VI Semester B.Sc.

Examination, May 2016

(Fresh)(2013-14 & Onwards)
CHEMISTRY-VII, Inorganic Chemistry
Scheme of Valuation
PART-A

Answer any eight of the following questions. Each question carries two marks.
(8x2=16)

Q.1 (i) Tetraaquachromium(II)Chloride 1M

(ii) Sodiumhexanitrito-Ncobaltate(III) 1M

Q.2 E.A.N. of Pt = Z - X + Y 1M
= 78 - 4 + 12
= 86 1M

Q.3 (i) When cobalamine or vitamin B12 reacts with ATP, results co-enzyme
which involves in effecting unusual rearrangement reaction.

(ii) The vitamin containing Co(I) plays an important role in the functioning of
vitamin B12 and readily undergoes alkylation via reductive oxidation

(iii) Cobalamine along with folic acid required for the development of red
blood cells.

(iv) Deficiency of vitamin B12 causes pernicious anemia in humans

Any two roles (1M each)

Q.4
Q.5 (i) In making grinding wheels for glass, granite etc.

(ii) For the preparation of high speed tools.

(iii) In making emery paper, emery cloth, drilling bits etc.

(Any two applications) 2M

Q.6 Laminated safety glass is made by binding two sheets of ordinary glass with a
thin layer of vinyl plastic in between them. 1M

When it is broken, the fragments are held in place by inter layer. The glass
pieces do not fly off i.e., it is shatter proof. 1M

Q.7 Peat, lignite, bituminous and anthracite ½ M each

Q.8 Resin, drying oils, thinners, driers and antiskinning agents

(Any four constituents) ½ M each

Q.9 The amount of heat evolved when unit mass of a fuel is burnt completely in
excess air and the products of combustion cooled to 298K 1M
SI Units: K.J.Kg-1 or K.J.m-3 1M

Q.10 Iodine is taken up by the thyroid gland for the synthesis of hormones
triiodotyromine and tetraiodotyromine. These hormones are essential for
normal physical and mental development. Deficiency of iodine in the diet
leads to a clinical condition called goiter 2M

Q.11 Carbon nanotube is a sheet of c-atoms joined in a pattern of hexagons and

rolled into a cylinder. The nanotube conducting properties depend upon
how the two ends of the sheet meet along. For a particular way of
arrangement of atoms along the meeting line makes the entire tube
conducting like a metal and for another type of arrangement, the tube
behaves like a semiconductor. When one type of nanotube is rolled inside
another tube we get a multiwalled nanotype. Nanotubes are non-reactive
and withstand high temperature (Value as a whole) 2M
Q.12 (i) Activated carbon is a nanoporous material. It is extensively used in
purification of certain gases, gold and water sewage treatment plants, air
filters and gas mask.
(ii) Zeolite used as catalytic agent in petroleum industry.

(iii) Nanomaterials are used in L.E.D’s (light emitting diodes), cancer

therapy, drug delivery, biosensors, nanotextile, nanocosmetics
(Any two applications) 2M

Q.13. a. In [Fe(CN)6]3-, the oxidation state of Fe is +3. The outer electron

configuration of Fe3+ is d5. Hence there are five unpaired electrons. In this
case, crystal field splitting energy ( ∆0 ) is more than pairing energy (P) i.e.
∆0 >P. As a result pairing of electrons take place in the t2g orbitals and there
is a one unpaired electron left in the t2g orbital. The complex ion is
paramagnetic and octahedral structure. 3M
Splitting of d-orbitals in octahedral field and distribution of electrons in t 2g
and eg set. 1M

b. K4[Fe(CN)6] is a low spin complex because it utilizes its inner(n-1)d orbitals and
the outer ns and np orbitals for hybridization and subsequent bond
formation. Two 3d orbitals, one 4s orbital and three 4p orbitals hybridise to
give six d2sp3 hybrid orbitals. Then, they receive electrons from cyanide
ligands and form an octahedral complex 2M

Q.14.a.
 1M

When six ligands(L) in an octahedral environment approaches the metal ion (M n+)
along the three co-ordinate - x, y, z, it would experience a sphere field.

