THE EXTRACTION OF METALS

INTRODUCTION
There are various factors which influence the choice of method for extracting metals from their ores, including
reduction by carbon or by electrolysis.

Carbon reduction
Carbon (as coke or charcoal) is cheap. It not only acts as a reducing agent, but it also acts as the fuel to provide heat
for the process.
Coke is a reducing agent for metals below aluminium in the reactivity series. In mostly however it’s the carbon (II)
oxide gas from coke that actually does the reduction.

Reduction by electrolysis
This is a common extraction process for the more reactive metals - for example, for aluminium and metals above it
in the electrochemical series. It is also used in the purification of copper.

From ore to metal

An ore is any naturally-occurring source of a metal that a metal can economically be extracted from, for example:
Bauxite (Al2O3), iron pyrite (FeS2) e.t.c.

Concentrating the ore

This is a means of getting rid of as much of the unwanted rocky material as possible before the ore is converted into
the metal.

In some cases this is done chemically. For example, pure aluminium oxide is obtained from bauxite by a process
involving a reaction with sodium hydroxide solution.

Some copper ores can be converted into copper (II) sulphate solution by leaving the crushed ore in contact with
dilute sulphuric acid for a long time. Copper can then be extracted from the copper (II) sulphate solution.

But, in many cases, it is possible to separate the metal compound from unwanted rocky material by physical means.
A common example of this involves froth flotation.

Froth flotation
The ore is first crushed and then treated with something which will bind to the particles of the metal compound and
make those particles hydrophobic.

In concentrating copper ores, for example, pine oil is often used. The pine oil binds to the copper compounds, but
not to the unwanted rocky material.

The treated ore is then put in a large bath of water containing a foaming agent (a soap or detergent), and air is blown
through the mixture to make a lot of bubbles.

Because they are water-repellent, the coated particles of the metal compound tend to be picked up by the air bubbles,
float to the top of the bath, and are allowed to flow out over the sides.

The rest of the rocky material stays in the bath.

IRON
Ores
 haematite ore (iron (III) oxide), Fe2O3
 Magnetite ore (lodestone), Fe3O4
 Siderite, FeCO3

Raw Materials:
 Iron Ore
 Coke (carbon, C), both fuel and reducing agent.
 Hot air (for the oxygen in it) to burn the coke
 Limestone (calcium carbonate, CaCO3) to remove certain impurities like silica.
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 Recycled 300oC
CO2
500oC CO + Fe2O3 → CO2 + Fe
Fire brick lining
600oC
CO2 + C → 2CO
800oC
Hot air 1600oC Hot air
C + O2 → CO2

Slag
Slag
 It is producedIron Molten
in a blast furnace by reducing iron with carbon and it is the carbon that removes the
iron oxides
oxygen from the iron oxides – the carbon is known as the reducing agent.
 A solid mixture of magnetite or haematite ore, coke and limestone is continuously fed into the top of the
blast furnace.
 Coke function as a fuel
 The coke is ignited at the base and hot air blown in to burn the coke to form carbon (IV) oxide.
 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.

C(s) + O2(g) → CO2(g)

 Coke also function as a reducing agent

At 800oC the carbon (IV) oxide formed, reacts with more coke to form carbon (II) oxide
CO2(g) + C(s) → 2CO(g)

 The carbon (II) oxide is the molecule that actually reduces the iron oxide ore.
 This frees the iron, which is molten at the high blast furnace temperature, and trickles down to the base of
the blast furnace and run off.

Fe2O3(s) + 3CO(g) → 2Fe(l) + 3CO2(g)

 Iron is initially formed as a liquid and then obviously solidifies on cooling.

 The role of limestone in the extraction of iron

The original ore contains acidic mineral impurities such as silica (SiO2).
These react with the calcium carbonate (limestone) to form a molten slag, the main ingredient being calcium
silicate.

CaCO3(s) + SiO2(s) → CaSiO3(l) + CO2(g)

There are two ways to show the formation of the waste slag, which is mainly calcium silicate.

 The molten slag forms a layer above the denser molten iron and they can be both separately, and regularly,
drained away. 

 The slag therefore shields the molten iron from re-oxidation.

 The iron is cooled and cast into pig iron ingots.

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  The waste gases and dust from the blast furnace must be appropriately treated to avoid polluting the
environment.

The highly toxic carbon (II) oxide can actually be burnt to provide a source of heat energy, and in the
exothermic reaction it is converted into relatively harmless carbon (IV) oxide.

