LESSON 1-METALLURGY

Answer the following questions:

Question 1.
What is the difference between minerals and ores?
Answer:
Naturally occurring substances obtained by mining which contain the metals in a
free state or in the form of compounds like oxides, sulphides etc. are called minerals.

Minerals that contain a high percentage of metal from which it can be extracted
conveniently and economically are called ores.

All ores are minerals but all minerals are not ores.

Question 2.
What are the various steps involved in the extraction of pure metals from their ores?
Answer:
The extraction of pure metals from the concentrated ores is carried out in two steps:

1. Conversion of the ore into oxides of the metal of interest.

2. Reduction of the metal oxides to elemental metals.
Question 3.
What is the role of Limestone in the extraction of Iron from its oxide Fe2O3?
Answer:
In the extraction of iron, a basic flux limestone is used. Limestone decomposes to
form CaO which reacts with silica gangue present in the iron ore is acidic in nature to
form calcium silicate (slag).

Question 4.
Which type of ores can be concentrated by froth floatation method? Give two
examples for such ores.
Answer:

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Sulphide ores can be concentrated by the froth floatation method.
(eg) Galena (PbS), Zinc blende (ZnS).

Question 5.
Out of coke and CO, which is better reducing agent for the reduction of ZnO? Why?
Answer:
Coke (C) is a better reducing agent for the reduction of ZnO. Because, when we use
coke, the reduction can be easily carried out at 673 K. Thus Carbon (Coke) reduces
zinc oxide more easily than carbon monoxide (CO). From the Ellingham diagrams, it
is quite clear that the reduction of zinc oxide is more favourable using coke ∆G for
the formation of carbon monoxide from carbon is more negative).

Question 6.
Describe a method for refining nickel.
Answer:
The impure nickel is heated in a stream of carbon monoxide at around 350K. The
nickel reacts with the CO to form a highly volatile nickel tetracarbonyl. The solid
impurities are left behind.
Ni (s) + 4 CO (g) → Ni(CO)4(g)
On heating the nickel tetracarbonyl around 460 K, the complex decomposes to give
pure metal.
Ni(CO)4 (g) → Ni (s) + 4 CO (g)

Question 7.
Explain zone refining process with an example using the Ellingham diagram given
below.
Answer:
Zone refining:

 The principle is fractional crystallization.

 When an impure metal is melted and allowed to solidify, the impurities will
prefer to remain in the molten region, ie; impurities are more soluble in the
melt than in the solid-state metal.
 In this process, the impure metal is taken in the form of a rod. One end of the
rod is heated using a mobile induction heater, melting the metal on that
portion of the rod.

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  When the heater is slowly moved to the other end pure metal crystallizes
while impurities will move on to the adjacent molten zone formed due to the
movement of the heater.
 As the heater moves further away, the molten zone containing impurities also
moves along with it.
 This process is repeated several times by moving the heater in the same
direction again and again to achieve the desired purity level.
 This process is carried out in an inert gas atmosphere to prevent the oxidation
of metals.
 Germanium, Silicon, and gallium which are used as semiconductors are refined
by this process.

Question 8.
1. Predict the conditions under which
(a) Aluminium might be expected to reduce magnesia.
(b) Magnesium could reduce alumina.
2. Carbon monoxide is a more effective reducing agent than carbon below 983 K but,
above this temperature, the reverse is true -Explain.
3. it is possible to reduce Fe2O3 by coke at a temperature around 1200 K.
Answer:
1. The conditions under which:
(a) Ellingham diagram is used to predict thermodynamic feasibility of reduction of
oxides of one metal by another metal. Any metal can reduce the oxides of other
metals that are located above it in the Ellingham diagram. In the Ellingham diagram,
for the formation of magnesia (magnesium oxide) occupy lower position than
aluminum oxide. Therefore aluminium cannot be used to reduce the oxides of
magnesium (magnesia). Above 1623K, A1 can reduce MgO to Mg, so that ArG°
becomes negative and the process becomes thermodynamically feasible.