The d-orbitals whose lobes are present along the co-ordinate axes (namely
dx2 -y2 and dz2) experiences more interaction hence they destabilize to some
extent and the d-orbitals whose lobes are present in between the
co-ordinate axes(dxy ,dyz & dzx) experiences less interactions and hence they
stabilize to the same extent.

Now there are two sets -one containing two orbitals which are having high
energy are called eg orbitals and other containing three orbitals which are
at low energy are called t2g orbitals. The difference between these two sets
are denoted by ∆0 or 10Dq and is called crystal field splitting energy.
The distance from the bary centre to the higher eg set is about 6Dq or 0.6∆0
and to the lower t2g set is about 4Dq or 0.4∆0 and are called crystal field
stabilization energy 3M

b. [Co(NH3)5Br]SO4 gives thick white precipitate with BaCl2 solution but not
[Co(NH3)5SO4]Br
 or [Co(NH3)5SO4]Br gives pale yellow precipitate with AgNO3 solution but not
[Co(NH3)5Br]SO4. 2M

Q.15.a. In a free state, the metal ion has degenerate d-orbitals and hence there
will be no spectra corresponding to d - d transitions. During the formation
of complex, the electrostatic field of the ligands splits the d-orbitals into
two groups t2g and eg.

The octahedral complex [Ti(H2O)6]3+, which has one d-electron. This

occupies one of the lower energy d-orbitals i.e., one of the t 2g orbitals. The
complex absorbs energy in the visible region thus promoting the electron
from t2g level to eg level. A single broad peak is observed at 20300cm-1 or at
493nm corresponding to the transition t2g1 --> eg1. The solution appears
purple as yellow and blue light are absorbed to excite the electron 2M

The tetrahedral complex [CoCl4]2- requires much less energy for the
excitation of its d-electron as the tetrahedral field splitting energy, ∆ t is
much lower than the octahedral field splitting energy (∆ t is about 4/9 ∆0).
The absorption bands have been observed at 3500cm-1 and 6300cm-1. The
∆t value has been calculated to be 3100cm -1 which is equal to 37.1K.J.mol-1.
This value appears almost in the IR region. The solution of the complex
absorbs in the red region of the visible spectrum and appears blue in
colour. 2M

b. The difference in energy caused by the splitting of five degenerate d-orbitals

into t2g set and eg set of orbitals is called crystal field splitting energy. 2M

Q.16.a. Raw materials (i) Lime stone (ii) Clay

(iii) Gypsum (iv) Powdered coal 1M

Manufacturing process:

Grinding : The raw materials are separately ground to a fine powder in ball mills
and then mixed in proper proportions to obtain a homogenized mix called
‘dry meal’.
Burning : The dry meal is introduced into a rotary kiln. This is a steel
tube lined with refractory bricks and kept in a slightly slanting
position. The charge moves down slowly. A blast of burning saw dust is sent
in from the other end. A maximum temperature of 17500 C is reached.

At the other end of the kiln where the temperature is highest, lime
and clay undergo chemical fusion resulting in calcium aluminates and
silicates.

CaCO3 ---------> CaO + CO2

2CaO + SiO2 ------> 2CaO.SiO2

3CaO + SiO2 -------> 3CaO.SiO2

3CaO + Al2O3 -------> 3CaO.Al2O3

The product is in the form of small hard, grayish stones called cement
clinker.

Grinding of clinker : After cooling, the clinkers are ground to a fine powder.
During this process, 2-3% gypsum is added to reduce the setting time of
cement. The cement is packed in air-tight bags. 2M
 1M

b. (i) To produce a decorative effect.

(ii) To make the surface impervious to water, liquids e.t.c.

(iii) To increase the durability of ceramic ware.

(iv) To protect the surface from any atmospheric action.

(v) To provide a smooth glassy surface (Any two points) 2M

Q.17.a. carborundum or silicon carbide is manufactured by heating a mixture of

sand and coke with a small amount of saw dust in an electric furnace at
about 2500K.

