B.Tech.

Solution of Question Paper

Session-2013-14, SEM- II
Engineering Chemistry
NAS 102/ 202
Time : 3 Hrs. MM. 100
Part-A
Q.1 a) Assign R and S configuration of the following:
Ans:

CHO CH20H

CH4 C 2 H5 Cl OH

H Ph

b) A body centered cubic element of density 10.3gm cm3 has a cell edge of 314 pm . Calculate
the atomic mass of the element. (Avagadro’s constant  6.023  10 23 mol 1
Ans.: Density of a cubic cell     10.3gm / cm 3
Edge length of cubic cell (a)  314 pm  3.14 10 8 cm.
No. of atoms of BCC cell (z)  2
Avagadro’s No.  N A   6.023  10 23
Atomic Mass M   ?
Z .M .
 or
N A .a 3
 .a 3 .N A
M 
Z

M 
10.3gm / cm . 3.14  10  .6.023  10
3 8 3 23
mol 1 
2
Atomic Mass M   96 .18 gm / mol
c) Explain why ethylene polymerizes but ethane does not.
Ans.: For a substance to polymerize it must have at least two reactive sites or bonding sites.
In case of ethylene.
CH 2  CH 2    *CH 2  CH 2 * 
There are two bonding sites, but in methane or ethane there is no any bonding site, so
it does not polymerize.
d) Explain why value of NCV is lower than GCV.

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Ans.: The GCV is the total amount of heat produced when unit mass/volume of fuel has
been burnt completely and the product of combustion are allowed to cool at room
temperature while NCV may be explained as the net heat produced when unit
mass/volume of fuel is burnt completely and the products are permitted to escape, so
latent heat of water vapors are not considered in case of NCV.
GCV – Latent heat of water vapors = NCV
e) Explain why Teflon is highly chemical resistant.
Ans.: Due to present of most electronegative element “F” in Teflon, there is very strong
attractive forces between its different chains. Hence it possesses extremely high
chemical resistance towards most chemicals.
f) What is EDTA? Give the chemical formula.
Ans.: EDTA is Ethylene Diamine tetraacetic Acid and its chemical formula is

g) What is Plaster of paris? Give reaction for its preparation.

Ans.: The Plaster of Paris is produced by heating fairly pure gypsum to a temperature about
120 0  160 0 C .

h) Explain why Lime Soda is not recommended for obtaining feed water for high
pressure boiler.
Ans.: Lime – Soda Process:
During softening process by Lime-Soda method, the free Na2 CO3 is usually present
in smaller proportion in the softened water. In high pressure boilers, Na2 CO3
decomposes to give sodium hydroxide and carbon dioxide.
Na 2 CO3  H 2 O  2 NaOH  CO2
and this makes the boiler water caustic. The NaOH containing water flows into the
minute hair-cracks, always present in the inner side of boiler by capillary action. Here
water evaporates and the dissolved caustic soda concentration increase progressively.
This caustic soda attacks the surrounding area thereby dissolving iron of boiler as
sodium ferroate. This causes embrittlement of boiler parts, particularly stressed parts,
causing even failure of water.
i) Calculate the GCV of fuel having the following compositions
C  85 %, H  8 %, S  1%, N  2% and ash  4% (Liquid flow of water vapour
 587 cal / gm )
Ans.: Gross Calorific Value

