NEET JEE 2019

Metallurgy
Revise Full theory in 1 video

Crash Course
 Introduction to Metallurgy

Elements

Non Metals Metals Metalloids

Free state Combine state

Example : Example :
Silver (Ag) Zinc blende (ZnS)
Gold (Au) Corrundun (Al2O3)
Platinum (Pt) Rock salt (NaCl)
 How to obtain a pure Metal?

80 %
Metallurgy terms :
Mineral The compounds of Metals that occur in nature along
with rocky and other impurities are called minerals.
May or may not give Profitable extraction

Ore The mineral from which a metal can be extracted

commercially or profitably is called ore.
Profitable extraction of element
Ore has appreciable quantity of metal in it

Gangue Impurities present in ore are called Gangue or matrix

Earthly impurities like Sand, Soil, etc.
Metallurgy terms :
70% Fe
Haematite
Fe2O3
Siderite Magnetite
FeCO3 Fe3O4

Iron

limonite
Iron pyrite
2Fe2O3 3H2O
FeS2
 What is Metallurgy?

Definition:
The Process of extraction of a pure metal from its ore is called Metallurgy.

Extraction
+
Process

Ore Impurities Pure Metal

 Extraction of metals

Concentration
of Ore

Reduction
of Ore

Refining
of Ore
Concentration of the ore Ore dressing or Benefaction
Used to remove earthly impurities like soil, silica (SiO2), etc…
Definition :
The process of removal of gangue from the
ore is known as concentration of an ore /
Ore dressing / Benefaction.
Methods of Concentration of Ore
1 Hydraulic washing
2 Froth flotation
3 Electromagnetic separation
4 Leaching
1.Hydraulic Washing

Jet of
water
Crushed Ore

1 Basic principle is density difference

2 Useful for ores of heavy metals like Sn, Pb, Fe
3 Light ores can not be concentrated
1.Hydraulic Washing Procedure :
➢ Jet of water is passed from
one side
Jet of
water ➢ Crushed ore is poured from
Hydraulic classifier
Crushed Ore
➢ Heavy ore particles gets
settled down
➢ Lighter gangue particles
are washed away
 2.Froth flotation

1 Used for sulphide ores of Cu, Zn, Fe and Pb

2 Sulphide ore is wetted by oil and moves

upward in the form of froth

➢ Why does S particle are wetted by oil not by water ?

‘S’ has large size thus poor hydration
Copper glance (Cu2S)
Zinc blend (ZnS)
3 Gangue particles are wetted by water and Iron pyrite (FeS2)
settles down at bottom Galena ( PbS )
 2.Froth flotation

Procedure :

➢ Finely powdered ore is mixed with water and pine oil

➢ Mixture is agitated with compressed air

➢ Ore particles rise to the surface along with froth

➢ Gangue being wetted by water remain in water below the foam

Main parameters of Froth Flotation

❖ Frothers
Pine oil or Eucalyptus oil :Oil should be less dense than H2O

❖ Collectors
Potassium ethyl xanthate : To Enhance the non-wettability of the mineral particles

❖ Froth stabilizers i. Aniline, Cresol

If N of aniline is in resonance
shows sp2 hybridisation
CH3
: NH2 OH
ii. Both the compounds are capable to show H-bonding
 ❖ Depressant Used when mixture of sulphide ore is present
NaCN, Na2CO3
Example Mixture of galena ( PbS ) and Zinc blende ( ZnS )

PbS + NaCN No reaction

ZnS + NaCN Na2[Zn(CN)4] Follow EAN rule
Sodium tetra cyano zincate

➢This complex is wetted with water and prevented coming into the froth
➢While PbS comes into forth because it cannot react with NaCN
Differential flotation Method
3.Electromagnetic separation

Magnetic
Ores
wolframite –
Tungsten
Magnetite – Earthly
impurities
1 Used if one of the ore or impurity is magnetic
2 Magnetic particles are attracted and fall
nearer the magnetic roller.
3 While non-magnetic particles fall
away from the roller
 Leaching
When metal is more soluble than impurities present in its ore.
Ores of following metals can be concentrated:
1 Aluminium
2 Silver or Gold
 Ore of Aluminum
Minerals of Aluminum
Alumina
(Al2O3)
Cryolite Diaspore
( Na3 [ AlF6] ) ( Al2O3 . 1H2O)

