in an electrolytic cell.
Cathode : Thin strips of pure metal.
Anode : Impure metal to be refined.
Electrolyte : Aqueous solution of the salt of the metal with dilute acid.
As current is passed, the metal of interest dissolves from the anode and pass into the
electrolytic solution.
At the same time same amount of metal ions from the electrolytic solution will be deposited
at the cathode.
Less electro positive impurities in the anode settle down as anode mud.
Electro refining of silver :
Cathode : Pure silver
Anode : Impure silver rods.
Electrolyte : Acidified aqueous solution of silver nitrate.

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On passing current the following reactions will take place.

Reaction at anode : 2Ag (s) → Ag+ (aq) + 1e-
Reaction at cathode Ag+ (aq) + 1e- → 2Ag (s)
During electrolysis, at the anode the silver atoms lose electrons and enter the solution. The
positively charged silver cations migrate towards the cathode and get discharged by gaining
electrons and deposited on the cathode.

15. The selection of reducing agent depends on the thermodynamic factor: Explain with
an example.
➢ A suitable reducing agent is selected based on the thermodynamic considerations.
➢ For a spontaneous reaction∆G should be negative.
➢ Thermodynamically, the reduction of metal oxide with a given reducing agent can
occur if ∆G for the coupled reaction is negative.
➢ Hence the reducing agent is selected in such a way that it provides a large negative ∆G
value for the coupled reaction.
➢ Ellingham diagram is used to predict thermodynamic feasibility of reduction of oxides
of one metal by another metal.
For example
• Above 1623 K , Al has more negative ∆𝐺 𝑜 value than Mg
• Hence Al is used to reduce magnesia
• Below 1623 K , Mg more negative ∆𝐺 𝑜 value than Al
• Hence Mg is used to reduce Al

16. Give the limitations of Ellingham diagram.

➢ Ellingham diagram is constructed based only on thermodynamic considerations.
➢ It gives information about the thermodynamic feasibility of a reaction.
➢ It does not tell anything about the rate of the reaction.
➢ More over it does not give any idea about the possibility of other reactions that might
be taking place.
➢ The interpretation of ∆G is based on the assumption that the reactants are in
equilibrium with the product which is not always true.

17. Write a short note on electrochemical principles of metallurgy.

➢ Reduction of oxides of active metals such as sodium, potassium etc. by carbon is
thermodynamically not feasible.
➢ Such metals are extracted from their ores by using electrochemical methods.
➢ In this method the metal salts are taken in fused form or in solution form.
➢ The metal ion present can be reduced by treating the solution with suitable reducing
agent or by electrolysis.
➢ Gibbs free energy change for the electrolysis is
∆G0 = - nFE0
n = number of electrons involved in the reduction

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F = Faraday = 96500 coulombs
E0 = electrode potential of the redox couple.
➢ If E0 is positive, ∆G0 is negative and the reduction is spontaneous.
➢ Hence a redox reaction is planned in such a way that the e.m.f of the net redox
reaction is positive.
➢ A more reactive metal displaces a less reactive metal from its salt solution.
eg : Cu2+(aq) + Zn(s) → Cu(s) + Zn2+ (aq)
➢ Zinc is more reactive than copper and displaces copper from its salt solution.

Book inside
Two Mark Questions
1. What is concentration of ores?
The removal of non metallic impurities, rocky materials and siliceous matter (called as
gangue) from the ores is known as concentration of ores.

2. What is leaching?
The process of dissolving metal present in an ore in a suitable solvent to form a soluble
metal salt or complex leaving the gangue undissolved is called leaching.

3. What is ammonia leaching?

Crushed ore containing nickel, copper and cobalt is treated with aqueous ammonia under
suitable pressure.
Ammonia selectively leaches these metals by forming their soluble complexes namely
[Ni(NH3)6]2+ , [Cu(NH3)4]2+ from the ore.

4. In the extraction of metal ore is first converted into metal oxide before reduction into
metal. why?
➢ In the concentrated ore the metal exists in positive oxidation state and hence it is to be
reduced to elemental state.
➢ From the principles of thermodynamics the reduction of oxide is easier compared to
the reduction of other compounds of metal.
➢ Hence before reduction the ore is first converted into metal oxide.

5. How will you extract the metal by the process of reduction by carbon.
➢ In this method oxide ore of the metal is mixed with coal (coke) and heated strongly in
a blast furnace.
➢ This method can be applied to metals which do not form carbides with carbon at the
reduction temperature.
ZnO(S) + C → Zn(S) + CO(g) ↑

6. What is auto reduction of metallic ores?

Simple roasting of some of the metallic ores give the crude metal.
Use of reducing agent is not necessary.

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E.x Cinnabar is roasted to give mercury.

HgS(S) + O2(g) →Hg(l) + SO2(g) ↑

7. Write the applications or uses of copper.

Used for making coins and ornaments along with gold and other metals.
Copper and its alloys are used for making wires, water pipes and other electrical parts.