2
 1   0 
 8080  C  34500 H    2240  S  K cal / kg
100   8 
1   0 
GCV  8080  85  34500 8    2240  1 K cal / kg
100   8 
1
 686800  276000  2240K cal / kg
100
 9650 .4 K cal / kg
Q.2 a) i) What is metallic bond? Explain it on the basis of molecular orbital theory.
Ans.: The force of attraction between positively charged kernels (atoms eliminated valence
electrons) and the electron cloud. The valence electrons are free to migrate throughout the
crystal lattice, making metals highly electrical conductive.
According to the molecular orbital theory of covalent bonds extended to solids. Take
the example of Li atom. Li has electronic configuration of 1s 2 , 2s1 , Li2 two 2s atomic
orbitals overlap to form two molecular orbital  2 s  and  * 2 s  is vacant. In Li , n th
atomic orbital combine to form n th molecular orbital. The separation between the
molecular orbitals decreases as the number of atoms increases, so that there is a band
of N closely spaced M.O. The band is half full, since each M.O. can hold 2 electrons
and there are only N valence electrons. The band containing the valence electrons is
called valence band.
It may be pointed here that they empty 2p atomic orbitals of Li atoms also overlap to
form a wide band of M.O. since the 2s and 2p orbitals do not differ much in energy,
the band of M.O. formed from the 2s atomic orbitals and the band of M.O. formed
from 2p orbitals, joined continuously and is called conduction band.
The gap between the valence band and the conduction band is called forbidden gap.
The width of the forbidden gap is called energy gap E g . 

ii) Draw molecular orbital diagram of HF. Calculate bond order and determine magnetic
property.
Ans.: The electronic configuration of H & F are:
1 H  1s 1
9 F  1s 2 , 2 p x2 , 2 p 2y , 2 p1z
In the formation of HF molecule, only the 2 p electrons of Fluorine atom would
combine effectively with the only electrons of H atoms. It is known a fact that 2 p z

3
 orbital is able to combine with an s-orbital. The combination of 2 p z and 2 p y orbitals
with an s-orbital is ruled out on symmetry consideration. The 2 p z orbitals of Fluorine
yield effective overlap with 3 orbital of H atom to form  sp  molecular orbital.

20
Band Order  N b  N a 2  1
2
In the molecular configuration of HF molecule all the electrons are in paired from, so
it will be diamagnetic in nature.
b) i) Derive Bragg’s equation for diffraction of X-rays crystals.
Ans.: We can determine the size of the unit cell and the arrangement of atoms in a crystal
from measurement of the diffraction of X-rays by the crystal. When a beam of
monochromatic X-rays strike two planes of atoms in a crystal at a certain angle, it is
reflected. Bragg’s equation is
n   2d sin 
n  Order of Reflection
  Wave Length of X-rays used
  Diffraction angle
d  Distance between two layers of plane

The horizontal lines in this figure represent parallel planes in the crystal structure separated
from one other by the distance “d”. Suppose a beam of X-rays falls on the crystal at glancing
angle " " . Some of these rays are reflected from upper plane at the same angle while some
others will be observed and get reflected from successive layers as shown. Let the planes
ABC and DEF be drawn perpendicular to the incident and reflected beams respectively.

4
The waves reflected by different layer planes will be in phase with one another only if the
difference in path angles of the wave reflected from successive planes is equal to an integral
number of wavelength.
The path difference between two layers may be equal to
 LN  NM
The path difference should be equal to a whole number multiple of wavelength  i.e.
LN  NM  n …..(1)
Since the triangle OLN and OMN are congruent, hence
LN  NM  d sin  ……(2)
Put the value of equation (2) and equation (1)
n  2d sin 
This is Bragg’s equation.
b) ii) 0 .75 gm of fuel containing 80% carbon, when burnt in a bomb calorimeter, increased
the temperature of water from 27 .3 0 C to 29.10 C . If the calorimeter contains 250 gm
of water and its water equivalent is 150 gm Calculate HCV of the fuel.
Ans.: Wt . of fuel  x   0 .75 gm
Wt. of water W   250 gm
Initial temperature  t1  27.3 0 C
Maximum temperature  t 2  29.10 C
W  wt 2  t1 
H .C.V . of fuel  K cal / kg
x