ALUMINIUM

Gibbsite Bauxite
(Al2O3 . 3H2O) (Al2O3 . 2H2O)
 Bauxite
(Al2O3 . 2H2O)

Red Bauxite White Bauxite

( Fe impurities) ( SiO2 impurities)

Process of leaching Process of leaching

1. Bayer’s process 1. Serpeck’s process

2. Hall’s process
Bayer’s process (Red Bauxite)
Leaching Agent (Solvent) : Caustic Soda (NaOH)

Impurity : Ferric oxide (Fe2O3)

Consist of 3 steps
 Bayer’s process (Red Bauxite)

Step I : Dissolution
473 to
530 K
Al2O3 . xH2O + NaOH Na[Al(OH)4] Soluble complex
Sodium tetra
hydroxy alluminate

Impurity + Flux Slag

2Fe2O3 + SiO2 2FeSiO3 +O2

➢ flux is agent getting attached with the impurities

➢ Slag is impurities are removed in the form of slag

Bayer’s process (Red Bauxite)
Step II : Neutralization

Na [Al(OH)4] + CO2 Al2O3 . xH2O + Na2CO3

Basic Complex Acidic Gas Dirty white colour

Step III : Calcinations heated to remove water

Al2O3. xH2O 1400-1500K

Al2O3 + xH2O
Alumina
Pure aluminium can be obtained by further reduction and
refining of alumina
 Leaching of Au/Ag

Mac Arthur Forrest cyanide process

Leaching Agent (Solvent) : NaCN or KCN Part of Hydrometallurgy

Step I : Dissolution
4Ag2S + 8NaCN + O2 4Na[Ag(CN)2] + 4Na2S
Sodium
argentocyanide
complex

4 Ag(s) + 8 CN-(aq) + 2 H2O + O2 4 [Ag(CN)2]- (aq) + 4 OH-

 Leaching of Au/Ag

Mac Arthur Forrest cyanide process

Leaching Agent (Solvent) : NaCN or KCN

Step II : Reduction
Zn=More electropositive metal
Zn
2Na[Ag(CN)2] 2Ag + Na2[Zn(CN)4 ]
Ag(+1) → Ag(0)
➢ This gold or silver is not pure but contains Pb as impurity
Zn(0) → Zn(+2)
➢ Pure Ag/Au is obtained by electrolytic refining

Zn is functioning as a reducing agent

Reduction of ore Extraction of metals

Concentration
of Ore

Reduction
of Ore

Refining
of Ore
 Reduction of ore
Used for converting concentrated ore to crude metal

Methods of reduction :
1. Roasting In presence of O2
Used for reducing sulphide ores

2. Calcination In absence of O2

Used for reducing carbonate and hydroxide ores

3. Smelting In presence of O2
Used for reducing metal oxide ores
 1) Roasting
Definition
The process of conversion of sulphide ores into
oxide ores in presence of air is known as roasting.
➢ It is carried out in reverboratory furnace.
➢ Ore is heated below melting point of metal.
➢After roasting ore becomes porous and dry.
Example
ZnS + O2 ZnO + SO2 ZnS is Obtained By froth flotation
white
heat
ZnO ZnO
white cool yellow
 Self reduction reactions in roasting :
The reduction in which species reacts with itself to form new species is known
as self reduction.
1. Cu2S + O2 Cu2O + SO2 Cu + SO2
Cu2S
Blister copper

Copper having blisters of SO2 gas on its surface is called as blister copper
HgS
2. HgS + O2 HgO + SO2 Hg + SO2

3. PbS + O2 PbO + SO2 PbS Pb + SO2

Large volume of SO2 obtained is used to prepare H2SO4 in industries.

