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Aluminium

Aluminium is the most widely used metal after iron. It has a low density, is malleable and easily
worked. It is also corrosion resistant and a good conductor of both heat and electricity. The important ores
of aluminum are silicates, oxides, fluorides, sulfates etc.
Silicates: Kaolin, Potash Feldspar, Potash Mica

Oxides: Bauxite, Gibbsite, Diaspore, Corundum

Fluorides: Cryolite

Sulfates: Alunite

Aluminium is extracted mainly from its oxide ore, Bauxite (Al2O3.nH2O).


Primary manufacture involves four processes:
a) purification of bauxite to pure aluminium oxide (alumina)
b) electrolytic reduction of aluminium oxide to aluminium
(a) Purification of bauxite to aluminium oxide
The principal impurities in bauxite are iron oxide (3 - 25%), silica (1 - 7%) and titanium dioxide (2 3%). Powdered bauxite is mixed with approximately 10% sodium hydroxide solution and the resulting
mixture heated under pressure (4 atm) at about 420K. Under these conditions the alumina dissolves as
sodium aluminate according to the reaction:

Al2O3.nH2O + 2NaOH 2NaAlO2 + nH2O


Sometimes lime is added to precipitate silica as calcium silicate. The insoluble residue (known as
red mud from the color of iron oxide) is allowed to settle, washed to recover sodium hydroxide, filtered and
then used in land restoration, where the deposited residue is covered with top soil and re-seeded. Sodium
aluminate is heated at 50C 60C and treated with CO2 as:

2NaAlO2 + CO2 + 3H2O 2Al(OH)3 + Na2CO3


Precipitates of aluminium hydroxide are washed to remove sodium carbonate; dried and heated up
to 1500C to get aluminium oxide (alumina).

2Al(OH)3 Al2O3 + 3H2O


(b) Electrolytic reduction of aluminium oxide to aluminium
The commercial operation for reducing alumina to aluminium is an electrolytic process. In this
process, the pure oxide, alumina, is dissolved in molten cryolite at 950C in an iron bath lined with graphite
which acts as cathode. The anode consists of carbon rods suspended in the molten electrolyte. Then
solution is electrolyzed to give metal:
At cathode:

Al3+ + 3e- Al

At anode:

2O2- O2 + 4e-

The aluminium metal then sinks to the bottom of solution and is tapped off.

Copper
About 80% of the world's primary copper comes from ores in which copper is present as a sulfide
mineral, for example, chalcopyrite (CuFeS2) (the most abundant copper ore), bornite (Cu5FeS4) and
chalcocite (Cu2S). These ores contain typically only about 0.5-2% copper. The remainder of primary
production comes from ores in which copper is present as silicates, sulfates, carbonates and oxides, which
have been formed by the weathering and oxidation of sulfide minerals. The method used to extract copper
from its ores depends on the nature of the ore. Sulfide ores such as chalcopyrite (CuFeS2) are converted
to copper by a different method from silicate, carbonate or sulfate ores. The ores typically contain low
percentages of copper and have to be concentrated before refining (e.g., via froth flotation).
The manufacture of the copper takes place in three stages:
a) concentration of the ore
b) conversion of the sulfides and other copper compounds to copper
c) purification of copper
(a) Concentration of the ore
The ore is enriched by froth flotation. The powdered ore is mixed with oil and agitated with water in
a large tank to which detergent has been added. Compressed air is forced through the mixture, and the
lightweight particles of copper sulfide are carried to the top and float on the froth. Heavier clays and other
silicates settle to the bottom of the tank.
(b) Conversion of sulfides to copper
The concentrated ore is heated strongly with silicon dioxide (silica) and air or oxygen in a furnace or
series of furnaces. The copper ions in the chalcopyrite are reduced to copper sulfide (which is reduced
further to copper metal in the final stage). The iron in the chalcopyrite ends up converted into an iron
silicate slag which is removed. Most of the sulfur in the chalcopyrite turns into sulfur dioxide gas. This is
used to make sulfuric acid via the Contact Process. An overall equation for this series of steps is:

2CuFeS2 + 2SiO2 + 4O2Cu2S + 2FeSiO3 + 3SO2


The copper sulfide produced is converted to copper with a final blast of air.

