Metals and Metallurgical Principle

Syllabus

• Definition of metallurgy and its types (pyrometallurgy, hydrometallurgy

and electrometallurgy)
• Introduction of ores
• Gangue or matrix, flux and slag, alloy and amalgam
• General principles of extraction of metals (different processes involved in
metallurgy): concentration, calcination and roasting, smelting, carbon
reduction, thermite and electrochemical reduction
• Refining of metals (poling and electro-refinement)

Metallurgy
Metallurgy is an art of science which deals with the study of extraction
and purification of metal from its ore. The activity of metals, nature of
impurities present in ore decides the method of metallurgy for the
extraction of metal in pure state from their ore.

Pyrometallurgy
• It is the process of extraction of metals by the application of heat (Pyro =
heat).
• It is a dry process where high temperature is applied for the reduction of
metal oxide to its molten form.
• Less reactive metals (generally having high MP and BP) like Cu, Zn, Fe, Ni,
Cr etc. are extracted by this method.

Hydrometallurgy
• It is a technique of extracting metals from aqueous solution of ore by the
method of precipitation.
• In this process, the pulverized ore is first treated with suitable chemical
reagent or solvent to convert metal into its complex solution however
impurity remains undissolved. The metal complex solution is further treated
with highly reactive/electropositive metals like Zinc to separate desired
metal as precipitate. Less reactive/less electropositive metals like Au and
Ag are extracted by this method.
 Ex: During the extraction of Au,Ag by Cyanide process, NaCN is used as
suitable reagent and Zn is used as precipitant (precipitating agent and
reducing agent).
Ag2S + 4NaCN → 2Na[Ag(CN)2] + Na2S + impurities
Argentite Sodium argentocyanide
(soluble complex)

2Na[Ag(CN)2] + Zn → Na2[Zn(CN)4] + 2Ag↓

Precipitant Sodium zincocyanide
(reducing agent)
Electrometallurgy
• This is a technique of extracting metals by the application of electricity in
fused or molten state i.e. electrolysable state of ore.
• Highly reactive/electropositive metals like Mg, Al, Ca, Na, K etc. are
extracted by this method because they have high affinity with carbon
and form carbide instead of reduction into metallic form. They cannot be
extracted by pyrometallurgy because they are easily converted into
vapor form which are highly reactive and corrode the vessels.

Difference between Minerals and Ores

Minerals Ores

1. Mineral is naturally occurring 1. Ore is the mineral from which metal

substance which contains metals in can be extracted economically as
it. well as in efficient manner.

2. Metal is present in variable 2. Whole proportion of ore can be

proportion. used to extract metal.

Ex: Clay (Al2O3.2SiO2.2H2O) E.g. Bauxite (Al2O3.2H2O)

*Note: from Bauxite (Al2O3.2H2O), Aluminum can be extracted

economically because it contains Aluminum in large amount. Therefore, it
is an ore of Aluminium.

But Clay (Al2O3.2SiO2.2H2O) contains less amount of Aluminium. So,

Aluminium cannot be extracted economically. Hence, it is a mineral of
Aluminium. Therefore we can say “All ores are minerals but all minerals
are not ores”.
 Types of ores
Sulphide ores: Copper pyrite or chalcopyrite (CuFeS2), zinc blende
(ZnS), galena (PbS), iron pyrite(FeS2) etc.

Oxide ores: Cuprite (Cu2O), haematite (Fe2O3), magnetite (Fe3O4),

pyrolusite (MnO2), Tinstone or Cassiterite(SnO2), Zincite or red zinc
oxide(ZnO), Franklinite ( ZnO.Fe2O3), Alumina(Al2O3) etc.

Halide ores: Rock salt or common salt (NaCl), horn silver (AgCl),
Carnallite (KCl.MgCl2.6H2O) etc.

Carbonate ores: Limestone (CaCO3), Magnesite(MgCO3),

Dolomite(MgCO3.CaCO3), Calamine (ZnCO3), Siderite(FeCO3),
Malachite[CuCO3.Cu(OH)2], Azurite[2CuCO3.Cu(OH)2], etc.

