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Introduction

The Earth's crust contains many different rocks. Rocks are a mixture
of minerals and from some we can make useful substances.
A mineral can be a solid metallic or non-metallic element or a compound
found naturally in the Earth's crust.
A metal ore is a mineral or mixture of minerals from which
economically viable amounts of metal can be extracted, i.e. its got to
have enough of the metal, or one of its compounds, in it to be worth
digging out! Ores are often oxides, carbonates or sulphides. They are
all finite resources so we should use them wisely!
In order to extract a metal, the ore or
compound of the metal must undergo a
process called reduction to free the metal
(i.e. the positive metal ion gains negative
electrons to form the neutral metal atom, or
the oxide loses oxygen, to form the free
metallic atoms).
o The chemical that removes the oxygen
from an oxide is called the reducing
agent i.e. carbon, carbon monoxide or
sometimes hydrogen.
o Detailed REDOX notes on the metal
reactivity page, and on this page where
appropriate.
Generally speaking the method of extraction depends on the metals
position in the reactivity series
The reactivity series of metals can be presented to include two nonmetals, carbon and hydrogen, to help predict which method could be
used to extract the metal.
o

lower Pt Au Ag Cu

(H) Pb Sn Fe Zn (C) Al Mg Ca

Na K higher in series
RULE: Any element higher in the series can displace any
other lower element
Metals above zinc and carbon in the reactivity series cannot usually
be extracted with carbon or carbon monoxide. They are usually
extracted by electrolysis of the purified molten ore or other suitable
compound
o e.g. aluminium from molten aluminium oxide or sodium from
molten sodium chloride.
o The ore or compound must be molten or dissolved in a solution in
an electrolysis cell to allow free movement of ions (electrical
current). Theory given in the appropriate sections.
Metals below carbon can be extracted by heating the oxide with
carbon or carbon monoxide. The non-metallic elements carbon will
o

displace the less reactive metals in a smelter or blast furnace e.g.


iron or zinc and metals lower in the series.
o Metals below hydrogen will not displace hydrogen from acids.
Their oxides are easily reduced to the metal by heating in a
stream of hydrogen, though this is an extraction method rarely
used in industry. In fact most metal oxides below carbon can be
reduced when heated in hydrogen, even if the metal reacts with
acid.
Some metals are so unreactive that they do not readily combine with
oxygen in the air or any other element present in the Earth's crust, and
so can be found as the metal itself. For example gold (and sometimes
copper and silver) and no chemical separation or extraction is needed. In
fact all the metals below hydrogen can be found as the 'free' or 'native'
element.
Other methods are used in special cases using the displacement rule. A
more reactive metal can be used to displace and extract a less
reactive metal but these are costly processes since the more reactive
metal also has to be produced in the first place! See Titanium or see at
the end of the section on copper extraction.
Sometimes electrolysis is used to purify less reactive metals which
have previously been extracted using carbon or hydrogen (e.g. copper
and zinc). Electrolysis is also used to plate one metal with another.
The demand for raw materials does have social, economic and
environmental implications e.g. conservation of mineral resources by
recycling metals, minimising pollution etc.
Historically as technology and science have developed the methods of
extraction have improved to the point were all metals can be produced.
The reactivity is a measure of the ease of compound formation and
stability (i.e. more reactive, more readily formed stable compound, more
difficult to reduce to the metal).
o The least reactive metals such as gold, silver and copper have
been used for the past 10000 years because the pure metal was
found naturally.
o Moderately reactive metals like iron and tin have been
extracted using carbon based smelting for the past 2000-3000
years.
o

BUT it is only in the last 200 years that very reactive metals
like sodium or aluminium have been extracted by electrolysis.

The Extraction of Iron

Raw Materials:

Iron Ore e.g.


haematite ore
[iron(III) oxide,
Fe2O3]
coke (carbon, C)
hot air (for the
O2 in it)
limestone (calcium
carbonate, CaCO3)

