LETS START WITH CHEMISTRY of

extraction

By
Shefali Jain

 Mineral

naturally occuring chemical substances in the

earths crust.
obtained by mining.

Ore

Minerals from which metals can be extracted

conveniently and profitably.

Gangue

Earthy and contaminated material present as

Impurities in ore other than metals.

The entire scientific and technological process used for isolation of

the metal from its ores.

Steps involved
Concentration

of ores
Isolation of metals
Purification of the metal

Removal of unwanted material(eg. Sand,

clay) from the ore.
Also called Dressing and benefaction.
Depends on the difference in the physical
properties of the compound (of metal)
present and gangue.

(gravity separation)

It is based on difference in gravities of the

ore and gangue particle.

Process

an upward stream of running water used to wash the powered ore.

Lighter gangue particles are washed away and heavier ones are left
behind.
Applicable for heavy ores like FeO.

It is based on the difference in the magnetic

properties of the ore and impurities present
(as gangue).

Process

Powered ore is passed over a conveyor belt having magnetic rollers,

that helps in removal of impurities.

Used for removing gangue from sulphide

ores like PbS, ZnS.

Collectors and froth stabilizers are added in suspension of

powdered ore in water.
Collectors: enhances the non-wettability like pine oil,
fatty acid etc.
Froth stabilizers: stabilizes the froth like cresol , aniline
etc.

Pulp of ore and oil is mixed. Mineral particles

become wet by oil while gangue particles by
water. When the suspension is agitated with air,
the mineral particles are attached to the froth,
that is skimmed being light.

These are the compounds that increases the

size of certain particles, preventing their
accumulation of froth.
Two sulphide ores can be separated using
depressants.
NaCN act as depressant for mixture of PbS,
ZnS
NaCN forms a layer of Na2[Zn(CN)4] on ZnS particles and
increases its size and prevents it from accumulating on froth.

Used,if the ore is soluble in some suitable solvents.

Used for concentrating Al, Ag, Au etc.

Separation of Alumina

Hydrometallurgy (for Au, Ag)

Al exist as Bauxite having Fe2O3 ,

TiO2, SiO2 as impurities.
Also called Baeyers Process.

Step 1: dissolution of bauxite in

NaOH.
Here only alumina is leached out
as sodium aluminate and SiO2 as
sodium silicate and rest
impurities left undissolved.

Step 2: passing CO2 gas

Sodium silicate remains in the
solution.

Step 3: on heating pure black

solid of alumina separates out.

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

Metal is leached with

dil. NaCN or dil. KCN
in presence of air

Precipitated using Zinc

metal.

Generally ores are concentrated into oxides as

they are easy to reduce.

For sulphides in presence of air

Ore is heated in a regular supply of air below melting point of

metal.
2 ZnS + 3O2

2 ZnO + 2 SO2

2 PbS + 3O2

2 PbO + 2 SO2

2 Cu2 S + 3O2

2 Cu2 O + 2 SO2

The SO2 released is used in manufacture of H2SO4 .

FeO exists as impurity in copper ore, which is removed using

silica.
FeO + SiO2 FeSiO3 (slag)

For carbonates and hydrated oxides in limited

supply of air or absence of air.

It involves heating when the volatile matter escapes leaving

behind the metal oxide.

Fe2O3. xH2O (s)

ZnCO3(s)
CaCO3(s)

Fe2O3 (s) + x H2O(g)

ZnO (s) + CO2(g)
CaO (s) + CO2(g)

The process of extraction of metal by heating the metal oxide at a

particular temperature with suitable reducing agent

Like
Thermite

welding

Reduction by Carbon

The oxide of less electronegative metals like Pb,

Zn, Fe etc. are reduced by strongly heating the n
with coal or coke.
Like iron oxide is reduced in blast furnace.
Eg.

Oxides and sulphides of unreactive metals like Cu,

Pb are directly reduced or after roasting

HgS + O2
2 Cu2S + 3O2
Cu2S + 2Cu2O
2 PbS + 3O2
PbS + 2 PbO

Hg + SO2
2Cu2O + 2SO2
6Cu + SO2
2 PbO + SO2
3 Pb + SO2

Highly electropositive metals like K, Na, Ca etc.

are extracted by electrolysis of their oxides,
hydroxides or chlorides in fused state.
The metal is liberated at cathode.

Eg.

NaCl

Na+(aq) + Cl- (aq)

Na+ + eCl2Cl

Na(s)
Cl + eCl2

Mn2O3 + 2 Al

Thermite

2 Mn + Al2O3

welding

Used for repairing railway tracks and

other heavy machine parts.

Method of purification of metal by removing impurities.

The process is used when the metal has low

melting point than impuroties like Pb, Sn etc.
The impure metal is heated on a sloping hearth
of furnace, that makes the metal melt.
Metals flows down leaving the impurities behind
on the heath.

The process is used for purification of volatile metals

having low boiling potin like Hg, Zn etc.

Process
The crude metal is heated in the retort and its vapors are
separately condensed in a receiver.
Metal distills leaving impurities behind.

Highly electro positive metals like Al, Cu, Zn etc. are refined by this
method.

Process
The impure metal is taken at anode and pure at cathode with
a soluble salt of metal as an electrolyte. On passing
current, pure metal gets deposited at cathode and
impurities gets collected below anode as anode mud.

Anode: M (s) Mn+ (aq) +n eCathode: Mn+ (aq) +n e- M (s)

This method is based on the principle of

fractional distillation, that the impurities are
more soluble in the melt than in solid state of
metal.
Useful for producing semi conductors and other
metals of very high purity e.g. Ge, Si, B, Ga, In.