8. Write the applications or uses of gold.

➢ Used for coinage and has been used as standard for monetary systems in some
countries.
➢ Extensively used in jewellery in its alloy form with copper.
➢ Used in electroplating to cover other metals with a thin layer of gold in watches,
artificial limb joints, cheap jewellery, dental fillings and electrical connectors.
➢ Gold nanoparticles are used for increasing the efficiency of solar cells.
➢ Used as catalyst.

9.What do you meant by Refining process

• The metal extracted from its ore contains some impurities such as unreacted oxide ore,
other metals, nonmetals etc...
• Removal of such impurities associated with the isolated crude metal is called refining
process.

10.How will you refine the metal by distillation

• This method is employed for low boiling volatile metals like zinc (boiling point 1180
K) and mercury (630 K).
• In this method, the impure metal is heated to evaporate and the vapours are condensed
to get pure metal.

11. How will you refine the metal by liquation

• This method, is employed to remove the impurities with high melting points from
metals having relatively low melting points such as tin (Sb; mp= 904 K), lead (Pb;
mp=600 K), mercury (Hg; mp=234 K), and bismuth (Bi; mp=545 K).
• In this process, the crude metal is heated to form fusible liquid and allowed to flow on
a sloping surface.
• The impure metal is placed on sloping hearth of a reverberatory furnace and it is
heated just above the melting point of the metal in the absence of air, the molten pure
metal flows down and the impurities are left behind.
• The molten metal is collected and solidified.

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12.What do you meant by cementation?
Gold can be recovered by reacting the deoxygenated leached solution with zinc. In this
process the gold is reduced to its elemental state (zero oxidation sate) and the process is
called cementation.
Long answers
1. Explain froth floatation method.
➢ This is used to concentrate sulphide ores
such as galena (PbS) Zinc blende (ZnS)
etc.
➢ Metallic ore particles preferentially
wetted by oil can be separated from
gangue.
➢ Crushed ore is mixed with water and a
frothing agent like pine oil or eucalyptus
oil.
➢ A small amount of sodium ethyl xanthate
is added as a collector.
➢ A froth is formed by blowing air through
the mixture.
➢ The collector molecules attach to the ore
particles and make them water repellent.
➢ As a result ore particles wetted by the oil rise to the surface along with the froth.
➢ The froth is skimmed off and dried to recover the concentrated ore.
➢ Gangue particles preferentially wetted by water settle at the bottom.
➢ If the sulphide ore contains other metal sulphides as impurities, they are selectively
prevented from coming to the froth by using depressing agents like sodium cyanide,
sodium carbonate etc.
➢ Sodium cyanide depresses the floatation property of the impurity ZnS present in
galena
➢ (PbS) by forming a layer of zinc complex Na2[Zn(CN)4] on the surface of ZnS.

2. Explain about concentration of ore by Gravity separation or Hydraulic wash

➢ In this method, the ore having high specific gravity is separated from the gangue that
has low specific gravity by simply washing with running water.
➢ Ore is crushed to a finely powdered form and treated with rapidly flowing current of
water. During this process the lighter gangue particles are washed away by the running
water.
➢ This method is generally applied to concentrate the native ore such as gold and oxide
ores such as hematite (Fe2O3), tin stone (SnO2) etc.

3. Explain about Magnetic separation

➢ This method is applicable to ferromagnetic ores and it is based on the difference in
the magnetic properties of the ore and the impurities.

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➢ For example tin stone can be

separated from the wolframite
impurities which is magnetic.
Similarly, ores such as chromite,
pyrolusite having magnetic
property can be removed from
the non magnetic siliceous
impurities.
➢ The crushed ore is poured on
to an electromagnetic
separator consisting of a belt
moving over two rollers of
which one is magnetic.
➢ The magnetic part of the ore is
attracted towards the magnet and falls as a heap close to the magnetic region while the
nonmagnetic part falls away from it

4. Explain about Van-Arkel method for refining zirconium/titanium:

➢ This method is based on the thermal decomposition of metal compounds which lead to
the formation of pure metals.
➢ Titanium and zirconium can be purified using this method. For example, the impure
titanium metal is heated in an evacuated vessel with iodine at a temperature of 550 K
to form the volatile titanium tetra-iodide.(TiI4).
➢ The impurities are left behind, as they do not react with iodine
Ti (s) + 2I2 (s) TiI4 (vapour)

➢ The volatile titanium tetraiodide vapour is passed over a tungsten filament at a

temperature aroud 1800 K.
➢ The titanium tetraiodide is decomposed and pure titanium is deposited on the filament.
The iodine is reused.
Ti (s) + 2I2 (s) TiI 4 (vapour)

5.What are Application of Al

➢ Aluminium is the most abundant metal and is a good conductor of electricity and heat.
It also resists corrosion. The following are some of its applications.
➢ Many heat exchangers/sinks and our day to day cooking vessels are made of
aluminium.
➢ It is used as wraps (aluminium foils) and is used in packing materials for food items,
➢ Aluminium is not very strong, However , its alloys with copper, manganese,
magnesium and silicon are light weight and strong and they are used in design of
aeroplanes and other forms of transport.
➢ As Aluminium shows high resistance to corrosion, it is used in the design of chemical
reactors, medical equipments ,refrigeration units and gas pipelines.