Alloy
An alloy is a homogeneous mixture of elements of which at least one is
metal. The homogeneous mixture of non-metal and non-metal is not alloy.
Basically, alloys are of two types i.e; Ferrous Alloys and Non- Ferrous
Alloys.

a) Ferrous alloys:
Those alloys which contain Iron in them are called ferrous alloys.
E.g: Steel (Fe+C) and stainless steel (Fe+Ni+Cr+C) etc.

b) Non- ferrous alloys:

Those alloys which do not contain Iron in them are known as non-ferrous
alloys.
E.g: Brass (Cu+Zn), Bronze (Cu+Sn), Gun metal (Cu+Zn+Sn),
German silver (Ni+Cu +Zn) etc.

Importance of Alloys/ Purpose of making alloys

• To prevent pure metals from rusting.
• To increase the mechanical strength of metals.
• To impart beautiful colors.
• To lower the melting and boiling point.
 Amalgam:
• The homogeneous mixture of Mercury with metal is known as amalgam.
• Mercury is liquid at ordinary conditions. So, Amalgam is formed by
dissolving metal on Mercury.
• Amalgam may be a liquid, a soft paste or a solid, depending upon the
proportion of mercury.

E.g: Hg+ Na → NaHg [Sodium amalgam]

E.g: Hg+ Cu → CuHg [Copper amalgam]
E.g: Hg + Sn → SnHg [Tin amalgam] and so on..

Note: Almost all metals form amalgam with mercury except Iron (Fe),
Cobalt (Co), Nickel (Ni), Platinum(Pt) and Ta(Tantalum) because they
don’t dissolve in Mercury (Hg is unable to break the metallic bonds
present in them).

Uses of Amalgam:
• Copper amalgam is used for filling the cavity in teeth.
• Sodium amalgam (NaHg) is used as reducing agent. It is also used during
high-pressure sodium lamp design to fine-tune the color and electrical
properties of the lamp.
• Tin amalgam is used in the reflective mirror coating.
• Zinc amalgam is used in the Clemmensen reduction in organic synthesis.
• Copper amalgam is an amalgam probe, which is a device used to detect
mercury in the environment.
• Silver amalgam used in silver mining.

Gangue/ Matrix:
The unwanted earthy particles (impurities like stony matter, clay, silicates,
carbonates, nitrates etc.) present in the ore are called Gangue.

Refractory Materials
• A refractory material or refractory is a material that is resistant
to decomposition by heat, pressure, or chemical attack, and retains
strength and form at high temperatures.
• They are typically composed of oxides or carbides, nitrides etc. of the
following
materials: silicon, aluminium, magnesium, calcium, boron, chromium and
Zirconium.
• Refractory materials are used in furnaces, kilns, incinerators, and reactors.
• Refractories are also used to make crucibles.

Flux
Flux is the chemical substance added during reduction for the removal of
gangue/matrix.

Types of flux:
a) Acidic Flux
The flux used for the removal of basic impurities is known as acidic flux. E.g:
SiO2, Borax (Na2B4O7.10H2O), P2O5 etc.
CaO + SiO2 → CaSiO3
Basic gangue acidic flux fusible slag

b) Basic flux
The flux used for the removal of acidic impurities is known as basic flux. E.g:
CaO, MgO, FeO, CaCO3, MgCO3, Dolomite (MgCO3.CaCO3) and so on..

SiO2 + MgO → MgSiO3

acidic gangue basic flux fusible slag

Slag
• The fusible substance/mass formed after treating gangue/matrix with
suitable flux is called slag.
• Slag is neutral in nature.
• Most of them are waste material for metallurgy but some of them can be
used as valuable fertilizers. Ex; Thomas slag- Ca3(PO4)2 and Gilchrist slag-
Mg3(PO4)2 are important fertilizers.

3CaO + P2O5 → Ca3(PO4)2

3MgO + P2O5 → Mg3(PO4)2

 General metallurgical steps in Metallurgy

1) Mining
The collection of ore from the mines is mining. It is the first step in
Metallurgy.

