METALLURGY

THE PROCESS USED FOR EXTRACTION OF METALS IN THEIR PURE FORM FROM THEIR
ORES IS REFERRED TO AS METALLURGY. METALLURGY DEALS WITH THE
PRODUCTION AND PURIFICATION OF METALS AND MANUFACTURE OF ALLOYS .
Total Elements Known to us are 118.
Metals are those elements which can be drawn into sheets or pulled into
wires, have high densities, high melting and boiling points and high tensile
strength and are good conductors of heat and electricity.
Copper was the first metal used by man. Metals are defined as the elements
which forms the positive ions by loss of electrons. Hydrogen is non-metal
which forms positive ions.
Non Metals are the elements which forms the negative ions by gain of
electron. Hydrogen is lightest known element. Nitrogen is most abundant
element.

Occurrence of Metals
The earth's crust is the biggest source of metals. Metals can either occur in
their native (free) state or in a combined state.
Occurrence of metals can be explained basis of activity series.
 • Metals which are less reactive and do not react under normal
conditions with oxygen, water, carbon dioxide and other common
reagents, occur in native state. Ex-Gold and platinum
• Most of the metals are reactive so they occur in combined state in the
form of their Chlorides, oxides, carbonates etc. mixed with mud, clay,
sand and [Link]-sodium and potassium occur mainly as their
chlorides, calcium and magnesium as carbonates, aluminium as its
oxide.

Minerals and Ores:

Minerals: Minerals are the naturally occurring compounds of metals which
are generally mixed with other substances such as soil, mud, sand, silica
(SiO₂) limestone, rocks, etc. These earthly impurities are called gangue or
matrix.
Ores: Ores are those minerals from which metals are extracted
commercially at a comparatively lower cost and with minimum effort.

Common Ores of Aluminium, Iron and Zinc

Main ore of aluminium is bauxite (Al2O3.2H₂O) from which it is extracted.

Iron is mainly extracted from its chief ore haematite.

Stages Involved in the Extraction of Metals
In order to extract the metals from ores, several physical and chemical
methods are used. The extraction method of a particular metal depends
upon the nature of its ore and the properties of that metal. Therefore, not all
metals can be extracted using the same method.
Extraction of a metal from its ore consists of the following steps.
1. Crushing and grinding of the ore.
2. Concentration or dressing or benefaction of the ore.
3. Conversion of concentrated ore to oxide by roasting or calcination.
4. Reduction of metallic oxides (smelting).
5. Refining or purification of metals.
 1. Ores are crushed into a fine powder in big jaw crushers and ball mills.
This process is called Pulverisation.

2. DRESSING (CONCENTRATION) OF ORES

The process of removing gangue, the rocky impurities like SiO2 present in
an ore, is called Concentration of an ore or Ore Dressing and the purified
ore is called concentrated ore.
Concentration methods :
(i) Hydraulic washing or Gravity separation or Levigation
The ore is poured over a sloping, vibrating corrugated
table with grooves and a jet of water is allowed to flow
over it. The denser ore particles settle down in the
grooves and lighter gangue particles are washed down
by water.
Oxide ores of iron and tin are concentrated by this
method.

(ii) Magnetic Separation

The crushed ore is placed over a conveyer belt, which
rotates around two metal wheels, one of which is
magnetic. The magnetic particles are attracted to
the magnetic wheel and fall separately apart
from the non-magnetic particles.
This method is used to concentrate tin stone
(SnO2). It contains magnetic oxide of iron
(Fe3O4) as impurity.
(iii) Froth floatation
Principle: This process depends on the preferential wettability of the ore
with oil (pine oil) and the gangue particles by water.
The impurities get wetted by water and remain
behind in the tank.
Since the ore is lighter, it comes on the surface
with the froth and impurities are left behind.
Sulphide ores like zinc blende (ZnS) and Galena
(PbS) are lighter than the impurities present.

3. CONVERSION OF CONCENTRATED ORE TO ITS OXIDE

Concentrated ore is converted to its oxide because oxides are easier to
reduce into metals. Depending upon the nature of the ores, two methods are
used to convert the ore into its oxide: (i) roasting and (ii) calcination.
(i) Roasting is a process of heating the concentrated ore to a high
temperature in presence of air.
During roasting
(i) Moisture is removed.
(ii) Organic matter is oxidised and removed.
(iii) Impurities of sulphur, phosphorus and arsenic are oxidised and
removed as volatile impurities.
S + O₂ →SO₂
P4 + 5O2 → P4O10
(iv) Metal sulphides are oxidised to metal oxides.
2ZnS + 3O2 → 2ZnO + 2SO2
2PbS + 3O2 →2PbO + 2SO2
(v) Roasting makes the ore porous and so ore gets heated uniformly.
(ii) Calcination: If an ore is a carbonate or a hydrated oxide, it is heated in
the absence of air to a temperature that is high but insufficient to melt the
ore. The process is known as Calcination.
Thus on calcination, metal carbonates and metal hydroxides get
decomposed to give metal oxide.
ZnCO3 → ZnO + CO₂
CaCO3 → CaO + CO₂
Moisture, water of hydration and other volatile impurities present in the ore
get removed. Ore becomes porous and heating of ore is uniform.