Iron oxide ore is mined in many parts of the


world. Examples are haematite Fe2O3 and
magnetite Fe3O4.
The solid mixture of haematite ore, coke
and limestone is continuously fed into the
top of the blast furnace.
The coke is ignited at the base and hot air
blown in to burn the coke (carbon) to form
carbon dioxide in an oxidation reaction (C
gains O).
The heat energy is needed from this very
exothermic reaction to raise the
temperature of the blast furnace to over
1000oC to effect the ore reduction. The
furnace contents must be he
carbon + oxygen ==> carbon
o
dioxide
C(s) + O2(g) ==> CO2(g)
o
at high temperature the carbon dioxide
formed, reacts with more coke (carbon) to
form carbon monoxide
carbon dioxide + carbon ==> carbon
o
monoxide
CO2(g) + C(s) ==> 2CO(g)
o
(note: CO2 reduced by O loss, C is
o
oxidised by O gain)
The carbon monoxide is the molecule that
actually removes the oxygen from the iron
oxide ore. This a reduction reaction (Fe2O3
loses its O, or Fe3+ gains three electrons to
form Fe) and the CO is known as the
reducing agent (the O remover and gets
oxidised in the process).
This frees the iron, which is molten at the
high blast furnace temperature, and trickles
down to the base of the blast furnace. The
main reduction reaction is ...
iron(III) oxide + carbon monoxide
o
==> iron + carbon dioxide
Fe2O3(s) + 3CO(g) ==> 2Fe(l) + 3CO2(g)
o
note, as in the two reactions above,
o
oxidation and reduction always go

together!
Other possible ore reduction

reactions are ...


iron(III) oxide + carbon

==> iron + carbon monoxide


Fe2O3(s) + 3C(g) ==> 2Fe(l) +

3CO(g)
or

iron(III) oxide + carbon

==> iron + carbon dioxide


2Fe2O3(s) + 3C(g) ==> 4Fe(l) +

3CO2(g)
The original ore contains acidic mineral
impurities such as silica (SiO2, silicon
dioxide). These react with the calcium
carbonate (limestone) to form a molten slag
of e.g. calcium silicate.

The Extraction of Aluminium

Aluminium is obtained from


mining the mineral bauxite.
The purified bauxite ore of
aluminium oxide is
continuously fed in. Cryolite
is added to lower the melting
point and dissolve the ore.
Ions must be free to move
to the electrode connections
called the cathode (-,
negative), attracting positive
ions e.g. Al3+, and the anode
(+, positive) which attracts
negative ions e.g. O2-.
When the d.c. current is
passed through aluminium
forms at the negative
cathode (metal*) and sinks to
the bottom of the tank.
At the positive anode, oxygen
gas is formed (non-metal*).
This is quite a problem. At
the high temperature of the
electrolysis cell it burns and
oxidises away the carbon
electrodes to form toxic
carbon monoxide or carbon
dioxide. So the electrode is
regularly replaced and the
waste gases dealt with!
It is a costly process (6x
more than Fe!) due to the
large quantities of
expensive electrical energy
needed for the process.
* Two general rules:
o Metals and hydrogen
(from positive ions),
form at the negative
cathode electrode.
o

Non-metals (from
negative ions), form
at the positive anode
electrode.

Raw materials for the electrolysis process:

Bauxite ore of impure aluminium oxide


[Al2O3 made up of Al3+ and O2- ions]
Carbon (graphite) for the electrodes.
Cryolite reduces the melting point of
the ore and saves energy, because the
ions must be free to move to carry the
current
Electrolysis means using d.c.
electrical energy to bring about
chemical changes e.g. decomposition
of a compound to form metal deposits
or release gases. The electrical energy
splits the compound!
At the electrolyte connections called
the anode electrode (+, attracts ions) and the cathode electrode (-,
attracts + ions). An electrolyte is a
conducting melt or solution of freely
moving ions which carry the charge of
the electric current.

The redox details of the electrode


processes:
At the negative (-) cathode,
reduction occurs (electron
gain) when the positive
aluminium ions are attracted
to it. They gain three
electrons to change to
neutral Al atoms.
Al3+ + 3e- ==> Al
o
At the positive (+) anode,
oxidation takes place
(electron loss) when the
negative oxide ions are
attracted to it. They lose two
electrons forming neutral
oxygen molecules.
2O2- ==> O2 + 4eo
or 2O2- - 4e- ==> O2
o
Note: Reduction and
Oxidation always go together!
The overall electrolytic
decomposition is ...
aluminium oxide =>
o
aluminium + oxygen
2Al2O3 ==> 4Al + 3O2
o
o

and is a very
endothermic process,
lots of electrical
energy input!