 2) Calcination :
Definition :
The process of heating the ore at high temperature in absence of air
is known as Calcination.
Hydrated salts & Metallic hydrated salts expel
Metal Carbonate Oxides water while carbonates expel CO2
➢ It is carried out in reverboratory furnace.
➢ volatile impurities are removed and make oxides porous.

Examples : CO2 is an Acidic gas

(1) CaCO3 CaO + CO2

(Calcite)
Examples of calcination reaction :
(2) ZnCO3 ZnO + CO2
(Calamine)

(3) FeCO3 Fe2O3 / FeO + CO2

( Siderite )

(4) PbCO3 PbO + CO2

(5) Al2O3. xH2O Al2O3 + xH2O

(6) CaCO3. MgCO3 CaO + MgO + CO2

(Dolomite)
 3) Smelting :
Definition :
The process of converting metal oxide into metal using
a suitable reducing agent is known as Smelting.
➢ Reducing agents used are C, CO , Al .

Examples Al is used in thermite welding

(1) ZnO + C Zn + CO
(Zincite)
O2
(2) SnO2 + C Sn + CO CO2
trace
(Tin stone)
 Smelting using Al ( Gold Schmidt alumino thermite process ):
➢ Metal oxide on reduction with aluminium powder gives metal.
➢ This method is for extraction of metals like Cr, Fe, Mn , Si
Examples (1) Al + Cr2O3 Al2O3 + Cr ( ΔH = –ve )
Al (0) → Al (+3)
Thus Al is functioning as a reducing agent
(2) Al + Fe2O3 Al2O3 + Fe ( ΔH = –ve )
Al2O3 -Due to very hard nature it is used for welding of rail joints

(3) Al + Mn3O4 Al2O3 + Mn ( ΔH = –ve )

(4) Al + SiO2 Al2O3 + Si ( ΔH = –ve )

Refining Crude metal → Pure metal.
 Refining
The process of removal of unwanted substance from impure metal or
crude metal is known as refining.
Methods of Refining :
1. Liquation
2. Distillation
3. Electrolytic refining
4. Zone refining
5. Vapour phase refining
6. Chromatography
1. Liquation

1) Liquation is carried out in reverboratory furnace

2) Used for metals having low melting point
Ex. Tin (Sn) , Lead (Pb), Bismuth(Bi)
1. Liquation
Procedure :
1. Crude metal is heated on
sloping hearth
➢ Hearth means floor of a furnace.
2. Fused metal flows down leaving
behind infusible impurities

➢ Impurities have high melting point

than metals thus remain on the slope
 2. Distillation
➢ Fractional distillation is used when boiling point difference less than 25 units .

➢ Distillation is used when the boiling point difference is 25 units.

1. Used for metals having low boiling point

Ex. Zinc (Zn) , Mercury (Hg), Cadmium (Cd)

Distillation is used for the elements that are liquids at room temperature or can be
converted to liquid at room temperature
2. Distillation
Procedure :
1. Crude metals is heated in a flask.
2. Pure metal vapourises and sepa-
rately condensed in a receiver.
3. Non - volatile impurities are left
in the flask.
3. Electrolytic Refining
Impure metal Anode
Pure metal cathode
salt of same M+
Solution
metal

➢ Used to refine elements like Cu and Zn

➢ Impurities like Sb, Se, Te, Ag, Au, Pt are left behind (near anode)

➢ These less electropositive impurities go on collecting near anode

called as anode mud.
4. Zone refining

❖ One of the most modern method

of refining
❖ Impurities are more soluble than
metal
❖ Impurities get concentrated at one end and that end is cut off
❖ Highly pure semiconductors are obtained like Ge, Si, Be, Ga, In.

➢ What is the difference between zone refining and Leaching ?

