Dr. A.P. J. K.

TECHNICAL UNIVERSITY, LUCKNOW(UP)

B.Tech. (SEM.I) THEORY EXAMINATION, 2022-23
ENGINEERING CHEMISTRY(BAS102)

Paper ID: 22014 Max.Marks:70

SECTION A

1. Attempt all questions in brief. 2 x 7 = 14

(a) On the basis of MO theory calculate the bond order of NO. Will NO be
paramagnetic or diamagnetic?
Ans. The electronic configuration of NO =
σ(1s2) σ∗(1s2) σ(2s2) σ∗(2s2) σ(2px)2 π(2py)2 π(2pz)2 π∗(2py)1 [1 Marks]

Bond order = Bonding electron – non-bonding electron

2
Bond order =10−5
2
Bond order = 2.5 [1 Marks]

Hence, the bond order of NO will be 2.5.

(b) What are Chiral Drugs? Give examples of Chiral Drugs.

Ans. Chirality is a property of a molecule in which the spatial distribution of the atoms is such
that it has a non-superimposable mirror image. Human body recognizes the enantiomers as
two different substances and therefore generates different response. This difference is due
to the presence of drug receptor sites that bind only to specific drugs. More than 50% of
the drugs that are used today are chiral compounds. [1 Marks]
Examples of chiral drugs are morphine, dobutamine, epinephrine, norepinephrine, etc.

[1 Marks]
(c) Give important applications of electrochemical series.

Ans. Electrochemical series is a series in which elements are arranged in an increasing or decreasing
order of their standard electrode potential. It is also called activity series of elements.
• Electrochemical series helps us to identify a good oxidizing agent or reducing agent.
• Calculation of Standard EMF) of Electrochemical Cell

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 • Predicting the Feasibility of Redox Reaction
• To calculate the standard reduction potential of half-cell reaction. [2 Marks]

(d) A water sample is found to contain 40.5 mg/L Ca(HCO3)2; 14.6 mg/L
Mg(HCO3)2; 22.2 mg/L CaCl2; 24 mg/L MgSO4 and 18mg/L NaCl.
Calculate the temporary and permanent hardness of the water sample.
Ans.
Constituents Amount mg/L Multiplicati CaCO3 eq. mg/L
on Factor
Ca( HCO3)2 40.5 100/162 40.5 X 100/162= 25
Mg( HCO3)2 14.6 100/146 14.6 X 100/146 = 10
CaCl2 22.2 100/111 22.2 X 100/111= 20
MgSO4 24 100/120 24 X 100/120 =20
NaCl 18 - Do not cause
hardness
[1 Marks]
Temporary Hardness = Hardness due to Ca(HCO3)2 + Mg( HCO3)2
= 25 + 10 = 35 mg/L

Permanent Hardness = Hardness due to CaCl2 + MgSO4

= 20 + 20 = 40 mg/L [1 Marks]

(e) Discuss the preparation and uses of PTFE.

Ans. Tetrafluoroethylene is polymerized by using free-radical initiators such as hydrogen peroxide or

ammonium per-sulphate at high pressure to produce polytetrafluoroethylene (teflon). Teflon is a
synthetic fluoropolymer made up of tetrafluoroethylene monomer. The chemical name of Teflon
is poly (1,1,2,2 tetrafluoroethylene). It is a thermoplastic polymer.

Teflon chemical formula is (C2F4)n. The Teflon formula shows repetitive or n numbers of C2F4
units. It has an ability to maintain high strength, toughness, and self-lubrication at low
temperatures (around 5 K), and good flexibility at temperatures above 194 K.
[1 Marks]
Applications:
It is used in making waterproof fabric.
It is used in making non-stick cookware.

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 It is used in making an anti-friction device.
It is used for coating medical appliances (surgical devices).
It is non-reactive, partly due to the strength of carbon and fluorine bonds. It is often in use in
containers and pipework for reactive and corrosive chemicals.
If in use as a lubricant, it reduces friction, wear, and energy consumption of machinery.
[1 Marks]

(f) How does Gross Calorific Value differ from Net Calorific Value?
Ans All fuel have sufficient amount of Hydrogen, which on combustion converted to steam. As the
product of combustion is cooled down to room temperature, the steam gets condensed into
water and latent heat is evolved. Thus, Gross calorific value (GCV) differs from Net Calorific
Value (NCV) because in determining the GCV, the latent heat get included in the measured
heat. [2Marks]

(g) What are Chromophores and Auxochromes? Give examples.