2CO(g) + O2(g) → 2CO2(g)

Acidic gases like sulphur (IV) oxide from sulphide ores, can be removed by bubbling through an alkali
solution such as calcium hydroxide solution where it is neutralised and oxidised to harmless calcium sulphate.
Cleaning a gas in this way is called gas scrubbing.

The waste slag is used for road construction or filling in quarries which can then be landscaped.

Uses
Cast iron:- this is the iron from the blast furnace and contains about 3-5% carbon, 2% phosphorus and 1%
Sulphur.
It is hard and brittle.

Uses
In making blast furnaces, crates, railing, drainage pipes, engine blocks e.t.c.
In the manufacture of wrought iron and steel

Wrought iron:- contains 0.1% carbon

It is made by melting cast iron in a hearth lined with haematite

Fe2O3(s) + 3C(s) → 2Fe(s) + 3CO2(g)

It is malleable (mouldable into flat sheets) and ductile (rolled into wires)

Uses
Making sheets, wires, nails, agricultural implements e.t.c.

Steel:-it is an alloy of iron and other elements

Stainless steel: - 10-12% chromium and nickel
- Used in making cutlery, surgical blades e.t.c.
Steel of carbon:- nails, car bodies, railway lines e.t.c.
Steel of tungsten:- cutting and drilling tools
Steel of cobalt:- electromagnets
Steel of vanadium:- spanners

ALUMINIUM:

It forms about 7% of the earth’s crust

Ores
Bauxite Al2O3.H2O
Mica K2Al2Si6O6
Corundum Al2O3
China clay Al2Si2O7.H2O

Bauxite is the most economical to use since it is the easiest to mine and more abundant.

 Aluminium is obtained from mining the mineral bauxite which is mainly aluminium oxide (Al2O3) and
bauxite must be purified prior to electrolysis. It has silica, SiO2 and iron (II) oxide, FeO as the main
impurities.

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  The bauxite is therefore ground then mixed with hot concentrated sodium hydroxide solution . Silicon
oxide and aluminium oxide being amphoteric both dissolve in the alkali to form sodium silicate and sodium
aluminate.
SiO2(s) + 2NaOH(aq) ⟶ Na2SiO3(aq) + H2O(l)

Al2O3(s) + 2NaOH(aq) + 3H2O(l) ⟶ 2NaAL(OH)4(aq)

 The insoluble iron (II) oxide impurity is therefore filtered off.

 Carbon (IV) oxide is then bubbled through the filtrate to precipitate the aluminium hydroxide

2NaAl(OH)4(aq) + CO2(g) ⟶ Na2CO3(aq) + 2Al(OH)3(s) + H2O(l)

 The aluminium hydroxide may also be precipitated by seeding using hydrated aluminium hydroxide
crystals.

NaAl(OH)4(aq) Al(OH)3(s) Al(OH)3(s) + NaOH-(aq)

 The hydroxide is then washed with water and then heated.

Al(OH)3(s) ⟶ Al2O3(s) + 3H2O(l)

 Due to its high melting point of 2015oC, aluminium oxide is dissolved in molten Cryolite (Na3AlF6) with
which lowers the melting point to 800oC.
This saves on energy costs.
Also Cryolite increases the conductivity of aluminium oxide which is reduced in molten state.

 The purified bauxite is the electrolyzed in Hall’s cell which consist of graphite anode suspended in the
electrolyte and graphite cathode lining a steel cage.
Graphite is preferred because apart from its good conduction and relative inertness it cannot form alloys
with the molten aluminium.

 At the positive anode, oxygen gas is formed.

6O2-(l) ⟶ O2(g) + 12e-

 The oxygen produced at the high temperature of the electrolysis cell burns and oxidises away the carbon
electrodes to form carbon (II) oxide or carbon (IV) oxide. So the carbon–graphite electrode is regularly
replaced and the waste gases scrubbed off

 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.