4. REDUCTION OF METAL OXIDES TO METALS

The metal oxide is reduced by heating it with reducing agents like carbon,
carbon monoxide or hydrogen to obtain the crude metal.
(i) Oxides of highly active metals like potassium, sodium, calcium,
magnesium and aluminium have great affinity towards oxygen and so
cannot be reduced by common reducing agents.
These metals are obtained by electrolytic reduction.
For example:
Potassium
Electrolyte : Fused potassium bromide
Reaction: KBr ⇌ K+ + Br-
Reaction at cathode : K+ + e- → K
Reaction at anode : Br- - e- → Br
Br + Br → Br2

Aluminium is also obtained from its oxide by electrolysis.

(ii) The metals in the middle of the activity series such as zinc, iron, lead,
copper, etc., are moderately reactive.
Sulphide ores are converted into oxides by heating in excess of air
(roasting) as oxides are easy to reduce.
The carbonate ores are heated in a limited supply of air (calcination) to
convert them into oxides.

The metal oxides are then reduced by using suitable reducing agents
(carbon reduction process).

Iron, lead and copper are obtained by the reduction of their oxides with
carbon, carbon monoxide and hydrogen.
The highly reactive metals can be used as reducing agents because they
can displace metals of lower reactivity from their compounds. For example,
in order to obtain manganese, its oxide is heated with aluminium powder.

3MnO2(s) + 4Al(s)→ 3Mn(l) + 2Al2O3(s) + Heat

Aluminium is a powerful reducing agent. When a mixture of aluminium

powder and iron oxide is ignited, the latter is reduced to metal. This process
is called Aluminothermy.
Fe2O3 + 2Al → 2Fe + Al2O3 + Heat

These displacement reactions are highly exothermic. The amount of heat

evolved produces metals in the molten state.

(iii) Metals low in the activity series are very less reactive. The oxides of
these metals can be reduced to metals by heating alone.

ELECTRO REFINING
In this method, an electrolytic cell is used which utilizes electrical energy to
drive a chemical reaction. This electrolytic cell has three components: an
electrolyte and two conducting electrodes (a cathode and an anode)
contained in a non- conducting vessel.
The impure metal is made the anode, while a thin sheet of pure metal is
made the cathode.
Electrolyte used is a salt solution of the metal, which is to be refined.
Pure metal deposits at the cathode and impurities settle down forming
anode mud.
Metals like copper, silver, gold, nickel, aluminium and zinc are refined by
this process.

Extraction of Aluminium:
Extraction of Aluminum Hall and Héroult, in 1885, developed the process for
the extraction of aluminum.
Aluminum is extracted from its main ore bauxite Al2O3.2H2O. Bauxite
contains 60% Al2O3 , the rest being sand, ferric oxide and titanium oxide.
It is concentrated or purified by chemical method.

Purification of bauxite ore (conversion of bauxite into alumina)(Bayer's

process)
Step I :- Bauxite is grinded finely and heated to remove volatile impurities.
Step II :- Heated under pressure with conc. caustic soda solution.
Al₂O3.2H₂O + 2NaOH → 2NaAlO₂ + 3H₂O.
Bauxite dissolves and forms sodium meta-aluminate. Red Mud is impurities
formed during the process is removed by filtration.
Step III :- On adding water at 50C diluting sodium meta-aluminate, it gets
hydrolysed to give aluminium hydroxide. Soluble impurities remain
dissolved in Sodium Hydroxide.
NaAlO2 +2H2O → NaOH + Al (OH)3↓

Step IV :- The precipitate is filtered, washed, dried and ignited at 1000°C to

get alumina (Al₂O3).
2AI(OH)3 → Al2O3 + 3H2O
Aluminium oxide due to its great affinity for oxygen is a very stable
compound. It is not reduce easily by common reducing agents like carbon,
carbon monoxide or hydrogen. Hence, electrolytic reduction was chosen as
the method for reducing alumina.
Hall discovered that aluminium can be extracted by adding to Alumina(20%)
cryolite-Sodium meta Aluminate(60%) and Fluorspar-Calcium Floride(20%).
This reduced cost of Aluminium extraction.

Electrolytic reduction of fused alumina (Hall-Héroult's process)

Electrolytic cell: Rectangular iron tank with sloping bottom. The tank is lined
with gas carbon.
Electrolyte: It is the mixture of molten alumina 20%, cryolite 60% and
fluorspar 20%. Powdered coke.
Temperature: 950°C.
Voltage used: 5 to 6 volts.
Cathode: 4Al3+ +12e- → 4Al
Anode: Thick rods of graphite are suspended into the fused electrolyte.
Anode is oxidized to carbon monoxide, which further forms carbon dioxide.
The anode has got to be replaced from time to time, as it gets oxidized by
the oxygen evolved at the anode.

Uses:
1. Cryolite: Lowers the fusion temperature from 2050 degrees C to 950
degrees C and enhances conductivity.
2. Fluorspar and cryolite
(i) act as a solvent for the electrolytic mixture.
(ii) increases its conductivity since pure alumina is almost a non-conductor
of electricity.
3. Powdered coke is sprinkled over the surface of the electrolytic mixture. It:
(i) reduces heat loss by radiation.
(ii) prevents the burning of anode.

