UNIT-1 METALLURGY

METAL ORE FORMULA

Bauxite Al2O3.nH2O
Aluminium
Cyrolite Na3AlF6
Haematite Fe2O3
Iron
Magnetite Fe3O4
Copper pyrite CuFeS2
Copper glance Cu2S
Copper
Cuprite Cu2O
Malachite CuCO3.Cu(OH)2
Zinc blende ZnS
Zinc Calamine ZnCO3
Zincite ZnO
Galena PbS
Lead Anglesite PbSO4
Cerrusite PbCO3
Silver glance (Argentite) Ag2S
Silver Pyrargyrite ( Ruby silver) Ag3SbS3
Chlorargyrite (Horn silver) AgCl
Tin Cassiterite (tin stone) SnO2
 What are the differences between minerals and ores?
 A naturally occurring substance obtained by mining which contains the metal in free
state (or) in the form of oxides, sulphides etc... is called a mineral.
 A mineral that contains a high percentage of metal, from which it can be extracted
conveniently and economically are called ores.
 What are gangue?
Non-metallic impurities, rocky materials and siliceous matter associated with the ores
are called as gangue.The process of removal of gangue from the ore is called as
concentration.
 Write a short note on gravity separation.
It is used to concentrate native ores such as gold and oxide ores (Fe2O3 & SnO2). Ore
having high specific gravityis separated from the gangue having low specific
gravity.Finely powdered ore is treated with rapidly flowing current of water. The lighter
gangue particles are washed away by the running water.

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 Write a short note on magnetic separation.
This method is applicable to ferromagnetic ores. This is based on the difference in the
magnetic properties of ore and impurities.Crushed ore is poured on to an
electromagnetic separator consisting of a belt moving over two rollers of which one is
magnetic.

The magnetic ore particles are attracted towards the magnet and collected as a heap close
to the magnetic region.Non-magnetic impurities are collected as a separate heap away from
magnetic region.For example:
(i) Tin stone (nonmagnetic) is separated from wolframite (magnetic) impurities.
(ii) Chromite and pyrolusite (magnetic) are separated from siliceous (non-magnetic)
impurities.
 Write a short note on froth floatation.

 This method is suitable only for sulphide ores. Example: PbS,ZnS etc.
 Metallic ore particles are preferentially wetted by oil can be separated from gangue.
 The crushed ore is suspended in water and mixed with frothing agent such as pine
oil, eucalyptus oil etc.

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  A small amount of sodium ethyl xanthate is added, it acts as a collector. The collector
molecules attach to the ore particle and make them water repellent.
 A froth is generated by blowing air through this mixture.
 Ore particles are wetted by the oil and rise to the surface along with the froth. The
froth is skimmed off and dried to get the concentrated ore.
 Gangue particles that are preferentially wetted by water settle at the bottom.
 Explain the role of depressing agents in froth floatation with an example.(or) Describe
the role of the Sodium cyanide in froth floatation.
❖ When a sulphide ore of a particular metal contains other metal sulphides as
impurities, depressing agents such as NaCN, Na2CO3 are used to prevent impurities
from coming to the froth.
❖ Galena (PbS) contains ZnS as an impurity. Sodium cyanide (NaCN) is added to depress
the flotation property of ZnS by forming a layer of zinc complex Na 2[Zn(CN)4] on the
surface of zinc sulphide.
 What is the principle behind a method called leaching?
✓ This method is based on the solubility of the ore in a suitable solvent.
✓ The crushed ore is allowed to dissolve in a suitable solvent.
✓ Metal is converted to its soluble salt or complex, gangue remains insoluble.
 What is acid leaching?
Sulphide ores are leached with hot aqueous sulphuric acid. Insoluble sulphide is
converted into soluble sulphate and elemental sulphur.
2ZnS + 2H2SO4 + O2 ⎯⎯→ 2ZnSO4 + 2S + 2H2O
 Explain how gold ore is leached by cyanide process.
Gold ore is concentrated by cyanide leaching.Crushed Gold ore is leached with aerated
solution of NaCN. Gold is converted into a soluble cyanide complex. The gangue,
aluminosilicate remains insoluble.
4Au+8NaCN+2H2O+O2 ⎯⎯→4Na Au (CN)2  + 4NaOH
Gold is recovered by treating leached solution with zinc metal. Gold is reduced to its
elemental state and the process is called cementation.
2Na  Au (CN)2  + Zn ⎯⎯→ Na2 Zn (CN)4  + 2Au 
 Explain how pure alumina is obtained by alkali leaching.
When Bauxite ore is heated with NaOH solution it forms soluble sodium meta-aluminate.
Impurities iron oxide and titanium oxide are left behind.
470-520K
Al2O3 + 2NaOH +3H2O ⎯⎯⎯⎯⎯
35atm → 2Na Al ( OH )4 
Sodium meta aluminate
This hot solution is decanted, cooled, diluted and then neutralised by passing CO2 gas, to
the form hydrated Al2O3 precipitate.
2Na  Al ( OH )4  + 2CO2 ⎯⎯ → Al2O3.xH2O + 2NaHCO3
Hydrated alumina

