This lecture

Extraction of metals from ores

General principles, then
Example: mining of copper Example: the Steel story

Metallurgy: (Extracting metal from ore)

Commercially important ores:

Use thermochemistry and equilibrium to investigate how these chemicals/materials are produced.

Good refs:

Silberberg Chemistry, 3rd ed., pp.963-968 McMurray and Fay, Chemistry, 3rd ed., pp. 910-918

Chemical composition of ores

More ionic More covalent
Ref: McMurray and Fay, p. 912

Metallurgy: (Extracting metal from ore)

One of Australias most important commodities

How are metals extracted from ores? Mining Pre-treatment

Chemical processing: mineral to compound Chemical processing: compound to metal Refining Alloying

Pretreatment
Several methods of pretreating the ore to obtain the mineral: Flotation, Cyclone, Magnetism, Leaching
Lighter particles (gangue) Agitator

Mineral to Compound
The most common way to convert the mineral into a uniform chemical compound is to roast it in air, e.g. CaCO3(s) + heat CaO(s) + CO2(g) or 2ZnS(s) + 3O2(g) + heat 2ZnO(s) + 2SO2(g)

Air

Pulverised ore

A source of acid rain.

Froth, including mineral
Ref: Petrucci, p.955

Upward moving air stream

Gangue

Now sulfur oxides are scrubbed from smokestack, and recycled into sulfuric acid (see next lecture)
Heavier particles (mineral)
Ref: Chemical Storylines, p.282

Ref: Silb., p.964

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)

Reduction with carbon

Consider the formation reactions:
(1) (2) (1)-(2) C(graphite) + 0.5O2(g) Zn(s) + 0.5 O2(g) Kp (300 K) 4.7x1023 2.3x1054 2.0x10-31

 ZnO(s) + more heat ZnO(s) + C(gr.) + heat  Zn(s) + CO(g)

Temp (K) 500 750 1000 1250 1500 1750 Kp 3.4x10-15 7.3x10-7 1.8x10-2 2.6 1.4x103 9.0x104

 CO(g) + heat

But
Adding heat as a reagent

Very Small. Favours reactants enormously! Le Chatelier at work!

Reduction with carbon

Ellingham diagram:
100

Reduction with C (other metals)

Ellingham diagram:
M.P. B.P.
100

80

Zn(s) + 0.5 O2(g)

 ZnO(s)
ln Kp

Ca - CaO Al - Al2O3

M.P. B.P.

80

Note ln scale

60

60

40

ZnO Zn
C CO

40

1RWLFH RUGHU RI HOHPHQWV

Zn - ZnO Fe - FeO Ni - NiO
600 800 1000 1200

ln Kp

20

C - CO

C(graphite) + 0.5O2(g)
0 400 600 800 1000

 CO(g)
1200 1400 1600 1800

20

0 400

1400

1600

1800

Temperature (K)

Temperature (K)

Reduction with C (other metals) Compound to Metal

Is there a chemical explanation for this trend? Metal Ca Al Zn Fe Ni Electron-attracting power of an element (in a compound) Most stable oxides

Electronegativity 1.0 1.5 1.6 1.8 1.9

Metal Least active Au, Pt Cu, Ag, Hg, Ni, Co V, Cr, Mn, Fe, Ti, Sn Most active Al, Li, Na, Mg

Reduction Method None; found in nature as free metal Roast sulfide to oxide reduction using carbon, hydrogen, or more active metal electrolysis

Oxygen is very electronegative. Which elements most readily give up their electrons to form stable oxides?

Example: Production of Copper

Copper has been mined since ancient times, maybe 3500 BC Copper deposits formed in magma pools and occur mostly as sulfides, CuS Near the surface, the minerals are altered by exposure to oxygen, into other minerals, e.g. cuprite (Cu2O), tenorite (CuO), malachite, Cu2(OH)2CO3

Example: Production of Copper

Surface deposits of copper oxides soon ran out. Larger deposits of sulfides were available. Sulfides converted to oxides by roasting.

Cu2S(s) + 1.5 O2(g) + heat

 Cu O(s) + SO (g)
2 2

Formation reaction for oxide: Cu(s) + 0.5 O2(g) Kp =4.3x1022 ln(K) = 52.1 electronegativity = 1.9

 CuO(s) + heat
T T

Largest deposits of copper are chalcopyrite, which contain iron Chalcopyrite is ground, then froth flotation is used to separate mineral from gangue T The sulfide is smelted directly to Cu metal

Look back at Ellingham plot and electronegativity table and predict how the ancients might have reduced CuO.

Example: Production of Copper

Waste gases, SO2 Chalcopyrite + silica (SiO2) Fuel Slag Copper (impure, 2% S) electrolytic Overall reaction: refining 4CuFeS2(s) + 10.5O2(g) 4Cu(s) + 2FeO(l) + Fe2O3(s) + 8SO2(g) Oxide

Example: The Steel Story

Iron/steel is the most widely used of all metals, with some 750 million tonnes per year produced worldwide. Iron has been smelted since ~1500 BC In 1773, a cheap process to produce coke (carbon) from coal, and the advent of the blast furnace, led to large-scale iron production and the Industrial Revolution. Important iron minerals: Mineral type Mineral, formula Hematite, Fe2O3 Magnatite, Fe3O4 Ilmenite, FeTiO3 Carbonate Sulfide Siderite, FeCO3 Pyrite, FeS2 Pyrrhotite, FeS

O2

Example: The Steel Story

The overall reaction uses CO as reducing agent:

Example: The Steel Story

Ore, CaCO3, C Temp

Fe2O3(s) + 3CO(g) 2Fe(l) + 3CO2(g)

Solids drop Hot gases rise

But this is the overall reaction and hides a multitude of processes. The process of converting iron ore into iron and steel involves a series of reductions of the ore, and acid-base steps. Although these seem simple enough, the detailed chemistry is very complex, and perhaps not fully understood even now.
Iron Forge (1772) Joseph Wright of Derby

3Fe2O3 + CO 2 Fe3O4 + CO2 Fe3O4 + CO 3FeO + CO2 CaCO3 CaO + CO2 C + CO2 2 CO FeO + CO Fe + CO2 Impure iron melts. Molten slag forms 2C + O2 2 CO

200C

700C 1200C 1500C 2000C

Hot air blast Slag Molten iron

Slag floats on iron, like Earths crust on core

Example: The Steel Story

The iron from the furnace is impure and called pig iron. Pig Iron Bob It contains typically 3-4% carbon Iron is purified and converted to steel by the basic oxygen process.

Example questions
CONCEPTS
reduction of metal oxide use of Ellingham graph knowledge of the production of Cu, steel

High pressure O2 is blown over the molten iron. Impurities with very stable oxides form (e.g. C, Si, P, Mn, S) It is too hot for less stable oxides, including iron.) CaO (lime) is added, which reacts with these oxides to form a variety of phosphates, silicates, etc, all termed slag, which again float on the surface of the molten steel. Now 1% C, and very low other impurities and ready to alloying, e.g. Cr. to make stainless steel.
Ref, Silberberg, p.972

CALCULATIONS
Equilibrium and thermochemistry calculations involving metallurgy.