Ans. The term chromophore is defined as “Any isolated covalently bonded group that shows a
characteristic absorption in the ultraviolet or visible region”. The absorption occurs irrespective of
the fact whether colour is produced or not. Some of the important chromophores are

There are two types of Chromophore:

• Chromophores containing π electrons: They undergo π- π* transition, e.g., ethylene, acetylene, etc.
• Chromophores containing both π and n electrons. They undergo n - π* transition. e.g., > C=O, - N= O
etc. [1 Marks]
An Auxochrome can be defined as any group which does not itself acts as chromophore but whose
presence brings about a shift of the absorption band towards the red end of the spectrum (longer
wavelength). The absorption at longer wavelength is due to the combination of a chromophore with
an auxochrome. Some common Auxochromic groups are
Hydroxyl Groups
Alkoxy Groups
Amine Groups
Mono substituted amino groups
Dialkyl amine group
Thiols [1 Marks]

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 SECTION B
2 Attempt any three of the following: 7 x 3 = 21
2(a) Describe different types of liquid crystals. Discuss the applications of Liquid crystals.

Ans. Liquid crystals are special substances that exhibit an intermediate state of matter that exists
between crystal and liquid states; ever since Reinitzer in 1888 reported for the first time several
Cholesteryl esters and later reported by 'Lehmann. Approximately 5% of all organic compounds
exhibiting LC behavior have important characteristic properties like anisotropy, magnetic and
electric susceptibility.
The distinguishing characteristic of the liquid crystalline state is the tendency of the molecules
(mesogens) to point along a common axis, called the director. This contrasts with molecules in the
liquid phase, which have no intrinsic order. In the solid state, molecules are highly ordered and
have little translational freedom. The characteristic orientation order of the liquid crystal state is
between the traditional solid and liquid phases, and this is the origin of the term “mesogenic state”
used synonymously with liquid crystal state. Polymorphism arises between the transformations of
crystal to isotropic fluid due to weak intermolecular forces that impart the equilibrium, resulting in
well-defined phase changes. This was known as meso-morphism and the phases known as
'mesophases’. The following parameters describe the extent to which the liquid crystal sample is
ordered.
(a) Positional order: Positional order refers to the extent to which an average molecule or group of
molecules shows translational symmetry.
(b) Orientation order: Orientation order represents a measure of the tendency of molecules to align
with the director on a long-range basis.
(c) Bond orientation order: Bond orientation order describes a line joining the centers of nearest
neighbor molecules without requiring a regular spacing along that line by virtue of the optical studies.

[2 Marks]

Compounds exhibiting mesomorphic behavior can broadly be categorized into two types:
(i) Lyotropic LC: They are natural and synthetic in origin, where the liquid crystalline order is solvent
induced. It has a lot of biological importance.
(ii) Thermotropic LC: They are formed (including polyschiff's base polymers and aromatic

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polyesters) where the liquid crystalline order is thermally induced. The general common molecular
feature is an elongated, narrow molecular frame work which usually is depicted as a rod or cigar-
shaped entity. Some disc shaped molecules also exhibit liquid crystalline properties. It has numerous
industrial applications in display devices, which earned the interest of physicists and chemists
towards its synthesis and characterization. They are categorized into three different types of
mesophases (Fig.1).
1 NEMATIC LC
i. The simplest form is a nematic liquid crystal i.e. long-range orientational order but no
positional order.
ii. The preferred direction is known as director.
iii. Despite the high degree of orientational order, the nematic phase as a whole is in disorder
i.e. NOMACROSCOPIC ORDER (orientation within a group is similar but not from one
group to another).
iv. The structure of a nematic phase can be altered in a few ways. E.g. electric or magnetic
field or treatment of surfaces of the sample container.

