ICH 305: Industrial Inorganic Chemistry (Dr.

Famojuro’s Part)

COURSE OUTLINES
A. Chemistry of Metals

i. Occurrence/extraction techniques/preparation of selected metals such

as Cu, Fe, Au, Ca, Mg, Al, Si, Zn, Na, K, Sn, Ti, Co, Cr, Mn, Ni, V, Bi
ii. Chemistry of corrosion
iii. Chemistry of Glass (SiO2).

B. Chemistry of Inorganic Compounds and complexes of Industrial Interest

i. Transition metals complexes involved in catalysis such as. Co, Ni, Fe, Pd
and Ir
ii. Metal complexes in biological systems such as, Fe complexes in
haemoglobin, Co in vitamin B12 and Mg in chlorophyII
iii. Other applications such as V in V2O5 in industrial production; iron oxide
in cosmetics, CaCO3 in powder and toothpaste; Pb compounds in hair
products etc

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 FIRST LESSON

METALS

Why is Metal crucial to human development?

Metals are crucial to modern society due to their diverse applications for in the
industries. The are needed for technologies, economics and societal
developments. They are essentially indispensable in both everyday life and global
economics and have been a determining factor in the development of humanity
since the dawn of the first advanced civilizations They are essentially utilized as
structural integrity in constructions, electrical conductivities in electrical fields,
catalysts in industrial chemical reactions, and moreso. they hold substantial
economic values due to global trading in metals.

A metal is a solid, opaque, shiny chemical element that can act as a conductor of
electricity and heat. Metals are characterized by their malleability and ductility
(some more than others), they can be moulded and stretched into different shapes
without breaking, and they are not easily damaged by exposure to high
temperatures. Metals are found in nature either in pure form — like gold,
silver, in the form of alloys (combinations of different metals), or in combination
with a non-metal, such as sulfides or carbonates.

Industrially, the term “metal” may be loosely referred to a chemical element such
as iron, an alloy such as stainless steel; or a molecular conductors such as
polymeric sulphur nitride. The general science of metals is called metallurgy, a
subtopic of material sciences; aspects of the electronic and thermal properties are

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also within the scope of condensed matter physics and solid-state chemistry. It is
a multidisciplinary topic.

Metal is extracted from rock as a solid, except for mercury, which is liquid at
room temperature. Currently, metals are used in a wide variety of objects and
structures —from tools and machinery to buildings and bridges— due to their
unique physical and chemical properties that give them great strength and
durability. For all these reasons, they played a key role in the development of
human civilization,

THE METAL AGE

The Metal Age is the last period of Prehistory, both in Asia and Europe. It is so
called because this was the era when metals began to be discovered and worked,
giving birth to the first metallurgical technologies. The period is divided, in turn,
into three different stages: the Copper Age, the Bronze Age and the Iron Age.

(I) The Copper Age

The Metal Age began with the first human discovery of metal: copper. The first
manipulation and working of this material was by cold beating with a hammer,
since the processes of smelting and forging had not yet been developed. As time
went by, metallurgy techniques and some alloying began to appear, culminating
in the discovery of bronze. This milestone marks the end of this first period and
the beginning of the next: the Bronze Age.

(II) The Bronze Age

The discovery of a certain copper alloy marked the birth of one of the most
important metals in history and one of the most used to this day: bronze. It began

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to be used to forge tools, kitchenware, weapons, ornaments and utensils of all
kinds.

(III) The Iron Age

The Iron Age is the last of the periods that make up the Metal Age. As with any
historical period, especially prehistoric ones, it is not 100% known when it began
or ended. Moreover, some civilizations began to use iron before others, the
transition being favoured by its abundance in their natural environments. What
can be said is that iron replaced copper to a large extent due to its many desirable
characteristics, such as its resistance. This was not an isolated event — it brought
with it enormous economic, cultural and technological changes that were key to
humanity’s development. Agricultural and artisan techniques also evolved, as
well as writing.