(b)

 (43)Al + O  → (23)Al O
2 2 3

2Mg + O2 → 2MgO

At the point of intersection of the Al2O3 and MgO curves in Ellingham diagram. ∆G°
becomes zero for the reaction:

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(23)Al O  → 2MgO + (43)Al
2 3

Below that point magnesium can reduce alumina.

2. From the Ellingham diagram, we find that at 983 K, the curves intersect.

The value of ∆G° for change of C to CO2 is less than the value of ∆G° for change of
CO to CO2. Therefore, coke (C) is a better reducing agent than CO at 983K or above
temperature. However, below this temperature (e.g. at 673K), CO is a more effective
reducing agent than C.
3. Yes, it is possible to reduce Fe2O3 by coke at a temperature around 1200 K. In the
Ellingham diagram, carbon line cuts across the lines of many metal oxides and hence
it can reduce all those metal oxides at sufficiently high temperature. Ellingham
diagram for the formation of Fe2O3 and CO intersects around 1000 K.
Below this temperature, the carbon line lies above the iron line which indicates that
Fe2O3 is more stable than CO and hence at this temperature range the reduction is
not thermodynamically feasible. However above 1000 K carbon line lies below the

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iron line and hence we can use coke as a reducing agent around 1200 K. Around
1200 K, coke is better reducing agent because above 1000 K, Gibb’s free energy for
the formation of Fe2O3 is more than the formation of CO2 from C.

Question 9.
Give the uses of zinc.
Answer:
Applications of Zinc (Zn):

1. Metallic zinc is used in galvanising metals such as iron and steel structures to
protect them from rusting and corrosion.
2. Zinc is also used to produce die-castings in the automobile, electrical and
hardware industries.
3. Zinc oxide is used in the manufacture of many products such as paints,
rubber, cosmetics, pharmaceuticals, plastics, inks, batteries, textiles arid
electrical equipment. Zinc sulphide is used in making luminous paints,
fluorescent lights and x-ray screens.
4. Brass an alloy of zinc is used in water valves and communication equipment as
it is highly resistant to corrosion.

Question 10.
Explain the electrometallurgy of aluminium.
Answer:
Electrochemical extraction of aluminium Hall-Herold process:
In this method, electrolysis is carried out in an iron tank lined with carbon, which acts
as a cathode. The carbon blocks immersed in the electrolyte acts as an anode. A 20%
solution of alumina, obtained from the bauxite ore is mixed with molten cryolite and
is taken in the electrolysis chamber. About 10%, calcium chloride is also added to the
solution. Here calcium chloride helps to lower the melting point of the mixture. The
fused mixture is maintained at a temperature of above 1270 K. The chemical
reactions involved in this process are as follows:

Ionisation of alumina:
Al2O3 → 2Al3 + 3OO2-
Reaction at cathode:
2Al3+ (melt) + 3e– → Al(l)

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Reaction at anode:
2O2- (melt) → O2 + 3e–
Since carbon acts as anode the following reaction also takes place on it.

 C (s) + O2- (melt) → CO + 2e–

 C (s) + 2O2- (melt) → CO2 + 4e–
Due to the above two reactions, anodes are slowly consumed during the electrolysis.
The pure aluminium is formed at the cathode and settles at the bottom. The net
electrolysis reaction can be written as follows:
4Al3+ (melt) + 6O2- (melt) + 3C(s) → 4A(l) + 3CO2(g)

Question 11.
Explain the following terms with suitable examples.

1. Gangue
2. Slag
Answer:
1. Gangue:
The impurities associated with the minerals are known as Gangue or Matrix.

2. Slag:
A compound formed when gangue is combined with flux is called slag.
Flux + Gangue → Slag

For example, the oxide of iron can be reduced by carbon monoxide as follows:
Fe2O3 + 3CO → 2Fe + 3CO2
In this extraction a basic flux, limestone is used.
Since the silica gangue present in the ore is acidic in nature, the limestone combines
with it to form Calcium silicate (Slag).