SiO2 + 3C -------> SiC + 2CO 1M

 1M

The furnace is made of fire bricks provided with carbon electrodes. The charge
consisting of pure sand (56%), coke (35%), saw dust (7%) and salt (2%) is placed
inside the furnace. The salt serves as a binding agent and also helps in converting
impurities as volatile chlorides. Saw dust makes the charge porous and facilitate
the escape of carbon monoxide.

An electric arc is struck between the electrodes and heated for about 36 hours.
The black crystals obtained are cooled for about 24 hours. It is crushed into
powder and washed successively with H2SO4 , NaOH and H2O to remove impurities
2M

b. Broken glass pieces are called cullets 1M

It brings down the melting point of the charge and the process is made
economical 1M

Q.18.a. Coal gas is produced by carbonization of bituminous coal at a high

temperature of about 1000-12000C.

Bituminous coal is fed into vertical silica retort. It is heated by burning a

mixture of producer gas and air in heating jacket surrounding the retort. An outlet
is provided at the top of retort through which coal gas is drawn.

The gas coming out of the retort is a complex mixture of various gases like H 2,
CH4, CO, CO2, N2, H2O, H2S, HCN, hydrocarbons e.t.c.

The gas is passed through scrubber containing water. Coal tar and little NH3
are condensed. The remaining NH3 is condensed by passing through a series of
water cooled condenser. Than, the mixture of gases is passed through moist Fe 2O3
followed by alkaline FeSO4 to remove H2S and HCN. Finally the gas is dried by
passing through anhydrous CaCl2. The purified coal gas is stored in steel cylinders.

3M
 1M

b. T.N.T. is prepared by nitration of toluene with a mixture of fuming HNO 3 and

concentrated H2SO4 (Nitrating mixture) 1M

1M

Q.19.a. (i) Low explosives: They burn but do not explode suddenly. They are used
as propellants and in fire works.

Ex: Gun powder or Black powder (75% KNO3, 15% charcoal & 10% S)
cordite is a smokeless powder 1M

(ii) Primary or Initiating explosives or Detonators: They are very sensitive to heat
and mechanical shock. They are generally used to initiate the explosion of high
explosive.

Ex: Leadazide-Pb(N3)2 , Mercury fulminate -Hg(ONC)2, Diazodinitrophenol 1M

(iii) High explosives: They do not explode on ignition but explode with great
violence if the explosion is initiated by detonators.

Ex: Trinitrotoluene (TNT), Glyceryl trinitrate (GTN), NH4NO3 , cellulose nitrate,

cyclonite(RDX) 2M
b. Prevent gelling and skinning of paint film. These substances prevent chalking of
the dispersed pigment particles and improve the stability of the paint during
storage 1M
Ex: tert-amylphenol, guiacol e.t.c. 1M (Attempt 2M)

Q.20.a. Hemoglobins are conjugated proteins which constitute the red colouring
matter of blood. They consist of proteins called globins and hence
(ferroprotoporphyrin). The hemoglobins of different species differ in properties
due to differences in the proteins. However all of them contain heme.
Hemoglobin is unique in its ability to bind to molecular oxygen in easily reversible
combination. The symbol Hb is used to denote unoxygenated or reduced
hemoglobin and HbO2 for oxyhemoglobin. It is Important to note that in both
reduced and oxidized states, the iron atom in heme remains in the ferrous state.

Hb + O2 ===== HbO2

In hemoglobin, the iron in heme is conjugated to the nitrogen atoms of the

aminoacid histidine with in the protein globin. When hemoglobin combines with
oxygen, the iron is displaced from bonding with one histidine nitrogen atom and
gets bound to a molecule of oxygen. Goblin, the protein constituent of
hemoglobin is composed of four polypeptide chains arranged in the configuration
of a tetrahedron. One set of chains are identical and are designated alpha and
beta chains. Each of the four chains is associated with a heme prosthetic group.

