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Class XII

Chapter 6 – General Principles and Processes of Isolation of Elements
Chemistry

Question 6.1:
Copper can be extracted by hydrometallurgy but not zinc. Explain.
Answer
The reduction potentials of zinc and iron are lower than that of copper. In
hydrometallurgy, zinc and iron can be used to displace copper from their solution.

But to displace zinc, more reactive metals i.e., metals having lower reduction potentials
than zinc such as Mg, Ca, K, etc. are required. But all these metals react with water with
the evolution of H2 gas.

As a result, these metals cannot be used in hydrometallurgy to extract zinc.
Hence, copper can be extracted by hydrometallurgy but not zinc.

Question 6.2:
What is the role of depressant in froth floatation process?
Answer
In the froth floatation process, the role of the depressants is to separate two sulphide
ores by selectively preventing one ore from forming froth. For example, to separate two
sulphide ores (ZnS and Pbs), NaCN is used as a depressant which selectively allows PbS
to come with froth, but prevents ZnS from coming to froth. This happens because NaCN
reacts with ZnS to form Na2[Zn(CN)4].

Question 6.3:
Why is the extraction of copper from pyrites more difficult than that from its
oxide ore through reduction?
Answer
The Gibbs free energy of formation (∆fG) of Cu2S is less than that of

and

.

Therefore, H2 and C cannot reduce Cu2S to Cu.

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Chapter 6 – General Principles and Processes of Isolation of Elements
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On the other hand, the Gibbs free energy of formation of

is greater than that of

. Hence, C can reduce Cu2O to Cu.

Hence, the extraction of copper from its pyrite ore is difficult than from its oxide ore
through reduction.

Question 6.4:
Explain: (i) Zone refining (ii) Column chromatography.
Answer
(i) Zone refining:
This method is based on the principle that impurities are more soluble in the molten
state of metal (the melt) than in the solid state. In the process of zone refining, a
circular mobile heater is fixed at one end of a rod of impure metal. As the heater moves,
the molten zone of the rod also moves with it. As a result, pure metal crystallizes out of
the melt and the impurities pass onto the adjacent molten zone. This process is repeated
several times, which leads to the segregation of impurities at one end of the rod. Then,
the end with the impurities is cut off. Silicon, boron, gallium, indium etc. can be purified
by this process.

(ii) Column chromatography:
Column chromatography is a technique used to separate different components of a
mixture. It is a very useful technique used for the purification of elements available in
minute quantities. It is also used to remove the impurities that are not very different in
chemical properties from the element to be purified. Chromatography is based on the
principle that different components of a mixture are differently adsorbed on an
adsorbent. In chromatography, there are two phases: mobile phase and stationary
phase. The stationary phase is immobile and immiscible. Al2O3 column is usually used as
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Chapter 6 – General Principles and Processes of Isolation of Elements
Chemistry

the stationary phase in column chromatography. The mobile phase may be a gas, liquid,
or supercritical fluid in which the sample extract is dissolved. Then, the mobile phase is
forced to move through the stationary phase. The component that is more strongly
adsorbed on the column takes a longer time to travel through it than the component that
is weakly adsorbed. The adsorbed components are then removed (eluted) using a
suitable solvent (eluant).

Question 6.5:
Out of C and CO, which is a better reducing agent at 673 K?
Answer
At 673 K, the value of

is less than that of

. Therefore, CO can be

reduced more easily to CO2 than C to CO. Hence, CO is a better reducing agent than C at
673 K.

Question 6.6:
Name the common elements present in the anode mud in electrolytic refining
of copper. Why are they so present ?
Answer
In electrolytic refining of copper, the common elements present in anode mud are
selenium, tellurium, silver, gold, platinum, and antimony.

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Chapter 6 – General Principles and Processes of Isolation of Elements
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These elements are very less reactive and are not affected during the purification
process. Hence, they settle down below the anode as anode mud.

Question 6.7:
Write down the reactions taking place in different zones in the blast furnace
during the extraction of iron.
Answer
During the extraction of iron, the reduction of iron oxides takes place in the blast
furnace. In this process, hot air is blown from the bottom of the furnace and coke is
burnt to raise the temperature up to 2200 K in the lower portion itself. The temperature
is lower in the upper part. Thus, it is the lower part where the reduction of iron oxides
(Fe2O3 and Fe3O4) takes place.
The reactions taking place in the lower temperature range (500 − 800 K) in the blast
furnace are:

The reactions taking place in the higher temperature range (900 − 1500 K) in the blast
furnace are:

The silicate impurity of the ore is removed as slag by calcium oxide (CaO), which is
formed by the decomposition of limestone (CaCO3).

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Chapter 6 – General Principles and Processes of Isolation of Elements
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Question 6.8:
Write chemical reactions taking place in the extraction of zinc from zinc blende.
Answer
The different steps involved in the extraction of zinc from zinc blende (ZnS) are given
below:
(i) Concentration of ore
First, the gangue from zinc blende is removed by the froth floatation method.

(ii) Conversion to oxide (Roasting)
Sulphide ore is converted into oxide by the process of roasting. In this process, ZnS is
heated in a regular supply of air in a furnace at a temperature, which is below the
melting point of Zn.

(iii) Extraction of zinc from zinc oxide (Reduction)
Zinc is extracted from zinc oxide by the process of reduction. The reduction of zinc oxide
is carried out by mixing it with powdered coke and then, heating it at 673 K.