Zone refining – impurities dissolves
Leaching – metal dissolves
 5. Vapour Phase Refining
❖ Metal is converted into a volatile compound
and then decomposed to give pure metal
❖ Used for refining of Ni, Zr and Ti
❖ Used for removing oxygen and nitrogen as impurities

❖ Methods of VPR:
1. Monds process (Ni)
2. Van arkel method (Zr, Ti)
Vapour phase refining
I) Monds process for Nickel

Reaction:
350 Κ
Ni + 4CO Ni (CO)4
Volatile
unstable
complex

470Κ
Ni (CO)4 Ni + 4CO
Highly Along with O
2
pure & N2
Vapour phase refining
II) Van Arkel’s method for Zr and
Ti 2075 Κ
870 Κ
Zr + 2I2 ZrI4 Zr + 2I2
Volatile Along with
unstable O2 & N2
complex

500 Κ 1700 Κ
Ti + 2I2 TiI4 Ti + 2I2
Volatile Along with
unstable O2 & N2
complex
 Thermodynamics Principle of Metallurgy:
➢ Reduction of metal oxide to metal ⇒ Smelting
Reducing Agent
MO M
(ie C, CO)
➢ Some metal oxides get reduce easily/while others are very
difficult to reduce
➢ In any case heating is required

➢ Study of variation in temperature during thermal reduction is

known as “Pyrometallurgy”
 Help of Thermodynamics Concept:

Gibbs Energy The energy associated with a chemical reaction

that can be used to do work
➢ Change in Gibbs energy i.e. ΔG at specific temperature and pressure,
ΔG = ΔH – TΔS
Where, ΔH : Enthalpy change
ΔS : Entropy change i.e. (randomness of system)

➢ For the reaction to be spontaneous ΔG should be negative

➢ So in equation ΔG = ΔH – TΔS
Feasibility of reaction(–ve value)
Role of reducing agent: Fictitious
1
FeO Fe + 2 O2 ΔG = +ve + 40 Not feasible
+ 1 +
C+ O CO ΔG = –ve – 100 feasible
2 2
FeO + C Fe + CO ΔG = –ve – 60 feasible

➢ So Reducing Agent helps us to make reaction feasible

Selection of suitable Ellingham

➢
Reducing Agent Diagram
Ellingham Diagram
Ellingham Diagram is used to select suitable reducing agent for
reduction of metal oxide to metal.
Features of Ellingham Diagram:

1) Plots of ΔG0 in KJ/mole of O2

Vs
Temperature of formation
of oxide
Features of Ellingham Diagram:
0
2) Each line of converting metals to
metal oxide slope upwards because
–100
4Cu + O 2
→ 2Cu 2O ΔG becomes less –ve at high
–200
temperature.
–300 → 2FeO
2Fe + O 2 C + O2 → CO2
–400 →2
CO 2
ΔG•/ kJmol–1 of O2

O
2C O+ 2 2C +
–500 O →
O 2 2CO
–600 O2 → 2Zn
2Zn +
–700
O
–800 3Al 2 3
→ 2/
l + O2
–900 4/3A

→ 2MgO
–1000 + O2
2Mg
–1100
–1200
00C 4000C 8000C 12000C 16000C 20000C
273 K 673 K 1073 K 1473 K 1873 K 2273 K
Temperature
Features of Ellingham Diagram:
0
–100 Boiling point of Zn is 9070 C
→ 2Cu 2O
–200 4Cu + O 2

→ 2FeO
–300 e + O2 C + O2 → CO2
2F
–400 CO 2
ΔG•/ kJmol–1 of O2

O →2 2C +
–500 2C O+ 2 O →
2 2CO
O
–600 O → 2Zn
2Zn + 2
–700 A
l O3
–800 → 2/3A 2
l + O2
–900 4/3A
2MgO
–1000 O →
2 Mg + 2
–1100
–1200
00C 4000C 8000C 12000C 16000C 20000C
273 K 673 K 1073 K 1473 K 1873 K 2273 K
Features of+ OEllingham
gO
→2A 2 Diagram: 4) With increase in temperature
4Ag 2 Ellingham Diagram
line crosses ΔG = 0
ie. ΔG becomes +ve
➢ Hence oxide becomes unstable and Theoretically this happens in case of :
decomposes on its own into metal Hg, Ag, Au.
and oxygen.
 General Conclusions:

- Ellingham diagram tells us about at

which temperature reduction is feasible
for given combination.
- Lower is the element → more negative will be
its ΔG value.