Cu2S + O22Cu + SO2


The end product of this is called blister copper - a porous brittle form of copper, about 98 - 99.5% pure.
(c) Purification of copper
Whatever method is used to manufacture copper from its ore, its final purification is by electrolysis.
The purification uses an electrolyte of copper sulfate solution, impure copper anodes, and strips of high
purity copper for the cathodes. At the cathode, copper ions are deposited as copper.

Cu2+ (aq) + 2eCu(s)


At the anode, copper goes into solution as copper ions.

Cu(s) Cu2+ (aq) + 2e


For every copper ion that is deposited at the cathode, in principle another one goes into solution at
the anode. The concentration of the solution should stay the same. All that happens is that there is a
transfer of copper from the anode to the cathode. The cathode gets bigger as more and more pure copper
is deposited; the anode gradually disappears.

Iron
The common ores of iron are both iron oxides, and these can be reduced to iron by heating them
with carbon (coke) at high temperatures in a blast furnace. Coke is produced by heating coal in the
absence of air. Coke is cheap and provides both the reducing agent for the reaction and also the heat
source. The most commonly used iron ores are hematite, Fe2O3, and magnetite, Fe3O4. The manufacture
of iron has two stages, the preparation of raw materials, and the reduction of iron oxide to iron.
(a) Preparation of raw materials
Iron is one of the most abundant elements on Earth and its ores commonly contain oxygen, silicon,
manganese, phosphorus and sulfur. The major minerals present in ores include hematite (Fe2O3) and
magnetite (Fe3O4). Most ores contain more than 60% iron and are used in their mineral state in a blast
furnace. Ore containing less than this is first crushed and ground into a powder and concentrated by
flotation. It is then rolled into balls and heated in a furnace to produce pellets the size of marbles. This
process eliminates the long-distance transport of waste material (clays and other silicates).
(b) The reduction of iron oxide to iron (The Blast Furnace)
The air blown into the bottom of the furnace is heated using the hot waste gases from the top. The
coke (essentially impure carbon) burns in the blast of hot air to form carbon dioxide - a strongly exothermic
reaction. This reaction is the main source of heat in the furnace.

C + O2 CO2
At the high temperature at the bottom of the furnace, carbon dioxide reacts with carbon to produce carbon
monoxide.

C + CO2 2CO
It is the carbon monoxide which is the main reducing agent in the furnace.

Fe2O3 + 3CO 2Fe + 3CO2


In the hotter parts of the furnace, the carbon itself also acts as a reducing agent. Notice that at these
temperatures, the other product of the reaction is carbon monoxide, not carbon dioxide.

Fe2O3 + 3C 2Fe + 3CO


The temperature of the furnace is hot enough to melt the iron which trickles down to the bottom where it
can be tapped off. Iron ore is not pure iron oxide - it also contains rocky material that would not melt at the
temperature of the furnace, and would eventually clog it up. The limestone is added to convert this into slag
which melts and runs to the bottom. The heat of the furnace decomposes the limestone to give CaO.

CaCO3 CaO + CO2


This is an endothermic reaction, absorbing heat from the furnace. It is therefore important not to add too
much limestone because it would otherwise cool the furnace. Calcium oxide is a basic oxide and reacts
with acidic oxides such as silicon dioxide present in the rock. Calcium oxide reacts with silicon dioxide to
give calcium silicate.

CaO + SiO2 CaSiO3


The calcium silicate melts and runs down through the furnace to form a layer on top of the molten iron. It
can be tapped off from time to time as slag. Slag is used in road making and as "slag cement" - a final
ground slag which can be used in cement, often mixed with Portland cement. The molten iron from the
bottom of the furnace can be used as cast iron, containing about 4% of carbon.

