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METALS AND METALS AND

METALLURGY METALLURGY
CHAPTER 23 CHAPTER 23
Metallurgy Metallurgy
Science and technology of extracting metals from
their ores and of compounding alloys.
Most metals are found in nature in solid inorganic
compounds (minerals)
except Au and PGMs (Pt, Pd, Rh, Ru, Ir, Os)
NB source of minerals oxides (O
2-
),
sulphides (S
2-
) and
carbonates (CO
3
2-
)
Silicates are abundant, BUT they are generally
difficult to treat (not economically viable)
What is involved?
Mining (then crushing and grinding)
Concentrating the ore remove the gangue
e.g. magnetic separation, flotation, amalgamation
Reducing the concentrate to obtain free metal
Refining/purifying the metal
Alloying mixing metal with other elements to
modify properties
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2
4
3
5
PYROMETALLURGY PYROMETALLURGY
Use high temperatures to alter
the mineral chemically and
reduce it to the free metal.
Requires large amounts of energy
+ often the source of atmospheric pollution.
Used in concentration reduction and refining
processes
Some Some pyrometallugical pyrometallugical processes processes
Calcination:
Heat ore to decompose and eliminate volatile
products
Carbonates often calcined to drive off CO
2
and form
metal oxide
e.g. PbCO
3
(s) PbO(s) +CO
2
(g)