Alloys:
An alloy is a homogeneous mixture of two or more metals or of one or more
metals with certain non-metallic elements.
Gold is too soft to be used without a small percentage of copper.
Amorphous alloys (used in transformer coils) are made by quick quenching
of the molten metals.
Alloys melting in the range of about 51°C to 260°C, usually contain bismuth,
lead, tin, etc. These alloys are called fusible alloys.
A steel containing up to 10% of elements such as chromium, molybdenum,
nickel, etc., usually with a low percentage of carbon is known as alloy steel.

Amalgam: A mixture or an alloy of mercury with a number of metals or

alloys such as sodium, zinc, gold and silver as well as with some non-
metals is known as amalgam.
Dental amalgam is a mixture of mercury and a silver-tin alloy.

Purpose of making alloys:

Alloys are made to change the property of their major constituents to
achieve a specific objective.
For example:
(i) Strength of iron is increased by making steel.
(ii) Brass is stronger than its components copper and zinc.
(iii) Aluminium bronze looks like gold.
(iv) Nichrome, an alloy of Ni, Fe and Cr, is more resistant to electricity.
(v) Carboloy, an alloy of tungsten, carbon and cobalt, is as hard as diamond.
(vi) Bell metal (Cu-78%, Sn-22%) is more sonorous than copper or tin.
(vii) Alnico, an alloy containing aluminium, nickel and cobalt, can lift 60
times its own mass.
(viii) Solder, an alloy of lead and tin. Tin lowers melting point of alloy, it
melts at 180°C. It is useful for making electrical connections (soldering
purposes) because its melting point is lower than the individual melting
points of both the component metals.
(ix) Type metal (an alloy of lead-75%, tin-10%, and antimony-15%) has a low
melting point and can easily be cast. It is used for printing.
(x) Sodium amalgam is much less reactive than sodium. It is a liquid alloy at
room temperature.
The purpose of an alloy is to improve the specific usefulness of the primary
component and not to adulterate and degrade it.

Reasons for Alloying

Depending upon the purpose for which the particular alloy is used:
1. To modify appearance and colour:
e.g. Aluminium bronze (Al + Cu) resembles gold as it is bright yellow.
2. To modify chemical activity
e.g. Sodium amalgam (Na + Hg) is less reactive than sodium.
3. To modify casting ability
e.g. Type metal (Pb + Sn + Sb) expands on solidification and is easily cast.
4. To lower the melting point.
e.g. Solder (Pb + Sn) melts at 180°C which lower than the melting point of
lead or tin.
5. To increase hardness, and tensile strength.
e.g. Brass (Cu + Zn) is harder than copper. Duralumin (Al + Cu) has a
strength up to six times greater than pure aluminium.
6. To increase resistance to electricity.
e.g. Nichrome (Ni + Fe + Cr) has more resistance (can produce much heat) to
electricity than copper.

Method of making alloys

1. By fusing the metals together.
For example, brass is made by melting zinc and copper.
2. By compressing finely divided metals.
For example, wood metal : an alloy of lead, tin, bismuth and cadmium
powder is a fusible alloy. This alloy is used in automatic sprinkler which
provides a spray of water to prevent fires from spreading.

Alloys as solid solutions

Alloys can be considered solid solutions in which the metal with a high
concentration is solvent and other metals are solute. For example, brass is a
solid of zinc (solute) in copper (solvent).

Common Alloys, their compositions, properties and uses

Principal Alloy’s name Composition Properties Used for
Metal making
Aluminium 1. Duralumin 95% Al Light, hard and 1. Bodies of
4% Cu resistant to aircraft, buses
0.5% Mg corrosion. and tube
0.5% Mn Highly ductile. trains.
Al-imparts 2. Light tools.
lightness. 3. Pressure
Mg-imparts cooker.
strength.
Iron 1. Stainless 73% Fe Resists 1. Utensils
Steel 18% Cr corrosion. 2. Cutlery
8% Ni Lustrous, hard. 3. Ornamental
1% C Resistant to pieces
acids and 4. Surgical
alkalis. instruments
Ni, Cr imparts
lustre.
C-imparts
hardness.
Zinc or 1. Brass 60 - 70% Cu Malleable and 1. Decorative
Copper 40 - 30% Zn ductile. hardware,
Can be easily utensils.
cast. 2. Screws and
Resists handles.
corrosion.
 Yellow/Silvery 3. Cartridge,
in colour. containers.
4. Parts of
watches and
taps.
5. Musical
instruments.
6. Electrical
goods.
7. Marine
engines.
Zinc or 2. Bronze 80% Cu Hard and easily 1. Medals.
Copper 18% Sn cast. 2. Statues.
2% Zn Can take up 3. Utensils.
polish. 4. Bearing
Resists 5. Coins.
corrosion
Lead 1. Solder or Pb 50% Low m.p., 1. Soldering
Fuse Metal Sn 50% 180°C purposes
High tensile 2. Fuse
strength