250  150 29.1  27.3
0.72
 4.2  1000 K . J . / kg
 42000 K .J . / kg
c) i) What is hardness of water? Describe zeolite process for making soft water from hard
water.
Ans.: The Hardness in water is that characteristic which prevents the lathering of soap. This
is due to presence of certain salts in water (salts of Calcium and Magnesium).
Softening of Water by Zeolite Method:
The sodium-Zeolite may be represented as Na 2 O. Al 2 O3 . xSiO 2 . yH 2 O. Zeolite is
hydrated sodium alumino silicate, capable of exchanging reversibly its sodium ions
with hardness producing ions present in water.
In this process hard water is percolated at a specified rate through a bed of zeolite,
kept, kept in a cylinder. The hardness producing ions are retained by Zeolite as CaZe
and MgZe, while the outgoing water contains sodium salts.
Na 2 Ze  CaCl 2  CaZe  2 NaCl
Na 2 Ze  MgSO 4  MgZe  Na 2 SO 4

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After some time, the zeolite is completely converted in calcium and Magnesium Zeolite and
it stops the further softening of water i.e. gets exhausted. At this stage the supply of hard
water is topped and the exhausted zeolite is reclaimed by treating the bed with concentrated
Brine  NaCl  solution.
CaZe  2 NaCl  Na 2 Ze  CaCl 2
MgZe  2 NaCl  Na 2 Ze  MgCl 2
The washing are led to drain and regenerated zeolite bed, thus obtained is used again for
softening purpose.
ii) What is optical activity? Write the possible optical isomerism in tartaric acid.
Ans.: The property by virtue of which the plane polarized light is rotated is called optical
activity, while the substance passing this properly are said to be optically active compounds.
Tartaric acid has two asymmetric carbon atoms, each linked to the same four different
groups i.e., -OH, - H, - COOH and –CH (OH) COOH.
The spatial arrangement of various groups in tartaric acid can be represented in the
following ways:
1. Dextro form: The dextro tartaric acid is one which rotate the plane polarized light is
clockwise direction.
2. Levo form: The levo tartaric acid is one which rotate the plane polarized light in
anticlockwise direction.
3. Racemic form: It is a 50:50 mixture of the above varieties and hence inactive. It can
however be resolved into active constituents.
4. Meso Form: It is inactive variety as the rotation of upper half is compensated by the
rotation due to the lower half & it cannot be resolved into active constituents.

d) i) Draw the energy profile diagrams for the reaction.

CH 2 3 C  Br  OH   CH 2 3 C  OH  Br 
Above reaction completed in the following two steps:
Step–1 It is a slow step, so it is shown as rate determination steps.

6
 Step–2 It is a very fast step

The energy profile diagram of the above reaction may be represent as –

ii) Discuss the structure, preparation, properties and application of Fullerene.

Ans.: Fullerenes are group of polymorphic form of pure Carbon Compounds, whose
discrete molecules consist of hollow spherical cluster of a large number of carbon
atoms. Each molecule is composed of group of Carbon atoms that are bonded to one
another to form both hexagon and pentagon geometrical configurations. One such
molecule is found to consist of 20 hexagons and 12 pentagons, which are arrayed such
that no two pentagons share a common side: the molecular surface thus exhibits the
symmetry of a Soccer Ball.

7
Preparation:
When Carbon are is struck under agron (0.05 to 0.1 atm pressure), a dust containing 5-15%
fullerenes. One extracting this black root like dustly material with solvents or by sublimation,
fullerenes mixture can be obtained. Then individual fullerenes can be separated by
chromatographic technique using alumina hexane.
Properties :
a) It is mustered color solid, which appears brown to black with increasing thickness of
its film.
b) It is moderately soluble in aromatic hydrocarbons, giving magenta colored solution.
c) On sublimation, its formed translucent magenta face cantered cubic crystal.
d) A pure solid fullerene (60) is electrically insulator, while on addition of proper
impurities it can be made highly conductive even super conductive.
Application: Applications of fullerenes are:
a) Preparation of super conductors.
b) Electronic devices.
c) Microelectronic devices.
d) In batteries as a charging carrier.