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Chapter 6 – General Principles and Processes of Isolation of Elements
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(iv) Electrolytic Refining
Zinc can be refined by the process of electrolytic refining. In this process, impure zinc is
made the anode while a pure copper strip is made the cathode. The electrolyte used is
an acidified solution of zinc sulphate (ZnSO4). Electrolysis results in the transfer of zinc
in pure from the anode to the cathode.

Question 6.9:
State the role of silica in the metallurgy of copper.
Answer
During the roasting of pyrite ore, a mixture of FeO and Cu2O is obtained.

The role of silica in the metallurgy of copper is to remove the iron oxide obtained during
the process of roasting as ‘slag’. If the sulphide ore of copper contains iron, then silica
(SiO2) is added as flux before roasting. Then, FeO combines with silica to form iron
silicate, FeSiO3 (slag).

Question 6.10:
What is meant by the term “chromatography”?
Answer
Chromatography is a collective term used for a family of laboratory techniques for the
separation of mixtures. The term is derived from Greek words ‘chroma’ meaning ‘colour’
and ‘graphein’ meaning ‘to write’. Chromatographic techniques are based on the
principle that different components are absorbed differently on an absorbent. There are

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Chapter 6 – General Principles and Processes of Isolation of Elements
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several

chromatographic

techniques

such

as

paper

chromatography,

column

chromatography, gas chromatography, etc.

Question 6.11:
What criterion is followed for the selection of the stationary phase in
chromatography?
Answer
The stationary phase is selected in such a way that the components of the sample have
different solubility’s in the phase. Hence, different components have different rates of
movement through the stationary phase and as a result, can be separated from each
other.

Question 6.12:
Describe a method for refining nickel.
Answer
Nickel is refined by Mond’s process. In this process, nickel is heated in the presence of
carbon monoxide to form nickel tetracarbonyl, which is a volatile complex.

Then, the obtained nickel tetracarbonyl is decomposed by subjecting it to a higher
temperature (450 − 470 K) to obtain pure nickel metal.

Question 6.13:
How can you separate alumina from silica in bauxite ore associated with
silica? Give equations, if any.
Answer
To separate alumina from silica in bauxite ore associated with silica, first the powdered
ore is digested with a concentrated NaOH solution at 473 − 523 K and 35 − 36 bar

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Chapter 6 – General Principles and Processes of Isolation of Elements
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pressure. This results in the leaching out of alumina (Al2O3) as sodium aluminate and
silica (SiO2) as sodium silicate leaving the impurities behind.

Then, CO2 gas is passed through the resulting solution to neutralize the aluminate in the
solution, which results in the precipitation of hydrated alumina. To induce precipitation,
the solution is seeded with freshly prepared samples of hydrated alumina.

During this process, sodium silicate remains in the solution. The obtained hydrated
alumina is filtered, dried, and heated to get back pure alumina.

Question 6.14:
Giving examples, differentiate between ‘roasting’ and ‘calcination’.
Answer
Roasting is the process of converting sulphide ores to oxides by heating the ores in a
regular supply of air at a temperature below the melting point of the metal. For example,
sulphide ores of Zn, Pb, and Cu are converted to their respective oxides by this process.

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On the other hand, calcination is the process of converting hydroxide and carbonate ores
to oxides by heating the ores either in the absence or in a limited supply of air at a
temperature below the melting point of the metal. This process causes the escaping of
volatile matter leaving behind the metal oxide. For example, hydroxide of Fe, carbonates
of Zn, Ca, Mg are converted to their respective oxides by this process.

Question 6.15:
How is ‘cast iron’ different from ‘pig iron”?
Answer
The iron obtained from blast furnaces is known as pig iron. It contains around 4%
carbon and many impurities such as S, P, Si, Mn in smaller amounts.
Cast iron is obtained by melting pig iron and coke using a hot air blast. It contains a
lower amount of carbon (3%) than pig iron. Unlike pig iron, cast iron is extremely hard
and brittle.

Question 6.16:
Differentiate between “minerals” and “ores”.
Answer
Minerals are naturally occurring chemical substances containing metals. They are found
in the Earth’s crust and are obtained by mining.
Ores are rocks and minerals viable to be used as a source of metal.
For example, there are many minerals containing zinc, but zinc cannot be extracted
profitably (conveniently and economically) from all these minerals.
Zinc can be obtained from zinc blende (ZnS), calamine (ZnCO3), Zincite (ZnO) etc.
Thus, these minerals are called ores of zinc.

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Chapter 6 – General Principles and Processes of Isolation of Elements
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Question 6.17:
Why copper matte is put in silica lined converter?
Answer
Copper matte contains Cu2S and FeS. Copper matte is put in a silica-lined converter to
remove the remaining FeO and FeS present in the matte as slag (FeSiO3). Also, some
silica is added to the silica-lined converter. Then, a hot air blast is blown. As a result, the
remaining FeS and FeO are converted to iron silicate (FeSiO3) and Cu2S is converted into
metallic copper.

Question 6.18:
What is the role of cryolite in the metallurgy of aluminium?
Answer
Cryolite (Na3AlF6) has two roles in the metallurgy of aluminium:
1. To decrease the melting point of the mixture from 2323 K to 1140 K.
2. To increase the electrical conductivity of Al2O3.

Question 6.19:
How is leaching carried out in case of low grade copper ores?
Answer
In case of low grade copper ores, leaching is carried out using acid or bacteria in the
presence of air. In this process, copper goes into the solution as Cu2+ ions.

The resulting solution is treated with scrap iron or H2 to get metallic copper.