Question 12.
Give the basic requirement for vapour phase refining.
Answer:
The two requirements for vapour phase refining are:

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 1. The metal should form a volatile compound with a suitable reagent.
2. The volatile compound is decomposed to give the pure metal.

Question 13.
Describe the role of the following in the process mentioned.

1. Silica in the extraction of copper.

2. Cryolite is the extraction of aluminium.
3. Iodine in the refining of Zirconium.
4. Sodium cyanide in froth floatation.
Answer:
1. The role of silica in the extraction of copper is to remove the iron oxide obtained
during the process of roasting as slag. If the sulphide ore of copper contains iron,
the silica (SiO2) is added as flux before roasting. Then, FeO combines with silica to
form iron silicate, FeSiO3 (Slag).
2. Cryolite reduces the melting point of Al2O3 and increases its electrical conductivity.
Aluminium is produced by the electrolytic reduction of fused alumina in the
electrolytic cell. Alumina is not an electrolyte. So it is made as an electrolyte by
dissolving it in the fused cryolite. The function of cryolite is to lower the fusion
temperature.
3. Zirconium crude metal is heated with iodine in an evacuated vapour to separate
from impurities and this decomposes at 1800 K to give a pure zirconium metal and
iodine. Initially, iodine is heated with zirconium to form a volatile compound.

4. Sulphide ores are concentrated by the froth floatation process. Depressants are
used to prevent a certain types of particles from forming the froth. NaCN act as a
depressant to separate ZnS from PbS.

Question 14.
Explain the principle of electrolytic refining with an example.
Answer:
The crude metal is refined by electrolysis. It is carried out in an electrolytic cell
containing an aqueous solution of the salts of the metal of interest. The rods of
impure metal is used as anode and thin strips of pure metal are used as a cathode.

The metal of interest dissolves from the anode, pass into the solution while the same
amount of metal ions from the solution will be deposited at the cathode. During

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electrolysis, the less electropositive impurities in the anode, settle down at the
bottom and are removed as anode mud. Let us understand this process by
considering electrolytic refining of silver as an example.

Cathode:
Pure silver

Anode:
Impure silver rods

Electrolyte:
An acidified aqueous solution of silver nitrate. When a current is passed through the
electrodes the following reactions will take place Reaction at the anode.
2Ag (s) → Ag+(aq) + 1 e–
The reaction at the cathode:
Ag+ (aq) + 1 e– → Ag (s)
During electrolysis, at the anode the silver atoms lose electrons and enter the
solution. The positively charged silver cations migrate towards the cathode and get
discharged by gaining electrons and deposited on the cathode. Other metals such as
copper, zinc etc.,can also be refined by this process in a similar manner.

The factor pairs of 96 are, how you find them and list them out for you to prove the
calculation works.
Question 15.
The selection of reducing agent depends on the thermodynamic factor. Explain with
an example.
Answer:
From the Ellingham diagram, it is clear that metals for which the standard free
energy of formation (∆fG0) of their oxides is more negative can reduce the metal
oxides for which the standard free energy of formation (∆fG0) of oxides is less
negative.
The thermodynamic factor has a major role in selecting the reducing agent for a
particular reaction. Only that reagent will be preferred which will lead to a decrease
in the free energy (AG°) at a certain specific temperature.
E.g – Carbon reduce ZnO to Zn but not CO.

 ZnO + C → Zn + CO …………..(1)
 ZnO + CO → Zn + CO2 ………………(2)

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In the first case, there is increase in the magnitude of ∆S° while in the second case, it
almost remains the same. In other words, ∆G° will have more negative value in the
first case, when C is the reducing agent then in the second case when CO acts as the
reducing agent. Therefore, C is a better reducing agent.

Question 16.
Give the limitations of Ellingham diagram.
Answer:
Limitations of Ellingham diagram:
1. Ellingham diagram is constructed based only on thermodynamic considerations. It
gives information about the thermodynamic feasibility of a reaction. It does not tell
anything about the rate of the reaction. Moreover, it does not give any idea about
the possibility of other reactions that might be taking place.

