METALS

AND
ALLOY INDUSTRY
CHM573 INDUSTRIAL CHEMISTRY
Why this
industry is
essentials?
 Metal from rocks
The substances (element or compounds) that
make up rocks are called minerals.

Extraction

Gold present in quartz rock Gold

Physical method: Crushing, grinding followed by separation by magnetic and gravity

Chemical method: Hydrometallurgical, pyrometallurgical and electrochemical

Other uses of minerals
 How do we extract minerals?
The primary methods used to extract minerals from the ground are:
o Underground mining
Underground mines are more expensive and are often used to reach deeper deposits.
o Surface (open pit) mining
Surface mines are typically used for more shallow and less valuable deposits.
o Placer mining
Placer mining is used to sift out valuable metals from sediments in river channels, beach sands, or other environments
o In-situ mining
Use to recover minerals such as copper and uranium through boreholes drilled into a deposit, then processing it at the
surface without moving rock from the ground.
Which method is the best?
The location and shape of the deposit, strength of the rock, ore grade, mining costs, and current market price of
the commodity are some of the determining factors for selecting which mining method to use.
How do we Surface (open pit) mining

extract
minerals? Placer mining

In-situ mining
Underground mining
 Natural forms of minerals
oSome metals like gold, silver,
copper and mercury can exist
in their native metals form.
oThe metals usually exist in the
forms of oxides, chlorides,
sulfides or carbonates.
 From rocks to metals

samples of common oxide minerals.

samples of common sulfide minerals.

 Classification of industrial minerals
They are usually classified according to the abundance:
1. Rare
These occur in small quantities, in limited areas, used in small quantities, and command a high
price. For example, diamonds, sheet mica, graphite, corundum, precious stones, and the semi-
precious stones
2. Widely available
These occur in large quantities in few geologic environments, are used in appreciable amounts, and
command a moderate price. For example asbestos, coal, phosphate, gypsum, kaolin, potash, salt,
sulphur, talc, trine, barite, borates, feldspar, fluorite, magnetite, and diatomite.
3. Abundant
These are abundant in all geologic environments, used in large amounts, and are relatively cheap.
For example, clay, limestone, sand, gravel, and stones.
Extracting metals
 Extraction of least reactive metals
o The least reactive metal are located at the bottom of the reactivity series. They can be found as
free metals in the minerals
o Thus, some of them can be obtained easily by physical methods
oThe rocks are usually collected and crushed to free metals.
 Extraction of less reactive metals
Metals in the middle of the series are less strongly bonded in their compounds. Their oxides
can be reduced by carbon to give the metal.
This extraction process also known as carbon reduction
Example : Zinc extraction
Zinc metal is extracted from zin oxide by removing oxygen atom. It could be achieved by
reduction method by “ROASTING” metal oxide with coke and metal is left and carbon dioxide is
produced
2 ZnO(s) + C(s) → 2Zn(s) + CO2(g)
 Extraction of less reactive metals
1) If the metal exist in metal sulfide form, it can be heated in the air to produce metal oxide:
2ZnS (s) + 3O2(g) → 2ZnO(s) + 2SO2(g)

2) Then, the oxide will be heated with carbon through carbon reduction process.
2ZnO(s) + C(s) → Zn(s) + CO(g)
 Extraction of less reactive metals
o Titanium is extracted from its ore, rutile - TiO2. It is first converted into titanium(IV)
chloride.
TiO2(s) + 2Cl2(g) + 2C(s) → TiCl4(s) + 2CO(g)
o Titanium is produced by reducing titanium (VI) chloride using a more reactive
metal such as sodium or magnesium. This is the only way to produce high purity
metal
TICI4(s) + 2Mg(l) → Ti(s) + 2MgCl2(s)
o Titanium(IV) chloride vapour is passed into a reaction vessel containing molten
magnesium in an argon atmosphere, and the temperature is increased to about
1000°C. The reduction process is very slow, taking about 2 days, followed by several
more days of cooling.
oWhen it is cool, the reaction mixture is crushed, and dilute hydrochloric acid is added
to react with any excess magnesium to form more magnesium chloride. All the
magnesium chloride dissolves in the water present, and the remaining titanium is
processed further to purify it.
 Extraction of less reactive metals
TiO2 + 2Cl2 + 2C → TiCl4 + 2CO