2 SMECTIC LC
i. The smectic phases, which are found at lower temperatures than the nematic, form well-
defined layers that can slide over one another in a manner like that of soap.
ii. The word "smectic" originates from the Latin word "smecticus", meaning cleaning, or
having soap like properties.
iii. The smectics are thus positionally ordered in one direction.
iv. In the Smectic A phase, the molecules are oriented along the layer normal, while in the
Smectic C phase they are tilted away from the layer normal.
v. SMECTIC phase occurs at temperatures below nematic or cholesteric.
vi. Molecules align themselves approx. parallel & tend to arrange in layers.
vii. Not all positional order is destroyed when a crystal melts to form a smectic liquid crystal.
viii. Chiral smectic C liquid crystals are useful in LCDS.

3 CHOLESTERIC LC
i. The chiral nematic phase exhibits chirality (handedness). This phase is often called the
cholesteric phase because it was first observed for cholesterol derivatives.
ii. Only chiral molecules (i.e., those that have no internal planes of symmetry) can give rise
to such a phase. This phase exhibits a twisting of the molecules perpendicular to the
director, with the molecular axis parallel to the director.
iii. In cholesteric phase, there is orientational order & no positional order, but director is in
helical order.
iv. The structure of cholesteric depends on the pitch, the distance over which the director
makes one complete turn one pitch - several hundred nanometers.
v. Pitch is affected by temperature, pressure, electric and magnetic fields.

[3 Marks]

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Applications of LC:

i. LCD displays: A liquid-crystal display (LCD) is a flat panel display, electronic visual
display, or video display that uses the light modulating properties of liquid crystals.
ii. Liquid Crystal Technology to Telecommunication Devices: A dense wavelength division
multiplexed (DWDM) optical network, as with any information network, requires switches
to perform routing of the signals. DWDM networks pass several information channels
along the same optical wave guide.
iii. Optical fiber: each channel corresponds to a different wavelength of light with the
wavelengths typically separated by less than a nanometer. Consequently, DWDM networks
require switches that are wavelength selective with very high resolution.
iv. Dyes (cholesterics)
v. Advanced materials (Kevlar)
vi. Membranes, Drug delivery.
vii. Temperature measurement (by changing colors).
viii. Solvents for GC, NMR, reactions, etc. [2 Marks]

2(b) What is Atropisomerism? Give five examples of compounds showing optical isomerism in
the absence of chiral carbons.

Ans. Atropisomerism refers to different spatial arrangements of groups, due to restricted rotation around a
single bond. Compounds containing a chiral carbon are optically active. However, there exist some
compounds which do not possess a chiral atom but are optically active provided that the molecule is
dissymmetric. Examples: allenes, biphenyls etc.
[2 Marks]
1. ALLENE DERIVATIVES

In allenes, the central carbon forms two sp-sp2 sigma bonds. The central carbon has also two p-
orbitals which are mutually perpendicular. These form pi-bonds with the p-orbitals on the other
carbon atoms. As a result, the substituents at one end of the molecule are in plane which is
perpendicular to that of the substituents at the other end, so that the compound exists in two forms
which are non-superimposable mirror images and are optically active.
Some derivatives of allenes (CH2=C=CH2) exhibit optical isomerism.
Example 1.

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Example 2

Example 3

Example 4

Example 5

These two forms are non-superimposable mirror images. They do not interconvert at room temperature
because the energy required to twist one ring through 180 angle relative to the other is too high. This in
turn is because, during the twisting process, the two -SO3H groups must come into very close proximity
when the two benzene rings become coplanar and strong repulsive forces are introduced. [5 Marks]

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 2(c) Explain the setting and hardening of cement with relevant chemical reactions
involved during the process.

Ans. Cement: Concrete is most widely used non-metallic material in construction of buildings, dams,
bridges, highways etc. In concrete, cement is the essential bonding material which binds sand and rock
when mixed with water.
Manufacture of Portland Cement:
The steps involve in the manufacturing process are as follows:
i) Crushing
ii) Mixing
iii) Burning
iv) Grinding
i) Crushing: In this step raw material of Portland cement lime, Silica, Alumina, Magnesia,
Ferric Oxide, Sulphur trioxide, Sulphur Oxide, Potassium Oxide are crushed and ground to
fine powder through ball mill.
ii) Mixing: In this step raw ingredients or fine powder are mixed in presence (wet process) or
absence (dry process) of water to form slurry, then slurry is stored in storage tank.
iii) Burning: The burning process is done in Rotary Kiln. The Rotary Kiln possesses three
different temperature zone like drying zone, calcinations zone and Clinkering zone.

