PRACTICAL PROJECT:-

General Principles and

Processes of
Isolation of Elements

BY – ASHISH GUPTA
CLASS -12 B
BOARD ROLL NO. -

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 CERTIFICATE
THIS IS TO CERTIFY THAT ASHISH GUPTA
OF CLASS XII HAS SUCCESFULLY
COMPLETED HIS CHEMISTRY PROJECT AS
PRESCRIBED BY MRS. REENA BISLA,
DURING THE ACADEMIC YEAR 2019-2020
AS PER THE GUIDELINES ISSUED BY THE
CENTRAL BOARD OF SECONDARY
EDUCATION – CBSE.

SIGNATURE OF SIGNATURE OF
EXTERNAL EXAMINAR CHEMISTRY TEACHER

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 ACKNOWLEDGEMENT
I would like to express my special thanks of
gratitude to my teacher (MRS. REENA BISLA)
who gave me the golden opportunity to do this
wonderful project on the topic GENERAL
PRINCIPLES AND PROCESS OF ISOLATION
OF ELEMENTS which also helped me in doing a
lot of research and I came to know about so many
new topics secondly I would also like to thank my
parents and friends who helped me a lot in
finalizing this project with in the limited time
frame .

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 CONTENTS
1. MINERALS
2. ORES
3. GANGUE
4. METALLURGY
5. OCURRENCE OF METALS
6. CONCENTRATION OF ORE
7. LEACHING
8. EXTRACTION OF CRUDE METAL
9. THERMODYNAMIC PRINCIPLE OF METALLURGY
10. ELLINGHAM DIAGRAM
11. ELECTROCHEMICAL PRINCIPLE OF METALLURGY
12. REFINNING

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 General Principles and
Processes of
Isolation of Elements
MINERALS
A mineral is a naturally occurring substance, representable by a chemical formula, that
is usually solid and inorganic, and has a crystal structure. It is different from a rock,
which can be an aggregate of minerals or non-minerals and does not have a specific
chemical composition. The exact definition of a mineral is under debate, especially with
respect to the requirement a valid species be abiogenic, and to a lesser extent with regard
to it having an ordered atomic structure. The study of minerals is called mineralogy

ORES
An ore is a type of rock that contains sufficient minerals with important elements
including metals that can be economically extracted from the rock.[1] The ores are
extracted from the earth through mining; they are then refined (often via smelting) to
extract the valuable element, or elements.

GAUGUE
In mining, gangue (pronounced "gang") is the commercially worthless material that
surrounds, or is closely mixed with, a wanted mineral in an ore deposit. It is thus distinct
from overburden, which is the waste rock or materials overlying an ore or mineral body
that are displaced during mining without being processed.

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Metallurgy
Metallurgy is a domain of materials science and engineering that studies the physical and
chemical behavior of metallic elements, their intermetallic compounds, and their
mixtures, which are called alloys. Metallurgy is also the technology of metals: the way in
which science is applied to the production of metals, and the engineering of metal
components for usage in products for consumers and manufacturers. The production of
metals involves the processing of ores to extract the metal they contain, and the mixture
of metals, sometimes with other elements, to produce alloys. Metallurgy is distinguished
from the craft of metalworking, although metalworking relies on metallurgy, as medicine
relies on medical science, for technical advancement

OCCURRENCE OF METALS
METAL ORES COMPOSITION
ALUMINIUM BAUXITE AlOx(OH)3-2x
{Where 0<x<1}
KAOLINITE {a form of clay} {Al2(OH)4Si2O5}
IRON HAEMATITE Fe2O3
MAGNETITE Fe3O4
SIDERITE FeCO3
IRON PYRITES FeS2
COPER COPPER PYRITES CuFeS2
MALACHITE CuCO3.Cu(OH)2
CUPRITE Cu2O
COPPER GLANCE Cu2S

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Concentration of Ores
Removal of the unwanted materials from the ore is known as concentration, dressing
or benefaction. It involves several steps and selection of these steps depends upon the
differences in physical properties of the compound of the metal present and that of the
gangue. The type of the metal, the available facilities and the environmental factors are
also taken into consideration. Some of the important procedures are described below:

1, Hydraulic washing
This is based on the differences in the gravities of the ore and the gangue particles. in
one such process, an upward stream of running water is used to wash the powdered ore.
The lighter gangue particles are washed away and heavier ores are left behind.