The most important Metal Age inventions

During the Metal Age inventions and advances were made that were essential for
the development of human civilization. Not only did metallurgy start to develop,
but other sectors progressively evolved too, driven by inventions in areas such as
mining, animal husbandry and agriculture.

Some of the most important inventions were:

• Different casting techniques, as well as metal molding.
• The plow: a metal utensil that made it possible to pierce the soil and rotate
it to stimulate its fertility. This made it possible for cultivated crops to
proliferate.
• Tools: for example, for working land.
• Weapons and armor: allowing many previously subjugated peoples to
come to the fore, forever changing the course of history.

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 • Fortifications and castles: the most developed fortifications began to
appear, giving rise to the first medieval castles and fortresses.
• Forging is also a vital process today, a key process for many indispensable
parts in manufacturing and construction. Not only does it allow the creation
of efficient tools and machinery, capable of withstanding heavy loads and
wear, but it also ensures their durability and resistance. In addition, it is
also fundamental in the creation of decorative elements of great beauty and
elegance, such as railings, lamps and other ornamental objects that
reinforce the value of the interior and exterior spaces where they are placed.

B. CHEMISTRY OF METALS
(i) Occurence

The majority of metals are found in the earth's crust in the form of combined
compounds known as mineral ore. Thus, minerals ore are naturally occurring
chemical substances in the form of which metals occur in the earth along with
impurities. The crust of the earth provides metals and it is a good source to
procure metals. Mostly, metals occur in nature in a combined state but sometimes
they can also occur in the free state. A native metal is a metal found in its metallic
state naturally, either in pure form or in the form of an alloy. Most metals can’t
resist natural processes like oxidation and corrosion etc. Hence, only non-reactive
metals like gold, silver, platinum, etc are found in the native or free state. Most
metals are obtained in the form of compounds and they need to be filtered from
their impurities to be further used for various applications. The process of
procuring metals from ores is called METALLURGY and metals are usually
extracted from the earth by mining the ores.

An ore is any naturally-occurring source of a metal that metal can be

economically extracted from (figure 1.0).

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Figure 1.0: Azure mineral ore (copper is obtained from it)

The concentration of valuable minerals in an ore may be high or low. Certain

places on Earth are more likely to have certain ores. Also, in some places, there
is a high content of metals in the ores. For example, if you want copper, you must
look at regions with particular geology. Copper is often found where hot fluids
once come off a magma intrusion. Aluminum is found in intensely weathered
soils in tropical areas and is the most common metal in the Earth's crust, occurring
in all sorts of minerals. However, it isn't economically worthwhile to extract it
from most of these minerals. Instead, the usual ore of aluminum is bauxite - which

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contains from 50 - 70% of aluminum oxide. Copper is much rarer, but fortunately
can be found in high-grade ores (ones containing a high percentage of copper) in
particular places. Because copper is a valuable metal, it is also worth extracting
it from low-grade ores as well. Ores are commonly oxides, for example:

• bauxite (Al2O3)
• haematite (Fe2O3)
• rutile (TiO2 )
. . . or sulfides, for example:
• pyrite (FeS2 )
• chalcopyrite (CuFeS2 )

Iron is the second most abundant metal in the earth's crust (about 4.7 % by mass).
Iron is also a necessary component of biological systems

Extraction of Metals

The occurrence of metals in nature is only a part of the process, also these metals
have to be extracted. Metallurgy is the process of extracting metals. The basic
step of extracting metals is called concentration of ores. The ores contain a lot of
impurities that need to be filtered. An ore is a mineral from which the metal can
be extracted easily and cheaply. All ores are mineral; however, all minerals are
not necessary ores. Metals can be found in a variety of minerals, but metal
extraction is difficult due to either low concentration or the presence of
impurities. For example, Aluminium, is found in the earth's crust as two minerals:
bauxite and china clay. Aluminium can be extracted from bauxite simply and cost-
effectively, whereas no simple and cost-effective method exists for extracting
aluminium from clay. As a result, bauxite is the ore of aluminium. The filtration
of these impurities from ores is known as concentration. Concentration can be
done by gravity separation or hydraulic washings, or froth flotation processes.