Rotary Kiln
Drying zone:
It is the upper part of Rotary Kiln having temperature around 250oC where the waterfrom the
slurry evaporates.
Calcinations zone:
It is middle portion of Rotary Kiln where temperature ranges from 700 o-1200oC. in this
region limestone undergoes decomposition to form quick lime and carbon dioxide(escape out).
Clinkering zone:
It is the lower part of Rotary Kiln where quick lime with clay to form calcium silicate,
aluminates and ferrite.
2CaO + SiO2 Ca2SiO4 (Ca2S)
Dicalcium silicate
3CaO + SiO2 Ca3SiO5 (Ca3S)

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 Tricalcium silicate
3CaO + Al2O3 Ca3Al2O6 (Ca3A)
Tricalcium aluminate
4CaO + Al2O3 + Fe2O3 4CaO.Al2O3.Fe2O3 (Ca4AF)
Tetracalcium alumino ferrite

The aluminates and silicates are mixed with CaO to form stone like structure, knownas
clinkers.
iv) Grinding:
The cooled clinkers are ground to a fine powder in ball mill. At this time 2-3% ofgypsum
is added to prevent the early setting of cement. [3 Marks]

Setting and hardening of cement

When water mixed with Cement, form a plastic paste. The past is subjected tohydration and gel
and finally crystalline products are formed.

3CaO.Al2O3 + 6H2O → 3CaO.Al2O3.6H2O + Heat

2(2CaO.SiO2) + 4H2O → 3CaO.2SiO2.6H2O + Ca(OH)2 + Heat

4CaO.Al2O3.Fe2O3+7H2O → Ca3Al2O6.6H2O + CaO.Fe2O3.H2O + Heat

Tobermonite gel, calcium hydroxide crystallization and hydrated tricalcium aluminateare responsible
for final setting and hardening of cement.

2(2 CaO.SiO2) + 6H2O 3CaO.2SiO2.3H2O + 3Ca(OH)2 + Heat

3CaO.Al2O3 + 6H2O → 3CaO.Al2O3.6H2O + Heat
[4 Marks]

2(d) Explain the stages involved in production of biogas from cattle dung. Compare the impact
of use of biogas and coal on the environment.
Ans. Biogas is a mixture of methane, CO2 and other trace gases produced by anaerobic
decomposition of organic matter.
Characteristics:
1. Composition

2. It is odourless, smokeless, and burns with blue flame.

3. The colorific value of biogas depends upon the CO2 content (Non-combustible gas). The greater
the CO2 content in biogas the lesser is its calorific value. [1 Marks]

Process: - Biogas production is carried out in biogas plant or digester made up of bricks or steel. A slurry
(mixture of cattle dung and water) is fed into the digester from the inlet and gas formed is trapped by

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dome (inverted drum). The gas is transported through pipe line, by opening gas valve, for distribution and
use.

[1 Marks]

[3 Marks]
Advantages:
1. Use for cooking and lighting
2. Generate power.
3. Gives excellent quality manure.
4. Heat generated by direct-burning of 1 kg cattle dung is 23.4 kcal. If cattle dung is converted
into biogas, it can supply 188 k cal of heat.
5. It does not contain poisonous CO gas.
6. It is free from smoke, dust, dirt etc. hence keep environment and intensely clean

Disadvantages
1.Not efficient enough on a large scale. Since it is difficult to enhance the efficiency of biogas, it
is not economically viable to use biogas on a large scale.
2. Contains impurities: It contains many impurities that are difficult to control even after
purification rounds. Biogas, when compressed, to be used as fuel, proves to be highly corrosive
to the container.

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 3. Unstable and hazardous: When methane meets oxygen, it reacts violently to produce carbon
dioxide. The highly inflammable nature of methane makes it prone to explosions.