2, Magnetic separation
This is based on differences in magnetic properties of the ore components. If either the
ore or the gangue (one of these two) is capable of being attracted by a magnetic field,
then such separations are carried out (e.g., in case of iron ores). The ground ore is carried
on a conveyer belt which passes over a magnetic roller

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3, froth floatation method
This process is used for sulphide ores. Sulphide ores are first ground to powder and water
is added. Then pine oil is added and the emulsion is agitated by passing compressed air.
Oil and froth float on the surface along with the sulphide ore. The gangue particles being
insoluble in oil remain at the bottom of the water tank. The froth is removed and allowed
to settle down. This is called the froth – floating process. This process is used for sulphide
ores of Cu, Pb and Zn.

Leaching
Leaching is a widely used extractive metallurgy technique which converts metals into
soluble salts in aqueous media. Compared to pyrometallurgical operations, leaching is
easier to perform and much less harmful, because no gaseous pollution occurs.
Drawbacks of leaching are the highly acidic and, in some cases, toxic residual effluent,
and its lower efficiency caused by the low temperatures of the operation, which
dramatically affect chemical reaction rates.

There are a variety of leaching processes, usually classified by the types of reagents used
in the operation. The reagents required depend on the ores or pretreated material to be
processed. A typical feed for leaching is either oxide or sulpide

Concentration is carried out by digesting the powdered ore with a concentrated solution
of NaOH at 473 – 523 K and 35 – 36 bar pressure. This way, Al2O3 is leached out as
sodium aluminate (and SiO2 too as sodium silicate) leaving the impurities behind:

Al2O3(s) + 2NaOH(aq) + 3H2O(l) → 2Na[Al(OH) 4](aq)

The aluminate in solution is neutralised by passing CO2 gas and hydrated Al2O3 is
precipitated. At this stage, the solution is seeded with freshly prepared samples of
hydrated Al2O3 which induces the precipitation:

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2Na[Al(OH)4](aq) + CO2(g) → Al2O3.xH2O(s) + 2NaHCO3 (aq)

The sodium silicate remains in the solution and hydrated alumina is filtered, dried and
heated to give back pure Al2O3:

Al2O3.xH2O(s) → Al2O3(s) + xH2O(g)

Extraction of crude metal

Ores can be concentrated by using any of the four methods - hydraulic washing, magnetic
separation, froth flotation and leaching.
Crude metal extraction concentrated ore:
The concentrated ore must be converted into an oxide, which is more suitable for
reduction.
The isolation or extraction of a metal from concentrated ore involves two major steps:
a) Converting ore into its metal oxide
b) Reducing the metal oxide into the metal

Concentrated ore can be converted into its metal oxide either by calcination (or) by
roasting. Calcination is the process of converting an ore into its oxide, by heating it
strongly below its melting point, in the presence of a limited supply of air. It is usually
carried out in a reverberatory furnace. This method is commonly used to convert
carbonate ores, such as calamine and dolomite into their oxides. Also, the hydrated ores
lose water of crystallization during calcination.
When calamine, is subjected to calcination, zinc oxide is formed and carbon dioxide is
liberated.
Δ
ZnCO3(s) → ZnO(s) + CO2
Calamine Calcination Zinc Oxide Carbon Dioxide
Similarly, when dolomite is calcined, it gives calcium oxide, magnesium oxide and CO2
gas. When hematite is calcined, it loses its water of crystallization.

Δ
FeO3.xH2O(s) → Fe2O3(s) + xH2O(g)
Hematite Calcination Iron(III)Oxide
Roasting is also used to convert an ore into its metal oxide. It is the process of heating
an ore in a furnace with a regular supply of excess air, at a temperature below the melting
point of the metal.
This process is commonly employed for sulphide ores.
Ex: Zinc sulphide is heated at about 850 °C to give zinc oxide and Sulphur dioxide.

850°C
2ZnS(s) + 3O2 → 2ZnO(s) + 2SO2 (g)
Zinc Sulphide Zinc Oxide Sulphur Dioxide
Lead sulphide is roasted at about 600 °C to give lead oxide and Sulphur dioxide.

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The iron oxide present as an impurity in the form of gangue is removed by adding flux
silica.
Gangue Slag
↑ ↑
FeO + SiO2 → FeSiO3
Iron Oxide Flux Silica Iron Silicate

Iron oxide reacts with silica and slags off as iron silicate. The slag can be separated more
easily than gangue.
Roasting (or) calcination converts an ore into metal oxide and makes it porous. The
metal oxide is porous because the volatile impurities are expelled and the moisture is
removed during roasting (or) calcination.
The metal oxide is reduced to metal by using a suitable reducing agent.
Ex: When carbon is used as the reducing agent, it combines with the oxygen of the metal
oxide to give metal and carbon monoxide (or) carbon dioxide.