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 Extraction of Metals

Metals that are least reactive such as gold, platinum, and silver occur in a free
state in the Earth's crust. However, the ores of these metals can be associated
with sulfide minerals such as pyrites, chalcopyrites, etc. However, other low
reactive metals such as mercury exist as its sulfide in cinnabar ore. Metals such
as zinc and iron, etc., that come in the middle of the series are moderately reactive
and occur as their oxides, sulfides and carbonates, in the Earth's crust. For
example, zinc occurs as its sulfide in the ore ‘zinc blende’ and as carbonate in the
ore ‘smithsonite’ while iron occurs as sulfides in iron pyrite and as an oxide
in magnetite ore. The most reactive metals, such as sodium, can occur as its
chloride in rock salt ore and as nitrate in Chile saltpetre. Therefore, metals can be
classified on the basis of their reactivity as metals with low reactivity, metals with
moderate reactivity, and metals with high reactivity.

(a) Metals in the top of the reactivity level such as sodium, magnesium, calcium,
etc cannot be obtained from their compound by heating with carbon as they
are very reactive. Electrolytic reduction is used to obtain such metals.

(b) Metals of medium reactivity level such as lead, zinc, copper, etc are moderately
reactive and are generally present as carbonates or sulphides.
• Sulphides ores are converted into oxides by heating strongly in the
presence of excess air. Sulphur impurities can escape as gas, this process
is known as roasting.

• Carbonates ores are calcinated to eliminate carbonate and moisture

impurities. Calcination is a process where the ore is converted into oxides
by heating strongly in the presence of less air.

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(c) Metals of low reactivity level

Metals that aren’t very reactive are placed low in the reactivity series. These
metals can be reduced to metals by heating alone. For example, Mercury is
procured from its ore, cinnabar (HgS), by the process of heating.

Now, there are various steps, such as the concentration of ore, roasting,
calcination, reduction, electrolysis, and refining, that can be involved in the
extraction of metals from their respective ores. Metals with different reactivities
undergo different steps for their extraction,

Figure 2.0: Schematic diagram of the extraction process for metals with
different reactivities.

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 EXTRACTION PROCESSES

The process used to extract a metal is determined by its physical and chemical
properties, as well as the impurities associated with it. Since different metals have
different physical and chemical properties, they require different extraction
methods.

1. ORE CONCENTRATION

The first step in extraction of metal is ore concentration Ores extracted from the
earth's crust are never pure and are usually associated with earthy and siliceous
impurities (along with other minerals' impurities) known as gangue or matrix.
Before the metal can be extracted, these impurities must be removed from the ore.
This involves getting rid of as much of the unwanted rocky material as possible
before the ore is converted into the metal. The removal of gangue particles can
be achieved using gravity separation, froth floatation, magnetic separation,
and leaching processes.

Also, could be done chemically, for example, pure aluminum oxide is obtained
from bauxite by a process involving a reaction with sodium hydroxide solution.
Some copper ores can be converted into copper(II) sulfate 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) sulfate solution. But, in many cases, it is possible
to separate the metal compound from unwanted rocky material by physical
means.