GENERAL NOTE ON ELECTROLYSIS:


Any molten or dissolved material in which the liquid contains free moving
ions is called the electrolyte.
Ions are charged particles e.g. Na+ sodium ion, or Cl- chloride ion, and their
movement or flow constitutes an electric current, because a current is moving
charged particles.
What does the complete electrical circuit consist of?
o There are two ion currents in the electrolyte flowing in opposite
directions:
positive cations e.g. Al3+ attracted to the negative cathode
electrode,
and negative anions e.g. O2- attracted to the positive anode

electrode,
BUT remember no electrons flow in the electrolyte, only in the
graphite or metal wiring!
The circuit of 'charge flow' is completed by the electrons moving
around the external circuit e.g. copper wire or graphite electrode, from
the positive to the negative electrode
This e- flow from +ve to -ve electrode perhaps doesn't make sense until
you look at the electrode reactions, electrons released at the +ve
anode move round the external circuit to produce the electron rich
negative cathode electrode.

Electron balancing: In the above process it takes the removal of four electrons
from two oxide ions to form one oxygen molecule and the gain of three
electrons by each aluminium ion to form one aluminium atom. Therefore for
every 12 electrons you get 3 oxygen molecules and 4 aluminium atoms formed.
This means you can do mole ratio product calculations. See section 13. on the
Chemical

Calculations page.

The Purification of Copper by Electrolysis

(extraction from

ore below)

The impure copper


from a smelter is cast
into a block to form
the positive anode. The
cathode is made of
previously purified
copper. These are
dipped into an
electrolyte of
copper(II) sulphate
solution.
When the d.c
electrical current is
passed through the
solution electrolysis
takes place. The
copper anode dissolves
forming blue
copper(II) ions Cu2+.

Raw materials for the electrolysis process:

Impure copper from a copper smelter.


Electrolyte of aqueous copper(II)
sulphate.
A pure copper cathode.

Electrolysis is using d.c. electrical energy to


bring about chemical changes at the
electrolyte connections called the anode and
cathode electrodes.

Scrap copper can be recycled and purified

See section below for


extraction of impure
copper from an ore.

The redox details of the


electrode processes:
At the positive (+)
anode, the process is
an oxidation, electron
loss, as the copper
atoms dissolve to form
copper(II) ions.
Cu(s) ==> Cu2+(aq) + 2e

An electrolyte is a conducting melt or solution


of ions which carry the electric charge as part
of the circuit.

These positive ions are


attracted to the
negative cathode and
become copper atoms.
The mass of copper
dissolving at the anode
exactly equals the
mass of copper
deposited on the
cathode. The
concentration of the
copper(II) sulphate
remains constant.
Any impurities present
in the impure copper
anode fall to the
bottom of the
electrolysis cell tank.
This 'anode sludge' is
not completely mineral
waste, it can contain
valuable metals such as
silver!

at the negative (-)


cathode, the process is
a reduction, electron
gain by the attracted
copper(II) ions to form

this way too ,and is cheaper than starting


from copper ore AND saves valuable mineral
resources.

neutral copper atoms.


Cu2+(aq) + 2e- ==> Cu(s)

Note: Reduction and


Oxidation always go
together, hence the
use of the term redox
change or reaction.

Electroplating is
mentioned on the
Industrial Chemistry
and Electrochemistry
pages.

The original extraction of copper from copper ores

From copper carbonate ores* ...


The ore can be roasted to concentrate the copper as its oxide.
o
Water is driven off and the carbonate thermally decomposed.
o
copper(II) carbonate ==> copper oxide + carbon dioxide
o
CuCO3(s) ==> CuO(s) + CO2(g)
o
The oxide can be smelted by heating with carbon (coke,
o
charcoal) to reduce the oxide to impure copper, though this
method isn't really used much these days (the 'bronze age'
method archaeologically!).
copper(II) oxide + carbon ==> copper + carbon dioxide
o
2CuO(s) + C(s) ==> 2Cu(s) + CO2(g)
o
The carbon acts as the reducing agent - the 'oxygen remover'.
o

From copper sulphide ores ...


o These include chalcocite/chalcosine = copper(I) sulphide Cu2S
and covellite = copper(II) sulphide CuS
and chalcopyrite CuFeS2. which is one of the most

important ores for the extraction of copper.


