General Principles and of Processes of Isolation

Elements

MUKESH SHARMA DPS JODHPUR

* elements like carbon, sulphur, gold and noble gases, occur in fre

state while others in combined forms in the earths crust.

* The extraction and isolation of an element from its combined
form involves various principles of chemistry
* Out of many minerals in which a metal may be found, only from
a few extraction is economic and convenient. Such minerals are
known as ores

MUKESH SHARMA DPS JODHPUR

1. Concentration of the ore,

2.Conversion of ore into oxide
3. reduction of oxide in to metal
4.Purification of the metal.

MUKESH SHARMA DPS JODHPUR

*Among metals, aluminium is the most abundant.

*It is a major component of many igneous minerals

including mica and clays.

*Many gemstones are impure forms of Al2O3and the
impurities range from Cr (in ruby) to Co (in
sapphire).
*Iron is the second most abundant metal in the earths
crust

MUKESH SHARMA DPS JODHPUR

METAL

ORES

BauxiteKaolinite (a
Aluminium form of clay)

Iron

Copper

Haematite
Magnetite
Siderite
Iron pyrites
Copper pyrites
malachite
cuprite
copper glance
Zinc blende or
sphalerite
calamine
Zincite

COMPOSITION

AlOx(OH)3-2x[where 0 < x < 1]

Fe2O3
Fe3O4
FeCO3
FeS2
CuFeS2
CuCO3.Cu(OH)2
Cu2O
Cu2S

ZnS
ZnCO3
ZnO
Zinc
Table
6.1:
Ores of Some5 Important Metals
MUKESHTable
SHARMA
DPSPrincipal
JODHPUR

*The removal of the gangue( impurity)from the ore

is called ore dressing (or) concentration of the ore.

*Hydraulic Washing
*Magnetic Seperation
*Froth Flotation Method
*Leaching
MUKESH SHARMA DPS JODHPUR

* This is based on the differences in gravities of the ore and the

gangue particles.

* It is therefore a type of gravity separation.

* In one such process, an upward strem of running water is used to
wash the powedered ore.

* The lighter gangue particles are washed away and the heavier ores
are left behind.

MUKESH SHARMA DPS JODHPUR

* 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).
* The ground ore is carried on a conveyer belt which passes over a
magnetic roller (fig.6.1).

MUKESH SHARMA DPS JODHPUR

*use for removing gangue from sulphide ores

*in this process, a suspension of the powdered ore is

made with water.

*To it, collectors and forth stabilizers are added.
* Collectors (e.g., pine oils, fatty acids, xanthates,
etc.) enhance non wettability of the mineral particles
*and froth stabilisers (e.g. , cresols, aniline) stabilise
the forth.

MUKESH SHARMA DPS JODHPUR

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* The mineral particles become wet by oils while

the gangue particles by water.

* A rotating paddle agitates the mixture and

draws air in it. As a result, forth is formed
which carries the mineral particles .

* The forth is light and is skimmed off. It is then

dried for recovery of the ore particles.

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*it is possible to seperate two sulphide ores by

adjusting proportion of oil to water or by using

depressants.

*For example in case of an ore containing Zns and

PbS,

*the depressant used is NaCN. it selectively prevents

ZnS from coming to the forth but allow PbS

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* Leaching is often used if the ore is soluble in

some suitable solvent. The following examples

illustrate the procedure:
(a) Leaching of alumina from bauxite
The principal ore of aluminium, bauxite,
usually contains SiO2, iron oxides and titanium
oxide (TiO2) as impurities.
.(6.3)

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* Concentration is carried out by digesting the powdered ore with a

concentrated solution of NaOH at 473 523 K
* . This way, Al2O3is leached out as sodium aluminate (and SiO2too
as sodium silicate) leaving the impurities behind:

* Al2O3(s) + 2NaOH(aq) + 3H2O(l) 2Na[Al(OH)4](aq)..(6.1)

*

The aluminate in solution is neutralised by passing CO2gas and

hydrated Al2O3is 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.xH2O(s) + 2NaHCO3(aq).