2. The interpretation of ∆G is based on the assumption that the reactants are in

equilibrium with the product which is not always true.

Question 17.
Write a short note on electrochemical principles of metallurgy.
Answer:
Electrochemical principles also find applications in metallurgical process. The
reduction of oxides of active metals such as sodium, potassium etc., by carbon is
thermodynamically not feasible. Such metals are extracted from their ores by using
electrochemical methods. In this technique, the metal salts are taken in a fused form
or in solution form. The metal ion present can be reduced by treating it with some
suitable reducing agent or by electrolysis. Gibbs free energy change for the
electrolysis process is given by the following expression
∆G° = -nFE°

Where n is number of electrons involved in the reduction process, F is the Faraday

and E° is the electrode potential of the redox couple. If E° is positive then the ∆G is
negative and the reduction is spontaneous and hence a redox reaction is planned in
such a way that the e.m.f of the net redox reaction is positive. When a more reactive
metal is added to the solution containing the relatively less reactive metal ions, the
more reactive metal will go into the solution. For example,

 Cu (s) + 2Ag+(s) → Cu2+ (aq) + 2Ag (s)

 Cu2+ (aq) + Zn (s) → Cu (s) + Zn+(aq)

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 LESSON II

Answer the following questions:

Question 1.
Write a short note on anamolous properties of the first element of p-block.
Answer:
In p-block elements the first member of each group differs from the other elements
of the corresponding group. The following factors are responsible for this anomalous
behaviour.

1. Small size of the first member.

2. High ionisation enthalpy and high electronegativity.
3. Absence of d-orbitals in their valance shell.
The first member of the group-13, boron is a metalloid while others are reactive
metals. Moreover, boron shows diagonal relationship with silicon of group -14. The
oxides of boron and silicon are similar in their acidic nature.

Question 2.
Describe briefly allotropism in p- block elements with specific reference to carbon.
Answer:
Some elements exist in more than one crystalline or molecular forms in the same
physical state. This phenomenon is called allotropism. Most common allotropes of
carbon are,

1. Graphite
2. Diamond
3. Fullerenes
4. Carbon nanotubes
5. Graphene.
1. Graphite:

 It is the most stable allotropic form of carbon at normal temperature and

pressure.
 It is soft and conducts electricity.
 It is composed of flat two dimensional sheets of carbon atoms.
 Each sheet is a hexagonal net of sp2 hybridised carbon atoms with a C – C
bond length of 1.41 A.

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  Structure of graphite,

2. Diamond:

 It is very hard.
 The carbon atoms in diamond are sp1 hybridised, with a C – C bond length of
1.54 A.
 In the diamond, carbon atoms are arranged in tetrahedral manner.
 Structure of Diamond,

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3. Fullerenes:

 It is a newly synthesised allotropes of carbon.

 The C60 molecules have a soccer ball-like structure and is called
buckminsterfullerene or buckyballs.
 It has a fused ring structure consists of 20 six-membered rings and 12 five-
membered rings.
 Each carbon atom is sp2 hybridised.
 The C – C bond distance is 1.44 A and C = C distance is 1.38 A.
 Structure of fullerene,

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4. Carbon nanotubes:

1. It is recently discovered allotropes, have graphite-like tubes with fullerene

ends.
2. These nanotubes are stronger than steel and conduct electricity.
3. Structure of Carbon nanotubes.

5. Graphene:

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  It has a single planar sheet of sp2 hybridised carbon atoms that are densely
packed in a honeycomb crystals lattice.
 Structure of Graphene,

Question 3.
Boron does not react directly with hydrogen. Suggest one method to prepare
diborane from BF3.
Answer:
Boron does not react directly with hydrogen. However it forms a variety of hydrides
called boranes. Treatment of gaseous boron trifluoride with sodium hydride around
450 K gives diborane.