This can be roasted in air to produce copper(I)

sulfide which is roasted again in a controlled


amount of air so as not to form a copper oxide
(see below).
2CuFeS2 + 4O2 ==> Cu2S + 3SO2 + 2FeO

Copper sulphide ores can be rapidly roasted in heated air


enriched with oxygen to form impure copper and this
extraction process is called 'flash smelting'.
Nasty sulphur dioxide gas is formed, this must be

collected to avoid pollution and can be used to make


sulphuric acid to help the economy of the process.
copper(I) sulphide + oxygen ==> copper + sulphur

dioxide
Cu2S(s) + O2(g) ==> 2Cu(s) + SO2(g)

or copper(II) sulphide + oxygen ==> copper + sulphur

dioxide
CuS(s) + O2(g) ==> Cu(s) + SO2(g)

It is also possible to dissolve an oxide or carbonate ore in dilute


sulphuric acid and extracting copper by ....
o (1) using electrolysis see purification by electrolysis above, or
o (2) by adding a more reactive metal to displace it e.g. scrap
iron or steel is used by adding it to the resulting copper(II)
sulphate solution.
iron + copper(II) sulphate ==> iron(II) sulphate +

copper
o

Fe(s) + CuSO4(aq) ==> FeSO4(aq) + Cu(s)

The Extraction of Chromium and Titanium by Displacement

Titanium ore is mainly the oxide TiO2, which is converted into titanium
tetrachloride TiCl4 by heating with carbon and chlorine.
The chloride is then reacted with sodium or magnesium to form titanium
metal and sodium chloride or magnesium Chloride.
This reaction is carried out in an atmosphere of inert argon gas so
non of the metals involved becomes oxidised by atmospheric oxygen.
o TiCl4 + 2Mg ==> Ti + 2MgCl2 or TiCl4 + 4Na ==> Ti + 4NaCl
Overall the titanium oxide ore is reduced to titanium metal (overall O
loss, oxide => metal) and the magnesium or sodium acts as a reducing
agent.
Chromium ore is processed and purified into chromium(III) oxide. This
is reacted, very exothermically, in a thermit style reaction, with
aluminium (see reactions of aluminium) to free the chromium metal.
o Cr2O3(s) + 2Al(s) ==> Al2O3(s) + 2Cr(s)
o The chromium(III) oxide is reduced to chromium by O loss, the
aluminium is oxidised to aluminium oxide by O gain, and the

aluminium is the reducing


agent i.e. the O remover.

These are examples of metal


displacement reactions e.g. the
less reactive chromium or titanium
are displaced by the more reactive
sodium, magnesium or aluminium.

The Extraction and Purification of Zinc

Zinc is extracted from either zinc blende/sphalerite ore (zinc


sulphide) or sometimes calamine/Smithsonite ore (zinc carbonate).
(1) The zinc sulphide ore is roasted in air to give impure zinc oxide.
2ZnS(s) + 3O2(g) ==> 2ZnO(s) + 2SO2(g)
o
Note: calamine ore can be used directly in a zinc smelter because
o
on heating it also forms zinc oxide.
ZnCO3(s) ==> ZnO(s) + CO2(g) (endothermic thermal

decomposition)
(2) The impure zinc oxide can be treated in two ways to extract the
zinc:
(a) It is roasted in a smelting furnace with carbon (coke,
o
reducing agent) and limestone (to remove the acidic impurities).
The chemistry is similar to iron from a blast furnace.
C(s) + O2(g) ==> CO2(g) (very exothermic oxidation, raises

temperature considerably)
C(s) + CO2(g) ==> 2CO(g) (C oxidised, CO2 reduced)

ZnO(s) + CO(g) ==> Zn(l) + CO2(g) (zinc oxide reduced by

CO, Zn undergoes O loss)


or direct reduction by carbon: ZnO(s) + C(s) ==> Zn(l) +

CO(g) (ZnO reduced, C oxidised)


The carbon monoxide acts as the reducing agent i.e. it

removes the oxygen from the oxide.


The impure zinc is then fractionally distilled from the

mixture of slag and other metals like lead and cadmium


out of the top of the furnace in an atmosphere rich in
carbon monoxide which stops any zinc from being
oxidised back to zinc oxide.
The slag and lead (with other metals like cadmium) form

two layers which can be tapped off at the base of the


furnace.

The zinc can be further purified by a 2nd fractional


distillation or more likely by dissolving it in dilute
sulphuric acid and purified electrolytically as described
below.
(b)Two stages
(i) It is dissolved and neutralised with dilute sulphuric

acid to form impure zinc sulphate solution.