Lead
The Lead is extracted from its ore by reduction with carbon. The most important lead ore is galena
(PbS). Other important ores, such as cerrusite (PbCO3) and anglesite (PbSO4), may be regarded as
weathered products of galena and are usually found nearer the surface.
The primary manufacture of lead involves three stages:
a) ore concentration

b) smelting

c) refining

(a) Ore concentration


Lead and zinc ores often occur together and may also contain silver, copper and gold. The ore has first
to be separated from clays and other silicates after which the lead ore and the zinc ore are separated. The
process used is froth flotation, a succession of stages each delivering a greater concentration of the lead ore.
The ore (which typically contains 3-8% lead) is mixed with water and a frothing agent (a detergent) and is
violently agitated by air to form a fine suspension with a froth of bubbles on the top. The process is carried out in
a series of tanks. As the lead and zinc minerals are less readily wetted than the gangue, they adhere to the air
bubbles which are carried to the surface. The rock particles sink and the lead and zinc ores are skimmed off.
Then the lead ore is separated from the zinc ore. A chemical called a depressant is added which is soluble in
water (for example, zinc sulfate) and the zinc ore sinks and the lead ore is skimmed off. Later, a chemical such
as copper sulfate is added and the zinc ore now floats and is skimmed off. The lead ore concentrate from the
flotation tanks now contains about 50% lead.

(b) Smelting
Smelting is usually a two-stage process as described here. After mixing with limestone the filtered
concentrated ore is roasted in air or oxygen-enriched air on a moving belt. Most of the sulfide is converted
to lead oxide:
Sulfur dioxide gas can then be cleaned and used to make sulfuric acid.
The lead oxide is heated and made into lumps, a process known as sintering. The lumps are crushed to a
suitable size for subsequent treatment in a blast furnace. Each lump is mixed with approximately 7% of its
mass in coke and limestone. The coke is added for two purposes, one as the reducing agent and the other
as a source of heat. The mixture is fed into the top of the blast furnace, and the lead oxide is reduced to
molten lead. Carbon and carbon monoxide, produced from the coke, are the reducing agents:

The molten lead is tapped off from the base of the furnace and put into a 'holding kettle' which keeps the
metal molten for the refining process. The product contains about 99.5% lead.
(c) Refining
99.5% lead is heated to just above its melting point. Solid copper and copper sulfide rise to the surface
and are skimmed off. Arsenic is then removed by stirring the lead with an air blast and skimming off the resulting
slag which contains arsenic oxides. Silver is removed by adding 2% zinc to the lead and a silver-rich zinc crust
forms. During cooling a solid silver/zinc crust separates, rises to the surface and is removed continuously. Zinc is
removed by dezincing which is carried out by vacuum distillation at 860K when the zinc vaporizes. Finally, all
traces of antimony and zinc are removed by mixing sodium hydroxide into molten lead at 760K (its melting point
is 600K). The resulting sodium zincate and antimonate form a skin on the surface of the molten lead which is
skimmed off. The refined lead is of 99.99% purity.

Nickel is a chemical element with symbol Ni and atomic number 28. It is a silvery-white metal. Nickel is
hard and ductile. On Earth, nickel occurs most often in combination with sulfur and iron in pentlandite,
with arsenic in the mineral nickeline, and with arsenic and sulfur in nickel galena.
Nickel is recovered through extractive metallurgy: it is extracted from its ores by conventional
roasting and reduction processes that yield a metal of greater than 75% purity. In many stainless
steel applications, 75% pure nickel can be used without further purification, depending on the composition
of the impurities.
Most sulfide ores have traditionally been processed using pyrometallurgical techniques to produce
a matte for further refining. Recent advances in hydrometallurgical techniques have resulted in significant
nickel purification using these processes. Most sulfide deposits have traditionally been processed by
concentration

through

a froth

flotation process

followed

by pyrometallurgical extraction.