Methods used in Ore concentration

• The gravity separation method is used when gangue particles are lighter
than the ore. This method is generally used for the concentration of heavier
ores such as oxides, carbonate ores and native gold. The method
involves the passing of crushed ore particles through a stream of water during

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 which the lighter gangue particles are washed away and heavier particles
settle down.
• The froth floatation method is used to remove gangue particles from sulfide
ores. In this method, the crushed ore and water are added to a tank in which a
frother, such as pine oil, is added and then air is blown under pressure to create
the froth. The gangue particles will be wetted by water and the metal comes up
with the froth. This involves crushing the ore and then treated with something
which will bind to the particles of the metal compound that you want and make
those particles hydrophobic. "Hydrophobic" literally means "water fearing". 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 of some kind), 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.
This method is commonly used to concentrate sulphide ores such as zinc
blende (ZnS), copper pyrites (CuFeS2) and others. The surface of sulphide ores
is preferentially wetted by oils, whereas the surface of gangue is preferentially
wetted by water. In a tank, the ore is crushed into a fine powder and mixed with
water to form a suspension. Collectors (e.g pine oil, xanthates) are added to
this suspension to improve the non-wettability of the ore particles. Froth-
stabilisers (e.g., cresols and aniline) are added to stabilise the froth. The
rotating paddle violently agitates the suspension, drawing in air and causing
frothing. During this process, the ore particles that are preferentially wetted by
the oil become lighter and rise to the surface with the froth, whereas the gangue
particles that are preferentially wetted by water become heavier and settle at

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 the tank's bottom. The froth is removed. It is allowed to collapse before being
dried, to obtain the concentrated ore.
• The magnetic separation method is used when either metal or gangue
particles have magnetic properties. In this method, the crushed ore is passed
over conveyor belts with magnetic rollers. A case study of Tinstone (or that
contain Tin), the magnetic tungstates form a heap beneath the magnetic roller,
while the ore particles, i.e., SnO, forms a separate heap away from the magnetic
roller.
• The Leaching method is used to concentrate ores of aluminium, silver, and
gold, etc. In this method, the crushed ore is treated with a solvent that dissolves
the ore leaving behind the impurities. Leaching is the process of extracting the
required metal from an ore in the form of an aqueous solution of its selected
compound, by treating the ore with acid, base or another reagent. For example,
bauxite ore is continuously stirred with 45 percent NaOH at 200-250 °C, to
collect the solution of sodium aluminate Na[Al(OH)4]. The sodium aluminate
is neutralised by passing carbon dioxide gas and as a result hydrated Al 2O3 is
precipitated. The solution is seeded with freshly prepared samples of hydrated
Al2O3, at this stage, which induces the precipitation. The solution is then
filtered, the hydrated Al2O3 is then dried and heated at 1470K, to give pure
Al2O3.

2. EXTRACTION OF THE METAL FROM THE ORE CONCENTRATE

After the ore has been fully concentrated, the ore is then further processed in
order to extract the pure metal. The process of extraction follows chemical
mechanisms which involves roasting, calcination and electrolysis. It is
important to note that sulfate and carbonate ores are converted to the oxides
because it is easier and economical to extract metals from metal oxides than
others.

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 (a) Roasting and Calcination

Roasting is the heating of concentrated metal ore in the presence of air. It is

mainly done for metal sulfide ores to convert them into their respective oxides.
For example, cinnabar is a sulfide ore of mercury with the chemical formula
of HgS. When the ore is heated in presence of air, it is first converted into
mercuric oxide and then upon further heating, liquid mercury is formed:
Δ
2HgS(s)+3O2(g) 2HgO(s)+2SO2(g)

2HgO(s) Δ 2Hg(l)+O2(g)

When zinc blende undergoes roasting, zinc sulfide present in the ore is converted
into zinc oxide:

Calcination is the process in which ore is heated in the absence or in a limited

supply of air. This method is commonly used to convert metal carbonates and
metal hydroxides into their respective oxides. Zinc oxide and carbon dioxide gas
are formed when smithsonite, the carbonate ore of zinc, is heated in absence of
air:
Δ
ZnCO3(s) ZnO(s) + CO2(g)

Similarly, calcium oxide and carbon dioxide gas are formed when limestone, the
carbonate ore of calcium, is heated in a limited supply of air:
Δ
CaCO3(s) CaO(s) + CO2(g)

b. Reduction and Electrolytic Reduction

The metal oxides produced in the roasting and the calcination processes further
undergo reduction to produce impure metal. Reduction can be done using an
appropriate reducing agent such as carbon or hydrogen. There are various
economic factors you need to think about in choosing a method of reduction for
a particular ore.

