Metals & Principles of

Extractive Metallurgy
Principles of Extractive
Metallurgy If the mineral deposit contains an
economically recoverable amount of
a metal, it is referred to as an ore.

Mining and Processing of The waste material of the rock

Metals formation is known as gangue, which
must be separated from the desired
portion of the ore through a variety of
processing steps.
 There are three main types of rocks, grouped according to their form of origin.

Igneous rocks are those Sedimentary rocks are those Metamorphic rocks are
formed from the formed through compaction those formations that have
solidification of molten of small grains deposited as changed composition and
mass following volcanic sediment in a riverbed or morphology over time
activity. Common examples sea. Common examples through the influence of
include granite, feldspar, include shale, limestone, temperature and pressure.
mica, and quartz; metals sandstone, and dolomite. Examples of these rocks
such as the alkali and Metals such as copper, iron, include marble, slate, and
alkaline earths, gold, zinc, lead, nickel, gneiss, and yield similar
platinum, and chromium are molybdenum, and gold may metals as igneous
isolated from these all be found together within formations.
formations. sulfur-based sedimentary
deposits.
Natural occurrence of selected metals and materials-based applications
Natural occurrence of selected metals and materials-based applications
 The most common mineral classes from which metals are extracted include:

(i) Silicates—e.g., feldspars, quartz, olivines (Mg/Fe), pyroxenes (XY(Si, Al)2O6), garnets
(X3Y2(SiO4)3), and micas (X2Y4–6Z8O20(OH, F)4)
(ii) Carbonates—e.g., calcite and aragonite (both CaSO4), dolomite (Mg/Ca), siderite (Fe)
(iii) Sulfates—e.g., anhydrite (CaSO4), celestine (SrSO4), barite, gypsum (hydrated CaSO4),
chromate, molybdate, selenate, sulfite, tellurite, tungstate
(iv)Halides—e.g., fluorite (CaF2), halite (NaCl), sylvite (KCl), sal ammoniac (NH4Cl)
(v) Oxides—e.g., hematite (Fe2O3), magnetite (Fe3O4), chromite (Fe/Cr), spinel (Mg/Al),
ilmenite (Fe/Ti), rutile (TiO2)
(vi) Sulfides—e.g., pyrite (FeS), chalcopyrite (Cu/Fe), pentlandite (Ni/Fe), galena (PbS),
sulfosalt (S/As), selenide/telluride/arsenide/antimonide minerals
(vii) Phosphates—e.g., AO4 (A = P, As, Sb, V), apatite (Ca5(PO4)3(OH, F, Cl))
 Pyrometallurgy
extractive metallurgy Hydrometallurgy
Electrometallurgy
flotation
Leaching
smelting Solution Concentration
slag Metal Recovery
Downs cell used to purify sodium metal Hall cell used to purify aluminum metal

Schematic of electrometallurgical processes used to purify metals

Processing routes for the conversion of bauxite
into alumina and aluminium metal
Flowchart illustrating the various steps involved
in steelmaking and processing
Schematic of a blast iron.
Shown are: (1) incoming pre-
heated air from the Cowper
stove; (2) melting zone; (3)
reduction zone of FeO; (4)
reduction zone of Fe2O3; (5)
pre-heating zone; (6) feed of
iron ore, limestone, and coke;
(7) exhaust gases; (8) column of
ore, coke, and limestone; (9)
removal of slag; (10) tapping of
molten pig iron
Reactions in blast furnace
Reactions in Pb/Zn
Reduction
Reactions in Wealz Process
(a) Transfer of pig iron from the blast
furnace to basic oxygen furnace
(BOF) in transfer ladles, (b) sulfur
removal via CaO addition, and (c)
charging the BOF with pig iron and
steel scraps.
Melt composition within the basic oxygen furnace.
Degassing unit used to remove carbon Schematic of continuous casting, with a
under vacuum. photograph of the resulting iron slabs.
Photographs of the
hot-rolling process.
Principles of Extractive
Metallurgy