Ti is then displaced from TiCl4 by a more reactive metal, such as

magnesium or sodium:

TiCl4 + 4Na → Ti + 4NaCl

Conditions are: ⚫ temperature of 550 °C

⚫ argon atmosphere
⚫ batch process.
 Extraction of less reactive metals
o The common ores of iron are both iron oxides haematite (Fe2O3) and magnetite (Fe3O4)
The Blast Furnace
 The Blast Furnace
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 Extraction of less reactive metals
o The method used to extract copper from its ores depends on the
nature of the ore. Sulphide ores such as chalcopyrite (CuFeS2) are
converted to copper by a different method from silicate, carbonate or
sulphate ores.
o The ores typically contain low percentages of copper and have to
be concentrated by, for example, froth flotation before refining.(
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o The treated ore is then put in a large bath of water containing a
foaming agent (a soap or detergent of some kind), and air is blown
through the mixture to make a lot of bubbles.
o 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. Product : Copper concentrate =
25% copper by mass
 Extraction of less reactive metals

The blister copper is already virtually pure (in

excess of 99% copper). But for today’s market,
this is not really pure enough!

It is purified further using electrolysis. This

is known as electrolytic refining

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Extraction of less reactive metals
 Extraction of less reactive metals
o The extraction of copper from copper(I) sulfide produces sulfur dioxide. This is an environmental
problem. Why?
o Rather than releasing the sulfur dioxide into the atmosphere, extraction plants trap it. It can then
be used in the Contact Process to make sulfuric acid.

SO2 + O2 → SO3

SO3 + H2SO4 → 2H2S2O7

H2S2O7 + H2O → 2H2SO4

 Extraction of less reactive metals
o As an alternative to reduction of a copper oxide or copper sulfide ore, copper can be
extracted by a displacement reaction with scrap iron.

o Low grade copper ore is dissolved in sulfuric acid to form a dilute solution of
copper(II) sulfate, CuSO4. Scrap iron is added, which displaces copper from the
mixture:

CuSO4 + Fe → Cu + FeSO4
 Extraction of less reactive metals
o Tungsten is extracted from an ore called wolframite, which is a mixture of iron
tungstate (FeWO4) and manganese tungstate (MnWO4).
o The first step is the conversion of the ore to tungsten oxide, WO3
o Pure tungsten can't be obtained by reducing tungsten(VI) oxide using carbon,
because it reacts with carbon to make tungsten carbide. Instead, the reducing
agent is hydrogen
o The next step is to reduce the ore by reacting it with hydrogen:
WO3 + 3H2 → W + 3H2O
o Powdered tungsten(VI) oxide is heated to temperatures in the range 550 - 850°C
in a stream of hydrogen
o An excess of hydrogen is used, and this carries away the steam produced during
the reaction. The hydrogen is dried and recycled.
 Extraction of very reactive metals
o Very reactive metals are difficult to extract. These metals include aluminum and metals above
it in the electrochemical series.
o Most of these reactive metals are extracted by decomposing their compounds with electricity
via electrolysis process
oThe downside (particularly in the aluminium case) is the cost of the electricity. An advantage is
that it can produce very pure metals.
o Aluminium ore is called bauxite. The bauxite is purified to produce aluminium oxide, a white
powder from which aluminium can be extracted.
o Aluminium oxide has a very high melting point (over 2000°C) so it would be expensive to melt
it.
o Aluminium oxide does not dissolve in water, but it does dissolve in molten cryolite (Cryolite
(Na3AlF6, sodium hexafluoroaluminate, MP = ).
Extraction of very reactive metals
o The diagram shows an aluminium oxide electrolysis cell. The
negative electrodes (cathodes) and the positive electrodes
(anodes) are made of graphite, a form of carbon.