BIOGAS: environmental impact on society

Reduce greenhouse emissions:
Unlike fossil fuels, the carbon dioxide that is released when biogas is burnt was recently taken
from the atmosphere by photosynthetic activity of plants. Biogas production by aerobic digestion
also reduces emission of methane and nitrous oxide from storage and the digestion of untreated
manure as fertilizer.
Waste reduction:
Biogas production can transform waste material into a valuable resource by using it as a substrate
for anaerobic digestion. This reduces the volume of waste and costs for waste disposal.
Reduces respiratory disorders:
The use of biogas reduces respiratory disorders caused by smoke from cooking with firewood
which especially affects women and their children.
Improved village hygiene:
Since biogas can be produced from toilets, it leads to the destruction of pathogens.
Fertilizer:
Digestion is an excellent fertilizer rich in N2, P, K and micronutrients which can be applied to
soils to increase its fertility.
Reduced dependency on imported fossil fuels:
Biogas production based on national and regional biomass resources increases security of national
energy supply and diminishes dependency on imported fossil fuels.
Flexibility to use different feed stock:
Various feedstocks can be used for production of biogas eg Animal manure and slurry, crop
residues, organic wastes from diary production, food industries, organic fraction of municipal
waste. [2 Marks]

2(e) What are organo metallic compounds? Discuss the preparation of Grignard Reagent. Predict
the final product obtained when C2H5MgBr reacts with
(i) HCHO (ii) CH3CHO (iii) (CH3)2CO?
Ans. Organometallic compound are chemical compounds containing at least one bond between a
carbon atom of an organic molecule and a metal including alkaline, alkaline earth, transition
metals, and metalloids like boron, silicon, and tin. Organometallic compounds provide a source
of nucleophilic carbon atoms which can react with electrophilic carbon to form a new carbon-
carbon bond. E.g., iodo(methyl)magnesium MeMgI, dimethyl magnesium (Me2Mg) etc.
[2 Marks]

Grignard reagent: They are called Grignard reagents after their discoverer, French chemist Victor
Grignard.
Preparation of Grignard reagents (RMgX): Organo magnesium halides are called Grignard
reagents. It is prepared in the laboratory by the action of alkyl halide (R is a hydrocarbon radical:
CH3, C2H5, C6H5, etc.; and X is a halogen atom, usually chlorine, bromine, or iodine) on magnesium
metal in the presence of dry ether.

Preparation:
Ether
RX + Mg −−−→ RMgX R= alkyl group
X= halogen [2 Marks]

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Product obtained with Grignard Reagent:
1. with HCHO primary alcohol formed

H2O
C2H5MgBr + HCHO −−→ C2H5CH2OH + Mg(OH)Br

2. with CH3CHO secondary alcohol formed

H2O
C2H5MgBr + CH3CHO −−→ C2H5CHCH3OH + Mg(OH)Br

3. with CH3COCH3 tertiary alcohol formed

H2O
C2H5MgBr + CH3COCH3 −−→ C2H5 (CH3)2COH + Mg(OH)Br [3 Marks]

SECTION C
3. Attempt any one part of the following: 7x1=7
3(a) Describe the structure and applications of Graphite and Fullerenes. Explain the
reasons for electrical and lubricating properties of graphite.
Ans. Structure of Graphite: The carbon atoms in graphite structure are arranged in a fused hexagon form

in a planar, condensed ring system. This crystal carbon has a structure that is planar and layered.
Different layers of this element are stacked together and held by weak covalent forces to form a giant
covalent structure.
Graphite is a big covalent structure with each carbon atom joined with three other carbon atoms with
covalent bonds. Each carbon atom is sp2 hybridized. These carbon atoms form a layer like structure
with a hexagonal arrangement of carbon atoms. These layers have weak forces between them. Due to
these weak forces, the layers can slip over each very easily. Each carbon atom has one non bonded
electron, which becomes delocalized.

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Applications of Graphite

1.Graphite can be used in the manufacture of 'lead' used in pencils.

2.It is also used in refractories and steel making.
3.Due to soapy nature, it is used as Lubricant.
4.Graphite is used in making electrodes and molds in foundry.
Electrical and lubricating properties of graphite: In graphite, three electrons are involved in
sigma bonding and the fourth electron is free to move on applying potential difference. So due to
its free delocalized electron, which is free to move throughout the sheets, it is good conductor of
electricity.