During respiration, hemoglobin combines with oxygen to form oxyhemoglobin

in the lungs. At a oxygen tension of 100mm Hg or more hemoglobin is completely
saturated. when the oxygenated blood reaches the tissue where oxygen tension
is low (40mm Hg) oxyhemoglobin dissociates and oxygen is readily made available
to the cells. 3M
 1M

b.(i) High energy phosphates are the building blocks of nucleic acids DNA and
RNA, present in bones, teeth and in all tissues, phosphorus metabolism are
regulated by the parathyroid hormone (Any one function) 1M

(ii) It is a component of chlorophyll, the green colouring pigment in plants, Mg 2+

ions are essential for muscle contraction, neuromuscular irritability, large number
of enzymes involved in the metabolism of carbohydrates and nucleic acids are
dependent on the presence of Mg2+ ions. (Any one function) 1M

Q.21.a. (i) Monohapto ligands (n1): The organic ligands are linked to the metal
atom through one carbon atom only.

Ex: -CH3, -C2H5, -C6H5, CH3MgX, C6H5MgX, (C2H5)4Pb e.t.c.

(ii) Dihapto ligands (n2): The organic ligands are attached to the metal atom
through two carbon atoms.

Ex: CH2 = CH2

(iii) Trihapto ligands (n3): The organic ligands are attached to the metal atom
through three carbon atoms.

Ex: Allylic radical,H2C = CH - CH2 has three pi- Electrons (one on the radical and
two for forming the pi-bond) which are completely delocalized over all the three
carbon atoms.
(iv) Tetrahapto ligands (n4): The conjugated dienes such as butadienes and
substituted butadiens, CH2 = CH - CH = CH2

(v) Pentahapto ligands(n5): Cyclopentadienyl radical, C5H5 - linked to iron atom in

ferrocene through all its 5 carbon atoms.

(iv) Hexahapto ligands(n6): The benzene rings in dibenzene chromium

Cr[n6(C6H6)2] is a hexahapto ligand. The linkage of Cr to the ligand is to all the six
carbon atoms of the ring through delocalized pi- electrons.

(Any four types ) 4M

b. It has been used as antidote to lead poisoning because of its great affinity for
Pb2+ ions. It has very low toxicity but has poor power to penetrate the cells. EDTA
is administered as the sodium salt of calcium chelate Na2[Ca(EDTA)] by injection
since the absorption is very low by the gastrointestinal tract. 2M

Q.22.a. (i) 80 - 83% SiO2, 10 - 12%B2O3, 4% Na2O, 2% Al2O3 and traces of CaO, MgO
and K2O 1M

Laboratory glass ware, baking dishes, high tension insulators, washers

(Any one application) 1M

(ii) SiO2, B2O3, BaO, ZnO, P2O5 and traces of CeO2 1M

Making lenses, prisms, scientific instruments (Any one application) 1M

b. (i) It can not be extended quantitatively.

(ii) It does not explain characteristic absorption spectra of the co-ordination
compounds and their colour.
(iii) Does not explain the relative stabilities of different structures. (iv)
The concept of classifying complexes as inner orbital and outer orbital on the
basis of magnetic nature is not satisfactory and often misleading
(v) Fails to account for the thermodynamic properties of co-ordination
compounds (Any two limitations) 2M

Q.23.a. It is a material which can withstand the action of high temperature,

thermal shock, heavy load, corrosive fluids and remain unmelted and undeformed
 1M

Classification: Depending on the chemical nature, refractories are classified into

three types.

(i) Acids refractories: Composed of acidic material such as silica and aluminium
silicate. They are acidic in nature and resistant to acidic materials but attacked by
basic materials

Ex: silica bricks (SiO2): Used as furnace lining in the manufacture of acids and
steel.

Fire clay bricks (Al2O3.2SiO2.2H2O): Used in the construction of furnace, kiln and
tank furnace for glass manufacture (Any one example) 1M

(ii) Basic refractories: Composed of basic materials such as dolomite and

magnesia. They are basic in nature and resistant to basic materials but attacked
by acidic materials.

Ex: Dolomite (MgO.CaO), Magnesia (MgO), Zirconia (ZrO2) 1M

(iii) Neutral refractories: These are neither acidic nor basic and applicable for
both the medium.

