GENERAL PRINCIPLES AND PROCESSES OF

ISOLATION OF ELEMENTS
MINERAL : a naturally occurring chemical substance in the earths crust
obtainable by mining
ORE : a mineral from which metal can be extracted profitably
GANGUE : earthly and undesirable impurities which contaminate ore
METALLURGY: entire scientific and technological process used for isolation of
metal from its ore
STEPS OF METALLURGY:
(i)Concentration of ore (ii) isolation of metal from its concentrated ore (iii)
purification of metal
1.CONCENTRATION OF ORE: removal of undesirable impurities(gangue) from
ore .
It is also called dressing or benefaction. Difference in physical properties of the
compound of metal and those of gangue decides the method to be used for
concentration of ore.
METHODS OF CONCENTRATION OF ORES AND THE PRINCIPLE INVOLVED
HYDRAULIC WASHING(or gravity separation): This is based on the
differences in gravities of the ore and the gangue particles. The lighter gangue
particles are washed away by a stream of water running over powdered ore
leaving behind heavier ore particles.
MAGNETIC SEPARATION: This is based on the differences in the magnetic
properties of the ore and gangue. The powdered ore moves over a magnetic
roller when magnetic and non magnetic particles make separate heaps.
FROTH FLOATATION: This is based on the difference in the wettability of ore
and gangue particles. Ore particles are wetted by pine oil/fatty acids/xanthates
(a collector) and become light whereas gangue particles are wetted by water and
become heavier.
On rotating the mixture of powdered ore and water containing pine oil and a
froth stabiliser (aniline/cresols) , heavier gangue particles settle down whereas
lighter ore particles form froth which is skimmed off.
This method is used for concentration of sulphide ores

Depressant: used to separate two sulphide ores eg. NaCN is used as a

depressant to separate ore containing PbS and ZnS. NaCN prevents
ZnS to come in the froth but allows PbS .
LEACHING: This is based on the difference in the solubility of ore and gangue
particles in a suitable solvent eg. Alumina is separated from silica and other
impurities present in bauxite ore by heating powdered ore with

concentrated NaOH at high temperature and high pressure. Alumina

forms sodium aluminate, silica forms sodium silicate and both remain in
solution leaving other impurities behind. From the solution alumina is
precipitated in hydrated form by passing CO 2 gas whereas sodium
silicate remains in the solution.
Al2O3(s) + 2NaOH(aq) + 3H2O(l) ------- 2Na[Al(OH)4](aq)
2Na[Al(OH)4](aq) + CO2(g) ------ Al2O3.xH2O(s) + 2NaHCO3(aq)
Al 2O3.xH2O(s)
temp. 1470K)

-----

Al 2O3(s)

x H 2O(g)

(on heating at a

2.ISOLATION OF METAL FROM CONCENTRATED ORE: The concentrated ore

is converted to a form of metal suitable for reduction.Thus isolation of metal from
its concentrated ore involves(i)conversion to oxide (oxides are easier to reduce and particularly if the
metal formed is in liquid state from solid metal oxide at the
temperature of reduction because S becomes positive and Go more
negative which makes reduction easier)
Calcination heating of concentrated ore in absence of air eg carbonate
ores
ZnCO3(s)

------

ZnO(s) + CO2(g)

Roastingheating of concentrated ore in a regular supply of air at a

temperature below the
melting point of the metal eg.sulphide ores
ZnS(s) + O2(g) ------ ZnO(s)

+ SO2(g)

(ii) reduction of oxide to metal by pyrometallurgy i.e. thermal reduction of

metal oxide by heating with a reducing agent like C, CO, a metal or
electrolytically ) eg.
FeO
+ CO
ZnO
+ C
Cr2O3 + 2Al

----
----
----

Fe
+
CO2
Zn +
CO
2Cr + Al2O3

EXTRACTION OF IRON FROM ITS OXIDE

(i)at lower temperature range in the upper part of blast furnace
3Fe 2O3 (ore) + CO ----- 2Fe3O4
---- CaO +CO2 ]

+ CO2

Fe 3O4 + CO -----
SiO2(flux) -- CaSiO3 (slag) ]

+ CO 2

3FeO

[ CaCO 3 (limestone)

(ii)at higher temperature range in the lower part of blast furnace

[ CaO +

FeO

CO

-----

FeO

+ C (coke)