- So that it can reduce all the metal oxides above it.

- Ex. Mg.
 Limitations of Ellingham Diagram
1) It only tells us about, whether reaction is feasible or not but cannot tell about
kinetics of reaction.
➢ How fast reaction could be?
(i.e rate of reaction → Cannot be explained)
2) As, ΔG0 = – RT lnK, where K is equilibrium constant.
Thus it presumes that the reactant and products
are in equilibrium
but its not true about all reactions.
 Ore of Aluminum
Minerals of Aluminum
Alumina
(Al2O3)
Cryolite Diaspore
( Na3 [ AlF6] ) ( Al2O3 . 1H2O)

ALUMINIUM

Gibbsite Bauxite
(Al2O3 . 3H2O) (Al2O3 . 2H2O)
 Bauxite
(Al2O3 . 2H2O)

Red Bauxite White Bauxite

( Fe impurities) ( SiO2 impurities)

Process of leaching Process of leaching

1. Bayer’s process 1. Serpeck’s process

2. Hall’s process
Bayer’s process (Red Bauxite)
Leaching Agent (Solvent) : Caustic Soda (NaOH)

Impurity : Ferric oxide (Fe2O3)

Consist of 3 steps
 Bayer’s process (Red Bauxite)

Step I : Dissolution
473 to
530 K
Al2O3 . xH2O + NaOH Na[Al(OH)4] Soluble complex
Sodium tetra
hydroxy alluminate

Impurity + Flux Slag

2Fe2O3 + SiO2 2FeSiO3 +O2

➢ flux is agent getting attached with the impurities

➢ Slag is impurities are removed in the form of slag

Bayer’s process (Red Bauxite)
Step II : Neutralization

Na [Al(OH)4] + CO2 Al2O3 . xH2O + Na2CO3

Basic Complex Acidic Gas Dirty white colour

Step III : Calcinations heated to remove water

Al2O3. xH2O 1400-1500K

Al2O3 + xH2O
Alumina
Pure aluminium can be obtained by further reduction and
refining of alumina
 Hall’s process (Red Bauxite)

Leaching Agent (Solvent) : Sodium carbonate (Na2CO3)

Impurity : Ferric oxide (Fe2O3)

Step I : Dissolution
Al2O3.2H2O + Na2CO3 2NaAlO2 + CO2 + 2H2O
Sodium meta
Red Bauxite
aluminate Now Impurities are
removed using flux.
Impurity + Flux Slag
2Fe2O3 + SiO2 2FeSiO3 +O2
Step II : Hydrolysis
hydrolysis
2NaAlO2 + CO2 + 3H2O 2Al(OH)3 + Na2CO3
Sodium meta (Dirty gelatinous
aluminate white)

Step III : Calcination

2Al(OH)3 Al2O3 + 3H2O

Alumina

Pure aluminium can be obtained by further

reduction and refining of alumina
Serpeck’s Process (White Bauxite)

Leaching Agent (Solvent) : Coke & nitrogen (C + N2)

Impurity : Silica (SiO2) 3 steps

Step I : Formation of Nitride
18000 C Oxidation states of Al and N
Al2O3 + 3C+ N2 AlN + 3CO
Aluminium
nitride
Al → + 3; N→ –3

18000 C
SiO2 + 2C Si + 2CO2
Now Impurities are removed using flux.
Step II : Hydrolysis All –ides have affinity for H+

AlN + H2O NH3 + Al(OH)3 Other examples of dirty

Dirty gelatinous gelatenious white compound are
white precipitate Zn(OH)2, Mg (OH)2
Step III : Calcination

Al(OH)3 Al2O3 + 3H2O

Alumina

Pure aluminium can be obtained by further

reduction and refining of alumina
Reduction of Alumina: Hall & Heroult process
Reduction Functions of Na3AlF6 , CaF2
Al2O3 Al At cathode 1) Reduces melting point of metal
Na3AlF6 + CaF2 ( 99 % pure )
1800°C 1000 °C
2) Increases electrical conductance
Na3AlF6 : Cryolite CaF2: Fluorspar of solution

,CaF2
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