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 • the cost of the reducing agent;
• energy costs;
• the desired purity of the metal.

There may be various environmental considerations as well - some of which will

have economic costs.

When zinc oxide is reduced with carbon, impure zinc metal and carbon monoxide
gas is produced:

ZnO(s)+C(s) Δ Zn(s)+CO(g)

When copper oxide is heated in presence of hydrogen, copper oxide is reduced to

copper:
Δ
CuO(s) + H2(g) Cu(s) + H2O(g)

Carbon (as coke or charcoal) is cheap. It acts as a reducing agent, also as the fuel
to provide heat for the process. However, in some cases (for example with
aluminum), the temperature needed for carbon reduction is too high to be
economical, therefore, a different method has to be used. Carbon may also be left
in the metal as an impurity. Sometimes this can be removed afterwards (for
example, in the extraction of iron); sometimes it can't (for example in producing
titanium), and a different method would have to be used.

The reduction of metal oxide can also be achieved by using a displacement

reaction in which a more reactive metal replaces the less reactive one. Since

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aluminium is a more reactive metal than copper, when copper oxide is heated with
aluminium metal, copper and aluminium oxide are produced. This is known as
the thermite reaction in which aluminium metal is oxidized by some other
metal:

3CuO(s) + 2Al(s) 3Cu(l)+Al2O3(s)

The copper metal is in a molten state due to excessive heat produced during the
reaction

A thermite reaction is used to join railway tracks. When iron oxide is heated with
aluminium, iron and aluminium oxide are produced along with a large amount
of heat that keeps the metal in a molten state which is helpful for joining the
railway tracks.

Fe2O3(s)+2Al(s) 2Fe(l)+Al2O3(s)

The highly reactive metals such as sodium and magnesium, etc., cannot be
obtained by the reduction of their respective metal oxides because these metals
have a high affinity for oxygen. Therefore, these metals can be isolated by
the electrolytic reduction of their molten salts.

The electrolytic cell consists of an anode and a cathode made of graphite and an
electrolyte which is the molten metal salt. The molten salts contain their
respective ions. For example, molten sodium chloride contains sodium ions and
chloride ions. When an electric current is passed through the cell, the sodium ions
present in the electrolyte get reduced at the cathode and converted into pure
sodium metal while the chloride ions are oxidized at the anode and released as
chlorine gas.

At the cathode:

Na+ + e− → Na

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At the anode:

2Cl− → Cl2 + 2e−

(c) Refining of Metals

The impure metal produced in the reduction process needs to be refined in order
to obtain pure metal. One of the refining methods is electrolytic refining in which
a strip of impure metal is made at the anode while pure metal is made at the
cathode. The metal salt solution is used as the electrolyte in this process.

When an electric current is passed through the cell, the pure metal from the anode
goes into the electrolyte and the same amount of pure metal then is deposited at
the cathode. During this process, the insoluble impurities settled below the anode
as anode mud.

Impure copper can be purified by the electrolytic refining method. An impure

copper strip acts as the anode, pure copper strip as the cathode, and the aqueous
solution of copper sulfate as the electrolyte. When an electric current is passed
through the cell, copper at the anode will be oxidized into copper ions and go into
the electrolyte solution. The copper ions in the electrolyte are reduced and get
deposited at the cathode.

Metal Extraction Processes Highlights

• A rock that contains important minerals is called ore.

• Metals are found as free or in a combined state with their respective ores.

• In order to extract pure metals from their respective ores, various steps such
as the concentration of ores, roasting, calcination, reduction, electrolytic
reduction, and electrolytic refining are involved depending upon the type
of metal ore.

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