METALLURGY: EXTRACTING A METAL

FROM ITS ORE

Pretreating the Ore
 Converting Mineral to Element
Converting the Mineral to Another Compound
Converting the Compound to the Element Through
Chemical Redox
Converting the Compound to the Element Through
Electrochemical Redox
Converting the Mineral to Another Compound

First, the mineral is often converted to another compound,

one that has more appropriate solubility properties, is easier
to reduce, or is free of a troublesome impurity.
Conversion to an oxide is common because oxides can be
reduced easily. Carbonates are heated to convert them to the
oxide:
CaCO3 (s) CaO(s) + CO2(g)
Metal sulfides, such as ZnS, can be converted to oxides by
roasting in air:
2 ZnS(s) + 3 O2(g) 2 ZnO(s) + 2 SO2(g)
 Converting the Compound to the Element Through
Chemical Redox
Reduction with carbon.
Carbon, in the form of coke (a porous residue from incomplete
combustion of coal) or charcoal, is a very common reducing agent. Heating
an oxide with a reducing agent such as coke to obtain the metal is called
smelting. Many metal oxides, such as zinc oxide and tin(lV) oxide, are
smelted with carbon to free the metal, which may need to be condensed
and solidified:
ZnO(s) + C(s) Zn(g) + CO(g)
SnO2s) + 2C(s) Sn(l) + 2CO(g)
Several nonmetals that occur with positive oxidation states in minerals can
be reduced with carbon as well. Phosphorus, for example, is produced
from calcium phosphate:
2Ca3(PO4)2(s) + 10C(s) + 6SiO2(s) 6CaSiO3(s) + 10CO(g) + P4(s)
(Metallic calcium is a much stronger reducing agent than carbon, so it is
not formed)
 Reduction with hydrogen.
For oxides of some metals, especially some
members of Groups 6B and 7B, reduction with
carbon forms metal carbides. These carbides
are difficult to convert further, so other
reducing agents are used. Hydrogen gas is
used for less active metals, such as tungsten:
WO3(s) + 3H2(g) W(s) + 3H2O(g)
 Reduction with an active metal.
When a metal might form an undesirable
hydride, its oxide is reduced by a more active
metal. In the thermite reaction, aluminum
powder reduces the metal oxide in a
spectacular exothermic reaction to give the
molten metal. The reaction for chromium is
Cr2O3(s) + 2AI(s) 2Cr(l) + Al2O3(s) , Ho <<0
 Oxidation with an active nonmetal.
Just as chemical reduction of a mineral is used
to obtain the metal, chemical oxidation of a
mineral is sometimes used to obtain a
nonmetal. A stronger oxidizing agent is used
to remove electrons from the nonmetal anion
to give the free nonmetal, as in the industrial
production of iodine from concentrated brines
by oxidation with chlorine gas:
2I-(aq) + Cl2(g) 2CI-(aq) + I2(s)
Converting the Compound to the Element Through
Electrochemical Redox

In these processes, the mineral components are converted to the

elements in an electrolytic cell. Sometimes, the pure mineral, in the
form of the molten halide or oxide, is used to prevent unwanted
side reactions.
The cation is reduced to the metal at the cathode and the anion is
oxidized to the nonmetal at the anode:
BeCl2(l) Be(s) + Cl2(g)
High-purity hydrogen gas is prepared by electrochemical reduction:
2H2O(l) 2H2(g) + O2(g)
Specially designed cells separate the products to prevent
recombination. Cost is a major factor in the use of electrolysis and
an inexpensive source of electricity is essential for large-scale
methods.
 Refining and Alloying the Element
Refining (Purifying) the Element
Refining is a purification procedure, often carried out by one of three
common methods:
- electrorefining (the impure metal acts as the anode and a sample of the
pure metal acts as the cathode),
- distillation (for metals with relatively low boiling points, such as zinc and
mercury), and
- zone refining (impurities are removed from a bar of the element by
concentrating them in a thin molten zone, while the purified element
recrystallizes.
Alloying the Purified Element
Alloying a metal with other metals (and, in some cases, nonmetals) is
done to alter the metal's melting point and to enhance properties such as
luster, conductivity, malleability, ductility, and strength.
 The manufacture of sulfuric acid
Obtaining sulfur
- Claus process, in which the H2S in "sour" natural gas is chemically
separated and then oxidized:
2H2S(g) + 2O2(g) low temperature 1/8S8(g) + SO2(g) + 2H2O(g)
2H2S(g) + SO2(g) Fe203 catalyst 3/8S8(g) + 2H2O(g)
- Frasch process, a nonchemical method that taps natural underground
deposits of sulfur.
A hole is drilled to the deposit and superheated water (about 160C) is
pumped down two outer concentric pipes to melt the sulfur. Then, a
combination of the hydrostatic pressure in the outermost pipe and the
pressure of compressed air sent through a narrow inner pipe forces the
sulfur to the surface. The costs of drilling, pumping, and supplying water
(5 X 10 6 gallons per day) are balanced somewhat by the fact that the
product is very pure (-99.7% S).
 From sulfur to sulfur dioxide.
Once obtained, the sulfur is burned in air to form SO2:
1/8S8(s) + O2(g) SO2(g) Ho = -297 kJ
Some SO2 is also obtained from the roasting of metal sulfide ores. About
90% of processed sulfur is used in making sulfur dioxide for production of
the all- important sulfuric acid.
From sulfur dioxide to trioxide.
The contact process oxidizes SO2 with O2 to SO3:
SO2(g) + 1/2O2(g) SO3(g) Ho = -99 kJ
The reaction is exothermic and very slow at room temperature. The
pressure effect is small and economically not worth exploiting. The
concentration effects are controlled by providing an excess of O2 in the
form of a 5:1 mixture of air:SO2, or about 1:1 O2:SO2.
The mixture is passed over catalyst beds (contact process : V2O5 on inert
silica at 400-600oC) in four stages, and the SO3 is removed at several
points to favor more SO3 formation. The overall yield of SO3 is 99.5%.
 From sulfur trioxide to acid.
Sulfur trioxide is the anhydride of sulfuric acid, so a hydration
step is next. However, SO3 cannot be added to water because,
at the operating temperature, it would first meet water vapor,
which catalyzes its polymerization to (SO3)x, and results in a
smoke of solid particles that makes poor contact with water
and yields little acid. To prevent this, previously formed
H2SO4 absorbs the SO3 and forms pyrosulfuric acid (or
disulfuric acid, H2S2O7), which is then hydrolyzed with
sufficient water:
SO3(g) + H2O(l) H2SO4(l) - [Iow yield]
SO3(g) + H2SO4(l) H2S2O7(l)
H2S2O7(l) + H2O(l) 2H2SO4(l)