This precipitate is filtered off and heated to 1670 K to get pure alumina Al2O3.
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 What is roasting?
The process in which the concentrated ore is heated in the presence of excess oxygen is
called roasting. Roasting is carried out below the melting point of the metal. During
Roasting sulphide ores are converted into their oxides.
Δ
2PbS + 3O2 ⎯⎯→ 2PbO + 2SO2
Δ
2ZnS + 3O2 ⎯⎯→ 2ZnO + 2SO2
Impurities such as S, P and As are converted into volatile oxides and removed.
heat
4As + 3O2 ⎯⎯⎯ →2As2O3
heat
S8 + 8O2 ⎯⎯⎯ →8SO2
heat
P4 + 5O2 ⎯⎯⎯ →P4O10
 What is Calcination?
The process in which the concentrated ore is heated in the absence of oxygen (Air) is
called Calcination. During calcination
(i) Organic matter expelled leaving behind a porous ore.
(ii) Water is expelled from hydrated ore.
(iii) Carbonate ore is converted into oxide ore.
Δ
PbCO3 ⎯⎯ → PbO + CO2
Δ
ZnCO3 ⎯⎯ → ZnO + CO2
 What is smelting? Explain with an example.
The process in which the ore is heated with reducing agents such as C, CO etc beyond its
melting point is called smelting. Smelting is carried out in the presence of a flux.For
example: Haematite ore is reduced by carbon monoxide as follows.
Fe2O3 + 3CO ⎯⎯→ 2Fe + 3CO2
The ore is smelted with basic flux limestone (CaO).
CaO + SiO2 ⎯⎯→ CaSiO3
(flux) (gangue) (slag)
 What is flux?
A substance that combines with gangue to form an easily fusible slag is called a flux.
Examples: SiO2, CaO… etc are used as fluxes in metallurgy.
 What is slag? Explain with an example.
An easily fusible substance obtained when the ore is heated with flux is called a slag. The
gangue present in the ore reacts with flux to form slag.
CaO + SiO2 ⎯⎯→ CaSiO3
(flux) (gangue) (slag)

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 What are acidic and basic flux? Explain the choice of flux in metallurgy.
Acidic flux: Acidic flux combines with basic gangue to form fusible slag.
FeO + SiO2 ⎯⎯→ FeSiO3
( gangue) (flux ) (slag)
basic acidic

Basic flux: Basic flux combines with acidic gangue to form fusible slag.
CaO + SiO2 ⎯⎯→ CaSiO3
(flux ) ( gangue) (slag)
basic acidic

 Explain the metallurgy of copper.

Copper is extracted from copper pyrite ore. The concentrated ore is mixed with acidic
flux silica (SiO2) and is heated in a reverberatory furnace.
2CuFeS2 + O2 ⎯⎯→ 2FeS + Cu2S + SO2
2FeS + 3O2 ⎯⎯→ 2FeO + 2SO2
FeO + SiO2 ⎯⎯→ FeSiO3 (slag)
Cu2S and 𝐹𝑒𝑆 are mutually soluble. This mixture is called a copper matte. Matte is
separated and fed into the converting furnace. 𝐹𝑒𝑆 is oxidised to FeO. This is removed
by slag formation with silica. The remaining Cu2S is further oxidised to Cu2O, which is
subsequently converted to metallic copper.
2Cu2S + 3O2 ⎯⎯→ 2Cu2O + 2SO2
2Cu2O + Cu2S ⎯⎯→ 6Cu + SO2
The metallic copper is solidified and it has blistered appearance due to evolution of SO 2
gas formed in this process. This copper is called blistered copper.
 What kind of metal oxides are reduced by carbon?
Metal oxides which do not form carbides with carbon at the reduction temperature are
reduced by carbon.
ZnO+C ⎯⎯
→Zn +CO
Cr2O3 +3C ⎯⎯
→2Cr+3CO
 What kind of metal oxides are reduced by hydrogen?
Metal oxides having less electropositive character than Hydrogen are reduced by
Hydrogen.
Ag2O + H2 ⎯⎯
→ 2Ag + H2O
 Explain Auto-reduction with an example.
Simple roasting of some of ores give the crude metal. In such cases, the use of
reducing agents is not necessary. For example, mercury is obtained by roasting cinnabar.
HgS + O2 ⎯⎯ → Hg + SO2