Require temps ~400-500

o
C (1000
o
C for CaCO
3
)
Hydrated minerals lose H
2
O at ~100-300
o
C
2
Roasting:
Themal treatment causes chemical reaction
between ore an furnace atmosphere.
Leads to reduction or oxidation (depending on
atm) and may be accompanied by calcination.
e.g. Roasting of sulphides to produce oxides
2ZnS(s) + 3O
2
(g) 2ZnO(s) + 2SO
2
(g)
e.g. Sulphides of less active metals can be roasted to
the free metal
HgS(s) + 3O
2
(g) Hg(g) + SO
2
(g)
e.g. Free metal also obtained by using reducing atm
PbO(s) + CO(g) Pb(l) + CO
2
(g)
Smelting:
Melting process in which material separates
into 2 or more layers in a chemical reaction.
Form molten metal + slag
Slag forms when basic metal oxide reacts at high
temps with molten silica (SiO
2
)
e.g. CaO(l) + SiO
2
(l) CaSiO
3
(l)
Slag = mainly molten silicate minerals (with
aluminates, phospates, fluorides and other inorganic
compounds)
Refining:
Treatment of crude, relatively impure metal
product to improve purity.
Produce pure metal or mixture of well-defined
composition
PYROMETALLURGY OF IRON PYROMETALLURGY OF IRON
Source: iron oxide minerals
hematite = Fe
2
O
3
magnetite = Fe
3
O
4
Reduction of iron oxides in blast furnace
Charged at the top with mixture of:
iron ore + coke + limestone
Coke = coal heated in absence of air to drive off
volatiles
= 85-90% C
Fuel produces heat as it is burned in lower
part of furnace
Source of reducing gases CO + H
2
Limestone = CaCO
3
Source of basic oxide in slag formation
Hot air blown in from bottom of furnace
for combustion of coke
3
Reactions in furnace: Reactions in furnace:
Combustion of coke:
2C(s) + O
2
(g) 2CO H = -221 kJ
Water vapour also reacts with coke:
2C(s) + H
2
O(g) CO +2H
2
H = +131 kJ
Limestone is calcined in upper part of furnace:
CaCO
3
(s) CaO(s) + CO
2
Iron oxides reduced by CO
2
and H
2
in upper part of
furnace:
e.g. Fe
3
O
4
(s) + 4CO(g) 3Fe(s) + 4CO
2
(g)
H = -15 kJ
Fe
3
O
4
(s) + 4H
2
(g) 3Fe(s) + 4H
2
O(g)
H = +150 kJ
Reduction of other elements also occurs in hottest
part of furnace where C is the major reducing agent.
Molten iron collects at bottom of furnace with a layer
of slag on top.
Tap furnace periodically to remove iron
(also drain off slag)
Tapped iron is NOT PURE
contains Si, Mn, P, S, C
Formation of steel Formation of steel
Remove impurities by oxidation in a converter
use O
2
or O
2
+ Ar as oxidising agent
C & S expelled as CO and SO
2
gases.
Si oxidised to SiO
2
and adds to slag.
Presence of basic slag NB for P removal:
3CaO(l) + P
2
O
5
(l) Ca
3
(PO
4
)
2
(l)
Monitor O
2
coming off to see when reaction is
complete.
Converter
Alloying elements added to produce steel.
Different elements and different amount
different properties
Types of steel
HYDROMETALLURGY HYDROMETALLURGY
Extract metal from ore
using aqueous reactions
Leaching:
Desired metal containing compound is
selectively dissolved
Leaching agents used:
H
2
O or aqueous solns of acid/base/salt
Often form a complex ion.
4
e.g. Gold concentrated by the process of cyanidation
Leaching agent = NaCNsoln in presence of air
4Au(s) + 8CN
-
(aq) + O
2
(g) + H
2
O(l)
4Au(CN)
2
-
(aq) + 4OH
-
(aq)
Au(CN)
2
-
is then reduced by zinc powder
2Au(CN)
2
-
+ Zn(s) Zn(CN)
4
2-
(aq) + 2Au(s)
ELECTROMETALLURGY ELECTROMETALLURGY
Electrolysis used to reduce
metal ores or refine metals
Electrolysis of molten salt or aqueous solution.
e.g. Na, Mg, Al
H
2
O more easily reduced
than metal ion
Electrorefining Electrorefining of Copper of Copper
Anodes = large slabs of crude Cu
Cathodes = thin sheets of pure Cu
Electrolyte = acid soln of CuSO
4
Apply voltage get oxidation of Cu at anode and
reduction of Cu
2+
at cathode
Oxid. & reduct. more readily than that for H
2
O
To obtain pure Cu
Impurities in anode includes:
Zn, Ni, As, Se, Te, precious metals incl. Au & Ag
Metallic impurities that are more active than Cu are
also readily oxidised at the anode, but to not plate at
the cathode because their reduction potentials are
more negative than that for Cu
2+
.
Less active metals are not oxidised at the anode
collect as sludge below the anode
Cell house
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Example:
Ni is one of the main impurities in the crude copper
of the anode. What happens to the nickel during the
electrolytic process?
ALLOYS ALLOYS
Alloy = Material containing more than 1 element and
has characteristic properties of metals.
Modify properties of metal.
e.g. Gold is often too soft generally alloy with
copper to harden it
24 karat = pure gold
Jewelry: generally ~14 karats 58% gold
Yellow/white gold depends on metal added
for alloying
Alloys
Solution
alloys
Heterogeneous
alloys
Intermetallic
compounds
Substitution
alloy
Interstitial
alloy
Solution alloys Solution alloys
Homogeneous mixtures in which the components are
dispersed randomly and uniformly.
Substitution alloy atoms of the solute take position
usually occupied by solvent atom.
2 metallic components have similar radii and
chemical-bonding characteristics e.g. Ag and Au.
When radii differ by >~15%, solubility limited.
Interstitial alloy atoms of the solute occupy
interstitial positions.
Component in interstitial positions must have much
smaller covalent radii than the solvent atoms.
Interstitial element typically non-metal
bonds to neighbouring atoms
extra bonds causes metal lattice to become
harder, stronger and less ductile.
e.g. C in steel
components are NOT dispersed uniformly.
Heterogeneous alloys Heterogeneous alloys
e.g. In pearlite (form of steel)
2 distinct phases in alternating layers:
1) pure iron
2) Fe
3
C (cementite)
NB the way in which the solid was formed
e.g. rapid cooling vs fast cooling of molten mixture
leads to different properties.
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Intermetallic Intermetallic compounds compounds
Homogeneous alloys that have definite properties and
compositions.
e.g. Ni
3
Al used in jet engines
strong, low density
e.g. Cr
3
Pt coat razor blades
- hard
e.g. Co
5
Sm permanent magnets in headsets
high magnetic strength per unit mass