The layers of the carbon crystal could swiftly move past each other as the layers could be separated
easily as van der Waals bonds that are weak-hold them together and have a high melting point used
as Lubricants. [4 Marks]

Structure of Fullerene:
Fullerene is an allotrope of carbon discovered by Richard Smalley, Robert Curl, Harry Kroto et al at
Rice University and Sussex University, in the year 1985, and awarded the Nobel Prize in 1996.
Fullerene Structure: The Buckminsterfullerene was the first fullerene to be discovered and was
named after the American architect, Buckminster Fuller, as it resembled the geodesic dome designed
by him. Also called as called soccer ball molecule due to its structure.
The C60 bucky ball is made of 60 carbons at 60 vertices that make a spherical structure. It is
composed of 12 pentagonal and 20 hexagonal rings that are adjacent to each other. These rings are
conjugated with double bonds. The C-C bond length for the hexagonal rings is 1.40 A° and 1.46
A° for the pentagonal rings, with the average bond length equal to 1.44 A°.
It has sp2 hybridized carbon atoms. These molecules have extremely high affinity for electrons and
can be reversibly reduced to take up electrons. Although this molecule is made of conjugated carbon
rings, the electrons here are not delocalized, and thus, these molecules lack the property of super
aromaticity. These molecules have very high tensile strength and bounce back to their original shape
after being subjected to over 3000 atmospheric pressures.

Applications

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 i. As organic photovoltaics (OPV),
j. ii. As antioxidants and biopharmaceuticals,
k. iii. As superconductors, iv. soft ferromagnets v. polymer additives, vi. As water purification and
bio-hazard protection catalysts, vii. portable power devices. [3 Marks]
OR
3(b) What are Carbon Nano Tubes? Discuss the applications of nanomaterials.

Ans. Carbon nanotubes (CNTs) are a type of carbon with a diameter of nanometers and a length of
micrometers (where the length to diameter ratio exceeds 1000) CNT is made up of enrolled cylindrical
graphite sheets (named graphene) wrapped up into a seamless cylinder with a nanometer-sized
diameter. Nanomaterials are of interest because at this scale unique optical, magnetic, electrical, and
other properties emerge.
These emergent properties have the potential for great impacts in electronics, medicine, and other
fields. Some nanomaterials occur naturally, but of particular interest are engineered nanomaterials
(EN), which are designed for, and already being used in many commercial products and processes.
Using nanotechnology, materials can effectively be made stronger, lighter, more durable, more
reactive, more sieve-like, or better electrical conductors, among many other traits.
[3 Marks]

Applications of Nanomaterials:
1.Nanoscale additives to or surface treatments of fabrics can provide lightweight ballistic energy
deflection in personal body armor, or can help them resist wrinkling, staining, and bacterial growth.
2. Clear nanoscale films on eyeglasses, computer and camera displays, windows, and other surfaces
can make them water- and residue-repellent, antireflective, self-cleaning, resistant to ultraviolet or
infrared light, antifog, antimicrobial, scratch-resistant, or electrically conductive.
3. Nanoscale materials are beginning to enable washable, durable “smart fabrics” equipped with
flexible nanoscale sensors and electronics with capabilities for health monitoring, solar energy
capture, and energy harvesting through movement.
4. Light weighting of cars, trucks, airplanes, boats, and space craft could lead to significant fuel
savings.
Nanoscale additives in polymer composite materials are being used in baseball bats, tennis rackets,
bicycles. [4 Marks]
4. (a) Why is TMS used as an internal standard in NMR spectroscopy? Two isomeric compounds
A and B have molecular formula C 10H14. The 1H NMR spectra of these isomers gave the
following data:
Isomer A: δ 1.30 (9H,s); δ 7.28 (5H, s)
Isomer B: δ 0.88 (6H, d); δ 1,86 (1H, m); δ 2.45 (2H, d); δ 7.12 (5H, s)
Giving reasons assign the structures for the two isomers.