Reduction
MO + C → M + CO ↑
Carbon Monoxide

Carbon is used to reduce zinc oxide to metallic zinc. In this reaction, carbon monoxide is
released.
Reduction
ZnO + C → Zn + CO ↑
Zinc Oxide Carbon Carbon Monoxide
Generally, heating is required for a metal oxide to be reduced to its metal.

Thermodynamic principles of
metallurgy
Thermodynamic principles can be applied to the ore extraction process.
The Gibbs energy equation that relates to the enthalpy and entropy of the system at a
certain temperature.
ΔG = ΔH - TΔS
ΔG = Gibbs Free Energy Change
ΔH = Change in Enthalpy
T = Temperature
ΔS = Change in Entropy

Spontaneous Process → ΔG = -ve

Non-Spontaneous Process → ΔG = +ve
According to Gibbs energy free energy can be utilized to do useful work. The term ∆H
represents the enthalpy change and ∆S is the change in entropy at temperature T.
Relation between free energy change and equilibrium constant,

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 ΔG = -RTlnK
The equilibrium constant K is obtained by taking the ratio of equilibrium concentrations
of reactants and products.
When a reaction proceeds from reactants to products, products are present in excess and
equilibrium constant is positive. Alternatively, the equilibrium constant is negative for a
reverse reaction.
For ∆G to be negative, the change in entropy should be positive and on increasing the
temperature, the value T∆S should exceed the enthalpy change for the reaction.
A reaction with a positive ∆G can also occur, if it is coupled with another reaction that
has a large negative ∆G value, so that the net value of ∆G would still be negative.
Ellingham diagrams are used as a tool in extraction of a metal in metallurgy to find the
appropriate conditions for reduction of ores of important metals.
In the reaction between metal oxide and carbon, carbon is the reducing agent, itself
undergoes oxidation to reduce the element.
Carbon may undergo a partial oxidation, it takes up only half mole of oxygen to form
carbon monoxide (or) it may undergo complete oxidation, takes up 1mole of oxygen to
form carbon dioxide.
MxO + C → xM + CO
MxO + C → xM + CO2
MxO + ½C → xM + ½CO2
It is a redox reaction. Redox reaction is one where oxidation and reduction take place. In
this reaction the metal oxide is reduced and carbon and carbon monoxide will be oxidized.
Heating favors a negative value for ∆G. Hence the temperature is chosen such that the
sum of ∆G in the two combined redox process is negative

Ellingham diagram
Thermodynamics useful to understand the variation in temperature required for the
thermal reduction of oxides and to predict which element will suit as the reducing agent
for a given metal oxide. The Gibbs energy is the most important thermodynamic term in
metal extraction.

For a spontaneous reaction the change in the Gibbs energy, ∆G, must be negative. ∆G
for any process at a given temperature is given by the equation
∆G = ∆H- T∆S
Where, ∆H = enthalpy
change T = absolute
temperature
∆S = change in entropy during the reaction.
The change in the Gibbs energy when 1gram molecule of oxygen, Sulphur (or) halogen
is used to form oxides, sulphides (or) halides of metals plotted against temperature. This
graphical representation is called an Ellingham diagram.
These plots are useful to determine the relative ease of reducing a given metal oxide to
the metal and also to predict the feasibility of the thermal reduction of an ore.

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An Ellingham diagram normally consists of plots of change in the Gibbs energy with
temperature for the formation of oxides. An Ellingham diagram for oxides has
several important features.
(i) The graphs for most metal to metal oxide reactions show a positive slope.
Ex: 2M + O2 →2MO.
In this reaction, the entropy (or) randomness decreases from left to right due to the
consumption of gases. Hence, ∆S becomes negative. If the temperature is raised, then T
∆S becomes more negative. So, ∆G becomes less negative.
(ii) The Gibbs energy changes follow a straight line, unless the materials melt (or)
vaporise. The temperature at which such a change occurs is indicated by an increase
in the slope on the positive side.
(iii) When the temperature is raised, a point will be reached where the graph crosses
the line "∆G is zero." Below this temperature, the free energy of formation of the oxide
is negative, so the oxide is stable. Above this temperature, the free energy of formation
of the oxide is positive the oxide becomes unstable and will decompose into the metal
and dioxygen.
Any metal will reduce an oxide of another metal that lies above it in an Ellingham diagram.
Ex: Al reduces FeO, CrO and NiO in termite reaction but Al will not reduce MgO at a
temperature below 1500 0C.