o During electrolysis:
1. positively charged aluminium ions gain electrons from the
cathode, and form molten aluminium
2. oxide ions lose electrons at the anode, and form oxygen
molecules

o The oxygen reacts with the carbon in the electrodes, forming

carbon dioxide which bubbles off. Carbon is therefore lost from
the positive electrodes, so they must be replaced frequently.
This adds to the cost of the process.
 Purifying the aluminium oxide-The Bayer Process
1. Reaction with NaOH solution

o Crushed bauxite is treated with moderately concentrated sodium hydroxide solution. The
concentration, temperature and pressure used depend on the source of the bauxite and exactly
what form of aluminium oxide it contains. Temperatures are typically from 140°C to 240°C;
pressures can be up to about 35 atmospheres.
o High pressures are necessary to keep the water in the sodium hydroxide solution liquid at
temperatures above 100°C. The higher the temperature, the higher the pressure needed.
o With hot concentrated sodium hydroxide solution, aluminium oxide reacts to give a solution of
sodium tetrahydroxoaluminate

Al2O3 + 2NaOH + 3H2O → 2NaAl(OH)4

 Purifying the aluminium oxide-The Bayer Process
1. Reaction with NaOH solution

The impurities in the bauxite remain as solids. For example, the other metal oxides
present tend not to react with the sodium hydroxide solution and so remain
unchanged. Some of the silicon dioxide reacts, but goes on to form a sodium
aluminosilicate which precipitates out.

All of these solids are separated from the sodium tetrahydroxoaluminate solution
by filtration. They form a "red mud" which is just stored in huge lagoons.
 Purifying the aluminium oxide-The Bayer Process
2. Precipitation of aluminium hydroxide

The sodium tetrahydroxoaluminate solution is cooled, and "seeded" with some

previously produced aluminium hydroxide. This provides something for the new
aluminium hydroxide to precipitate around.
NaAl(OH)4 → Al(OH)3 + NaOH

3. Formation of pure aluminium oxide

Aluminium oxide (sometimes known as alumina) is made by heating the aluminium

hydroxide to a temperature of about 1100 - 1200°C.

2Al(OH)3 → Al2O3 + 3H2O

Purifying the aluminium oxide-The Bayer Process
4. Conversion of Al2O3 into aluminium by electrolysis

The aluminium oxide is electrolysed in solution in molten cryolite, Na3AlF6. Cryolite

is another aluminium ore, but is rare and expensive, and most is now made
chemically.
In the current process of extracting aluminium from bauxite, an electrolytic cell made
of steel using graphite electrodes is used. The current used is 100,000 A and the
temperature is 1,223K (1000 C).
Pure alumina (aluminium oxide) which melts at 2050oC is dissolved in molten
cryolite (sodium aluminium fluoride), Na3AlF6.
The presence of the cryolite also gives the melt better conducting properties and, in
addition, it does not mix with the aluminium metal formed in the electrolysis.
Purifying the aluminium oxide-The Bayer Process
4. Conversion of Al2O3 into aluminium by electrolysis
Purifying the aluminium oxide-The Bayer Process
4. Conversion of Al2O3 into aluminium by electrolysis
 Alloys
Alloys are metallic compounds made up of one metal and one or more metal or non-metal elements.
Examples of common alloys:
•Steel: A combination of iron (metal) and carbon (non-metal)
•Bronze: A combination of copper (metal) and tin (metal)
•Brass: A mixture of copper (metal) and zinc (metal)

