Topic II

Basic principles of extraction of metals

from ores & purification

Extraction of Metals
-the chemistry within
Iron Pillar of Delhi
The History of
metallurgy in the
Indian subcontinent
dates back to 1700 BC.

 Metals and related

concepts were
mentioned in various
early Vedic age texts.

 The Rig-Veda already

uses the Sanskrit term
Ayas (metal).
Composition: Iron Pillar of Delhi
[Fe(O)(OH)]
Oxygen 46.71 1774
Silicon 27.69 1824
Aluminum 8.07 1825 92 %
Iron 5.05 ancient All other
Calcium 3.65 1808
99.5 % elements =
Sodium 2.75 1807
0.03 %
Potassium 2.58 1807
Magnesium 2.08 1755
Titanium 0.62 1791
Hydrogen 0.14 1776 99.97 %
Phosphorus 0.13 1669
Carbon 0.094 ancient
Manganese 0.09 1774

Need for
Sulfur 0.052 ancient

efficient
Barium 0.05 1808
Chlorine 0.045 1774
Chromium 0.035 1797
separation
Fluorine 0.029 1886 techniques
Zirconium 0.025 1789
Nickel 0.019 1751
 Methods of Separation / Extraction

1.Mechanical separation

2. Thermal decomposition
3. Displacement
4. High temperature chemical reduction
5. Electrolytic reduction
And so on ……
 (i) Mechanical Separation
Free elemental form – unreactive elements

Coinage & Pt metals

Gold; 19.3 g/cm-3, separated by panning

 (ii) Thermal Decomposition
Unstable compounds  Constituent elements

Ag2O  2Ag + ½O2

Marsh test: As, Sb salt + Zn/H2SO4 As/SbH3 Silver
mirror of the metal
Decomposition of ammonium compounds
Ammonium dichromate on heating yields nitrogen, water
and chromium(III) oxide.
(NH4)2Cr2O7(s)  Cr2O3(s) + N2(g) + 4H2O(g)

Please refer to text

book or other
resources for more
examples of thermal
decomposition
reactions: Self study
Thermal Decomposition of Carbonate and
Azide
Carbonate decomposition
CuCO3 → CuO + CO2
CaCO3 → CaO + CO2
Azide decomposition / Life saving reaction
2NaN3 + 1/2O2  Na2O + 3N2
NaN3  Na + 3/2N2

0.03 SECONDis all it

takes to inflate an air bag.

130 g. needed (~ Rs. 100)

(iii) Displacement Of One Element By Other
In principle, any element
may be displaced by
another element which
has more negative Eo in
electrochemical series.
Cu2+ + Fe  Fe2+ + Cu
-0.44 +0.16

Cl2 + 2Br-  2Cl- + Br2

+1.36 +1.09

Cd2+ + Zn  Cd + Zn2+
How does this work?
 Demonstration !!!
Cu2+ + Fe  Fe2+ + Cu
-0.44 +0.16

Demonstration II
Which one can oxidize Cu then?

AgNO3  Ag(s) + NO3- couple E0 =+ 0.8 V

High Temperature Chemical Reduction

1. Many metals are found as their oxides

2. Oxide Ores: Directly reduced (smelted) to
the metal. General reducing agents: C , Al,
Si, H2. Carbon is the most widely used
reducing agent (can form carbide)
3. Sulfide Ores: First roasted to convert them
to oxide and then reduced to the metal (for
thermodynamic reasons oxides rather than
sulfides used) (SELF REDUCTION)
4. Other metals as reducing agents

(all points will be elaborated)

 Chemical Reduction
Mond’s Process (For pure nickel):

Kroll’s Process (for pure titanium):

 First Industrial Process For Zr and Ti
Van Arkel-deBoer’s Process (for metallic Zr / Ti):
Vacuum

Mo
electrode
And net
Chamber
raw
material
W- Wire
 Electrolytic Reduction

1. Electron – the strongest known reducing agent.

2. Highly electropositive metals, e.g. alkaline earth

metals are produced this way (Electrolytic reduction

of their fused halides)

3. Ionic materials (salts) are electrolyzed – reduction at

cathode

4. Excellent method, gives pure metal, but expensive

 Methods of Separation / Extraction

1.Mechanical separation

2. Thermal decomposition
3. Displacement of one element by other
4. High temperature chemical reduction
5. Electrolytic reduction
And so on ……
 High –T Chemical Reduction-
Thermodynamic Considerations….
1. Used to identify which reactions are spontaneous
under the prevailing conditions.
2. To choose most economical reducing agent and
reaction condition

Criterion for spontaneity

Go = − RT ln K

•Negative Go corresponds to K > 1; favorable reaction

•Kinetics is not important as reductions are done at high. temp &
fast
 High –T Chemical Reduction-
Thermodynamic Considerations….