Fe

CO2

[ CO2

+ C --

2CO ]
-----

Fe

+ CO

[ C + O2

----

CO2 ]
(iii)at very high temperature at the bottom of the blast furnace
Iron in the molten form collects with molten slag above it which protects its
oxidation by hot blast of air entering the furnace.
PIG IRON iron collected from blast furnace which contains about 4% C and
smaller amounts of S,P,Si,Mn as impurities
CAST IRON pig iron is heated with scrap iron and coke to get cast iron which
contains about 3% C and is extremely hard and brittle.
WROUGHT IRONit is the purest form of iron and is prepared by heating cast
iron with limestone in a furnace lined with haematite. Impurities like S,P,Si are
removed as slag and haematite oxidises C to CO and thus contains about 0.5% C
and is malleable.
EXTRACTION OF COPPER FROM ITS OXIDE
Cu2O from roasted/smelted sulphide ore is heated with coke (reducing agent) to
get Cu
Cu2O
+
-- 2Cu2O +2SO2]

C ----

2Cu

(copper matte)

CO

[ 2Cu 2S + 3O2
(ore)

Copper matte contains Cu, Cu2S and FeS. It is heated in a converter

lined with silica by a hot blast of air to convert FeS(impurity) to FeS which
reacts with SiO2 to form slag(FeSiO3). Cu2S oxidises to Cu2O which reacts
with remaining Cu2S to form Cu.
2FeS + 3O
FeO

---

2FeO

+ SiO 2 ---

2Cu 2S +

3O2 ---

2SO2

FeSiO3(slag)
2Cu2O

Cu 2O + 2Cu2S -- 6Cu

2SO2

+ 2SO2

Copper obtained solidifies and shows blisters on its surface due to evolution of
SO2 and is thus
called blister copper.
EXTRACTION OF ZINC FROM ITS OXIDE
Zinc oxide from roasted zinc blende(ZnS) is heated with coke(reducing agent) at
temp. 673K to get Zn. (CO is not used to reduce ZnO as its reaction with
O2 has less negative rGo value. On the other hand for carbon rGo has
high negative value particulary at 673K)

---

ZnO
ZnO

+ C
-----
+ SO2 ]

Zn

CO

[ ZnS

O2

(ore)
Zinc is distilled off and collected.
EXTRACTION OF ALUMINIUM FROM ITS OXIDE
Alumina(Al2O3) mixed with fluorite(CaF2)/cryolite(Na3AlF6) is electrolysed in a steel
cell lined with
carbon(cathode) and multi graphite rods(anode). Aluminium collects at the
cathode.
Fluorite/cryolite is used to lower the melting point of the mixture.
Multi graphite rods (anode) is used as oxygen liberated at anode reacts
with carbon
to form CO and CO2 , thus it is burnt away.
Cathode -

Al +3 +

Anode -

O-2

-----

CO(g) + 2e-

2O -2

-----

CO2(g) + 4e-

Overall reaction

3e-

2Al2O3

----

Al(l)

+ 3C -----

4Al

3CO2

HYDROMETALLURGY : extraction of metal from its solution using hydrogen as a

reducing agent eg.
Copper is extracted from low grade
electropositive is reduced by hydrogen.
Cu +2 (aq)

H2 (g)

ores.Copper

-----

being

less

Cu (s) + 2H+1(aq)

Zinc can not be extracted by this method as zinc is more electropositive

than hydrogen.
Similarly scrap iron/scrap zinc can also be used to extract copper from low grade
ore as iron and zinc
both are more electropositive than copper. However zinc being costlier is not
used even though
reduction will be faster. Therefore using iron scraps is advantageous and
advisable.

OXIDATION-REDUCTION

EXTRACTION OF GOLD OR SILVER

Gold or silver is extracted from its ore by oxidation reduction reaction. The ore
is leached with
cyanide (CN-1) when the metal forms a complex and goes in the solution. This is
an oxidation
reaction(M--- M+1). From the solution metal is obtained by reacting with zinc
which reduces the
metal ion to metal( M+1 --- M).
4Au (s) + 8CN-1 (aq)
4OH-1(aq) (oxidation)

2[Au(CN)2 ]-1(aq)
(reduction)

Zn(s)

2H2O (l)

-----

O2 (g)

----- 4[Au(CN)2 ]-1(aq) +

2Au(s)