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Question 6.20:
Why is zinc not extracted from zinc oxide through reduction using CO?
Answer
The standard Gibbs free energy of formation of ZnO from Zn
is lower than that of CO2 from CO. Therefore, CO cannot reduce ZnO to Zn. Hence, Zn is
not extracted from ZnO through reduction using CO.

Question 6.21:
for formation of Cr2O3 is − 540 kJmol−1 and that of Al2 O3 is − 827

The value of

kJmol−1. Is the reduction of Cr2O3 possible with Al?
Answer
for the formation of Cr2O3 from Cr (−540 kJmol−1) is higher than that of

The value of

Al2O3 from Al (−827 kJmol−1). Therefore, Al can reduce Cr2O3 to Cr. Hence, the reduction
of Cr2O3 with Al is possible.
Alternatively,

Subtracting equation (ii) from (i), we have

As

for the reduction reaction of Cr2O3 by Al is negative, this reaction is possible.

Question 6.22:
Out of C and CO, which is a better reducing agent for ZnO ?
Answer

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Reduction of ZnO to Zn is usually carried out at 1673 K. From the above figure, it can be
observed that above 1073 K, the Gibbs free energy of formation of CO from C and above
1273 K, the Gibbs free energy of formation of CO2 from C is lesser than the Gibbs free
energy of formation of ZnO. Therefore, C can easily reduce ZnO to Zn.
On the other hand, the Gibbs free energy of formation of CO2 from CO is always higher
than the Gibbs free energy of formation of ZnO. Therefore, CO cannot reduce ZnO.
Hence, C is a better reducing agent than CO for reducing ZnO.

Question 6.23:
The choice of a reducing agent in a particular case depends on
thermodynamic factor. How far do you agree with this statement? Support
your opinion with two examples.
Answer

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The above figure is a plot of Gibbs energy

vs. T for formation of some oxides.

It can be observed from the above graph that a metal can reduce the oxide of other
metals, if the standard free energy of formation

of the oxide of the former is more

negative than the latter. For example, since

is more negative than

, Al can reduce Cu2O to Cu, but Cu cannot reduce Al2O3. Similarly, Mg can
reduce ZnO to Zn, but Zn cannot reduce MgO because

is more negative than

.

Question 6.24:
Name the processes from which chlorine is obtained as a by-product. What
will happen if an aqueous solution of NaCl is subjected to electrolysis?
Answer
In the electrolysis of molten NaCl, Cl2 is obtained at the anode as a by product.

At cathode:
At anode:

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The overall reaction is as follows:

If an aqueous solution of NaCl is electrolyzed, Cl2 will be obtained at the anode but at
the cathode, H2 will be obtained (instead of Na). This is because the standard reduction
potential of Na (E°= − 2.71 V) is more negative than that of H2O (E° = − 0.83 V).
Hence, H2O will get preference to get reduced at the cathode and as a result, H2 is
evolved.

At cathode:
At anode:

Question 6.25:
What is the role of graphite rod in the electrometallurgy of aluminium?
Answer
In the electrometallurgy of aluminium, a fused mixture of purified alumina (Al2O3),
cryolite (Na3AlF6) and fluorspar (CaF2) is electrolysed. In this electrolysis, graphite is
used as the anode and graphite-lined iron is used as the cathode. During the electrolysis,
Al is liberated at the cathode, while CO and CO2 are liberated at the anode, according to
the following equation.

If a metal is used instead of graphite as the anode, then O2 will be liberated. This will not
only oxidise the metal of the electrode, but also convert some of the Al liberated at the
cathode back into Al2O3. Hence, graphite is used for preventing the formation of O2 at
the anode. Moreover, graphite is cheaper than other metals.

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Chapter 6 – General Principles and Processes of Isolation of Elements
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Question 6.27:
Outline the principles of refining of metals by the following methods:
(i) Zone refining
(ii) Electrolytic refining
(iii) Vapour phase refining
Answer
(i) Zone refining:
This method is based on the principle that impurities are more soluble in the molten
state of metal (the melt) than in the solid state. In the process of zone refining, a
circular mobile heater is fixed at one end of a rod of impure metal. As the heater moves,
the molten zone of the rod also moves along with it. As a result, pure metal crystallizes
out of the melt and the impurities pass to the adjacent molten zone. This process is
repeated several times, which leads to the segregation of impurities at one end of the
rod. Then, the end with the impurities is cut off. Silicon, boron, gallium, indium etc. can
be purified by this process.

(ii) Electrolytic refining;
Electrolytic refining is the process of refining impure metals by using electricity. In this
process, impure metal is made the anode and a strip of pure metal is made the cathode.
A solution of a soluble salt of the same metal is taken as the electrolyte. When an
electric current is passed, metal ions from the electrolyte are deposited at the cathode as
pure metal and the impure metal from the anode dissolves into the electrolyte in the
form of ions. The impurities present in the impure metal gets collected below the anode.
This is known as anode mud.

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(iii) Vapour phase refining
Vapour phase refining is the process of refining metal by converting it into its volatile
compound and then, decomposing it to obtain a pure metal. To carry out this process,
(i) the metal should form a volatile compound with an available reagent, and
(ii) the volatile compound should be easily decomposable so that the metal can be easily
recovered.
Nickel, zirconium, and titanium are refined using this method.

Question 6.28:
Predict conditions under which Al might be expected to reduce MgO.
Answer
Above 1350°C, the standard Gibbs free energy of formation of Al2O3 from Al is less than
that of MgO from Mg. Therefore, above 1350°C, Al can reduce MgO.