4Al3+(l) + 12e– ⟶ Al(s)

The current method for extracting aluminium is expensive because it involves several stages and uses large
amounts of costly electrical energy.
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 o About 39% of the aluminium in foil, car components etc. is recycled aluminium.
o This makes good economics because recycling saves on costs and allows a mineral resource like
bauxite ore to last a lot longer – slower depletion of the Earth's mineral ore resources will make it
last longer.
o The savings are partly reduced by the cost of collecting waste/scrap metal and purifying for further
use.
 It is estimated that recycling aluminium only uses 5% of the energy required to extracted
the same mass of aluminium from its ore – the original aluminium extraction uses very
expensive electrical energy for the electrolysis.

uses of aluminium
 Aluminium is very useful metal and used as a lightweight construction material eg greenhouse frames.
 Aluminium is a reactive metal but it is resistant to corrosion. This is because aluminium reacts in air to
form a layer of aluminium oxide which then protects the aluminium from further attack.
This is why it appears to be less reactive than its position in the reactivity series of metals would
predict.
 For some uses of aluminium it is desirable to increase artificially the thickness of the protective oxide layer
in a process is called anodising.
o This involves removing the oxide layer by treating the aluminium sheet with sodium hydroxide
solution.
o The aluminium is then placed in dilute sulphuric acid and is made the positive electrode (anode)
used in the electrolysis of the acid.
o Oxygen forms on the surface of the aluminium and reacts with the aluminium metal to form a
thicker protective oxide layer. 
 Aluminium can be alloyed to make 'Duralumin' by adding copper (and smaller amounts of magnesium,
silicon and iron), to make a stronger alloy used in aircraft components (low density = 'lighter'!), greenhouse
and window frames (good anti–corrosion properties), overhead power lines (quite a good conductor and
'light')

 As a reducing agent in the Thermit process in the extraction of chromium, titanium, cobalt and
manganese from their oxides
 Aluminium mixed with oil is used as a protective paint.
 It’s a better reflector than silver. It is sprayed on glass for mirrors of telescopes

SODIUM

 Sodium occurs naturally in compound form. The compounds being sodium chloride in sea water, trona
(Na2CO3.NaHCO3.2H2O) in saline lakes and as Chile saltpeter (NaNO3)
 The ores of sodium are referred to as rock salt.

 The extraction of sodium is through electrolysis of molten sodium chloride in the Down’s cell.
 Because of its position in the reactivity series of metals, sodium cannot be extracted using carbon.
 The apparatus consist of iron shell lined with fire bricks on the outside.
 The anode made of carbon is located at the centre surrounded by steel cathode.
 The anode is fenced by a diaphram which prevents the recombining of sodium and chlorine from the cathode
and anode respectively.
 Since the melting point of sodium hydroxide is 801oC, it is mixed with calcium chloride which lowers its
melting point to 600oC.
 In the molten salt the positive sodium ions migrate to the negative cathode electrode and are reduced by
electron gain to form liquid sodium atoms.
 At the (–) cathode: Na+(l) + e– ⟶ Na(l)

 Chloride ions migrate to the positive anode electrode and get oxidised by electron loss to form green chlorine
gas molecules. Initially two chlorine atoms are formed and these rapidly combine to give chlorine molecules.

 At the (+) anode overall: 2Cl-(l) ⟶ Cl2(g) + 2e–

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 Molten sodium is less dense than molten sodium chloride and thus it floats on top of the mixture and floats out
at the top.
 This is also possible because sodium has a much lower melting point.
 Liquid calcium is also formed in small quantities but it solidifies faster when the sodium-calcium mixture is
cooled

Uses
 As a heat transfer agent (coolant) in nuclear reactors
This is possible due to the following reasons;
a) It has a low melting point
b) It is cheap
c) It has a wide liquid state range between 98oC and 892oC
d) It has low viscosity-it flows easily
e) It has high thermal conductivity
 In manufacture of sodium cyanide used in the extraction of gold.
 In the manufacture of sodium peroxide
 In the manufacture of sodalime (NaNH2)
 Sodium vapour is used in street lighting due to its yellow flame.
 Sodium-lead alloy is used in the manufacture of petrol engine antiknock additives e.g. tetraethyl lead
 In the extraction of titanium from titanium tetrachloride
 Sodium potassium alloy is used in the manufacture of high temperature equipment

COPPER

Ores of copper
Copper pyrites CuFeS2
Malachite CuCO3.Cu(OH)2
Chalcocite Cu2S
Cuprite Cu2O

 Copper can be extracted from copper pyrites.