e)i)On the basis of molecular orbital theory, explain why N 2 is diamagnetic and O2 is
paramagnetic.
Ans.: The molecular orbital configuration of N 2
 2 p 2y *
2  2py
0
ls 2 ,  * ls 2 ,  2 s 2 ,  * 2 s 2 , ,  2 p x , ,  * 2 p x0
 2 p z2  * 2 p 1z
The molecular orbital configuration of O2 molecule

 2 p 2y  * 2 p1y * 0
ls 2 ,  *ls 2 ,  2 s 2 ,  * 2 s 2 ,  2 p x2 , , 2 px
 2 p z2  * 2 p1z
From above electronic configuration it is clear that only Oxygen has unpaired
electrons in their molecular configuration so it will be paramagnetic while N 2
molecule consist of all the paired electrons so it will be diamagnetic in nature.
ii) A water sample having the following MgCO3  21mg / L, CaCO3  40mg / L,
CaCl 2  111mg / L, MgCl 2  95 mg / L, KCl  20 mg / L , . Calculate the amount of
Lime 86%  and Soda 90 % pure  needed for the treatment of 80 ,000 litres of water.
Ans.: Calculations of CaCO3 equivalents:
S.No. Constituent Amount Equivalent CaCO3 Equivalent
wt.
1 MgCO3 21mg / L 42 21  50
 25mgL CaCO 3
42
2. CaCO3 40 mg / L 50 40  50
 40 mg / L CaCO 3
50
3. CaCl 2 111mg / L 55.5 111 50
 100mgL CaCO3
55.5

8
 4. MgCl 2 95mg / L 47.5 95  50
 100mg / L CaCO3
47.5
5. KCl 20 mg / L Not required because it does not
produce hardness in water

Lime required for softening of 1 L water

74
 CaCO 3  MgCO 3  MgCl 2 
100
74
 40  25  100  74 165  122.1 mg of Lime
100 100
For 80,000 of water, required Lime
 122 .1  80,000
 9768000 mg
 9768 gm of Lime
Actual amount of Lime 86% 
100
 9768   11358.14 gm of Lime
86
106
Soda required  CaCl 2  MgCl 2 
100

106
100  100  106  200  212 mg of Soda
100 100
For 80,000 L of water sample, required Soda
 21280 ,000  16960000 mg of Soda
 16960 gm of Soda
Purity of Soda is 90% , so required Soda
 16960 100 / 90  18844.44 gm of soda.
Q.3a)i) What are organometallic compounds? Give the preparation and applications of
Grignard reagent.
Ans.: organic Compounds that contain carbon – metal bond are called organometallic
compounds. General structure of the compounds is represented by R-M. The nature of
Carbon – metal bond varies widely varying from bonds thats are essentially ionic to
those that are primarily covelent.
Organomagnesium halides were discovered by the French chemist Victor Grignard in
1900 and these compounds are called Grignard regent in his honour.
Grignard reagents are usually prepared by the action of Organic halides and
magnesium turning in an ether solvent.
ether
R  X  Mg R  MgX

Inert atmosphere
Almost all halides undergo this reaction to give Grignard reagent which are stable at
refluxing ether temperature, but they do react with oxygen and moisture. Due to this
reason the reagent is prepared in inert atmosphere.

9
 The formation of Grignard reagent takes place at metal surface. The reaction appears
to begin at discrete sites. Reaction commences with an electron transfer and
decomposition of the radical ion, followed by rapid combination of the organic group
with magnesium ion.
Chemical Properties of Grignard Reagent:
1. Grignard reagent react with compounds having acidic hydrogen to form hydrocarbon
AH O O
R  MgX   R  H  A  Mg  2  x
weak Acid
2. The most important reaction of Grignard Reagent are those in which these act as a
nucleophile and attack on unsaturated carbon specially the carbon of a carbonyl
group.
3. It reacts with CO 2 & form acids.

ii) Explain sacrificial anodic and impressed cathodic protection method for protection of
corrosion.
Ans.: Sacrificial anodic protection: In this method the metallic structure is connected by a
wire to a more anodic metal, so that all the corrosion of concentrated at this more
active metal. The more active metal itself gets corroded slowly, while the parent
structure is protected. The more active metal so employed is called sacrificial anode.
The corroded sacrificial anode block is replaced by fresh one, when consumed
completely. The important applications of this method include protection of
underground cables, ship hulls, water tank etc.