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Text solution

Question 6.1:
Which of the ores mentioned in Table 6.1 can be concentrated by magnetic separation
method?
Answer
If the ore or the gangue can be attracted by the magnetic field, then the ore can be
concentrated by the process of magnetic separation. Among the ores mentioned in table
6.1, the ores of iron such as haematite (Fe2O3), magnetite (Fe3O4), siderite (FeCO3), and
iron pyrites (FeS2) can be separated by the process of magnetic separation.

Question 6.2:
What is the significance of leaching in the extraction of aluminium?
Answer
In the extraction of aluminium, the significance of leaching is to concentrate pure
alumina (Al2O3) from bauxite ore.
Bauxite usually contains silica, iron oxide, and titanium oxide as impurities. In the
process of leaching, alumina is concentrated by digesting the powdered ore with a
concentrated solution of NaOH at 473-523 K and 35-36 bar. Under these conditions,
alumina (Al2O3) dissolves as sodium meta-aluminate and silica (SiO2) dissolves as
sodium silicate leaving the impurities behind.

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The impurities are then filtered and the solution is neutralized by passing CO2 gas. In
this process, hydrated Al2O3 gets precipitated and sodium silicate remains in the
solution. Precipitation is induced by seeding the solution with freshly prepared samples
of hydrated Al2O3.

Hydrated alumina thus obtained is filtered, dried, and heated to give back pure alumina
(Al2O3).

Question 6.3:
The reaction,

is thermodynamically feasible as is apparent from the Gibbs energy value.
Why does it not take place at room temperature?
Answer
The change in Gibbs energy is related to the equilibrium constant, K as
.
At room temperature, all reactants and products of the given reaction are in the solid
state. As a result, equilibrium does not exist between the reactants and the products.
Hence, the reaction does not take place at room temperature. However, at a higher
temperature, chromium melts and the reaction takes place.
We also know that according to the equation

Increasing the temperature increases the value of

making the value of

more

and more negative. Therefore, the reaction becomes more and more feasible as the
temperature is increased.

Question 6.4:

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Is it true that under certain conditions, Mg can reduce SiO2 and Si can reduce MgO?
What are those conditions?
Answer

The temperature range in which
to

is lesser than

, Mg can reduce SiO2

Si.

On the other hand, the temperatures range in which

is less than

, Si

can reduce MgO to Mg.

The temperature at which ∆fG curves of these two substances intersect is 1966 K. Thus,
at temperatures less than 1966 K, Mg can reduce SiO2 and above 1966 K, Si can reduce
MgO.

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Chapter 6 general principles and processes of isolation of elements