2) Crushing and Pulverization

The process of converting big lumps of ore into smaller pieces by using jaw
crusher is known as crushing. The process of converting crushed ore into a
fine powder by using ball mills/stamp mills/pulverizer is known as
pulverization.

3) Concentration of Ore
• This is the method of removing unwanted earthy impurities present in
powdered ore/pulverized ore in order to increase the extent of ore.
• Depending upon the nature of ore and impurities present on given ore,
concentration can be carried out by following ways:

a) Hand picking
If impurities present in given ore are distinct in color and with different
particle size, they can be removed by hand picking. This is a lengthy and
conventional process.

b) Gravity separation/Levigation/Washing of the ore

• If the densities of the impurities and ore are different, then impurities can
be separated out by using this method.
• Two types of instruments have been suggested for this process; Wilfley
table and Hydraulic Classifier.
• During the separation, given ore is transferred into the vessel (hydraulic
classifier) where stream of water is passed from the bottom. Inside the
vessel, lighter impurities will be washed away with water whereas heavier
ore particles get settled down at bottom. Generally oxide and hydroxide
ore can be concentrated by this method. E.g: Bauxite ore of aluminium,
Hematite or Magnetite ore of Iron etc.
 Fig: Gravity separation method (hydraulic classifier)

Fig: Wilfley table used in gravity separation

c) Froth floatation method:

• It is a specific method used for the concentration of Sulphide ores like PbS
(Galena), ZnS (Zinc blende), CuFeS2 (copper pyrite), HgS (Cinnabar) and
so on.
• This method is based on the principle that solids have the different
attraction towards liquids. In another words, it is based on the principle of
wettability(different abilities to be wet with different liquids i.e; oil or water).
• In this method, powdered/pulverized ore is mixed with water along with
Pine oil or Eucalyptus oil in a vessel known as froth flotation tank. On
passing compressed air inside the vessel, agitation and vigorous bubbling
 occurs. Sulphide ore which gets preferentially wetted with oil forms bubble
and collected at a surface as a scum or forth whereas impurities which
get preferentially wetted with water settle down at a bottom of vessel. The
concentrated sulphide ore is collected by skimming for further
metallurgical operation.

Fig: Froth floatation process

d) Electromagnetic separation
• If one of the impurities or ore particles is magnetic in nature, then such
type of ore can be concentrated by using electromagnetic separation
method.
• During this process, powdered ore is transferred into the rotating
belt/leather belt/conveyor belt fitted with rotator or wheel where one of
the rotator/wheel is magnetic in nature. On passing the ore in rotating
belt, magnetic particles will be attracted by magnetic rotator collected
near the rotator whereas non-magnetic particles will be collected away
from rotator. Non-magnetic ore tin stone (SnO2) is separated from
magnetic iron impurities, Wolframite (FeWO4).
 e) Leaching (Chemical separation method)
Leaching is a part of hydrometallurgy. It is a chemical method of
concentration of ore. In this method, powdered/pulverized ore is treated
with suitable chemical reagent or solvent so that metallic portion present
in given ore gets dissolved, however, impurities don’t. By filtration,
impurities can be separated as residue while the concentrated metallic
portion is obtained as filtrate. Generally, ores of Aluminum, gold and silver
can be concentrated by leaching.

Ex: Bayer’s process uses hot and aqueous NaOH as suitable reagent
during the extraction of Al from bauxite.
Al2O3.2H2O + 2NaOH 2NaAlO2 + 3H2O + impurities
Impure bauxite Sodium meta aluminate
NaAlO2 + 2H2O heat NaOH + Al(OH)3

2Al(OH)3 ignition Al2O3 + 3H2O

Pure alumina

Ex: Cyanide process, uses NaCN as suitable reagent to dissolve impure

pulverized argentite ore. After filtration, concentrated ore is obtained.