Impressed current cathodic protection: In this method an impressed current is

applied in opposite direction to nullify the corrosion current and convert the corroding
metal from anode to cathode. Usually, the impressed current is derived from direct
current source (like battery or rectifier) with an insoluble anode (like graphite, scrap
iron). Usually a sufficient d.c. current is applied to an insoluble anode, buried in the
soil and connected to the metallic structure to be protected. The anode is usually, in a
backfill so as to increase to electrical contact with the surrounding soil. This type of
cathodic protection has been applied to open water box coolers, water tanks

10
 condenser, laid up ships etc. this kind of protection techniques is, particularly useful
for large structures for long term operations.

b) Define and explain the terms involved in phase rule. Draw a neat labeled diagram of
water system and explain the area and curves in it. What is the significance of the
triple point and meta stable curves in this system.
Ans.: The main terms involved in phase rule are:
1. Phase: A phase is defined as an homogenous, physically distinct and mechanically
separable portion of system, which is separated from other such parts of the system by
definite boundary surface. For example if two liquids are immiscible then there will
be two phase while in case of miscible liquids there will be one phase only.
2. Components: The small number of independent variables constituents, taking part in
the state of equilibrium by means of which the composition of each phase can be
expressed in the form of chemical equation. For example – in water system
Ice ( s )  Water (i)  Vapour ( g )
H 2O H 2O H 2O
The chemical composition of all the three phases in H 2 O , hence it is one component
system.
3. Degree of Freedom: The degree of freedom is meant by the minimum number of
independently variable factors, such as temperature, pressure and composition of
phases, which must be arbitrarily specified in order to represent perfectly the
condition of a system. For example, for a system constituting of water in contact with
its vapors.
Water (l )  Water ( v)
We must state either the temperature of pressure to define to define it completely.
Hence its degree of freedom will be I.
Triple Point: The triple point of a system is the point at which the gaseous, liquid and
solid phase of a substance co-exist in equilibrium. For a given substance the triple
point occurs at a unique set of values of the temperature, pressure and volume. For
example triple point of water is 4.58mmHg pressure and 0 .0098 0 C temperature.
Metastable State: It is the state of super cooled water or supersaturated solution in
which the phase which is normally stable under the given conditions, does not form
unless a small amount of the normally stable state is already present. Thus

11
 supercooled water remains as liquid water below 0 0 C, until a small crystal of ice is
introduced.

Q.4 a) Give the stereo chemical aspect of S 1N and SN2 reactions with their mechanism.
Explain the factors affecting their stability.
Ans.: The nucleophilic substitution reaction may proceed through either of two mechanism:
 
1. Two step substitution mechanism S 1N` . It involves two steps, in which first step is
slow while the second is fast. In general it may be represent as
Step –I A  X Slow
  A   X  (Rate determination step)
O
Step –II Nu A  Fast

 Nu  A
As the first step does not involve the attacking nucleophile and molar concentration of
one reactant (A – X) is only changed, so the overall reaction is of first order because
the time taken by the reaction depends mainly on step –I, such reaction are S 1N
reactions, for example the nucleophilic substitution of ter. Butyl
S

2. One step substitution mechanism: It involves simultaneous bond breaking and bond
forming thus.
In this the attacking nucleophile, attacks at carbon of substrate and forming a high
transition state in which bond between carbon and nucleophile is in process of
forming and the bond between carbon and halide is in process of breaking.
In this one step reaction the molar concentration of two reactants are changed and
hence the reaction is of second order, as it is called S N2 reaction.
There are certain factors that influence the mechanism of nucleophilic substitution
reaction:
1. Effect of Solvent: The nature of the solvent in which reaction is carried out exerts a
profound effect on the mechanism of the reaction. For example hydrolysis of a halide
in a polar solvent proceeds via S 1N rather than S N2 mechanism.
2. Nature of Carbon Skeleton: it is Prominently exhibited in the behavior of the
primary, secondary and tertiary alkyl halide towards hydrolyzing agent.