Properties
Individual pure metals may possess useful properties such as good electrical conductivity, high strength,
and hardness, or heat and corrosion resistance. Commercial metal alloys attempt to combine these
beneficial properties in order to create metals more useful for particular applications than any of their
component elements.
Steel, for example, requires the right combination of carbon and iron (about 99% iron and 1% carbon) in
order to produce a metal that is stronger, lighter, and more workable than pure iron.
 Alloys
Cast iron
The molten iron from the bottom of the furnace can be used as cast iron.
Cast iron is very runny when it is molten and doesn't shrink much when it solidifies. It is therefore ideal for making
castings - hence its name. However, it is very impure, containing about 4% of carbon. This carbon makes it very hard,
but also very brittle. If you hit it hard, it tends to shatter rather than bend or dent.
Cast iron is used for things like manhole covers, guttering and drainpipes, cylinder blocks in car engines, Aga-type
cookers, and very expensive and very heavy cookware.

Wrought iron
If all the carbon is removed from the iron to give high purity iron, it is known as wrought iron. Wrought iron is quite soft
and easily worked and has little structural strength. It was once used to make decorative gates and railings, but these
days mild steel is normally used instead.
 Alloys
Mild steel
Mild steel is iron containing up to about 0.25% of carbon. The presence of the carbon makes the steel
stronger and harder than pure iron. The higher the percentage of carbon, the harder the steel becomes.
Mild steel is used for lots of things - nails, wire, car bodies, ship building, girders and bridges amongst
others.

High carbon steel

High carbon steel contains up to about 1.5% of carbon. The presence of the extra carbon makes it very
hard, but it also makes it more brittle. High carbon steel is used for cutting tools and masonry nails (nails
designed to be driven into concrete blocks or brickwork without bending).
Alloys (Iron)
Type of iron % Carbon Properties Uses
Making castings, manhole
Hard, brittle
covers, guttering and
Runny when molten and
Cast iron 4 drainpipes, cylinder blocks
doesn’t shrink when
in car engines, Aga-type
solidifies
cookers
Decorative gates and
Wrought iron 0 Soft and easily worked
railings

Stronger and harder than Nails, wire, car bodies, ship

Mild steel 0.25
pure iron building, girders and bridges

High carbon for cutting tools and

1.5 Harder and more brittle
steel masonry nails
Special Steel
Iron mixed with : Special properties Uses include
Chromium (≤11%),
Cutlery, cooking
carbon(0.03% - 1%)
utensils, kitchen sinks,
and other element
Stainless steel Resists corrosion industrial equipment
including nickel,
for food and drink
chromium and
processing
molybdenum
Withstands high Gas turbines,
Titanium steel Titanium
temperatures spacecraft

Rock-breaking
machinery, some
Manganese steel Manganese Very hard
railway track , military
helmets
Alloys (copper)
Uses of copper
Amongst other things copper is used for:
Electrical Wiring. It is a very good conductor of electricity and is easily drawn out into wires.
Domestic plumbing. It doesn't react with water, and is easily bent into shape.
Boilers and heat exchangers. It is a good conductor of heat and doesn't react with water.
Making brass. Brass is a copper-zinc alloy. Alloying produces a metal harder than either copper or zinc individually. Bronze is
another copper alloy - this time with tin.
Coinage. In the UK, as well as the more obvious copper-coloured coins, "silver" coins are also copper alloys - this time with nickel.
These are known as cupronickel alloys. UK pound coins and the gold-coloured bits of euro coins are copper-zinc-nickel alloys.
 ALLOYS (Aluminium)
Uses Reason
light, strong, resists
aircraft
corrosion
o Aluminium is usually alloyed with other elements other transport such as
such as silicon, copper or magnesium. ships' superstructures, light, strong, resists
o Pure aluminium isn't very strong, and alloying it container vehicle bodies, corrosion
adds to it strength tube trains (metro trains)
overhead power cables light, resists corrosion,
(with a steel core to good conductor of
strengthen them) electricity
light, resists corrosion,
saucepans good appearance, good
conductor of heat