Ex: Silicon carbide or carborundum (SiC), chromite (FeO.Cr2O3) 1M

b. Polyaniline, polyacetylene, polyphenylene, polythiophenes e.t.c.

(Any two examples) 2M

Q. 24. a. It is based on the formation of ‘cooper pairs’ and it is purely a ‘quantum

mechanical concept’.

When a current flows in a superconductor, the electron approaches the +ve

ion core of the lattice, it experiences an attractive force due to the opposite
charges between the electron and the +ve ion, as a result the +ve ion will be
displaced from its position called ‘lattice distortion’. Now a second electron which
approaches the distorted +ve ion core experiences a coulombic attractive force.
This process can be looked upon as interaction on apparent force of attraction
develops between the electrons and then tend to move in pairs.

The lattice vibrations are quantized in terms of what are called ‘phonons’.
Thus the process is called electron-lattice-electron interaction via the phonon
field. The attractive force established may exceed the coulombic repulsive force
between the two electrons at temperature below critical temperature (Tc) leading
to the formation of “COOPER PAIRS” .

Cooper pair is a bound pair of electrons formed by the interaction

between the electrons with opposite spin and momenta in a phonon field. When
the electrons flow in the form of cooper pairs in materials, they do not encounter
any scattering by the lattice ions and do not get slow down, finally the resistance
factor vanishes i.e., the material has zero resistivity which is named as super
conductivity (value as a whole) 4M

b. (i) Fullerenes can be used as superconductors at low temperature of 10 to 40K

(ii) Used as lubricants.

(iii) Used as polymer additives to prepare co-polymers with specific physical and
chemical properties.

(iv) Used in aircrafts, electronics, fiber optics, material science

(v) Used in medical applications such as HIV virus detection, Aids treatment e.t.c.

(Any two applications) 2M

Q. 25. a. Sol gel synthesis of production of nanomaterials is carried out at room

temperature. The solution form of nanomaterial in their oxides state is
synthesized by this method.

In this method, first the hydrolysis followed by polymerisation of metal

alkoxide of Silica, titania, zirconia e.t.c. are prepared. These oxides are reacted
with each other in solution to form stable gels, that dries up to form rigid metal
oxides at perticular temperature is called sol-gel transition point. The materials
prepared by this method are
(i) Aluminium gel butoxide
(ii) Trimethyl borate
(iii) Tetraethylorganosilicate (TEOS) e.t.c.

Ex: Al(OC4H9)3 + H2O -------> Al(OC4H9)2OH + C4H9OH

2Al(OC4H9)2OH + 2H2O -------> 2Al(OH)3 + 2C4H9OH

2Al(OH)3 ------------> Al2O3 + 3H2O (value as whole) 4M

Process: 1) Mixing of single or multiple alkoxide and colloidal sol processes, the
partical size smaller than wave length of light is obtained.

2) Gelling: In this step solution of alkoxide does not show any flow. The
time required to form gel is known as ‘time of gel’. During gel formation viscosity
reduces and material becomes rigid.

3) Shape forming: Above material so obtained is converted into bulk

material by casting and moulding.

4) Drying: After making particular size, shape or geometry, materials to

be dried by various methods. They are (i) Air, to get smaller dimensions size up to
1micron is obtained.(ii)Aerogel, dried in an autoclave by hyper critical technique.
(iii)zerogel, this method involves natural evaporation, the material becomes 60%
dence (iv) Densification, it is done by sintering. During this process porasity is
completely reduced. (value as a whole) 4M

b. (i) Production of high tension underground cables

(ii) Used in super conducting generators
(iii) super conducting magnets, used in magnetic levitation train
(iv) Used in super conducting electrical transformers, electrical motors
(v) Used to increase the speed of computer chips.
(vi) Used in transistors, digital information in communications
(vii) Used in electronics microwave antena for submarines.
(viii) Used as SQuid - which is used to take the image of human body.
(Squid- super conducting quantum interference device)
(Any two applications) 2M