Ag2S + 4NaCN → 2Na[Ag(CN)2] + Na2S + impurities

Argentite Sodium argentocyanide
(soluble complex)

Preliminary heating (Calcination & Roasting)

Calcination
• Calcination is a process of heating concentrated ore in absence or
sometimes in limited supply of air or oxygen below the melting point of
ore.
• The purpose of calcination is to convert concentrated ore into oxide form.
Calcination is mainly carried out for oxides, hydroxides, carbonates and
nitrate ores (ores which already contain oxygen in them).
• Calcination is carried out in Reverberatory furnace or Sinterer.
• During calcination following chemical changes take place;
a) Moisture gets removed.
 b) Volatile impurities get removed.
c) Water of crystallization gets removed.

Al2O3.xH2O Al2O3 + 2H2O↑

d) Decomposition of ore takes place as

ZnCO3 ZnO + CO2↑

Calamine

CaCO3 CaO + CO2↑

e) Impurities like C, S, P, As etc. are removed as their volatile oxides if
calcination is carried out in limited supply of air or oxygen.

C + O2 → CO2↑

S + O2 → SO2↑

P4 + 5O2 →2P2O5↑

4As + 3O2 → 2As2O3↑

Roasting
• Roasting is the process of heating concentrated ore in excess of air or
oxygen below the melting point of ore.
• The purpose of roasting is to convert concentrated ore into oxide form. It is
mainly carried out for sulphide ores (ores which don’t contain oxygen in
them).
• Roasting is also carried in Reverberatory furnace or Sinterer.
• During roasting following chemical changes take place:
a) Moisture gets removed.
b) Volatile impurities and organic matters get removed.
c) Oxidation of ores take place as;
2ZnS + 3O2 → 2ZnO + 2SO2↑

2PbS + 3O2 → 2PbO + 2SO2↑

2HgS + 3O2 → 2HgO + 2SO2↑

 d) If impurities like C, S, P, As etc. are present, they are removed as
respective volatile oxides.

C + O2 → CO2↑

S + O2 → SO2↑

P4 + 5O2 →2P2O5↑

4As + 3O2 → 2As2O3↑

Figure: Reverberatory furnace

Differences between Calcination and Roasting:

Calcination Roasting
• It is the process of heating • It is the process of heating
concentrated ore in the absence concentrated ore in the presence
or sometimes in limited suppy of of excess air or oxygen below its
air or oxygen below its melting melting point to convert it into
point to convert it into oxide form. oxide form.

• It is mainly carried out for oxides,

hydroxides, carbonate and • It is mainly carried out for sulphide
nitrates ores which already ores which donot contain oxygen.
contain oxygen.

• Decomposition of ore takes place. • Oxidation of ore takes place.

ZnCO3 → ZnO + CO2↑ 2ZnS + 3O2 → 2ZnO+ 2SO2↑
• Ore obtained after roasting is • Ore obtained after calcination is
called roasted ore. called calcined ore.

Reduction
• Metals can be extracted in crude form from metallic oxide after removing
oxygen. Such process of removal of oxygen with the help of suitable
reducing agent is known as reduction.
• Depending upon the nature of metal, reduction can be carried out by
Smelting in pyrometallurgy, Electrolysis in electrometallurgy and
precipitation method in hydrometallurgy.
• Reduction is carried out by using suitable chemicals like Carbon, Carbon
monoxide, Aluminum, Magnesium, Zinc, Hydrogen, Water gas (CO + H2)
etc.
• Different furnaces are used during reduction. Ex: Blast furnace for Fe and
Cu, Continuous vertical retort for Zn, Shaft furnace for Hg, Down’s cell for
the extraction of Na etc.

1)Smelting
Smelting is a method of reduction in pyrometallurgy. In another words, it is
a process of applying heat to ore, to extract a base metal (common and
inexpensive metal). It is used to extract many metals from their ores,
including iron, copper, and other base metals. Smelting uses heat and a
chemical reducing agent to decompose the ore, driving off (removing)
other elements as gases or slag and leaving the metal base behind. The
reducing agent is commonly a fossil fuel source of carbon, such as coke
or charcoal.