(6.2)

* The sodium silicate remains in the solution and hydrated alumina

is filtered, dried and heated to give back pure Al2O3:
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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:
O2(g) + 2H2O(aq)+ 4M(s)+ 8CN(aq) 4[M(CN)2](aq) + 4OH(aq)

*(M= Ag or Au)
*2[M(CN)2](aq) + Zn(s) [Zn(CN)4]2
For gold

* 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)
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* 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:

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* (ii) Roasting:
* In roasting, the ore is heated in a regular supply of air 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(6.9)

* 2PbS + 3O2 2PbO + 2SO2(6.10)
* 2Cu2S + 3O2 2Cu2O + 2SO2..(6.11)

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* 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.
FeO
+ SiO2
gangue
flux

MUKESH SHARMA DPS JODHPUR

FeSiO3
(slag)

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* 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= reducing 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 predict which element will be the reducing agent
for a given MO
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Which is better reducing agent X or Y for reduction of MO

for reduction of MO(s) M(s or l) + 1/2O 2(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
after coupling M with X and using Hess law
MO(s) + X(s) M(s or l) + XO , [G= -200 Kj ]
after coupling M with y and using Hess law
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
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* 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 ,

* C(s) + 1/2 O2(g) CO(g), [G(C, CO)]

* G = H TS ,
* higher temperature
* more ve G
* better reducing
agent at higher
temperature

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* 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

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23
MUKESH SHARMA DPS JODHPUR

*Out of C and CO, which is a better reducing agent at 673 K?

Ans-

*At 673 K, the value of is less than that of .

Therefore, CO can be reduced more easily to CO2

than C to CO. Hence, CO is a better reducing agent
than C at 673 K.

MUKESH SHARMA DPS JODHPUR

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* Suggest a condition under which magnesium could reduce alumina. The

two equations are:

* Ans
* At the point of intersection of the Al O and MgO curves
2

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* Why is the reduction of a metal oxide easier if the metal

formed is in liquid state at the temperature of reduction

* Ans* 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

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 20Why is zinc not extracted from zinc oxide through

reduction using CO?
Answer
The standard Gibbs free energy of formation of ZnO
from Zn is lower than that of CO2 from CO.
Therefore, CO cannot reduce ZnO to Zn. Hence, Zn
is not extracted from ZnO through reduction using
CO.

MUKESH SHARMA DPS JODHPUR

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*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?

*Answer
*The value of for the formation of Cr2O3 from Cr (540 kJmol1) is higher than
that of Al2O3 from Al (827 kJmol1). Therefore, Al can reduce Cr2O3 to Cr.
Hence, the reduction of Cr2O3 with Al is possible.

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 Question 6.37Free energies of formation of [fG] MgO(s) and CO(g) at 1273

K and 2273K are given below

On the basis of above data, predict the temperature at which carbon can be
used as a reducing agent for MgO(s).

MUKESH SHARMA DPS JODHPUR

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* 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 silicate
impurity of the ore as slag.
The slag is CaSiO3
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32
MUKESH SHARMA DPS JODHPUR

*(a) Distillation
*(b) Liquation
*(c) Electrolysis
*(d) Zone refining
*(e) Vapour phase refining
*(f ) Chromatographic methods

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*(a) 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.
*(b) Liquation
*metal like tin can be made to flow on a sloping surface. In
this way it is separated from higher melting

MUKESH SHARMA DPS JODHPUR

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* The reactions are:

* Anode: M Mn++ ne
* Cathode: Mn++ ne MCopper is refined using an electrolytic method.
* 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 to the cathode:
* Anode:Cu Cu2++ 2 e
* Cathode:Cu2++ 2e Cu

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* 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

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*In this method,two requirements are:

*

(i) the metal should form a volatile compound with an

available reagent,

*(ii) the volatile compound should be easily

decomposable, so that the recovery is easy.

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* In this process, nickel is heated in a stream of carbon

monoxide forming a volatile complex, nickel
tetracarbonyl:

*The carbonyl is subjected to higher temperature so that

it is decomposed giving the pure metal:

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* Zr + 2I2 ZrI4..(

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based on the principle that different

components of a mixture are differently
adsorbed on an adsorbent.

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General flow chart

41
MUKESH SHARMA DPS JODHPUR

Reactivity based flow chart

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