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 Write a note on Aluminothermite process.
Cr2O3 is mixed with Aluminium powder in a fire clay crucible.
The reduction process is initiated by an ignition mixture (Mg + BaO 2).
BaO2 + Mg ⎯⎯→BaO + MgO +Heat
During the above reaction a large amount of heat is evolved which facilitates the
0
reduction.((»2400 C))
Δ
Cr2O3 + 2Al ⎯⎯ →2Cr + Al2O3
 Explain the Observations from the Ellingham diagram.
Ellingham diagram

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 1 For most of the metal oxide formation, the slope is positive. Oxygen gas is
consumed during the formation of metal oxides. Hence, ΔS becomes negative and
it makes, TΔS positive in the straight line equation.
2 The graph for the formation of CO is a straight line with negative slope. In this case
ΔS is positive as 2 moles of CO gas is formed by the consumption of one mole of
oxygen gas. It indicates that CO is more stable at higher temperature.
3 As the temperature increases, ΔG for the formation of the metal oxide become
less negative and becomes zero at a particular temperature. Below this
temperature, ΔG is negative and the oxide is stable and above this temperature
ΔG is positive. Generally metal oxides are less stable at higher temperatures and
they decompose easily.
4 There is a sudden change in the slope at a particular temperature for some metal
oxides like MgO, HgO. This is due to the phase transition (melting or vaporisation).
 Give the limitations of Ellingham diagram.
1. It gives information about thermodynamic feasibility but not rate of the reaction.
2. It does not explain the possibility of other reactions that may take place.
3. The interpretation of ΔG is based on the assumption that the reactants are in
equilibrium with the products which is not always true.
 Explain the electrometallurgy of aluminium. (Hall-Herold process)
Cathode : Iron tank lined with carbon.
Anode : Carbon blocks immersed in the electrolyte.
Electrolyte : A 20% solution of alumina + molten cyrolite + 10% CaCl2.
The fused mixture is maintained at a temperature of above 1270 K. Here CaCl2 helps to
lower the melting point of the mixture.
Δ
Ionisation of alumina : Al2O3 ⎯⎯→ 2Al3+ + 3O2-
Reaction at cathode : 2Al3+ + 6e- ⎯⎯→2Al
2-
Reaction at anode : 6O ⎯⎯ → 3O2 + 12e-
Since carbon acts as anode the following reaction also takes place on it.

C + O2- ⎯⎯→CO+ 2e-

C + 2O2- ⎯⎯→CO2 + 4e-
Due to the above two reactions, anodes are slowly consumed during the electrolysis.
Pure aluminium is formed at the cathode and settles at the bottom. The net electrolysis
reaction can be written as follows.
Δ
4Al3+ + 6O2- + 3C ⎯⎯→ 4Al + 3CO2 

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 Explain the process liquation.
This method is used to remove high melting impurities from low melting metals. Impure
metal is heated on sloping hearth just above its melting point in the absence of air. Pure
metal melts and flows down and the impurities are left behind. The molten metal is
collected and solidified.
For example: Tin (904 K), lead (600 K), mercury (234 K), and bismuth (545 K).
 Explain the principle of electrolytic refining with an example.
The crude metal is refined by electrolysis in an electrolytic cell.
Anode : Impure silver rod
Cathode : Pure silver strip
Electrolyte : Acidified aqueous solution of silver nitrate
When a current is passed through the electrodes,
 Silver atoms from anode, lose electrons and enter the solution.
At anode : Ag ⎯⎯→ Ag+ + e-
 Silver cations migrate towards the cathode and gets reduced and deposited.
At cathode : Ag+ + e- ⎯⎯→ Ag
 Explain the principle involved in zone refining.
Principle:
The principle involved in Zone refining is fractional crystallisation. When the molten
impure metal is allowed to solidify, the impurities prefer to be in the molten region.
Process:
Impure metal is taken in the form of a rod. One end of the rod is heated using a mobile
induction heater which results in melting of the metal on that portion of the rod. When
the heater is slowly moved to the other end, the pure metal crystallises while the
impurities will move on to the adjacent molten zone. As the heater moves further away,
the molten zone containing impurities also moves along with it.
The process is repeated several times in the same direction to get high purity. This
process is carried out in an inert gas atmosphere to prevent the oxidation of metals. Ge,
Si and Ga are refined by this process.
 How is nickel refined by Mond’s process?
Impure nickel is heated in a stream of carbon monoxide at 350 K. Nickel reacts with CO
to form a highly volatile Nickel tetra carbonyl. The solid impurities are left behind.
Ni + 4CO ⎯⎯⎯⎯ 350K → Ni CO
( )4
Nickel tetracarbonyl is decomposed at 460 K to get pure Nickel.
Ni(CO)4 ⎯⎯⎯⎯
460K → Ni + 4CO