  • 1. Class XII Chapter 6 – General Principles and Processes of Isolation of Elements Chemistry Question 6.1: Copper can be extracted by hydrometallurgy but not zinc. Explain. Answer The reduction potentials of zinc and iron are lower than that of copper. In hydrometallurgy, zinc and iron can be used to displace copper from their solution. But to displace zinc, more reactive metals i.e., metals having lower reduction potentials than zinc such as Mg, Ca, K, etc. are required. But all these metals react with water with the evolution of H2 gas. As a result, these metals cannot be used in hydrometallurgy to extract zinc. Hence, copper can be extracted by hydrometallurgy but not zinc. Question 6.2: What is the role of depressant in froth floatation process? Answer In the froth floatation process, the role of the depressants is to separate two sulphide ores by selectively preventing one ore from forming froth. For example, to separate two sulphide ores (ZnS and Pbs), NaCN is used as a depressant which selectively allows PbS to come with froth, but prevents ZnS from coming to froth. This happens because NaCN reacts with ZnS to form Na2[Zn(CN)4]. Question 6.3: Why is the extraction of copper from pyrites more difficult than that from its oxide ore through reduction? Answer The Gibbs free energy of formation (∆fG) of Cu2S is less than that of and . Therefore, H2 and C cannot reduce Cu2S to Cu. Page 1 of 20 Website: www.vidhyarjan.com Email: contact@vidhyarjan.com Mobile: 9999 249717 Head Office: 1/3-H-A-2, Street # 6, East Azad Nagar, Delhi-110051 (One Km from ‘Welcome’ Metro Station)
  • 2. Class XII Chapter 6 – General Principles and Processes of Isolation of Elements Chemistry On the other hand, the Gibbs free energy of formation of is greater than that of . Hence, C can reduce Cu2O to Cu. Hence, the extraction of copper from its pyrite ore is difficult than from its oxide ore through reduction. Question 6.4: Explain: (i) Zone refining (ii) Column chromatography. Answer (i) Zone refining: This method is based on the principle that impurities are more soluble in the molten state of metal (the melt) than in the solid state. In the process of zone refining, a circular mobile heater is fixed at one end of a rod of impure metal. As the heater moves, the molten zone of the rod also moves with it. As a result, pure metal crystallizes out of the melt and the impurities pass onto the adjacent molten zone. This process is repeated several times, which leads to the segregation of impurities at one end of the rod. Then, the end with the impurities is cut off. Silicon, boron, gallium, indium etc. can be purified by this process. (ii) Column chromatography: Column chromatography is a technique used to separate different components of a mixture. It is a very useful technique used for the purification of elements available in minute quantities. It is also used to remove the impurities that are not very different in chemical properties from the element to be purified. Chromatography is based on the principle that different components of a mixture are differently adsorbed on an adsorbent. In chromatography, there are two phases: mobile phase and stationary phase. The stationary phase is immobile and immiscible. Al2O3 column is usually used as Page 2 of 20 Website: www.vidhyarjan.com Email: contact@vidhyarjan.com Mobile: 9999 249717 Head Office: 1/3-H-A-2, Street # 6, East Azad Nagar, Delhi-110051 (One Km from ‘Welcome’ Metro Station)
  • 3. Class XII Chapter 6 – General Principles and Processes of Isolation of Elements Chemistry the stationary phase in column chromatography. The mobile phase may be a gas, liquid, or supercritical fluid in which the sample extract is dissolved. Then, the mobile phase is forced to move through the stationary phase. The component that is more strongly adsorbed on the column takes a longer time to travel through it than the component that is weakly adsorbed. The adsorbed components are then removed (eluted) using a suitable solvent (eluant). Question 6.5: Out of C and CO, which is a better reducing agent at 673 K? Answer At 673 K, the value of is less than that of . Therefore, CO can be reduced more easily to CO2 than C to CO. Hence, CO is a better reducing agent than C at 673 K. Question 6.6: Name the common elements present in the anode mud in electrolytic refining of copper. Why are they so present ? Answer In electrolytic refining of copper, the common elements present in anode mud are selenium, tellurium, silver, gold, platinum, and antimony. Page 3 of 20 Website: www.vidhyarjan.com Email: contact@vidhyarjan.com Mobile: 9999 249717 Head Office: 1/3-H-A-2, Street # 6, East Azad Nagar, Delhi-110051 (One Km from ‘Welcome’ Metro Station)
  • 4. Class XII Chapter 6 – General Principles and Processes of Isolation of Elements Chemistry These elements are very less reactive and are not affected during the purification process. Hence, they settle down below the anode as anode mud. Question 6.7: Write down the reactions taking place in different zones in the blast furnace during the extraction of iron. Answer During the extraction of iron, the reduction of iron oxides takes place in the blast furnace. In this process, hot air is blown from the bottom of the furnace and coke is burnt to raise the temperature up to 2200 K in the lower portion itself. The temperature is lower in the upper part. Thus, it is the lower part where the reduction of iron oxides (Fe2O3 and Fe3O4) takes place. The reactions taking place in the lower temperature range (500 − 800 K) in the blast furnace are: The reactions taking place in the higher temperature range (900 − 1500 K) in the blast furnace are: The silicate impurity of the ore is removed as slag by calcium oxide (CaO), which is formed by the decomposition of limestone (CaCO3). Page 4 of 20 Website: www.vidhyarjan.com Email: contact@vidhyarjan.com Mobile: 9999 249717 Head Office: 1/3-H-A-2, Street # 6, East Azad Nagar, Delhi-110051 (One Km from ‘Welcome’ Metro Station)
