Extraction of Elements

-the chemistry behind

 In nature, few elements are found in free state.

Others are found in combined state.
Formation of compound is the result of natural
tendency of any element to acquire more stable,
low energy state.
This is achieved either by oxidation or reduction.
Hence isolation of an element involves reduction or
oxidation

Chemical composition of ores

More ionic

More covalent

s-block

Group 3B

p,d-block
3

Some basic definitions

Minerals are naturally occurring substances in the earths

crust obtainable by mining

Ores are minerals from which extraction of metal is

economically viable.
Gangue is earthly or undesired material, mineral is
contaminated with.
4

Principal Ores of Some Important Metals

Metal

Ores

Composition

Aluminum

Bauxite

AlOx(OH)3.2x

Iron

Haematite

Fe2O3

Magnetite

Fe3O4

Siderite

FeCO3

Iron pyrites

FeS2

Copper pyrites

CuFeS2

Malchite

CuCO3.Cu(OH)2

Zinc blende

ZnS

Calamine

ZnCO3

Zincite

ZnO

Copper
Zinc

How do we get metal from an ore?

Identification of the source material
Mining
Pre-treatment
Mineral to compound
Compound to metal
Refining

Alloying

Pretreatment

Comminution
Benefaction
Preparatory treatment
(Roasting/ Calcinations)

Pretreatment
Comminution :crushing, grinding, classification

..

.
..
.
Uncrushed ore

..
.

crushed ore

Concentration/Benefaction
Gravity Separation
Magnetic Separation
Froth flotation
Leaching

Concentration by cyclone
Lighter particles,
Gangue

Pulverized ore

Up ward
moving air
stream

Heavier particles
mineral
10

Froth flotation
Collectors are added to enhance
hydrophobic character
Froth stabilizers are basically
co-surfactants
Depressants are masking agents.

11

Leaching
Extraction of metals from ores/Scrap to aqueous solutions by
means of chemicals.
Leaching involves the use of aqueous solutions containing a
leaching agent which is brought into contact with a material
containing a valuable metal. The leaching solution may be
acidic or basic in nature.

12

Leaching of alumina from bauxite

Al2O3 is leached out as sodium aluminate leaving the impurities
behind:

Al 2O3(s) +2 NaOH(aq) + 3H2O

2Na[Al(OH)4](aq) + CO2(g)

2Na[Al(OH)4](aq)
Al2O3 x H2O(s) +NaHCO3

Amphoteric nature of aluminum oxide is used for concentration

by leaching and selective precipitation.

13

Calcination
Originally, calcination referred to the heating of limestone above
900C to drive off the CO2 and produce lime:
CaCO3(s) ===> CaO(s) + CO2(g)
In current practice, calcination refers to any process where the
material is heated to drive off volatile organics, CO2, chemically
bound water, or similar compounds. For example:
2Al(OH)3(s) ===> Al2O3(s) + 3H2O(g)
2FeOOH(s) ===> Fe2O3(s) + H2O(g)

14

Roasting
Roasting involves not only heating, but also reaction with a gas.
It is typically used to convert sulfides to oxides by reaction with
air (air is usually used as an oxidizing agent, because it is free).
For example:
2ZnS(s) + 3O2(g) ===> 2ZnO(s) + 2SO 2 (g)
(H = -211 kilocalories)
4FeS2 (s) + 11O2 (g) ===> 2Fe2O3 (s) + 8SO2 (g)
(H = -796 kilocalories)

15

Compound to metal

There are two main ways to form the pure metal

from its oxide, depending on how reactive the metal is:

a) Reduction with carbon

(smelting, known since Egyptian times);
b) Reduction with hydrogen
(when carbide formation is a problem);
c) Reduction with more active metal
(when hydride formation is a problem);
and
Electrochemical reduction (known for about 150 years)

16

Pyrometallurgy
Pyrometallurgy consists of the thermal treatment of minerals
and concentrates for extraction of metals.
The Ellingham diagram is a tool most often used in extraction
metallurgy to find the conditions necessary for the reduction of
the ores of important metals.

17

Thermodynamics of reduction
The Gibbs free energy, G, of a system can be described as the
energy in the system available to do work.
It is defined as:
G = H-TS
T is temperature and S is entropy or disorder and H is enthalpy
Defined as
H =U + pv
U is internal energy, p is pressure and v is volume.
18

 The free energy change, G, of a chemical reaction is the

difference in free energy between the products of the reaction
and the reactants.
If the free energy of the products is less than the free energy of
the reactants there will be a driving force for the reaction to
occur.
For a reaction
A+ B
C+D
The free energy change G should be negative

19

The Equilibrium Constant

A chemical reaction will occur if the total free energy
of the products is less than the total free energy of the
reactants. (ie. The free energy change for the reaction
is negative.)
If the system containing the reactants and products is closed (if
there is no input of reactants, for example), the concentration of
reactants will decrease and the concentration of products will
increase as the reaction proceeds.

This will alter the state of the system and therefore alter the
free energy change for the reaction

20

The reaction will continue if the free energy change remains

negative. Hence, the system proceeds down a free energy gradient
with respect to composition and this gradient provides the driving
force for the reaction to proceed. The system alters the quantities of
reactants and products in response to the driving force until a
minimum in free energy is reached and the gradient is zero. This is a
point of equilibrium.