 Give the basic requirement for vapour phase refining.

 Metal must be able to form a volatile compound with the particular reagent.
 The volatile compound must decompose to give the pure metal.

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 Explain how Titanium is refined by Van-Arkel method.
Impure Titanium is heated with iodine at 550 K in an evacuated vessel to form the volatile
titanium tetra-iodide (𝑇𝑖𝐼4 ). Impurities do not react with Iodine and are left behind.
Ti + 2I ⎯⎯⎯⎯ 550K → TiI
2 4
When 𝑇𝑖𝐼4 vapour is passed over a tungsten filament at 1800 K, it decomposes to give
pure titanium which deposits on the filament.
TiI4 ⎯⎯
→ Ti + 2I2
 List the uses of Aluminium.

s.no Items Uses

Exchangers, sinks, cooking vessels.

1 Aluminium Chemical reactors, medical equipment, refrigerators.

Electric cables with steel core for strength.

2 Al foils Wraps for food items

Aluminium (Al-Cu), (Al-Mn), (Al-Mg), (Al-Si) alloys are light weight and
3
alloys strong. They are used in design of aeroplanes and vehicles.
 List the uses of Zinc.
s.no Items Uses

1 Zinc galvanisation of iron and steel.

2 ZnS Luminous paints, fluorescent lights and x-ray screens.

3 ZnO Paints, rubber, cosmetics, , plastics, inks, batteries etc.

4 Brass an alloy of Zn and Cu : valves and communication equipment

 List the uses of copper.
s.no Items Uses

1 Cu-Au alloy Coins and jewellery

2 Cu alloys wires, water pipes, electrical parts

 List the uses of gold.
s.no Items Uses
1 Gold coinage, as standard for monetary systems

2 Au-Cu alloy jewellery

3 Gold plated metals watches, artificial limb joints, dental filling etc.,

4 Gold nanoparticles solar cells , catalysts

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 EVALUATION
1. Bauxite has the composition
a) Al2 𝑂3 b) 𝐀𝐥𝟐 𝑶𝟑 . 𝒏𝑯𝟐 𝑶
c) 𝐹𝑒2 𝑂3 . 𝑛𝐻2 𝑂 d) None of these
2. Roasting of sulphide ore gives the gas (A). This compound (A) is a colourless gas. Aqueous
solution of (A) is acidic. The gaseous compound (A) is
a) CO2 b) SO3
c) SO2 d) H 2S
3. Which one of the following reaction represents calcinations?
a) 2Zn + O2 → 2𝑍𝑛𝑂 b) 2ZnS + 3O2 → 2𝑍𝑛𝑂 + 2𝑆𝑂2
c) 𝐌𝐠𝐂𝐎𝟑 → 𝑴𝒈𝑶 + 𝑪𝑶𝟐 d) Both (a) and (c)
4. The metal oxide which cannot be reduced to metal by carbon is
a) PbO b) 𝐀𝐥𝟐 𝐎𝟑
c) ZnO d) FeO
5. Which of the metal is extracted by Hall-Heroult process?
a) Al b) Ni
c) Cu d) Zn
6. Which of the following statements, about the advantage of roasting of sulphide ore
before reduction is not true?
a) G0f of sulphide is greater than those for CS2 and H2S.

b) G r is negative for roasting of sulphide ore to oxide.