12
 3. Nature of halide ion: It has been reported that the speed of the reaction varies with
the different halides ion present. A given alkyl iodied hydrolysis most rapidly and its
chloride does so with slowest rate.
b) What is electromechanical corrosion? Write down the mechanism involved in
electrochemical corrosion.
Ans.: The electrochemical corrosion refers the decay of metal involving a electrochemical
process. The electrochemical corrosion involves (i) the formation of anodic and
cathodic areas or parts in contact with each other (ii) presence of a conducting
medium (iii) corrosion of anodic only (iv) formation of corrosion product somewhere
between anodic and cathodic areas.
M  M  n  ne  (At anode)
On the other hand the cathodic reaction consumes electrons with either by –
a) Evolution of Hydrogen b) Absorption of Oxygen
a) Evolution of Hydrogen: This type of mechanism usually occurs in acidic
environment. Considering metal like Fe, the anodic reaction may be represent as –
Fe  Fe 2  2 e  (Anode)
These, electrons flow through the metal, from anode to cathode, where H  are
eliminated as hydrogen gas.
2 H   2e   H 2 (Cathode)
The overall reaction
Fe  2 H   2e   Fe 2  2e   H 2
Fe  2 H   Fe 2  H 2 
This type of corrosion causes displacement of hydrogen ion from the acidic solution
by metal ions. Consequently all the metals above hydrogen in the electrochemical
series have a tendency to get dissolved in acidic solution with simultaneous evolution
of hydrogen.
b) Absorption of Oxygen: Rusting of Iron in natural aqueous solution of electrolytes in
presence of atmospheric oxygen is a common example of this type of Corrosion. This
surface is iron is usually coated with a thin film of Iron Oxide. However if this iron
oxide film develops some cracks, anodic areas are created on the surface, while the
will metal parts act as Cathodes. It follows that the anodic area are small surface parts
while rest of the metal surface forms large cathode.
At the anodic area of the metal
Fe  Fc 2  2 e  (Anode)
These liberated electrons flow from anodic to cathodic area
1
O2  H 2O  2e   2OH  (Cathode)
2
The Fe 2 ions and OH  are diffused and forms ferrous hydroxide.
Fe 2  2OH   Fe OH 2
If enough oxygen is present then ferrous hydroxide easily converted into ferric
hydroxide.
4 FeOH 2  O2  2 H 2 O  2 FeOH 3  Fe 2 O3 .xH 2 O

