*

Hydraulic WashingThis is based on the differences

in gravities of the ore and the gangue particles. It
is therefore a type of gravity separation.
* The lighter gangue particles are washed away and
the heavier ores are left behind
Magnetic Seperation
* This is based on differences in magnetic properties
of the ore ot the gangue
* (one of these two) is capable of being attracted by
a magnetic field, then such seperations are carried
out (e.g. in case of iron ores).

General Principles and of Processes

of Isolation Elements
The extraction and isolation of an element from its
combined form involves various principles of chemistry

minerals in which a metal extraction is economic and

convenient. Such minerals are known as ores Occurence of
Metals (important ores )
METAL
Aluminium

Iron

Copper

ORES
Bauxite
(a form of clay)

Al2O3. 2H2O

Haematite
Magnetite
Siderite
Iron pyrites

Fe2O3
Fe3O4
FeCO3
FeS2

Copper pyrites
malachite
cuprite
copper glance

CuFeS2
CuCO3.Cu(OH)2
Cu2O
Cu2S

Zinc blende or
Zinc sphalerite
calamine
Zincite

1.
2.
3.
4.

COMPOSITION

ex. chromite ore, FeCr2O4 being magnetic can be separated

from nonmagnetic silicons impurities tinstone or
cassiterite, SnO2 (non-magnetic) containing wolfram, FeWO4
(magnetic)

ZnS
ZnCO3
ZnO

major steps in extraction

Concentration of the ore,
Conversion of ore into oxide
reduction of oxide in to metal
Purification and refining of the metal

*
*
*

Concentration of ore
The removal of the gangue( impurity)from the ore is called
ore dressing (or) concentration of the ore.
Methods used are
1. Hydraulic Washing
2. Magnetic Seperation
3. Froth Flotation Method
4. Leaching

MUKESH SHARMA

Froth Flotation Method

used for removing gangue from sulphide ores
in this process, a suspension of the powdered ore is made
with water., collectors and forth stabilizers
Collectors enhance non wettability of the mineral
particles (e.g., pine oils, fatty acids, xanthates, etc.)
and froth stabilisers stabilise the forth. (e.g. , cresols,
aniline)
* The mineral particles become wet by oils while the
gangue particles by water.
* Depressant in Froth Flotation Method
* To perform selective Froth Flotation of only one
sulphide ore out of many sulphide present inore
we use the depressant like NaCN. it selectively
prevents ZnS from coming to the forth but allow
PbS

Leaching
Leaching is often used if the ore is soluble in some
suitable chemical but not impurity
(a) Leaching of alumina from bauxite
The principal ore of aluminium, bauxite, usually
contains SiO2, iron oxides and titanium oxide (TiO2)
as impurities

DPS JODHPUR

*
*

Concentration is carried out by heating the

powdered ore with a concentrated solution of
NaOH at 473 523 K
. This way, Al2O3 is leached out as sodium
aluminate (and SiO2 too as sodium silicate)
leaving the impurities behind:

Al2O3(s) + 2NaOH(aq) + 3H2O(l) 2Na[Al(OH)4](aq)

The aluminate in solution is neutralised by passing

CO2 gas and hydrated Al2O3 is precipitated.
At this stage, the solution is seeded with freshly
prepared samples of hydrated Al2O3. which induces
the precipitation:
2Na[Al(OH)4](aq) + CO2(g) Al2O3.2 H2O(s) +
2NaHCO3 (aq
* The sodium silicate remains in the solution and
hydrated alumina is filtered, dried and heated to
give back pure Al2O3:
Leaching of silver and gold
In the metallurgy of silver and that of gold, the
respective metal is leached with a dilute solution of
NaCN or KCN in the presence of air (for O2) from
which the metal is obtained later by replacement:
1. O2(g) + 2H2O(aq)+ 4M(s)+ 8CN (aq) 4[M(CN)2](aq) +
2.

4OH(aq) , (M= Ag or Au)

2[M(CN)2](aq) + Zn(s) [Zn(CN)4]2

For gold
1.
2.

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

4OH (aq)
2[Au(CN)2] (aq) + Zn(s) 2Au(s) + [Zn(CN)4]2 (aq)

Conversion of concentrated ore to oxide

By (i).Calcination(ii). Roasting
* ore is converted to oxide before reduction. Oxides are
easier to reduced
* (i) Calcination: Calcinaton involves heating when the
volatile matter escapes leaving behind the metal oxide:
Al2 O3 .2 H 2 O Al2 O3 2 H 2 O
2 Fe2O3 .3 H 2O 2 Fe2O3 6 H 2O
ZnCO 3 ZnO CO 2

; CaCO 3 CaO CO 2

CuCO 3 . Cu(OH )2 2CuO CO 2 H 2 O

(ii) Roasting:
In roasting, the ore is heated in a regular supply of
air/oxygen in a furnace at a temperature below the
melting point of the metal. Some of the reactions
involving sulphide ores are:
2ZnS + 3O2 2ZnO + 2SO2
2PbS + 3O2 2PbO + 2SO2
2Cu2S + 3O2 2Cu2O + 2SO2
* Roasting of copper sulphide :-The sulphide ores
of copper are heated in reverberatory furnace.
* If the ore contains iron, it is mixed with silica
before heating.
* Iron oxide slags of * as iron silicate and copper
is produced in the form of copper matte which
contains Cu2S and FeS.