Types of Smelting
a) Reduction with Carbon (Carbon reduction process):
In this method, calcined or roasted ore is mixed with carbon/coke/coal/
charcoal along with suitable flux. On providing sufficient heat
(approximately 1400-1500°C), reduction proceeds and metal is obtained
in a molten state. Flux combines with impurities to form slag which on
being lighter floats over the molten metal and can be easily removed.

Ex: Fe2O3 + C → Fe + CO↑

 Ex: ZnO + C → Zn + CO↑

Ex: SnO2 + C → Sn + CO↑

Limitations:
i) Highly reactive metals like Na, K, Ca etc cannot be extracted from this
method.

ii) Metal can’t be extracted from metallic oxide in which oxygen has the
strong affinity with metal than with Carbon.

Figure: Blast Furnace

 b) Reduction with Aluminium/Aluminothermite
process/Thermite process/Goldschmidt process

Figure: Aluminothermite process

• Metallic oxides in which Oxygen has strong affinity with metal than
Carbon, such type of oxides can’t be reduced by Carbon. So, aluminum
is used as a reducing agent instead of Carbon.
• Generally metals like Manganese, Chromium and Nickel are extracted by
this method. In this method, calcined or roasted ore is thoroughly mixed
with Aluminium powder along with little amount of Barium Peroxide (BaO2)
and kept in a suitable crucible fitted with magnesium ribbon. Heat energy
required to initiate reduction is supplied by burning of BaO2 and
magnesium ribbon. Once the reduction is started, heat is evolved inside a
crucible because the reaction is exothermic in nature. Finally, metal is
obtained in molten state.

E.g: 3MnO2 + 4Al → 3Mn + 2Al2O3 + Heat

Pyrolussite
Cr2O3 + 2Al → 2Cr + Al2O3 + Heat
 2) Electrolytic Reduction
Highly reactive metals like Na, K, and Ca etc. can’t be extracted from
their oxide by chemical method of reduction because in order to reduce
their oxide huge amount of heat is required and at very high temperature
these metals form undesired products. Extraction of such metal can be
done by carrying out electrolysis of molten or fused salt. Therefore the
mode of reduction is Electrolysis.

E.g: Na can be extracted by electrolysis of molten NaCl. During this

process, Na is collected at cathode.

Reaction: NaCl → Na+ + Cl-

At Anode (Oxidation): 2Cl- → Cl2 (gas) + 2e-

At Cathode (Reduction): Na+ + e- → Na

Purification of Metal
Metal obtained after reduction still contains lot of impurities. Some
methods employed during refining are discussed below:

1) Poling:
In this process, molten metal is stirred with pole of green wood.
Hydrocarbon present in green wood acts as reducing agent so that oxide
impurities get reduced into respective metal. This method is specially used
for purification of Copper and tin.

Cu2O + Hydrocarbon → Cu(pure) + CO2↑ +H2O↑

2) Electrolytic Refining/Electro-Refinement/Electrolysis:
• This refining method is cheap and convenient.
• Metals like Cu, Ag, and Zn etc can be refined by this process.
• The impure metal that needs to be refined is made anode and a sheet of
pure metal (already available) is made cathode. Both of these electrodes
are dipped into electrolyte of acidified salt solution of concerned metal.
On passing electricity, pure metal gets deposited at cathode as the
anode undergoes dissolution. Insoluble impurities fall behind the anode in
the form of anode mud/anode sludge/anode slime and soluble impurities
pass into the solution.
• Some other refining processes are Distillation, Fractional Distillation, and
Liquation etc.

Ex: The figure below represents the refining of zinc where impure Zn is
anode and pure Zn is cathode and acidified ZnSO4 is electrolyte.

Figure: Electro-refinement process

The reactions occurring at Anode and Cathode during the purification of

zinc are mentioned below:

At anode (Oxidation): Zn (impure) → Zn2+(aqueous) + 2e-

At cathode (Reduction): Zn2+ (aqueous) + 2e- → Zn(pure)