ZnO(s) + H2SO4(aq) ==> ZnSO4(aq) + H2O(l)

or using calamine ore/zinc carbonate directly:

ZnCO3(s) + H2SO4(aq) ==> ZnSO4(aq) + H2O(l)+ CO2(g)

(ii) Quite pure zinc is produced from the solution by

electrolysis. It can be deposited on a pure zinc negative


electrode (cathode) in the same way copper can be
purified. The other electrode, must be inert e.g. for
laboratory experiments, carbon (graphite) can be used
and oxygen is formed.
Zn2+(aq) + 2e- ==> Zn(s)

A reduction process, electron gain, as

zinc metal is deposited on the (-)


electrode.
You can't use solid zinc oxide directly because its

insoluble and the ions must free to carry the


current and migrate to the electrodes in some
sort of solution.
For more details of the type of electrolysis

system used, see purification of copper (just


swap Zn for Cu in the method/diagram).

PLEASE note: In the industrial production of


zinc by electrolysis (called electro-winning) the
negative (-) cathode is made of aluminium (Al,
where zinc deposits) and the positive (+)
electrode is made of a lead-silver alloy (Pb-Ag,
where oxygen gas is formed). Why these
particular electrode metals are used in this
'electrowinning' process I'm not quite sure, but
aluminium is so unreactive that it is effectively
inert, and lead and silver are also of low activity,
but ... ???

The electrolytic extraction of sodium


Sodium, like many reactive metals,
can be extracted by electrolysis
of its molten chloride. This can
be done in the 'Down's Cell' shown
in the diagram.
The positive sodium ions migrate
to the negative cathode electrode
and are reduced by electron gain
to form liquid sodium atoms.
Na+ + e- ==> Na
The negative chloride ions migrate to the positive anode electrode and get
oxidised by electron loss to form green chlorine gas molecules.
2Cl- ==> Cl2 + 2e-

Environmental Impact and Economics of Metal and other Mineral


Extraction - Sociological, environmental issues etc.

One of the problems of metal or mineral extraction is


balancing ecological, environmental, economic, social advantage
factors.
It doesn't matter whether you are mining and processing iron ore or
limestone, many of the advantages and disadvantages are common to
these operations.
Examples of advantages of a country exploiting it's own mineral
resources:
o Valuable revenue if the mineral or its products are exported.
o Jobs for people, especially new sources of employment in poor
countries or areas of high unemployment in developed countries.
o Wages earned go into the local economy.
o Increase in local facilities promoted e.g. transport systems, like

roads, recreational and health social facilities.


Examples of disadvantages of a country exploiting it's own mineral
resources and reduction of its social and environmental impact:
o Dust from mining-quarrying or processing can be reduced by air
filter and precipitation systems and even hosing water on dusty
areas or spoil heaps or carried away to somewhere else via tall
chimneys.
o Noise from process operation or transport of raw materials and
products (lorries/trucks/wagons).
Difficult to deal with, sound-proofing often not practical,
but operations can be reduced for unsociable hours e.g.
evening movement.
o Pollution can be reduced by cleaning the 'waste' or 'used' air,
water and waste gases etc. of toxic or acidic materials e.g.
Toxic carbon monoxide from the blast furnace extraction
of iron, it can be burnt as a fuel, but it must not be
released into the air unless converted to biologically
harmless carbon dioxide.
Sulphur dioxide gas from copper extraction of its
sulphide ore is an irritating poisonous gas which can also
cause acid rain, but it can be converted to the useful,
therefore saleable, industrial chemical concentrated
sulphuric acid, so you can remove a harmful pollutant and
recover back some of the metal extraction costs, good
green economics? Acidic gases like sulphur dioxide can be
removed by bubbling through an alkali solution such as
calcium hydroxide solution ('limewater') where it is
neutralised and oxidised to harmless calcium sulphate.
Cleaning a gas in this way is called 'gas scrubbing'.
o Mining operations will disfigure the landscape BUT it can be reclaimed and 'landscaped' in an attempt to restore the original
flora and fauna. However in the case of a limestone quarry, I'm
afraid there is no way round the fact that huge chunks of
beautiful hills get carted away if we want to use it as useful
mineral.
There is also an 'economics' section on the "Extra Industrial
Chemistry" page too.
The cost of extracting and purifying metals is quite varied for
several reasons.
o If the ore is plentiful it is cheaper e.g. iron ore, but silver ores
and gold are much rarer and on that basis alone they would be a
more valuable commodity.
o Reduction of ores using coke (e.g. iron), made from cheap coal, is
cheaper than the electricity bill for extracting aluminium from
its molten oxide by electrolysis, but different metals have

different properties best suited for particular and different


uses.
o

Generally speaking, more reactive metals (like Al) are more costly
to extract than less reactive metals (like Fe) because of the
different energy demands and ease of extraction, which may
sometimes be due to more costly technology.

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