Limitations:
The reactants and products are in equilibrium, which is not often
true. It does not explain about the rate of the reaction

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Electrochemical Principles of
Metallurgy
The principles of metallurgy are effective in the reduction of metal ions to their respective
metals in their solution (or) molten states. The reduction is carried out through electrolysis
(or) using reducing elements. Such methods are based on electrochemical principles.

Mn+ + A → M + An+
Metal ion reducing Element Metal Reduced ion
These electrochemical principles are explained in
ΔG° = -nE°F
n = Number of Electrons Gained
E° = Electrode Potential of Redox Couple
The value of E0 for a metal depends on its reactivity. Thus, it differs from metal to metal.
More reactive metals have high E0, whereas less reactive metals have low E0. It is difficult
to reduce metals that have high E0.
If the difference between the E0 values of two metals is positive, then the value of ∆G0
will be negative.
Hence, the less reactive metal will come out of the solution and the more reactive metal
will go into the solution.
An+ + B → A + Bn+
Less Metal ion More reducing Element Less Reactive Metal More Reduced
ion Ex: The reduction of copper (II) to copper in the presence of iron.
Cun+ + Fe → Cu + Fen+
Copper(II) ion Iron Copper Iron(II) ion
In a simple electrolysis process, the positive ions always move towards the negative
electrode called the cathode.
Precautions to be taken:
• · Consider the reactivity of the metal produced in the electrolysis.
• · Use suitable material as the electrodes.
• · Sometimes flux is needed to increase the conductivity of the molten mass.

Metallurgy of aluminium:

Addition of cryolite and fluorspar as flux to aluminium oxide because pure aluminium
oxide is a bad conductor of heat and electricity. The fused substance is used as the
electrolyte.

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During this process, the electrolyte is taken in a steel container lined with carbon, which
acts as the cathode. A bunch of graphite rods immersed in the electrolyte act as the
anode. This process is also known as the Hall-Heroult process. When current is passed,
all the Al+3 ions move towards the cathode. Oxygen is liberated at the anode, which reacts
with the carbon atoms of the anode to form carbon monoxide and carbon dioxide.

Cathode: Al3+ + 3e- → Al(l)

Anode: C(s) + O2- → CO(g) + 2e-

C(s) + 2O2- → CO2(g) + 4e-
Generally, copper is extracted from its low concentrated ores by a process known as
"hydrometallurgy". In this process, a solution containing Cu+2 ions is treated with a scrap
of iron or hydrogen.
Cu+2 + Fe → Cu + Fe+2
Copper(II) ion Iron Copper Ferrous(II) ion
Cu+2 + H2 → Cu + 2H+
Copper(II) ion Hydrogen Copper Hydrogen ion

Oxidation reduction
Oxidation and reduction are two types of chemical reactions that often work together.
Oxidation and reduction reactions involve an exchange of electrons between reactants.
For many students, the confusion occurs when attempting to identify which reactant was
oxidized and which reactant was reduced.

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Refining
A metal extracted by any method is usually contaminated with some impurity. For
obtaining metals of high purity, several techniques are used depending upon the
differences in the properties of the metal and the impurity. Some of them listed below,

A, Distillation

B, Liquation

C, Electrolysis

D, Zone refining

E, Vapour phase refining

F, chromatographic methods

A, Distillation
Distillation is a process of separating the component substances from a liquid mixture by
selective evaporation and condensation. Distillation may result in essentially complete
separation (nearly pure components), or it may be a partial separation that increases the
concentration of selected components of the mixture. In either case the process exploits
differences in the volatility of mixture's components. In industrial chemistry, distillation
is a unit operation of practically universal importance, but it is a physical separation
process and not a chemical reaction.
Commercially, distillation has many applications. For example:

• In the fossil fuel industry distillation is a major class of operation in obtaining materials
from crude oil for fuels and for chemical feedstocks.
• Distillation permits separation of air into its components — notably oxygen, nitrogen,
and argon — for industrial use.
• In the field of industrial chemistry, large ranges of crude liquid products of chemical
synthesis are distilled to separate them, either from other products, or from
impurities, or from unreacted starting materials.
• Distillation of fermented products produces distilled beverages with a high alcohol
content, or separates out other fermentation products of commercial value.