[Zn(CN) 4]-2 (aq)

EXTRACTION OF CHLORINE FROM BRINE(aq NaCl solution)

Electrolysis of aq.NaCl solution releases chlorine gas at the anode , hydrogen at
cathode and
NaOH(aq) is formed as by-product. Chlorine is obtained by oxidation of Cl -1
and water is reduced to
hydrogen.
NaCl(aq)

--- Na+1(aq)

2Cl-1(aq) + 2H2O(l)

+ Cl-1(aq)

-- 2OH(aq)

+ H2(g) + Cl2(g)

However electrolysis of molten NaCl results in deposition of sodium at cathode

instead of hydrogen
and NaOH does not form. Chlorine liberates at the anode.

3.REFINING/PURIFICATION OF METAL: removal of impurities from the metal

extracted from its ore
METHODS OF REFINING AND THE PRINCIPLE INVOLVED
DISTILLATION : It is used to separate low boiling metals from high boiling
impurities eg. Zn , Hg
On heating, the metal distills off leaving impurities behind.

LIQUATION: It is used to separate low melting metals from high melting

impurities eg. Sn , Pb
On heating the metal flows down the sloping hearth(furnace)
leaving impurities behind.
ZONE REFINING: Impurities are more soluble in the molten form of the metal
than in its solid form.
The metal is heated by a circular heater moving from one end to
another
repeatedly.The impurities collect on one end and are cut off from
pure metal.
This method is useful for getting metals of high purity eg. Ge , Si , B ,
Ga , In
VAPOUR PHASE REFINING: The metal is converted to a volatile compound by
reacting with a
suitable reagent whereas impurities are left behind.
The volatile compound easily decomposes to give metal in pure state
on heating.
MONDS PROCESS: it is used to purify Ni
of 330 350 K)

Ni + 4CO --- ----

Ni(CO) 4

Ni(CO) 4 (volatile) (on heating at a temp.

----------

Ni

+ 4CO

(on heating at a temp.

of 450 470 K)
VAN ARKEL METHOD: it is used to purify Zr and Ti
Zr + 2I 2 --------

ZrI4

ZrI 4

Zr

--------

2I 2

(on heating at a temp. of 1800

K)
ELECTROLYTIC REFINING: Impure metal is made the anode and pure metal
strip is used to make
cathode. The two electrodes are put in an electrolytic solution of metal
salt. On passing
current metal in pure form deposits at the cathode eg. Cu
anode:
cathode:

Cu ----- Cu+2
Cu +2

+ 2e-

+ 2e- ----- Cu

Less electropositive metal impurities like Sb, Se, Te, Ag, Au, Pt present
in impure copper
collect as anode mud below the anode.
CHROMATOGRAPHY (column): Different components of a coloured mixture are
adsorbed differently
on an adsorbent surface(stationary phase). These coloured components
adsorbed at

different levels of adsorbent surface are removed using a suitable

solvent(mobile phase).

ASSIGNMENT
1.Why is extraction of copper from copper pyrites more difficult than from its
oxide ore by
reduction?
2.Is reduction of Cr2O3 possible by Al ?(fGo for Cr2O3 is -- 540 kJ/mol and for
Al2O3 is --827 kJ/mol)
3.(i)The choice of a reducing agent in reduction of a metal oxide depends on
thermodynamic factor.
Support your answer with an example.
(ii)How does electrochemical principle affect reduction of concentrated ore to
the metal?
Explain with an example.
4.Predict conditions under which (i) Al can reduce MgO
Al2O3

(ii) Mg can reduce

5.What criterion is followed for the selection of the stationary phase in

chromatography?
6.Give the principle ore (name and formula) from which following metals are
extracted (i) Al (ii) Fe
(iii) Cu (iv) Zn
Give use of each of the above metals.
7.Reduction of alumina by Mg below 1350K is thermodynamically feasible but in
practice
alumina is not reduced by magnesium. Why?
8.Explain how extraction of silver/gold by cyanide method is an oxidation
reduction process?
9.What is the significance of leaching in the extraction of aluminium from
bauxite ore?

10.Which ores can be concentrated by magnetic separation method :

bauxite,zinc blende,calamine,
copper pyrites, haematite,cuprite,magnetite,zincite or malachite?

Do all questions asked in exercise(page 163,164 of text book) and

previous board papers
and find answers from the notes