MUKESH SHARMA

FeO
+ SiO2

FeSiO3
gangue
flux
(slag)
Flux :- during calcination ,roasting or smelting generally metal
oxides are used to remove gangue by converting into a molten
form called slag

Reduction of oxide to the metal

By (i) C (ii) more reactive metal
(iii) CO (iv) electrolytic reduction
Reduction of the metal oxide involves heating it
with some other substance acting as a reducing
agent (C or CO or even another metal).
The reducing agent (e.g., carbon) combines with
the oxygen of the its oxide.
MxOy + yR xM + y ROhere R= red.agent
Some metal oxides get reduced easily while others
are very difficult to be reduced
For Spontaneity of reduction
Grn = GRO-GMO must be -ve
To have Grn -ve , GRO must be more ve than
GMO
In every case, heating is required. The role of
temperature Depend upon that , on rising
temperature how GRO and GMO change
Based on it, we decide which element will be a
better reducing agent for a given MO
Reducing power and G of oxide formation of reducing
agent ,Illustration:Q Which is better reducing agent X or Y for reduction of MO
If for reduction of MO(s) M(s or l) + 1/2O2(g)[G (M,MxO)= +800kj
X(s) + 1/2 O2 (g) XO(g) [G(X, XO)]= - 1000 kj
Y(s) + 1/2 O2 (g) YO(g) [G(Y, YO)]= - 2000 kj
Ans
By using Hess law and after coupling M with X and using
MO(s) + X(s) M(s or l) + XO , [G= -200 Kj ]
using Hess law after coupling M with y
MO(s) + Y(g) M(s or l) + YO [G= -1200 Kj ]
Based on Coupled rn concept G for reduction by Yis more
ve i.e more spontaneous i.e Y is better rducing agent *
*If activation energy permits
Moral of the story :In general more ve G Of oxide(RO) formation, stronger
reducing power of reducing agent R
Effect of temperature on reducing power
The role of temperature Depend upon , on rising temperature how GRO
change and it depend upon sign of S
(i)Case one if S = +VE , like in CCO
C(s) + 1/2 O2 (g) CO(g), [G(C, CO)]
G = H TS ,in this case ,at higher temperature G be more ve
and better reducing agent at higher temperature

DPS JODHPUR

Case (ii) if S = - VE ,
CO(g) + 1/2O2 CO2(g), [G(CO, CO2)]
G = H TS , higher temperature ,less ve G Poor reducing
agent At higher temperature

On the basis of above data, predict the temperature at which

carbon can be used as a reducing agent for MgO(s).
Smelting :- extracting a metal from oxide by reduction in the state of fusion
is called smelting.
in this ore is mixed with carbon, and heated in suitable furnace
SnO 2 2C Sn 2CO ; ZnO C Zn CO
Fe2 O3 3CO 2 Fe 3CO 2
Flux and slag : Flux is a substance that is added during smelting to
convert infusible impurities into fusible material known as slag.
Impurities + Flux = Slag.
If the impurities in the ore are acidic (SiO2) in nature, a basic flux e.g.,
CaO, MgO, FeO etc. are added; and if the impurities are basic (CaO,
FeO, etc.) then on acidic flux (SiO2) is used

Ellingham Diagram

Extraction of iron from its oxides [Smelting of iron oxide ]

* At 500 800 K (lower temperature range in the blast
furnace)
* 3 Fe2O3 + CO 2 Fe3O4 + CO2
* Fe3O4 + 4 CO 3Fe + 4 CO2
* Fe2O3 + CO 2FeO + CO2
* At 900 1500 K
(higher temp. range in the blast furnace):
* C + CO2 2CO
* FeO + CO Fe + CO2
FeO + C Fe + CO
Limestone is also decomposed to CaO which removes silica
impurity of the ore as CaSiO3 slag.

Q The value of for formation of Cr2O3 is 540 kJmol1 and that of

Al2 O3 is 827 kJmol1. Is the reduction of Cr2O3 possible with Al?