The majority of refining reactions

required in liquid melts occur
around the liquid slag-liquid metal
Slags interface and are commonly called
slag-metal reactions.
The functions of a slag used in liquid metal processing:
(i) protection of the melt from contamination from the furnace
atmosphere and combustion products of the fuel;
(ii) insulation of the melt;
(iii) accepting unwanted liquid and solid components;
(iv) controlling the supply of refining media to the melt through
additions to the slag.
To be able to apply these functions slags must have certain fundamental
properties:
(i) Lower melting point than the melt in order to maintain a liquid slag of high
fluidity which covers the whole of the liquid metal surface, and allows good
contact with the liquid metal. Fluxes such as lime, fluorspar, quartz or iron oxide
may be added which lower the melting point of the slag and thereby increase its
fluidity.
(ii) Lower specific gravity than and immiscible in the melt, so that it rests above
the melt as a separate liquid layer and can therefore accept impurities which are
generally lighter than the liquid metal.
(iii) Correct composition so that it can accept and react with impurities from
and be immiscible in the melt.
 Liquid slags are ionic in structure, thus the molten oxides forming
the slag are present as cations and anions. These oxides are present
as two main types:
Basic oxides, which donate O2- ions to Acidic oxides which accept O2- ions,
the slag, e.g.. CaO, FeO, MgO, Cu2O, e.g. SiO2, P2O5 , Al2O3, and which
Na2O, K2O , and which ionise as produce complex cations by reaction
follows: with the oxygen anions, i.e.

CaO = Ca2+ + 02- SiO2 + 2O2- = SiO44-(silicate or

orthosilicate ion)
P2O5 + 3 O2- = 2PO43- (phosphate or
orthophosphate ion)
Al2O3 + 3O2- = 2AlO33- (aluminate or
orthoaluminate)
One molecule of SiO2 is neutralised by two molecules of basic oxide
(two O2- ions), while one molecule of Al2O3 and P2O5 are each
neutralised by three molecules of basic oxide.

When the slag is composed of these ratios of basic and acidic oxides it
has neither basic nor acidic properties and is said to be a neutral slag

SiO2 + 2CaO = Ca2SiO4 or 2CaO.SiO2 or 2Ca2+ + SiO44-

(calcium orthosilicate)
P2O5 + 3CaO = Ca3(PO4)2 or 3CaO.P2O5 or 3Ca2+ + 2 PO43-
(calcium orthophosphate)
Al2O3 + 3CaO = Ca3(AlO3)2 or 3CaO.Al2O3 or 3Ca2+ + 2AlO33-
(calcium orthoaluminate)
A basic slag is one which contains more basic oxide than the neutral
ortho-compound composition and in this state the slag will have an
excess of O2- ions.
An acidic slag is one which contains more acidic oxide than the
neutral ortho-compound composition and will therefore have an
excess of SiO2, P2O5 or Al2O3.

A typical basic slag composition would be three moles of CaO and

one mole of SiO2…

An acidic slag composition would contain one mole of CaO to one

volume of SiO2…
 Silica tetrahedron of four O2- ions (large open
circles) and one Si4+ ion (smaller, black circle)

Schematic representation of the tetrahedral

network structure of pure silica: (a) solid
crystalline silica; (b) silica in the liquid state
Miscibility limits for various binary
silicate systems
Phase diagram for the CaO-SiO2
system
Liquidus surfaces and immiscibility region in the
ternary system CaO-FeO-SiO2
Application areas of amorphous materials:
➢ Military applications (Transparent armors, tank materials etc.)
➢ Solar cells
➢ Glassware

Relationship between slags and refractory materials…

Principles of Extractive
Metallurgy

According to the Brønsted-Lowry

theory acids are proton ( H+ ion)
Acids and Bases donors.
For example, hydrogen chloride is a covalent gas but in
aqueous solution it reacts as follows:

The proton, H+, produced by HCl is so small that it bonds

strongly with at least one molecule of water :
 In very dilute solution, acids such as Ethanoic (acetic) acid is only 1.3%
HCl, HBr, HNO3 and HClO4 are dissociated in a 0.1 [Link]-3 solution
considered completely dissociated but and 13% dissociated in a 10-3 [Link]-
above about 10-3 [Link]-3 association 3 solution at 298 K.

(recombination of the dissociated

species) can occur at 298 K.

Complete or nearly completely Partial dissociation

dissociation

STRONG ACIDS WEAK ACIDS

Dissociation of the general weak acid:

A base is a proton acceptor

Oxides such as CuO and hydroxides such

as Ca(OH)2 are bases and their reaction
with H+ is most simply represented by the
following ionic equations:
Soluble bases such as KOH are also known as alkalis though alkaline solutions
can be produced, not only by dissolving bases but also salts of weak acids and
strong bases, e.g. aqueous Na2CO3, since their hydrolysis yields OH- ions:

The bases mentioned above are strong. A good example of a weak base is an
aqueous solution of ammonia which dissociates as follows:
 A salt is an ionic compound containing a
positive ion other than the hydrogen ion, and
a negative ion other than the hydroxy ion.