Go = Ho - TS

For the formation of metal oxide,

2M(s) + O2(g)  2MO(s)
•ΔS is negative; because oxygen gas is used up.

•If temperature is raised, TΔS becomes more

negative & hence (– TΔS) is more positive

•Thus the free energy change (ΔGo) increases with

increase in the temperature
 Go = Ho - TS

The free energy

changes that occur
when one gram
molecule of a common
reactant (O2) is used,
is plotted against
temperature.
~-900
This graph is called
Ellingham Diagram
 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)
Carbon As The Reducing Agent

Go = Go(C,CO) - Go(M,MO)

 CO(g) + ½O2(g)  CO2(g) (S –ve)

710 oC

C + O2(g)  CO2(g) (S constant)

C + ½O2(g)  CO(g) (S +ve )

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.
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?
Thermit Process – Sacrificial Method
Cr2O3

-600
Go (kJmol-1)

-800 Al2O3

-1000

-1200

Temperature (oC)
4/3 Al + O2  2/3 Al2O3 H = -266 Kcal/mol
4/3 Cr + O2  2/3 Cr2O3 H = -180 Kcal/mol
4/3 Al + 2/3 Cr2O3  4/3 Cr + 2/3 Al2O3 H = -86 Kcal/mol

G ≈ H (since S is similar)
 Thermit Process – Details
4/3 Al + 2/3 Cr2O3  4/3 Cr + 2/3 Al2O3 H = -86 Kcal/mol

G is negative at all temperatures.

S is very small since there are no gaseous products
Hence, G is approximately same at different temperatures
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.
 H2- A Poor Reducing Agent
H2O

Go (kJmol-1) H2
MO

Temperature (oC)

• 2H2(g) + O2(g)  2H2O; entropy decreases

• points upwards and runs parallel to many MO curves.
• Up above in the diagram
• Metal hydride formation
• Dissolved (interstitial) hydrogen – poor properties
 Reduction of Metal Sulfides
Many metals, which are chemically soft, occur as sulfide
ores. e.g. Cu, Hg, Zn, Fe, etc.
Carbon is not a good reducing agent to for sulfide ores.
MS + C  CS2 has no slope in ED.

First roasted to MO and Self reduction:

then reduced to metal CuS  [CuS + CuO] 
2MS + 3O2  2MO + 2SO2 Cu + SO2
C

H2 is also a poor reducing agent for metal sulfides.

Ellingham Diagram - Metal Sulfides
HgS
Hgs H2S
CS2
-40 Zns
ZnS
Fes
FeS
- 80

Go( KCal/ mole S2(g) )

MnS

- 120
SO2
- 160
CaS
Cas

- 200

- 240
0 1000 oC 2000 oC
Ellingham Diagram - Metal Halides

CCl4 CF4

SnCl4 ZrCL4
MgCl2
TiCl4
-40

HCl NaCl
HF
NaF
MgCl2
NbF5
CaCl2 UF4

CaF2
-100
Gfo

300oC 500oC 1500oC 2500oC

Figure 2. Graph of Go/T for halide formation

 Purification of Elements
Special attention to metals
1. Fusion, distillation, crystallization.
– Fusion removed adsorbed gases (SO2, O2, etc.)
– Distillation of volatile metals to remove impurities
– Fractional distillation of OsO4 and RuO4 from other Pt-metals in the
presence of oxidising agents.
– Fractional Crystallization of Pt/Ir as (NH4)2MCl6
2. Oxidative refining
– When impurities have more affinity to oxygen than the metal.
– Pig iron contains C, Si, P, and Mn, which can be purified by
blowing air through the molten metal in Bessimer Convertor.
– CO, SiO2, P4O10, MnO formed combine with added CaO to give slag
- Ca3(PO4)2, MnSiO3
3. Thermal Decomposition
– Carbonyl (Mond process) for purification of Fe, Ni, etc.
– Van Arkel de Boer’s filament growth method (ZrI4, BI3, etc.)
– Decomposition of Hydrides (AsH3, SbH3 etc.)
 Purification of Elements
Special attention to metals

4. Electrolytic refining
5. Zone refining
6. Chromatographic methods
7.Solvent Extractions
8. Ion-Exchange Methods