  • 5. Class XII Chapter 6 – General Principles and Processes of Isolation of Elements Chemistry Question 6.8: Write chemical reactions taking place in the extraction of zinc from zinc blende. Answer The different steps involved in the extraction of zinc from zinc blende (ZnS) are given below: (i) Concentration of ore First, the gangue from zinc blende is removed by the froth floatation method. (ii) Conversion to oxide (Roasting) Sulphide ore is converted into oxide by the process of roasting. In this process, ZnS is heated in a regular supply of air in a furnace at a temperature, which is below the melting point of Zn. (iii) Extraction of zinc from zinc oxide (Reduction) Zinc is extracted from zinc oxide by the process of reduction. The reduction of zinc oxide is carried out by mixing it with powdered coke and then, heating it at 673 K. Page 5 of 20 Website: www.vidhyarjan.com Email: contact@vidhyarjan.com Mobile: 9999 249717 Head Office: 1/3-H-A-2, Street # 6, East Azad Nagar, Delhi-110051 (One Km from ‘Welcome’ Metro Station)
  • 6. Class XII Chapter 6 – General Principles and Processes of Isolation of Elements Chemistry (iv) Electrolytic Refining Zinc can be refined by the process of electrolytic refining. In this process, impure zinc is made the anode while a pure copper strip is made the cathode. The electrolyte used is an acidified solution of zinc sulphate (ZnSO4). Electrolysis results in the transfer of zinc in pure from the anode to the cathode. Question 6.9: State the role of silica in the metallurgy of copper. Answer During the roasting of pyrite ore, a mixture of FeO and Cu2O is obtained. The role of silica in the metallurgy of copper is to remove the iron oxide obtained during the process of roasting as ‘slag’. If the sulphide ore of copper contains iron, then silica (SiO2) is added as flux before roasting. Then, FeO combines with silica to form iron silicate, FeSiO3 (slag). Question 6.10: What is meant by the term “chromatography”? Answer Chromatography is a collective term used for a family of laboratory techniques for the separation of mixtures. The term is derived from Greek words ‘chroma’ meaning ‘colour’ and ‘graphein’ meaning ‘to write’. Chromatographic techniques are based on the principle that different components are absorbed differently on an absorbent. There are Page 6 of 20 Website: www.vidhyarjan.com Email: contact@vidhyarjan.com Mobile: 9999 249717 Head Office: 1/3-H-A-2, Street # 6, East Azad Nagar, Delhi-110051 (One Km from ‘Welcome’ Metro Station)
  • 7. Class XII Chapter 6 – General Principles and Processes of Isolation of Elements Chemistry several chromatographic techniques such as paper chromatography, column chromatography, gas chromatography, etc. Question 6.11: What criterion is followed for the selection of the stationary phase in chromatography? Answer The stationary phase is selected in such a way that the components of the sample have different solubility’s in the phase. Hence, different components have different rates of movement through the stationary phase and as a result, can be separated from each other. Question 6.12: Describe a method for refining nickel. Answer Nickel is refined by Mond’s process. In this process, nickel is heated in the presence of carbon monoxide to form nickel tetracarbonyl, which is a volatile complex. Then, the obtained nickel tetracarbonyl is decomposed by subjecting it to a higher temperature (450 − 470 K) to obtain pure nickel metal. Question 6.13: How can you separate alumina from silica in bauxite ore associated with silica? Give equations, if any. Answer To separate alumina from silica in bauxite ore associated with silica, first the powdered ore is digested with a concentrated NaOH solution at 473 − 523 K and 35 − 36 bar Page 7 of 20 Website: www.vidhyarjan.com Email: contact@vidhyarjan.com Mobile: 9999 249717 Head Office: 1/3-H-A-2, Street # 6, East Azad Nagar, Delhi-110051 (One Km from ‘Welcome’ Metro Station)
  • 8. Class XII Chapter 6 – General Principles and Processes of Isolation of Elements Chemistry pressure. This results in the leaching out of alumina (Al2O3) as sodium aluminate and silica (SiO2) as sodium silicate leaving the impurities behind. Then, CO2 gas is passed through the resulting solution to neutralize the aluminate in the solution, which results in the precipitation of hydrated alumina. To induce precipitation, the solution is seeded with freshly prepared samples of hydrated alumina. During this process, sodium silicate remains in the solution. The obtained hydrated alumina is filtered, dried, and heated to get back pure alumina. Question 6.14: Giving examples, differentiate between ‘roasting’ and ‘calcination’. Answer Roasting is the process of converting sulphide ores to oxides by heating the ores in a regular supply of air at a temperature below the melting point of the metal. For example, sulphide ores of Zn, Pb, and Cu are converted to their respective oxides by this process. Page 8 of 20 Website: www.vidhyarjan.com Email: contact@vidhyarjan.com Mobile: 9999 249717 Head Office: 1/3-H-A-2, Street # 6, East Azad Nagar, Delhi-110051 (One Km from ‘Welcome’ Metro Station)
  • 9. Class XII Chapter 6 – General Principles and Processes of Isolation of Elements Chemistry On the other hand, calcination is the process of converting hydroxide and carbonate ores to oxides by heating the ores either in the absence or in a limited supply of air at a temperature below the melting point of the metal. This process causes the escaping of volatile matter leaving behind the metal oxide. For example, hydroxide of Fe, carbonates of Zn, Ca, Mg are converted to their respective oxides by this process. Question 6.15: How is ‘cast iron’ different from ‘pig iron”? Answer The iron obtained from blast furnaces is known as pig iron. It contains around 4% carbon and many impurities such as S, P, Si, Mn in smaller amounts. Cast iron is obtained by melting pig iron and coke using a hot air blast. It contains a lower amount of carbon (3%) than pig iron. Unlike pig iron, cast iron is extremely hard and brittle. Question 6.16: Differentiate between “minerals” and “ores”. Answer Minerals are naturally occurring chemical substances containing metals. They are found in the Earth’s crust and are obtained by mining. Ores are rocks and minerals viable to be used as a source of metal. For example, there are many minerals containing zinc, but zinc cannot be extracted profitably (conveniently and economically) from all these minerals. Zinc can be obtained from zinc blende (ZnS), calamine (ZnCO3), Zincite (ZnO) etc. Thus, these minerals are called ores of zinc. Page 9 of 20 Website: www.vidhyarjan.com Email: contact@vidhyarjan.com Mobile: 9999 249717 Head Office: 1/3-H-A-2, Street # 6, East Azad Nagar, Delhi-110051 (One Km from ‘Welcome’ Metro Station)