At equilibrium the free energy change for the reaction is equal to

zero:

G ln K
G 0 = -RT

21

Construction of an Ellingham Diagram

An Ellingham diagram is a plot of G versus temperature.

The graph consists of lines of

The enthalpy change (H) is a measure of the actual energy that is

liberated when the reaction occurs (the heat of reaction). If it is
negative, then the reaction gives off energy, while if it is positive
the reaction requires energy.
The entropy change (S) is a measure of the change in the
possibilities for disorder in the products compared to the reactants.
For example, if a solid (an ordered state) reacts with a liquid (a
somewhat less ordered state) to form a gas (a highly disordered
state), there is normally a large positive change in the entropy for
the reaction.

22

 Since H and S are essentially constant with temperature

unless a phase change occurs, the free energy versus
temperature plot can be drawn as a series of straight lines, where
-S is the slope and H is the y-intercept.
The slope of the line changes when any of the materials
involved melt or vaporize.
Free energy of formation is negative for most metal oxides, and
so the diagram is drawn with G=0 at the top of the diagram,
and the values of G shown are all negative numbers.
Temperatures where either the metal or oxide melt or vaporize
are marked on the diagram.
The oxygen partial pressure is taken as 1 atmosphere, and all of
the reactions are normalized to consume one mole of O2.

23

24

25

2 Zn(s) + O2(g) -------2 ZnO(s)

G(298 K) = 636 kJ/mol

26

27

28

 For metal oxide to be reduced to metal, one of the three

following reactions must have a more negative G
(a.) C(s) + O2(g) CO(g)

G(C,CO)

(b.) C(s) + O2(g) CO2(g) G(C,CO2)

(c.) CO(g) + O2(g) CO2(g)

G(CO,CO2)

than a reaction of the form

(d.) xM(s or l) + O2(g) MxO(s)

G(M,MxO)

29

 For one of the following, one must have a more

negative G
(a-d) MxO(s) + C(s) + xM(s or l) + CO(g)
G(C,CO) - G(M,MxO)
and/or
(b-d) MxO(s) + C(s) xM(s or l) + CO2(g)
G(C,CO2) - G(M,MxO)
and/or
(c-d) MxO(s) + CO(g) xM(s or l) + CO2(g)
G(CO,CO2) - G(M,MxO)
30

31

32

33

 When C_CO line is below M_MO line, C reduces

the MO and produces CO.
When C_CO2 line is below M_MO line, C
reduces the MO and produces CO2.
When CO_CO2 line is below M_MO line, CO
reduces the MO and produces CO2.

The three curves intersect at 710 oC

Below 710 oC, CO is better reducing agent.
Above 710 oC, carbon is better reducing agent.

34

Thermodynamic data for the oxidation of

metals
693-1181

2Zn + O2 = 2ZnO

-355,890 + 107.5 T

911-1376

2Ni + O2 = 2NiO

-233,580 + 84.9 T

923-1380

2Mg(l)+O2=2 MgO

-608,200 - 1.00 T

1380-2500

2Mg(g)+O2=2 MgO

-759,600 - 30.83 T

35

36

2Cu+O22CuO

S<0
2Fe+O22FeO
CO

2C+O22CO

Cu

Fe

300

700

S>0

TC

37

Using ED, find out what is the

lowest temp. at which ZnO can
be reduced to Zn by carbon.
What is the overall reaction?

What is the minimum temp.

required for the reduction of
MgO by carbon?

38

Thermit Process Sacrificial Method

Cr2O3

4/3 Al + O22/3
Al2O3
H = -266 Kcal/mol
4/3 Cr + O22/3
Cr2O3
Al2O3
H = -180 Kcal/mol
4/3 Al + 2/3 Cr2O3

Temperature

4/3Cr + 2/3 Al2O3

H = -86 Kcal/mol

39

 However Al reduction requires higher temperature to

trigger off.
Kinetic factor: Activation energy
Priming the reaction with Mg-ribbon and barium
peroxide / a KNO3+S+Al pellet is necessary.
The reduction is usually exothermic. Once initiated, the
whole mass gets reduced spontaneously.
Alloy formation with Al can take place in some cases.

40

From Ellingham diagram to see whether a

reduction reaction will take place
~
GR 0

2Ni + O2 = 2NiO
2H2 + O2 = 2H2O
1000K

2H2 + O2 = 2H2O
2NiO = O2 + 2Ni
2H2 + 2NiO = 2Ni + 2H2O

~
GR 0

2H2 + O2 = 2H2O
2Mn + O2 = 2MnO
1000K

2H2 + O2 = 2H2O
2MnO = O2 + 2Mn
2H2 + 2MnO = 2Mn + 2H2O

T
41

Properties of Ellingham diagram

All metal oxide curves slop upwards
If materials melt / vaporize, the slope changes
When the curve crosses Go = 0, decomposition
of oxide begins (Ag, Au, Hg)
Electropositive metal curves are at the bottom of
the diagram

Any metal will reduce the oxide of other metal

which is above in Ellingham diagram (the Go
will become more negative by an amount equal
to the difference between the two graphs at a
particular temperature)
42

Drawbacks of Ellingham diagram

It can not predict rate of reaction.

The calculations are at equilibrium condition which may

not be the condition, always.

43