A circular mobile heater is fixed at the one end of impure

metal. The molten zone moves forward,the pure metal
crystallises out the melt and impurities pass on into molten
zone. The process is repeated several times and at one end
impurities get concentrated. This end is cut off

In this method, metal is converted into its

volatile compound and collected separately
which will be decomposed into pure metal.

 Ni

is heated in a stream of CO forming a

volatile compounds which is collected and
decomposed.
Ni + 4 CO
Ni(CO)4
Ni(CO)4

Ni + 4 CO

 Used

for removal of all oxygen, nitrogen

present in metal like Zr, Ti as impurities.
Crude metal is heated in evacuated vessel
with a little iodine to form iodide. This metal
iodide being covalent, volatises easily.
On further heating electrically using tungsten
filament. Pure metal is observed.
Zr + 2 I2
ZrI4 (volatile)
ZrI4

Zr + 2 I2

It is based on the principle that different components of a mixture are

differently adsorbed on the adsorbent.

Useful for purification of elements which are available in

minute quantities and have similar chemical properties
with the impurities present.

Process

The mixture is put in liquid or gaseous medium which is

moved through the adsorbent. Different components are
adsorbed differently and then some solvent is used to
remove back the adsorbed component by dissolving with it
known as Eluent(mobile phase) and the process as Elution.

Stationary phase should be immobile and immiscible.

Column of Al2O3 is prepared in a glass tube and

moving medium containing solution is in
liquid form.

Gibbs energy change is given by second law of

thermodynamics
G = H- T S
G = - RT ln K
For spontaneous reaction G should be negative
i.e.,
i)
S >0 highly positive for increase in
temperature.
ii)
T S > H
iii) Individual reaction for coupled reaction should
also have G < 0
iv) K>1 i.e., forward reaction

 The

graph of G with temperature for a

reaction is known as Ellingham Diagram.
Helps in predicting the feasibility of thermal
reduction of an ore.
S <0 for formation of oxides from solid
metals.thus, with increase in temperature
TS<0 and G>0 i.e., non-spontaneous
reaction.
With increase in temperature, for halide,
sulphide,oxide formation G increases or
become less negative and slope will b
negative.

Graphs are straight line

unless phase transition
takes place (lg) , (
sl) etc.
If graph cross G0 =0,
above this oxide formed
is not stable and below
this it is stable.
Coupling or combination
reaction can be easily
be explained.
More negative value of
G0, better reducing
agent i.e., metal can
reduce oxide of metal
having graph above it.
Used to predict the
feasibility of reaction.

In a blast furnace, reduction of iron oxide takes place in different

ranges. Hot air is blown from the bottom of furnace and coke is
combusted to give temperature upto about 2200K in lower portion.

At 2170 K :
FeO + C Fe + CO
At 1500-900 K (with decrease in temperature)
C+ O2 CO2
C + CO2 2CO
FeO + CO Fe + CO2
CaCO3 CaO + CO2
CaO+ SiO2 CaSiO3
At 500-800 K
3Fe2O3 + CO 2Fe3 O4 + CO2
Fe3 O4 + CO 3FeO + CO2

Limestone

is added to produce flux (CaO) to form slag to remove

impurities of S, Si, P and slag also prevents the further
oxidation of FeO.
Being lighter, separates above molten iron.
Pig iron

Obtained from blast furnace containing 4% C and impurities (P,Si, S

etc).

Cast iron
Made by melting pig iron with coke using hot air blast.
Contains approx. 3% carbon
Expands on solidifying.
Hard and brittle as compared to pig iron
2Fe2O3 + C 4Fe + 3CO2

Wrought or Malleable iron

Is the purest form of commercial iron.
Prepared from cast iron by oxidising impurities in reverberatory
lined with haematite.
Fe2O3 + 3C 2Fe + 3CO

(Cu,CuO) comes almost at the top in Ellingham Diagram,

thus can easily be reduced from its ores.
2Cu2O + 2SO2
2Cu2S +3O2
Cu2O + C 2Cu +CO
In copper ore FeO is present as impurity, thus practically
Cu ore is heated in reverberatory with a lining of silica
(SiO2) to form slag and leaving copper matte(Cu2S+ traces
of FeS).
FeO+ SiO2(flux) FeSiO3 (slag)
FeO recombines with Cu2O and forms Cu2S.
Hot air is blown through copper matte and silica to form
metallic copper.
FeS+ 3O2 2FeO + 2SO2
FeO+ SiO2 FeSiO3
2Cu2S + 3O2 2Cu2 O + 2SO2
2Cu2O + Cu2S 6Cu + SO2

Cu obtained is called Blister Copper because of

appeance of Blisters due to evolution of SO2.

Metal is distilled off and collected by rapid

chilling after reduction with coke at 1673 K
ZnO + C

Zn + CO

For purifying aluminium: electrolysis of fused alumina

Steps involved

Step1: concentration of ore by chemical separation.

Step 2: Reduction into metal(Hall- Heraults method).

Purified alumina, Al2O3 is mixed with Na3AlF6 (cryolite)or
CaF2 (feldspar).
Steel cathode and graphite anode are used.
At anode : C(s) + O2- (melt) CO (g) + 2eC(s) + 2O 2-(melt) CO2 (g) + 4eAt cathode : Al3+ (melt) + 3 e- Al(l)
Net reaction: 2Al2O3 + 3C
4 Al(l) + 3CO2(g)

 CRYOLITE

Acts as sovent
Lowers the melting point of alumina to about
1173 K.
Increases the electrical conductivity.

GRAPHITE

Helps in reduction of alumina to aluminium.