0

c) Roasting of the sulphide to its oxide is thermodynamically feasible.

d) Carbon and hydrogen are suitable reducing agents for metal sulphides.
7. Match items in column - I with the items of column – II and assign the correct code.
Column-I Column-II
A Cyanide process (i) Ultra-pure Ge
B Froth floatation process (ii) Dressing of ZnS
C Electrolytic reduction (iii) Extraction of Al
D Zone refining (iv) Extraction of Au
(v) Purifcation of Ni
a) (i)-A , (ii)-B, (iii)-C, (iv)-D b) (iii)-A , (iv)-B, (v)-C, (i)-D
c) (iv)-A , (ii)-B, (iii)-C, (i)-D d) (ii)-A , (iii)-B, (i)-C, (v)-D
8. Wolframite ore is separated from tinstone by the process of
a) Smelting b) Calcination
c) Roasting d) Electromagnetic separation
9. Which one of the following is not feasible
a) Zn ( s ) + Cu ( aq ) ⎯⎯
→ Cu ( s ) + Zn 2+ ( aq )
2+

b) 𝐂𝐮(𝐬) + 𝒁𝒏𝟐+ (𝒂𝒒) → 𝑪𝒖𝟐+ (𝒂𝒒) + 𝒁𝒏(𝒔)

c) Cu ( s ) + 2Ag ( aq ) ⎯⎯
→ Cu 2+ ( aq ) + 2Ag ( s )
+

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 d) Fe ( s ) + Cu ( aq ) ⎯⎯
→ Cu ( s ) + Fe 2+ ( aq )
2+

10. Electrochemical process is used to extract

a) Iron b) Lead
c) Sodium d) silver
11. Flux is a substance which is used to convert
a) Mineral into silicate b) Infusible impurities to soluble impurities
c) Soluble impurities to infusible impurities d) All of these
12. Which one of the following ores is best concentrated by froth – floatation method?
a) Magnetite b) Haematite
c) Galena d) Cassiterite
13. In the extraction of aluminium from alumina by electrolysis, cyrolite is added to
a) Lower the melting point of alumina
b) Remove impurities from alumina
c) Decrease the electrical conductivity
d) Increase the rate of reduction
14. Zinc is obtained from ZnO by
a) Carbon reduction b) Reduction using silver
c) Electrochemical process d) acid leaching
15. Extraction of gold and silver involves leaching with cyanide ion. Silver is later recovered
by (NEET-2017)
a) Distillation b) Zone refining
c) Displacement with zinc d) liquation
16. Considering Ellingham diagram, which of the following metals can be used to reduce
alumina? (NEET-2018)
a) Fe b) Cu
c) Mg d) Zn
17. The following set of reactions are used in refining Zirconium
Zr (impure) + 2I 2 ⎯⎯⎯
523K
→ ZrI 4
This method is known as
ZrI 4 ⎯⎯⎯
1800 K
⎯→ Zr (pure) + 2I 2
a) Liquation b) van Arkel process
c) Zone refining d) Mond’s process
18. Which of the following is used for concentrating ore in metallurgy?
a) Leaching b) Roasting
c) Froth floatation d) Both (a) and (c)
19. The incorrect statement among the following is
a) Nickel is refined by Mond’s process
b) Titanium is refined by Van Arkel’s process
c) Zinc blende is concentrated by froth floatation
d) In the metallurgy of gold, the metal is leached with dilute NaCl solution

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20. In the electrolytic refining of copper, which one of the following is used as anode?
a) Pure copper
b) Impure copper
c) Carbon rod
d) Platinum electrode
21. Which of the following plot gives Ellingham diagram
a) S Vs T b) G 0 Vs T

c) G 0 Vs  1  d) G 0 Vs T 2
T
22. In the Ellingham diagram, for the formation of carbon monoxide
 ΔG 0 
a)  ΔS  is negative
0
b)   is positive
 ΔT   ΔT 
 ΔT 
c)  ΔG  is negative  ΔG 0 
0
d) Initially  0  is positive, after 7000C ,   is
 ΔT   ΔG   ΔT 
negative
23. Which of the following reduction is not thermodynamically feasible?
a) 𝐶𝑟2 O3 + 2 𝐴𝑙 → 𝐴𝑙2 𝑂3 + 2𝐶𝑟 b) 𝑨𝒍𝟐 𝐎𝟑 + 𝟐 𝑪𝒓 → 𝑪𝒓𝟐 𝑶𝟑 + 𝟐𝑨𝒍
c) 3𝑇𝑖O2 + 4 𝐴𝑙 → 2𝐴𝑙2 𝑂3 + 3𝑇𝑖 d) none of these
24. Which of the following is not true with respect to Ellingham diagram?
a) Free energy changes follow a straight line. Deviation occurs when there is a phase
change.
b) The graph for the formation of CO2 is a straight line almost parallel to free energy
axis.
c) Negative slope of CO shows that it becomes more stable with increase in temperature.
d) Positive slope of metal oxides shows that their stabilities decrease with increase in
temperature.

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