13
Q.5 (a) What is liquid crystal? Differentiate between nematic and sematic liquid crystal and
give their applications.
Ans.: The Liquid Crystals are highly anisotrophic fluids that exists between the boundaries
of the solid and conventional, isotropic I liquid phase. An isotropic liquid has no
orientation order. Substances that are not as ordered as a solid, yet have some degree
of alignment are properly called Liquid Crystals.
Difference between Nematic and Sematic Liquid Crystals:
1. Nematic Liquid Crystals: The molecules in the nematic structure maintain a parallel
of nearly parallel arrangement to each other along the long molecular axis. They are
mobile in three directions and can rotate above one axis. This structure is one
directional. When the nematic structure is heated, it is generally transformed.into the
isotropic liquid. The nematic structure is the highest temperature mesophase in
thermotropic liquid crystals.
2. Sematic L.C.: The word sematic is derived from the Greek is explained by the fact
that the thick, slippery substance often found at the bottom of a soap dish is actually a
type of sematic liquid crystals. Molecules in this phase show a degree of translational
order not present in nematic. In this state the molecule maintain the general
orientation order to nematics, but also tend to align themselves in layers or planes.
Motions is restricted within these planes and separate planes are observed to flow past
each other.
Application : Liquid Crystal technology has had a major effect in many areas of
science and technology. They are used as display in digital wrist watches, calculators,
panel meters and industrial products. They can be used to record store and display
images which can be projected onto a large screen.
Q.5 (b) What is biogas? Describe the mechanism of biogasification.
Ans.: Biogas is produced by the degradation of biological matter by the bacterial action (of
anaerobic bacteria) in the absence of free oxygen. For example-Natural gas is a
biogas, which results after a long period decay of animal and vegetable matters,
buried inside the earth. Biogas can also be produced form the sewage waste and other
organic wastes.
Mechanism of Biogasification:
The Biogas is produced by the anaerobic degradation of cattle dung. It is carried out
in a gobar gas plant which consist of a well shaped underground tank called digester
covered with dome shaped roof, both made of bricks and cement. The dome of the
digester is fixed so that it acts as a gas holder for the biogas produced. At the top of
the dome there is a gas outlet pipe and a gas valve. On the left side of the digester,
there is sloping inlet chamber and on the right side there is rectangular outlet
chamber, both made of bricks and cement. Fresh cattle dung and water slurry is
introduced from the inlet chamber, while spent dung slurry gets collected in the outlet
chamber. The inlet chamber is connected to the mixing tank while the outlet chamber
is connected to overflow tank.
The slurry (made by mixing cattle dung and water is equal proportion in mixing tank)
is fed into the digester tank via inlet chamber, till the slurry level becomes nearly
equal to the cylindrical top level. In approx 50 to 60 days, the biogas plant start

14
 functioning. During this period, the cattle dung undergoes fermentation in the
presence of anaerobic bacteria with gradual evolution biogas, which starts collecting
in dome shaped space. As the time passes more and more biogas collect inside the
dome. From time to time fresh slurry is fed to the digester so as to get regular supply
of biogas.

Q.6 (a) What is crystal imperfection. Explain the one and two dimensional imperfections in
solid.
Ans.: Imperfection in ionic crystal means any deviation from perfectly ordered arranged
constituents ions or crystals, thereby resulting in change in the properties. The
common types of imperfection in ionic crystals are –
(a) Electric Imperfections: Which corresponds to defects in ionic crystals, due to
electrons for example when trivalent impurity or pentavalent impurity is present in Si
or Ge crystal, it becomes semiconductor due to the presence of excess holes or excess
electrons respectively.
(b) Atomic Imperfection: These arise due to irregularity in the arrangement of atoms or
ions in the crystal lattice. These arises when any of the constituent particles has been
1. Missing from the normal crystal lattice site.
2. Dislocated to a position which is meant for another particles.
3. Shifted to an interstitial void in the crystal lattice.
For ease of their characterization, defects are classified on the basis of their geometry,
which is realistic as defects are disrupted region in a volume of a solid.
Defects are:
a) Point defect (Zero dimensional)
b) Line defects (Single dimensional)
c) Surface defects (Two dimensional)
d) Volume defects (Three dimensional)
Line Imperfection (defects) i.e. one dimensional: It is also called dislocation. These
are abrupt change in the regular. Ordering of atoms along a line in the solids. They
occur in high densities and strongly influence the mechanical properties of material.
Interfacial defect (Two dimensional imperfection): it can be defined as boundaries
that have two dimensional imperfection in crystalline solid and have different crystal
structures and crystallographic orientations on either side of them. They refer to the
regions of distortion that lie about a surface having thickness of a few atomic
diameters.