Salts constitute a class of compounds obtained by a partial

or total replacement of the replaceable hydrogen atoms or
the atoms present in the molecule of an acid by a metal or
a group of elements behaving like a metal.

Salts are generally grouped into three classes:

✓ normal salts,
✓ acid salts or bisalts,
✓ and basic salts.
 Classification of
solutions based on
Arrhenius’ theory.
Different nomenclatures of oxy-acids.
(A) Hydration of ions
 (B)–(D) ionization
phenomenon for HCI acid
depicted in different ways
(E) reaction between sulphuric acid and water
 Classification of salts
(The table describes essentially the simple salts. There are, in addition, two special types of
salts. They are known as the double salts and the complex salts).
Nomenclature of
salts – certain
general rules.
Principles of Extractive
Metallurgy When solutions of an acid and an
alkali are mixed in the correct
proportions the resulting solution
has no acidic or alkaline character,
and on evaporation it gives a solid
Neutralization and salt.
Hydrolysis
This reaction is called neutralization
because the product has neither
acidic nor alkaline properties
 Solutions of salts prepared by the combination In many cases,
of equivalent quantities of acid and base may be however, this is not
expected to show a neutral character. true.

For example, although solutions of sodium The nature

chloride are neutral, as would be expected, of this effect depends upon
the relative strengths of the
solutions of potassium cyanide are alkaline, acid and the base from
while those of ferric chloride are acidic. which the salt results.
Thus, sodium chloride is the salt of a strong acid
and a strong base and is, therefore, neutral.

On the other hand, hydrocyanic acid is a very

weak acid and hence its potassium salt This behavior of salts
(potassium hydroxide being a strong base) is is known as salt
alkaline in solution. hydrolysis.
In a similar fashion, as ferric hydroxide is a weak
base, its salt with strong hydrochloric acid is
acidic in aqueous solution.
Water itself is very slightly dissociated into
hydrogen and hydroxy ions:

A salt AB that results from the combination of

the acid HA and the base BOH is considered
to be in solution:

The salt in solution will be largely ionized:

The solution will contain high
concentrations of A+ ions and B–
ions.

If HA and BOH are both strong, nothing

particular will occur.
Salt hydrolysis may be defined as a reaction in which the anion or the
cation of a salt reacts with the solvent water to produce acidity or
alkalinity.

It is the nature of the anion or the cation constituting the salt which
will determine whether the solution produced as a result of hydrolysis
will be acidic or alkaline.
 THE FIRST CASE

The hydrolysis of salts of strong acids

and weak bases:
The common ion
A– is disregarded.
In this case only the cation B+ reacts
with water, and the mass law equation
(K is the familiar equilibrium constant)
for the above reaction is:

Since H2O is in large excess as the solution

is dilute, its concentration is taken as
constant. It is amalgamated with the
equilibrium constant K to give a new
constant Kh, called the hydrolysis constant:
 THE FIRST CASE

In the same solution, there are two more equilibria:

(Kw: the ionic product of water)

(Kb: the dissociation or ionization

constant of the weak base)
 THE FIRST CASE

If h is the degree of hydrolysis of the salt, c moles per liter is its

concentration, and v liters per mole is its dilution:
 THE FIRST CASE

when h is so small that (1 – h) may be taken as 1

Substituting v = 1/c
 THE SECOND CASE

The hydrolysis of salts of strong bases or

and weak acids:

Disregarding the common B+ ion, then

only an anion A– reacts with water:

(Kh, the hydrolysis constant)

(Ka, is the dissociation or ionization constant of the weak acid)
(Kw, ionic product of water)
 THE THIRD CASE

The hydrolysis of salts of weak acids

or
and weak bases:

Both cation B+ and anion A– react with

water:

the three equilibria in

the solution
(involvement of
ionization of weak base (Ka, the dissociation constants for the weak acid)
BOH; weak acid HA and (Kb, the dissociation constants for the weak base)
H2O): (Kh, the hydrolysis constant)
Hydrolysis constant and degree of hydrolysis for hydrolysis of salts.
Neutralization:
REVERSE
Hydrolysis:
Distinction between neutralization and hydrolysis.
Principles of Extractive
Metallurgy neutral

(K′, The equilibrium constant)

Ionization of Water

Since Kw is larger (the forward reaction is

encouraged) at higher temperatures, the
forward reaction must consume heat, so the
ionization of water must be endothermic.
 pH measurement
Principles of Extractive
glass electrode
Metallurgy pH meter
saturated calomel electrode

Ionization of Water

pH scale at 298 K