In

hydrometallurgical processes, nickel sulfide ores undergo flotation and then smelted. After producing the
nickel matte, further processing is done via the Sherritt-Gordon process. First, copper is removed by
adding hydrogen sulfide, leaving a concentrate of only cobalt and nickel. Then, solvent extraction is used to
separate the cobalt and nickel, with the final nickel concentration greater than 99%.
Purification of nickel oxides to obtain the purest metal is performed via the Mond process, which
increases the nickel concentrate to greater than 99.99% purity. This process makes use of the fact
that carbon monoxide combines with nickel readily and reversibly to give nickel carbonyl. No other element
forms a carbonyl compound under the mild conditions used in the process.
This process has three steps:
1. Nickel oxide reacts with H2 gas at 200 C to give nickel, together with impurities including iron and cobalt.

NiO(s) + H2(g) Ni(s) + H2O(g)


2. The impure nickel reacts with carbon monoxide at 5060 C to form the gas nickel carbonyl, leaving the
impurities as solids.

Ni(s) + 4 CO(g) Ni(CO)4(g)


3. The mixture containing nickel carbonyl (and synthesis gas) is heated to 220250 C, resulting in
decomposition back to nickel and carbon monoxide:

Ni(CO)4(g) Ni(s) + 4 CO(g)


Nickel is re-obtained from the nickel carbonyl by one of two processes. It may be passed through a large
chamber at high temperatures in which tens of thousands of nickel spheres, called pellets, are constantly
stirred. It then decomposes, depositing pure nickel onto the nickel spheres. Alternatively, the nickel
carbonyl may be decomposed in a smaller chamber at 230 C to create a fine nickel powder. The resultant
carbon monoxide is re-circulated and reused through the process. The highly pure nickel produced by this
process is known as "carbonyl nickel".

Chromium is a chemical element with symbol Cr and atomic number 24. It is a steely-gray, hard and
brittle metal which takes a high polish and has a high melting point. The name of the element is derived
from the Greek word chrma, meaning color, because many of its compounds are intensely colored. Nearly
all chromium is commercially extracted from the single commercially ore chromite, which is iron chromium
oxide (FeCr2O4). Chromite is also now the chief source of chromium for chromium pigments. Chromium
metal and ferrochromium alloy are commercially produced from chromite by silicothermic or aluminothermic
reactions, or by roasting and leaching processes.
The two main products of chromium ore refining are ferrochromium and metallic chromium. For the
production of ferrochromium, the chromite ore (FeCr2O4) is reduced in large scale in electric arc furnace or
in smaller smelters with either aluminium or silicon in an aluminothermic reaction. For the production of
pure chromium, the iron has to be separated from the chromium in a two steps roasting and leaching
process. The chromite ore is heated with a mixture of calcium carbonate or sodium carbonate in the
presence of air. The chromium is oxidized to the hexavalent form, while the iron forms the stable Fe 2O3.
The subsequent leaching at higher elevated temperatures dissolves the chromates and leaves the
insoluble iron oxide. The chromate is converted by sulfuric acid into the dichromate.

4 FeCr2O4 + 8 Na2CO3 + 7 O2 8 Na2CrO4 + 2 Fe2O3 + 8 CO2


2 Na2CrO4 + H2SO4 Na2Cr2O7 + Na2SO4 + H2O
The dichromate is converted to the chromium oxide by reduction with carbon and then reduced in an
aluminothermic reaction to chromium.