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 For example: external surface, grain boundaries, twin boundaries etc. these
imperfections are not thermodynamically stable, rather they are metastable
imperfections.
b) What is Portland Cement? Give chemical reactions involved during setting and
hardening of cement.
Ans.: The Portland cement may be defined as “an extremely finely ground product obtained
by calcining together, at about 1500 0 C , and intimate and properly proportioned
mixture of clay containing (argillaceous) and lime containing (calcareous) raw
material without addition of anything subsequent to calcimation, except retarted
gypsum.
Chemical reaction involved during setting & hardening:
1. Initial setting: The initial setting of cement paste is due to the hydration of tricalcium
aluminate C 3 A and get formation of tetraclacium aluminoferric C 4 AF 
3CaO. Al2O3  6 H 2O  3CaO. Al2O3 . Al2O3 .6 H 2O  880KJ / kg or
C 3 A  6 H 2 O  C 3 A.6H 2 O  880KJ / kg
Tricalcium Aluminate Hydrated Tricalcium Aluminate
4CaO. Al 2 O3 .Fe 2 O3  7 H 2 O  3CaO. Al 2 O3 .6 H 2 O  CaO.Fe 2 O3 .H 2 O  420 KJ / kg
Tetracalcium Alumino Ferrite (Crystalline) (Gel)
Also dicalcium silicate starts hydrolyzing to tobernmonite gel (which possesses a very
high surface area and thus very high adhesive property), which also contribute to
initial setting.
22CaO.SiO 2   4 H 2 O 
 2CaO.2 SiO 2 .6 H 2 O  Ca OH 2  250 KJ / kg
Dicalcium silicate Tobermonite Gel
2. Final setting and hardening: The final setting and hardening of cement paste is due to
the formation of tobermobite gel, crystallization of calcium hydroxide and hydrated
tricalcium aluminate
23CaO.SiO2   6 H 2 O 
 3CaO.2SiO3 .3H 2 O  3CaOH 2  500KJ / kg Tricalcium
silicate Tobermonite Gel Crystalline Calcium Hydroxide
The sequence of chemical reaction during setting & hardening

Cement + Hydration of Gelation Gelation of

1
day
 1
day
 1day
of C 3 S 
Water C 3 A & C 4 AF C2 S & C3 S

Q.7(a) For an XY2 molecule, show various properties of stretching and bending in R
spectroscopy.
Ans.: The R Light is observed only when oscillating dipole moment due to molecular
vibrations interacts with the oscillating electric vector of an infracted beam. The
simplest vibrational motion in molecules giving rise to absorption of infrared
radiations are stretching & bending.
1. Stretching Vibrations:
In this type of vibrations, the distance between atoms increases or decreases but the
atoms remain in the same bond axis. It is of two types – symmetry and antisymmetric.
For the molecule of XY2 the vibrations can be illustrated as the following figures.

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 Symmetric: In symmetric stretching the movement of the atoms with respect to the
particular atoms in a molecule is in the same direction.
Anti symmetric: In this, one atom approaches the central atom while the other moves
away.
2. Bending Vibrations:
In this types of vibrations, the positions of the atom change with respect to the
original bond axis but the distance between the atoms remain constant. Bending
vibration are of two types:
Scissoring: In this both atoms swing in opposite direction.
Rocking: Atoms move in same direction.

Out of Plane: These are of two types:

Wagging: In this both the atoms swing up and below the plane with respect to central
atom
Twisting: in this one atom moves up & other down.
b) i) 200ml of water sample has hardness equivalent of 25ml of 0.08N EDTA. What is its
hardness in ppm?
Ans.:  1ml of 1N EDTA  50mg of CaCO3
 25ml of 0.08N EDTA  50  25  0.08mg of CaCO3
 100mg of CaCO3
 200ml of water sample contains  100mg of CaCO3
100
 1ml of water sample contains  mg of CaCO 3
200
100  1000
 1000ml of water sample contains  mg of CaCO3 / liter
200
 500mg / liter of CaCO3
 500 ppm

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