  • 10. Class XII Chapter 6 – General Principles and Processes of Isolation of Elements Chemistry Question 6.17: Why copper matte is put in silica lined converter? Answer Copper matte contains Cu2S and FeS. Copper matte is put in a silica-lined converter to remove the remaining FeO and FeS present in the matte as slag (FeSiO3). Also, some silica is added to the silica-lined converter. Then, a hot air blast is blown. As a result, the remaining FeS and FeO are converted to iron silicate (FeSiO3) and Cu2S is converted into metallic copper. Question 6.18: What is the role of cryolite in the metallurgy of aluminium? Answer Cryolite (Na3AlF6) has two roles in the metallurgy of aluminium: 1. To decrease the melting point of the mixture from 2323 K to 1140 K. 2. To increase the electrical conductivity of Al2O3. Question 6.19: How is leaching carried out in case of low grade copper ores? Answer In case of low grade copper ores, leaching is carried out using acid or bacteria in the presence of air. In this process, copper goes into the solution as Cu2+ ions. The resulting solution is treated with scrap iron or H2 to get metallic copper. Page 10 of 20 Website: www.vidhyarjan.com Email: contact@vidhyarjan.com Mobile: 9999 249717 Head Office: 1/3-H-A-2, Street # 6, East Azad Nagar, Delhi-110051 (One Km from ‘Welcome’ Metro Station)
  • 11. Class XII Chapter 6 – General Principles and Processes of Isolation of Elements Chemistry Question 6.20: Why is zinc not extracted from zinc oxide through reduction using CO? Answer The standard Gibbs free energy of formation of ZnO from Zn is lower than that of CO2 from CO. Therefore, CO cannot reduce ZnO to Zn. Hence, Zn is not extracted from ZnO through reduction using CO. Question 6.21: for formation of Cr2O3 is − 540 kJmol−1 and that of Al2 O3 is − 827 The value of kJmol−1. Is the reduction of Cr2O3 possible with Al? Answer for the formation of Cr2O3 from Cr (−540 kJmol−1) is higher than that of The value of Al2O3 from Al (−827 kJmol−1). Therefore, Al can reduce Cr2O3 to Cr. Hence, the reduction of Cr2O3 with Al is possible. Alternatively, Subtracting equation (ii) from (i), we have As for the reduction reaction of Cr2O3 by Al is negative, this reaction is possible. Question 6.22: Out of C and CO, which is a better reducing agent for ZnO ? Answer Page 11 of 20 Website: www.vidhyarjan.com Email: contact@vidhyarjan.com Mobile: 9999 249717 Head Office: 1/3-H-A-2, Street # 6, East Azad Nagar, Delhi-110051 (One Km from ‘Welcome’ Metro Station)
  • 12. Class XII Chapter 6 – General Principles and Processes of Isolation of Elements Chemistry Reduction of ZnO to Zn is usually carried out at 1673 K. From the above figure, it can be observed that above 1073 K, the Gibbs free energy of formation of CO from C and above 1273 K, the Gibbs free energy of formation of CO2 from C is lesser than the Gibbs free energy of formation of ZnO. Therefore, C can easily reduce ZnO to Zn. On the other hand, the Gibbs free energy of formation of CO2 from CO is always higher than the Gibbs free energy of formation of ZnO. Therefore, CO cannot reduce ZnO. Hence, C is a better reducing agent than CO for reducing ZnO. Question 6.23: The choice of a reducing agent in a particular case depends on thermodynamic factor. How far do you agree with this statement? Support your opinion with two examples. Answer Page 12 of 20 Website: www.vidhyarjan.com Email: contact@vidhyarjan.com Mobile: 9999 249717 Head Office: 1/3-H-A-2, Street # 6, East Azad Nagar, Delhi-110051 (One Km from ‘Welcome’ Metro Station)
  • 13. Class XII Chapter 6 – General Principles and Processes of Isolation of Elements Chemistry The above figure is a plot of Gibbs energy vs. T for formation of some oxides. It can be observed from the above graph that a metal can reduce the oxide of other metals, if the standard free energy of formation of the oxide of the former is more negative than the latter. For example, since is more negative than , Al can reduce Cu2O to Cu, but Cu cannot reduce Al2O3. Similarly, Mg can reduce ZnO to Zn, but Zn cannot reduce MgO because is more negative than . Question 6.24: Name the processes from which chlorine is obtained as a by-product. What will happen if an aqueous solution of NaCl is subjected to electrolysis? Answer In the electrolysis of molten NaCl, Cl2 is obtained at the anode as a by product. At cathode: At anode: Page 13 of 20 Website: www.vidhyarjan.com Email: contact@vidhyarjan.com Mobile: 9999 249717 Head Office: 1/3-H-A-2, Street # 6, East Azad Nagar, Delhi-110051 (One Km from ‘Welcome’ Metro Station)
  • 14. Class XII Chapter 6 – General Principles and Processes of Isolation of Elements Chemistry The overall reaction is as follows: If an aqueous solution of NaCl is electrolyzed, Cl2 will be obtained at the anode but at the cathode, H2 will be obtained (instead of Na). This is because the standard reduction potential of Na (E°= − 2.71 V) is more negative than that of H2O (E° = − 0.83 V). Hence, H2O will get preference to get reduced at the cathode and as a result, H2 is evolved. At cathode: At anode: Question 6.25: What is the role of graphite rod in the electrometallurgy of aluminium? Answer In the electrometallurgy of aluminium, a fused mixture of purified alumina (Al2O3), cryolite (Na3AlF6) and fluorspar (CaF2) is electrolysed. In this electrolysis, graphite is used as the anode and graphite-lined iron is used as the cathode. During the electrolysis, Al is liberated at the cathode, while CO and CO2 are liberated at the anode, according to the following equation. If a metal is used instead of graphite as the anode, then O2 will be liberated. This will not only oxidise the metal of the electrode, but also convert some of the Al liberated at the cathode back into Al2O3. Hence, graphite is used for preventing the formation of O2 at the anode. Moreover, graphite is cheaper than other metals. Page 14 of 20 Website: www.vidhyarjan.com Email: contact@vidhyarjan.com Mobile: 9999 249717 Head Office: 1/3-H-A-2, Street # 6, East Azad Nagar, Delhi-110051 (One Km from ‘Welcome’ Metro Station)