Na2Cr2O7 + 2 C Cr2O3 + Na2CO3 + CO


Cr2O3 + 2 Al Al2O3 + 2 Cr
Progress of Atomic Models
In 1803, John Dalton, proposed his atomic theory. He suggested that atoms were indivisible solid
spheres.
J.J.Thomson proposed that an atom was a solid sphere of positively charged material and
negatively charged particles, electrons were embedded in it like the seeds in a guava fruit. But later
this concept was proved wrong.
Rutherford suggested the planetary model, but this model was rejected.
In 1913, Neils Bohr proposed that electrons revolve around the nucleus in a definite orbit with a
particular energy. Based on the facts obtained from spectra of hydrogen atom, he introduced the
concept of energy levels of atom.
In 1916 Somerfield modified Bohrs model by introducing elliptical orbits for electron path. He
defined sub energy levels for every major energy level predicted by Bohr.
The concept of Quantum numbers was introduced to distinguish the orbital on the basis of their size,
shape and orientation in space by using spin quantum numbers.
From the study of quantum numbers, various rules are put forward for filling of electrons in various
orbitals by Aufbau principle and Pauli Exclusion Principle.
In 1921 Burry and Bohr gave a scheme for the arrangement of electrons in an atom. Further the
nature of electron (s) is studied.

Dalton Atomic Model


1. Atoms are tiny, invisible particles.

3. Atoms of different elements are different.

2. Atoms of one element are all the same.

4. Compounds form by combining atoms.

Thomson Atomic Model


Thomson discovered electrons.
He also proposed the existence of a (+) particle.
Atoms are made mostly out of (+) charged material, like dough in a bun.
The (-) charged electrons are found inside the (+) dough.

Rutherford Atomic Model


The Rutherford model is a model of the atom devised by Ernest Rutherford which suggested, that the socalled Thomson Model of the atom was incorrect. Rutherford overturned Thomson's model in 1911 with
his well-known gold foil experiment in which he demonstrated that the atom has a tiny, heavy nucleus.
Rutherford designed an experiment to use the alpha particles on gold foil emitted by a radioactive element
as probes to the unseen world of atomic structure.
Most a particles went through the gold. The atom is mostly empty space.
Some particles deflected and others even bounced back.
He showed that atoms have (+) particles in the center, and he called these (+) particles, protons.
The atom had a very dense (+) center. He called the center of atoms; the nucleus.
Rutherford discovered protons and the nucleus.
Bohr Atomic Model
Niels Bohr improved on Rutherfords model. Bohr model depicts the atom as a small, positively
charged nucleus surrounded by electrons that travel in circular orbits around the nucleussimilar in
structure to the solar system, but with attraction provided by electrostatic forces rather than gravity.
He proposed that electrons move around the nucleus in specific layers, or shells. Every atom has a specific
number of electron shells. These shells are associated with definite energies and are also called energy
shells. The Bohr model of an atom was based upon Planck's quantum theory of radiation. Electrons can
only gain and lose energy by jumping from one allowed orbit to another, absorbing or emitting
electromagnetic radiation with a frequency determined by the energy difference of the levels according to
the Planck relation:

Where h is Planck's constant. The frequency of the radiation emitted at an orbit of period T is as it would be
in classical mechanics; it is the reciprocal of the classical orbit period:

Molecular Weight of a Polymer


When we speak of molecular-mass of a polymer, it is, however quite different from that applied to
small sized compounds. Polymers are polydisperse and quite heterogeneous in molecular mass. In other
words, polymers are mixtures of different molecular masses. Three main types of molecular mass of
polymers have been recognized:
1) Number-average molecular mass

is determined by measurement of colligative properties

such as freezing point depression, boiling point elevation, osmotic pressure and lowering of vapor
pressure.

is defined as the total mass (w) of all the molecules in a polymer sample divided by

the total number of molecules present. Thus, the number-average molecular mass is defined by:

Where, Ni is the number of molecules of mass Mi.


2) Weight-average molecular mass

is obtained from light-scattering and ultra-centrifugation

techniques, which measure molecular size. It is defined as

Where, wi is the weight-fraction of molecules of mass Mi.

Where,

can also be defined as:

ci = weight-concentration of Mi molecules;
c = total weight-concentration of all polymer molecules

Weight-average molecular mass is always greater than number-average molecular mass.


3) Viscosity-average molecular mass

is obtained from viscosity measurement. It is defined by:

Where a = constant. The viscosity and weight-average molecular masses are equal, when a = unity.
However,

is almost always less than

polydisperse polymer

, since a is usually in the range of 0.5-0.9. Thus, for a

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