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B, Liquation
Liquation is a metallurgical method for separating metals from an ore or alloy. The
material must be heated until one of the metals starts to melt and drain away from the
other and can be collected. This method was largely used to remove lead containing silver
from copper, but it can also be used to remove antimony minerals from ore, and refine
tin

C, Electrolytic refining
The purest copper is obtained by an electrolytic process, undertaken using a slab of
impure copper as the anode and a thin sheet of pure copper as the cathode. The
electrolyte is an acidic solution of copper sulphate. By passing electricity through the cell,
copper is dissolved from the anode and deposited on the cathode. However, impurities
either remain in solution or collect as an insoluble sludge. This process only became
possible following the invention of the dynamo; it was first used in South Wales in 1869.

In this method, the impure metal is made to act as anode. A strip of the same metal in
pure form is used as cathode. They are put in a suitable electrolytic bath containing
soluble salt of the same metal. The more basic metal remains in the solution and the less
basic ones go to the anode mud. This process is also explained using the concept of
electrode potential, over potential, and Gibbs energy which you have seen in previous
sections. The reactions are:
Anode: M →Mn++ ne–

Cathode: Mn++ ne– →M

Copper is refined using an electrolytic method. Anodes are of impure copper and pure
copper strips are taken as cathode. The electrolyte is acidified solution of copper sulphate
and the net result of electrolysis is the transfer of copper in pure form from the anode to
the cathode:
Anode: Cu →Cu2+ + 2 e–
Cathode: Cu2+ + 2e– →Cu
Impurities from the blister copper deposit as anode mud which contains antimony,
selenium, tellurium, silver, gold and platinum; recovery of these elements may meet the
cost of refining. Zinc may also be refined this way.

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D, Zone refining
This method is based on the principle that the impurities are more soluble in the melt
than in the solid state of the metal. A circular mobile heater is fixed at one end of a rod
of the impure metal .The molten zone moves along with the heater which is moved
forward. As the heater moves forward, the pure metal crystallises out of the melt and the
impurities pass on into the adjacent molten zone. The process is repeated several times
and the heater is moved in the same direction. At one end, impurities get concentrated.
This end is cut off. This method is very useful for producing semiconductor and other
metals of very high purity, e.g., germanium, silicon, boron, gallium and indium.

E, Vapour phase refining

In this method, the metal is converted into its volatile compound and collected elsewhere.
It is then decomposed to give pure metal. So, the two requirements are:

(i) the metal should form a volatile compound with an available reagent,
(ii) the volatile compound should be easily decomposable, so that the recovery is easy.
Following examples will illustrate this technique.

Mond Process for Refining Nickel: In this process, nickel is heated in a stream of
carbon monoxide forming a volatile complex, nickel tetracarbonyl: Ni + 4CO 330 – 350
K -------- Ni(CO)4
The carbonyl is subjected to higher temperature so that it is decomposed giving the pure
metal:
Ni(CO)4 450 – 470 K--------------- Ni + 4CO
Van Arkel Method for Refining Zirconium or Titanium: This method is very useful
for removing all the oxygen and nitrogen present in the form of impurity in certain metals
like Zr and Ti. The crude metal is heated in an evacuated vessel with iodine. The metal
iodide being more covalent, volatilises:
Zr + 2I2------->ZrI4
The metal iodide is decomposed on a tungsten filament, electrically heated to about
1800K. The pure metal is thus deposited on the filament.
ZrI4 -------> Zr + 2I2

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F, Chromatographic methods
Chromatography which means "color" and is the collective term for a set of laboratory
techniques for the separation of mixtures. The mixture is dissolved in a fluid called the
mobile phase, which carries it through a structure holding another material called the
stationary phase. The various constituents of the mixture travel at different speeds,
causing them to separate. The separation is based on differential partitioning between
the mobile and stationary phases. Subtle differences in a compound's partition coefficient
result in differential retention on the stationary phase and thus changing the separation.
Chromatography may be preparative or analytical. The purpose of preparative
chromatography is to separate the components of a mixture for more advanced use (and
is thus a form of purification). Analytical chromatography is done normally with smaller
amounts of material and is for measuring the relative proportions of analytes in a mixture.
The two are not mutually exclusive

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