A The value of for the formation of Cr2O3 from Cr (540 kJmol1) is
less ve that of Al2O3 from Al (827 kJmol1). Therefore, Al can reduce
Cr2O3 to Cr. Hence, the reduction of Cr2O3 with Al is possible.
(Above process is called Gold-schmidt alumino thermic process)
Q.Out of C and CO, which is a better reducing agent at 673 K?
A- from Ellingham diagram G of CO-CO2 is more ve than C-CO
i.e. CO is better reducing agent above 673 C is better reducing agent
Q Suggest a condition under which magnesium could reduce

alumina. The two equations are:

At the point a
A:-before intersection of the Al2O3 and MgO curves
Q Why is the reduction of a metal oxide easier if the metal
formed is in liquid state at the temperature of reduction
A:-The entropy is higher if the metal is in liquid state than when
it is in solid state. The value of entropy change S) of the
reduction process is more on +ve side
QWhy is zinc not extracted from zinc oxide through reduction
using CO?
A:-The standard Gibbs free energy of formation of ZnO from Zn
is more ve that of CO2 from CO. Therefore, CO cannot reduce
ZnO to Zn. Hence, Zn is not extracted from ZnO through
reduction using CO.
Try your self:Q Free energies of formation of [fG] MgO(s) and CO(g) at
1273 K and 2273K are given below

MUKESH SHARMA

Electrolytic reduction
of Al2O3

Hall-Heroult process
2Al O + 3C 4Al + 3CO
Cathode: Al (melt) + 3e Al(l
Anode:C(s) + O CO(g) + 2e
2

3+

Refining By (i) Distillation(ii) Liquation(iii) Electrolysis(iv)

Zone refining (v) Vapour phase refining (vi ) Chromatographic
methods

DPS JODHPUR

i) distillation
This is very useful for low boiling metals like zinc and
mercury.
* The impure metal is evaporated to obtain the pure metal
as distillate.
(ii) Liquation
metal like tin can be made to flow on a sloping surface. In this
way it is separated from higher melting
(iii) Electrolytic refining
* Copper is refined using an electrolytic method.

Van Arkel Method for Refining Zirconium or

Titanium
Zr + 2I2 ZrI4 (at 700K)
ZrI4 Zr + 2I2 (1200K)
By poling : The molten metals is stirred with green wood poles.
Wood at the high temperature of the molten metals form
hydrocarbons like methane which being about the reduction of
any oxide present in the metal e.g., copper oxide present in the
blister copper. In the case of the tin the impurities are oxidised
and float on the molten metal as scum which is removed.
Reactivity based flow chart

Anodes are of impure copper and pure copper strips are

taken as cathode.
* The electrolyte is acidified solution of copper sulphate
and the net result of electrolysis is the transfer of copper
in pure form from the
* Anode: M Mn+ + ne
* Cathode: Mn+ + ne M anode to the cathode:
* Anode: Cu Cu2+ + 2 e
* Cathode: Cu2+ + 2e Cu
(iv) Zone refining
* the principle that the impurities are more soluble in the
melt than in the solid state of the metal.
*
A circular mobile heater is fixed at one end of a rod of
the impure metal. The molten zone moves along with
the heater which is moved forward

(v)Vapour phase refining

principle of the method or ,two requirements for this method to
be used are:
(i) the metal should form a volatile compound on
heating with an available reagent,
(ii) on further heating ,the volatile compound should be
easily decomposable, so that the recovery is easy.
Method based on principal of Vapour phase refining are
(i) Mond Process for Refining Nickel (ii) Van Arkel Method
for Refining Zirconium or Titanium
Mond Process for Refining Nickel
* In this process, nickel is heated in a stream of carbon
monoxide forming a volatile complex, nickel tetracarbonyl:

Chromatography
based on the principle that different components of a mixture are
differently adsorbed on an adsorbent. The mixture is put in a
liquid or gaseous medium which is moved through the
adsorbent. Different components are adsorbed at different levels
on the column. Later the adsorbed components are removed
(eluted) by using suitable solvents (eluant).
Main types of metallurgical processes
Different metallurgical processes can be broadly
divided into three main types
(1) Pyrometallurgy : Extraction is done using heat
energy. The metals like Cu, Fe, Zn, Pb, Sn, Ni, Cr, Hg etc. Which
are found in the nature in the form of oxides, carbonates,
sulphides are extracted by this process.
(2) Hydrometallurgy : Extraction of metals involving
aqueous solution is known as hydrometallurgy. Silver, gold etc
are extracted by this process.
(3) Electrometallurgy : Extraction of highly reactive
metals such as Na, K, Ca, Mg, Al etc. by carrying electrolysis of
one of the suitable compound in fused or molten state
By MUKESH SHARMA DPS JODHPUR

The carbonyl is subjected to higher temperature so that it is

decomposed giving the pure metal:

MUKESH SHARMA

DPS JODHPUR