Question 4.
Give the uses of Borax.
Answer:
Uses of borax:

1. Used for the identification of coloured metal ions (Borax bead test)
2. Manufacture of optical and borosilicate glass, enamels and glazes for pottery.
3. Flux in metallurgy.
4. Good preservative.

Question 5.
What is catenation? describe briefly the catenation property of carbon.

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Answer:
Catenation is an ability of an element to form a chain of atoms.

The conditions for catenation are

 The valency of the element is greater than or equal to two.

 The element should have the ability to bond with itself.
 The self-bond must be as strong as its bond with other elements.
 Kinetic inertness of catenated compound towards other molecules.
Carbon possesses all the above properties and shows catenation.

Carbon forms a wide range of compounds with itself and with other elements such
as H, O, N, S and halogens.

Question 6.
Write a note on Fisher tropsch synthesis.
Answer:
The reaction of carbon monoxide with hydrogen at a pressure of less than 50 atm
using metal catalysts at 500-700 K yields saturated and unsaturated hydrocarbons.

Question 7.
Give the structure of CO and CO2.
Answer:
Structure of CO:

Structure of CO2:

Question 8.
Give the uses of silicones.
Answer:
Uses of silicones:

1. Silicones are used for low temperature lubrication and in vacuum pumps, high
temperature oil baths etc.
2. They are used for making water proofing clothes.

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 3. They are used as insulting material in electrical motor and other appliances
4. They are mixed with paints and enamels to make them resistant towards high
temperature, sunlight, dampness and chemicals.
Question 9.
AlCl3 behaves like a lewis acid. Substantiate this statement.
Answer:
In AlCl3, Al in electron-deficient it needs two electrons to complete octet so it act as
lewis acid. AlCl3 usually exist as a dimer to achieve octet by bridged Cl atom electron
deficient compounds are lewis acids.

Question 10.
Describe the structure of diborane.
Answer:
In diborane two BH2 units are linked by two bridged hydrogens. Therefore, it has
eight B-H bonds. However, diborane has only 12 valance electrons and are not
sufficient to form normal covalent bonds. The four terminal B-H bonds are normal
covalent bonds (two centre – two electron bond or 2c-2e bond). The remaining four
electrons have to used for the bridged bonds, i.e. two three centred B-H-B bonds
utilise two electrons each.
Hence, these bonds are three centre – two electron bonds. The bridging hydrogen
atoms are in a plane as shown in the figure. In dibome, the boron is sp3 hybridised.
Three of the four sp3 hybridised orbitals contains single electron and the fourth
orbital is empty.
Two of the half-filled hybridised orbitals of each boron overlap with the two
hydrogens to form four-terminal 2c-2e bonds, leaving one empty and one half filled
hybridised orbitals on each boron. The Three centre – two-electron bonds, B-H-B
bond formation involves overlapping the half filled hybridised orbital of one boron,
the empty hybridised orbital of the other boron and the half-filled 1s orbital of

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hydrogen.

Question 11.
Write a short note on hydroboration.
Answer:
Diborane adds on to alkenes and alkynes in ether solvent at room temperature. This
reaction is called as hydroboration and is highly used in synthetic organic chemistry
especially for anti-Markovnikov addition.
B2H6 + 3RCH = CHR → B( CH2 – CH2R )3+ 6H2
Question 12.
Give one example for each of the following:

1. icosogens
2. tetragen
3. prictogen
4. chalcogen
Answer:
1. Icosogens:

 Boron
 Aluminium

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  Gallium
2. Tetragen:

 Carbon
 Silicon
 Germanium
3. Prictogen:

 Oxygen
 Sulfur
 Selenium
4. Chalcogen:

 Fluorine
 Chlorine
 Bromine

Question 13.
Write a note on the metallic nature of p-block elements.
Answer:

1. The tendency of an element to form a cation by loosing electrons is known as

an electropositive or metallic character.
2. This character depends on the ionisation energy.
3. Generally on descending a group the ionisation energy decreases and hence
the metallic character increases.
In p-block, the elements present in lower left part are metals while the elements in
the upper right part are non-metals. Elements of group 13 have metallic character
except the first element boron which is a metalloid, having properties intermediate
between the metal and nonmetals. The atomic radius of boron is very small and it
has a relatively high nuclear charge and these properties are responsible for its
nonmetallic character.