 Copper ores are concentrated by a technique known as froth flotation.
 The ore is then heated in limited supply of oxygen in a reverberator furnace to produce copper (I) sulphide and
iron (II) oxide

2CuFeS2(s) + 4O2(g) ⟶ Cu2S(s) + 2FeO(s) + 3SO2(g)

 Silica is then added to the mixture and heated. The silica reacts with iron (II) oxide to form iron (II) silicate
which forms a slag

FeO(l) + SiO2(l) ⟶ FeSiO3(l)

 The slag and copper (I) sulphide separates out

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 The copper (I) sulphide is then heated to 1300oC in a regulated supply of air and some of it is converted to
copper (I) oxide
2Cu2S(l) + 3O2(g) ⟶ 2Cu2O(l) + 2SO2(g)

 The remaining copper (I) sulphide then converts the copper (I) oxide to copper

Cu2S(l) + 2Cu2O(l) ⟶ 6Cu(l) + SO2(g)

 The copper produced is called blister copper and is about 97.5% pure.
 The impurities include iron, sulpher and traces of silver and gold.

 The copper is purified by electrolysis.

 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. 

 The copper anode dissolves forming blue copper (II) ions Cu2+.

 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.
Anode: Cu(s) ⟶ Cu2+(aq) + 2e–
Cathode: Cu2+(aq) + 2e– ⟶ Cu(s)

Impure Pure
copper copper
Copper (II) sulphate
solution

uses of copper
 Copper has properties that make it useful for electrical wiring and plumbing.
Copper is a good conductor of electricity and heat, can be bent but is hard enough to be used to
make pipes or tanks and does not react with water.
 In making brass alloy, is a mixture copper and zinc. It is a much more hard wearing metal than copper (too
soft) and zinc (too brittle) but is more malleable than bronze for 'stamping' or 'cutting' it into shape.
 Copper is used in domestic hot water pipes because it is relatively unreactive to water and therefore doesn't
corrode easily.
 In making bronze alloy which is a mixture of copper and tin (Sn) and is stronger than copper and just as
corrosion resistant, e.g. used for sculptures.
 Copper compounds are used in fungicides and pesticides e.g. a traditional recipe is copper sulphate solution
plus lime is used to kill greenfly.
 Copper is alloyed with nickel to give 'cupro–nickel', an attractive hard wearing 'silvery' metal for coins

ZINC
Ores
Calamine ZnCO3
Zinc blende ZnS with lead sulphide and silica as impurities

 The zinc sulphide ore is roasted in air to give impure zinc oxide and sulphur (IV) oxide.
2ZnS(s) + 3O2(g) ⟶ 2ZnO(s) + 2SO2(g)
 Lead sulphide also reacts to form lead oxide

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 2PbO(s) + 3O2(g) ⟶ 2ZnO(s) + 2SO2(g)

Note: calamine ore can be used directly in a zinc smelter because on heating it also forms zinc
oxide.
ZnCO3(s) ⟶ ZnO(s) + CO2(g)

 The impure zinc oxide may be processed through reduction or electrolysis.

a) Reduction
 It is roasted in a smelting furnace with carbon (coke, reducing agent) and limestone (to remove the acidic
impurities).
C(s) + O2(g) ⟶ CO2(g)

C(s) + CO2(g) ⟶ 2CO(g)

ZnO(s) + CO(g) ⟶ Zn(g) + CO2(g)

 or direct reduction by carbon:

ZnO(s) + C(s) ⟶ Zn(g) + CO(g)

 Lead oxide is also reduced to liquid lead

PbO(s) + CO(g) ⟶ Pb(l) + CO2(g)

 These reactions take place at temperatures of about 1200oC above the boiling point of zinc hence it form
vapours.

 The zinc gas is cooled in molten lead to prevent reoxidation.

 Lead which is denser flows to the bottom and is tapped off.

 The impure zinc is purified by fractional distillation.

 Calcium oxide from the decomposition of limestone reacts with silica to form a slag.

 The mixture of slag also flows to the bottom with lead where it is tapped off.

 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 second fractional distillation

b) Electrolysis
It is dissolved and neutralised with dilute sulphuric acid to form impure zinc sulphate solution.

ZnO(s) + H2SO4(aq) ⟶ ZnSO4(aq) + H2O(l)

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 or using calamine ore (zinc carbonate) directly:

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

Lead oxide is converted to lead sulphate and is precipitated out.

PbO(s) + H2SO4(aq) ⟶ PbSO4(s) + H2O(l)

The zinc sulphate solution is the eletrolysed

The apparatus consists of a lead cathode containing 1% silver and the anode is made of aluminium

At the cathode: Zn2+(aq) + 2e– ⟶ Zn(s)

At the anode: 4OH-(aq) ⟶ 2H2O(l) + O2(g) + 4e-

Uses
 Galvanization of iron
 Making outer casing for dry cells
 In the making brass

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