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➢ Aluminium is a good electrical conductor and cheap, hence used in electrical overhead
electric cables with steel core for strength.

6.Explain about leaching

This method is based on the solubility of the ore in a suitable solvent and the
reactions in aqueous solution. In this method, the crushed ore is allowed to dissolve in a
suitable solvent, the metal present in the ore is converted to its soluble salt or complex while
the gangue remains insoluble.
Cyanide leaching
The crushed ore of gold is leached with aerated dilute solution of sodium cyanide. Gold is
converted into a soluble cyanide complex. The gangue, aluminosilicate remains insoluble.

4Au (s) + 8CN- (aq) + O2 (g) + 2H2O (l) 4[Au(CN)2]- (aq) + 4OH-(aq)

Ammonia leaching
When a crushed ore containing nickel, copper and cobalt is treated with aqueous ammonia
under suitable pressure, ammonia selectively leaches these metals by forming their soluble
complexes viz. [Ni(NH3)6]2+, [Cu(NH3)4]2+, respectively from the ore leaving behind the
gangue, iron(III) oxides/hydroxides and aluminosilicate.

Alkali leaching
In this method, the ore is treated with aqueous alkali to form a soluble complex. For
example, bauxite, an important ore of aluminium is heated with a solution of sodium
hydroxide or sodium carbonate in the temperature range 470 - 520 K at 35 atm to form
soluble sodium meta-aluminate leaving behind the impurities, iron oxide and titanium oxide.
Al2O3 (s) + 2NaOH (aq) + 3H2O (l) 2Na[Al(OH)4] (aq)

The hot solution is decanted, cooled, and diluted. This solution is neutralised by passing CO2
gas, to the form hydrated Al2O3 precipitate.
2Na[Al(OH)4] (aq) + CO2 (g) Al2O3.xH2O (s) + 2NaHCO3 (aq)
The precipitate is filtered off and heated around 1670 K to get pure alumina Al2O3.

Acid leaching
Leaching of sulphide ores such as ZnS, PbS etc., can be done by treating them with hot
aqueous sulphuric acid.
2ZnS (s) + 2H2SO4 (aq) + O2(g) 2ZnSO4 (aq) + 2S (s) + H2O
In this process the insoluble sulphide is converted into soluble sulphate and elemental
sulphur

7.How will you convert metal into metal oxide by roasting and calcination
Roasting
Roasting is the method, usually applied for the conversion of sulphide ores into their oxides.

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In this method, the concentrated ore is oxidised by heating it with excess of oxygen in a
suitable furnace below the melting point of the metal.

2PbS + 3O2 2PbO + 2SO2 ↑

Roasting also removes impurities such as arsenic, sulphur, phosphorous by converting them
into their volatile oxides.

Calcination
• Calcination is the process in which the concentrated ore is strongly heated in the
absence of air.
• During this process, the water of crystallisation present in the hydrated oxide escapes
as moisture.
• Any organic matter (if present) also get expelled leaving behind a porous ore.
• This method can also be carried out with a limited supply of air.
• During calcination of carbonate ore, carbon dioxide is expelled
PbCO3 PbO + CO2

8.Explain about Smelting

In this method, a flux (a chemical substance that forms an easily fusible slag with gangue)
and a reducing agent such as carbon, carbon monoxide (or) aluminium is added to the
concentrated ore and the mixture is melted by heating at an elevated temperature (above the
melting point of the metal) in a smelting furnace. For example the oxide of iron can be
reduced by carbon monoxide as follows.
Fe2O3 (s) + 3CO (g) 2Fe (s) + 3CO2 (g)

9.Explain about extraction of copper from copper pyrite

• Ore is concentrated by froth flotation process
• The concentrated ore is heated in a reverberatory furnace after mixing with silica, an
acidic flux. The ferrous oxide formed due to melting is basic in nature and it combines
with silica to form ferrous silicate (slag).
• The remaining metal sulphides Cu2S and FeS are mutually soluble and form a copper
matte.
2CuFeS2 (s)+ O2 (g) 2FeS (l)+ 2Cu2S (l)+ 2SO2 (g)
FeS (l) + O (g) FeO (l) + SO2 (g)
FeO (s) + SiO2 (s) FeSiO3 (s)
Flux Gangue Slag

• The matte is separated from the slag and fed to the converting furnace. During
conversion, the FeS present in the matte is first oxidised to FeO. This is removed by

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slag formation with silica. The remaining copper sulphide is further oxidised to its
oxide which is subsequently converted to metallic copper as shown below.
Cu2S (l,s) + 3O2 (g) 2Cu2S (l,s) + 2SO2 (g)
2Cu2O (l) + Cu2S (l) 6Cu (l) + SO2 (g)
• The metallic copper is solidified and it has blistered appearance due to evolution of
SO2 gas formed in this process. This copper is called blistered copper.

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