In the subsequent groups the non-metallic character increases. In group 14

elements, carbon is a nonmetal while silicon and germanium are metalloids. In group
15, nitrogen and phosphorus are nonmetals and arsenic & antimony are metalloids.

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In group 16, oxygen, sulphur and selenium are nonmetals and tellurium is a
metalloid. All the elements of group 17 and 18 are non-metals.

Question 14.
Complete the following reactions:
(a) B(OH)3 + NH3 →
(b) Na2B4O7 + H2SO4+ H2O →
(c) B2H6 + 2NaOH + 2H2O →
(d) B2H6 + CH3OH →
(e) BF3 + 9H2O →
(f) HCOOH + H2SO4→
(g) SiCl4 + NH3 →
(h) SiCl4 + C2H5OH →
(i) B + NaOH →
(j) H2B4O7 𝑅𝑒𝑑ℎ𝑜𝑡−→−−−−−−
Answer:

Question 15.
How will you identify borate radical?
Answer:

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When boric acid or borate salt is heated with ethyl alcohol in presence of
concentrated H2SO4, an ester triethyl borate is formed. The Vapour of this ester burns
with a green edged flame and this reaction is used to identify the presence of
borate.

Question 16.
Write a note on zeolites.
Answer:
Zeolites:

1. Zeolites are three-dimensional crystalline solids containing aluminium, silicon

and oxygen in their regular three-dimensional framework.
2. They are hydrated sodium alumino silicates with general formula, Na 2O.
(Al2O3). x(SiO2)y(H2O) (x = 2 to 10; y = 2 to 6)
3. Zeolites have the porous structure in which the monovalent sodium ions and
water molecules are loosely held.
4. The Si and Al atoms are tetrahedrally coordinated with each other through
shared oxygen atoms.
5. Zeolites structure looks like a honeycomb consisting of a network of
interconnected tunnels and cages.
6. Zeolite crystal to act as a molecular sieve. They help to remove the permanent
hardness of the water.
Question 17.
How will you convert boric acid to boron nitride?
Answer:
Fusion of urea with boric acid B(OH)3, in an atmosphere of ammonia at 800 – 1200 K
gives

Question 18.
A hydride of 2nd period alkali metal
(A) on reaction with compound of Boron
(B) to give a reducing agent
(C) identify A, B and C.
Answer:

1. A hydride of 2nd period alkali metal (A) is lithium hydride (LiH).

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 2. Lithium hydride (A) reacts with diborane (B) to give lithium borohydride (C)
which is acts as a reducing agent.

(A) Lithium hydride – LiH

(B) Diborane – B2H6
(C) Lithium borohydride – LiBH4

Question 19.
A double salt which contains fourth-period alkali metal
(A) on heating at 500K gives
(B) Aqueous solution of (B) gives white precipitate with BaCl2 and gives a red colour
compound with alizarin. Identify A and B.
Answer:
1. A double salt which contains fourth-period alkali metal (A) is potash alum
K2SO4. Al2(SO4)3. 24H2O
2. On heating potash alum (A) 500 k give anhydrous potash alum (or) burnt alum (B).

3. Aqueous solution of burnt alum, has sulphates ion, potassium ion and aluminium
ion. Sulphate ion reacts with BaCl2 to form white precipitate of Barium Sulphate
(SO4)2 + BaCl2 → BaSO4 + 2Cl–
Aluminium ion reacts with alizarin solution to give a red colour compound.
Question 20.
CO is a reducing agent. Justify with an example.
Answer:
Both thermodynamic and kinetic factors make carbon monoxide (CO) a better
reducing agent. When CO is used to reduce a metal oxide, it gets oxidized to
CO2 Thermodynamically, CO2 is much more stable than CO. For example,
CO + Fe2O3 → 2Fe + 3CO2

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