  • 15. Class XII Chapter 6 – General Principles and Processes of Isolation of Elements Chemistry Question 6.27: Outline the principles of refining of metals by the following methods: (i) Zone refining (ii) Electrolytic refining (iii) Vapour phase refining Answer (i) Zone refining: This method is based on the principle that impurities are more soluble in the molten state of metal (the melt) than in the solid state. In the process of zone refining, a circular mobile heater is fixed at one end of a rod of impure metal. As the heater moves, the molten zone of the rod also moves along with it. As a result, pure metal crystallizes out of the melt and the impurities pass to the adjacent molten zone. This process is repeated several times, which leads to the segregation of impurities at one end of the rod. Then, the end with the impurities is cut off. Silicon, boron, gallium, indium etc. can be purified by this process. (ii) Electrolytic refining; Electrolytic refining is the process of refining impure metals by using electricity. In this process, impure metal is made the anode and a strip of pure metal is made the cathode. A solution of a soluble salt of the same metal is taken as the electrolyte. When an electric current is passed, metal ions from the electrolyte are deposited at the cathode as pure metal and the impure metal from the anode dissolves into the electrolyte in the form of ions. The impurities present in the impure metal gets collected below the anode. This is known as anode mud. Page 15 of 20 Website: www.vidhyarjan.com Email: contact@vidhyarjan.com Mobile: 9999 249717 Head Office: 1/3-H-A-2, Street # 6, East Azad Nagar, Delhi-110051 (One Km from ‘Welcome’ Metro Station)
  • 16. Class XII Chapter 6 – General Principles and Processes of Isolation of Elements Chemistry (iii) Vapour phase refining Vapour phase refining is the process of refining metal by converting it into its volatile compound and then, decomposing it to obtain a pure metal. To carry out this process, (i) the metal should form a volatile compound with an available reagent, and (ii) the volatile compound should be easily decomposable so that the metal can be easily recovered. Nickel, zirconium, and titanium are refined using this method. Question 6.28: Predict conditions under which Al might be expected to reduce MgO. Answer Above 1350°C, the standard Gibbs free energy of formation of Al2O3 from Al is less than that of MgO from Mg. Therefore, above 1350°C, Al can reduce MgO. Page 16 of 20 Website: www.vidhyarjan.com Email: contact@vidhyarjan.com Mobile: 9999 249717 Head Office: 1/3-H-A-2, Street # 6, East Azad Nagar, Delhi-110051 (One Km from ‘Welcome’ Metro Station)
  • 17. Class XII Chapter 6 – General Principles and Processes of Isolation of Elements Chemistry Page 17 of 20 Website: www.vidhyarjan.com Email: contact@vidhyarjan.com Mobile: 9999 249717 Head Office: 1/3-H-A-2, Street # 6, East Azad Nagar, Delhi-110051 (One Km from ‘Welcome’ Metro Station)
  • 18. Class XII Chapter 6 – General Principles and Processes of Isolation of Elements Chemistry Text solution Question 6.1: Which of the ores mentioned in Table 6.1 can be concentrated by magnetic separation method? Answer If the ore or the gangue can be attracted by the magnetic field, then the ore can be concentrated by the process of magnetic separation. Among the ores mentioned in table 6.1, the ores of iron such as haematite (Fe2O3), magnetite (Fe3O4), siderite (FeCO3), and iron pyrites (FeS2) can be separated by the process of magnetic separation. Question 6.2: What is the significance of leaching in the extraction of aluminium? Answer In the extraction of aluminium, the significance of leaching is to concentrate pure alumina (Al2O3) from bauxite ore. Bauxite usually contains silica, iron oxide, and titanium oxide as impurities. In the process of leaching, alumina is concentrated by digesting the powdered ore with a concentrated solution of NaOH at 473-523 K and 35-36 bar. Under these conditions, alumina (Al2O3) dissolves as sodium meta-aluminate and silica (SiO2) dissolves as sodium silicate leaving the impurities behind. Page 18 of 20 Website: www.vidhyarjan.com Email: contact@vidhyarjan.com Mobile: 9999 249717 Head Office: 1/3-H-A-2, Street # 6, East Azad Nagar, Delhi-110051 (One Km from ‘Welcome’ Metro Station)
  • 19. Class XII Chapter 6 – General Principles and Processes of Isolation of Elements Chemistry The impurities are then filtered and the solution is neutralized by passing CO2 gas. In this process, hydrated Al2O3 gets precipitated and sodium silicate remains in the solution. Precipitation is induced by seeding the solution with freshly prepared samples of hydrated Al2O3. Hydrated alumina thus obtained is filtered, dried, and heated to give back pure alumina (Al2O3). Question 6.3: The reaction, is thermodynamically feasible as is apparent from the Gibbs energy value. Why does it not take place at room temperature? Answer The change in Gibbs energy is related to the equilibrium constant, K as . At room temperature, all reactants and products of the given reaction are in the solid state. As a result, equilibrium does not exist between the reactants and the products. Hence, the reaction does not take place at room temperature. However, at a higher temperature, chromium melts and the reaction takes place. We also know that according to the equation Increasing the temperature increases the value of making the value of more and more negative. Therefore, the reaction becomes more and more feasible as the temperature is increased. Question 6.4: Page 19 of 20 Website: www.vidhyarjan.com Email: contact@vidhyarjan.com Mobile: 9999 249717 Head Office: 1/3-H-A-2, Street # 6, East Azad Nagar, Delhi-110051 (One Km from ‘Welcome’ Metro Station)
  • 20. Class XII Chapter 6 – General Principles and Processes of Isolation of Elements Chemistry Is it true that under certain conditions, Mg can reduce SiO2 and Si can reduce MgO? What are those conditions? Answer The temperature range in which to is lesser than , Mg can reduce SiO2 Si. On the other hand, the temperatures range in which is less than , Si can reduce MgO to Mg. The temperature at which ∆fG curves of these two substances intersect is 1966 K. Thus, at temperatures less than 1966 K, Mg can reduce SiO2 and above 1966 K, Si can reduce MgO. Page 20 of 20 Website: www.vidhyarjan.com Email: contact@vidhyarjan.com Mobile: 9999 249717 Head Office: 1/3-H-A-2, Street # 6, East Azad Nagar, Delhi-110051 (One Km from ‘Welcome’ Metro Station)