Ans. Tetrametyl silane is used as an internal standard in NMR because of following reasons.
1. It gives a single sharp and strong peak because of 12 identical protons with a chemical shift at low
resonance frequency relative to almost all other 1H resonance.
2. It is volatile and easily removed from samples.
3. It does not show association with the sample.
[1 Marks]

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Interpretation of NMR data for organic compound (C10H14)

NMR Data Reason Structure

Isomer A: δ 1.30 • Since C10H14
(9H,s); δ 7.28 (5H, molecule shows 2
s) signals, indicates 2
sets of protons
present on the
molecule.
• A signal having 9
identical protons
with shielded
environment
indicates presence
of three -CH3 group
attached on same
carbon.
• Another signal due
to 5 identical
protons in de-
shielded state
indicates -C6H5
group.
Isomer B: δ 0.88 • Since C10H14 shows
(6H, d); δ 1,86 4 signals, indicates
(1H, m); δ 2.45 4 sets of protons
present on the
(2H, d); δ 7.12 molecule.
(5H, s) • A signal having 6
identical protons
with shielded
environment
indicates presence
of two -CH3 group
attached on same
carbon.
• Another signal due
to 2 identical
protons in
shielded state
indicates CH2
group.
• Another signal due
to 1 proton in
shielded state
indicates CH
group.
• Another signal due
to 5 identical
protons in De-
shielded state
indicates C6H5
group.
[(1.5 Marks for structure + 1.5 Marks for Explanation) x 2]

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 OR
3 (b) (i) Explain the basic principle of IR Spectroscopy. What is the significance of
Fingerprint region in IR spectroscopy?
Ans. Principle of IR spectroscopy: Molecules are made up of atoms linked by chemical bonds. The
movement of atoms and the chemical bonds is like spring and balls (vibration). These characteristic
vibrations are called Natural frequency of vibration.
When energy in the form of infrared radiation is applied then it causes the vibration between the atoms
of the molecules. On passing an IR radiation a molecule can absorb it and can undergo a transition
from lower vibrational level (V=0) to higher vibrational level (V=1) only if there is a change in dipole
moment during the vibration (IR Active vibration).

Energy associated with a vibrational level can be calculated from the formula-
(V + 1/2) hv Where V is vibrational quantum no. (V=0,1,2,3…….). At room
temperature, when a molecule exists in ground state (V=0), the energy will be
½ hv. This amount of energy is called zero-point energy.

Conditions for IR spectroscopy: -

1. The molecule which undergoes a net change in dipole moment. du/dq = 0

2. The frequency of the vibration must be equal to the radiation frequency. (v0) =v [2 Marks]

Significance of Fingerprint region in IR:

The IR region below 1500 cm (1500 cm-1 – 600 cm-1) is known as fingerprint region. The region, above
it, is the functional group region and is useful for identification of functional group. Functional group
region shows the absorption due to stretching mode whereas finger print region contains absorption due
to bending vibrations. As there are many bending vibrations in a molecule than the stretching vibration
thus the spectra in this region becomes complex. Each organic molecule has its own unique absorption
pattern in region. If two pure samples have same spectra in same medium and same condition, then
the samples are of same compound. If two different molecules contain the same functional group, they
show similar absorption above 1500 cm- (in functional group region) but their spectra differ in this
region that is why it is called as fingerprint region [2 Marks]

4 (b)(ii) Identify the chromophoric groups present in cyclopentene, toluene, butanone and
methanethiol in UV spectroscopy.

S. Molecule Structure Chromophoric Group

No.
1. Cyclopentene -C=C-

2. Toulene

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 3. Butanone

4. Methanethiol
¨
S-H
¨

[3 Marks]

5. Attempt any one part of the following: 7x1=7

5(a) Discuss the mechanism of electrochemical theory of corrosion by absorption of
oxygen. What effect will have increased oxygen supply have on such corrosion? How
can corrosion be minimized by proper design?

Ans: Mechanism of Rusting of Iron Electrochemical Theory of Rusting

Oxygen absorption mechanism: The overall rusting involves the following steps,
Oxidation occurs at the anodes of each electrochemical cell. Therefore, at each anode neutral
iron atoms are oxidized to ferrous ions.
The surface of iron will be usually coated with a thin film of iron oxide. However, if this oxide
film develops some cracks, anodic areas are created on the surface. While pure metal parts act
as cathode. Thus, anodic areas have very small surface parts. The rest of the surface of the
metal forms cathodes. Thus, at the anodic part iron metal dissolves as Fe+2 ions with the
liberation of electrons
At anode Fe→ Fe+2+ 2e- (oxidation) X 2
The liberated electrons flow from anodic to cathodic areas through iron metal during which they
interact with dissolved oxygen and moisture.

At cathode O2 + 2H2O +4e→4OH- (reduction)

Overall reaction 2Fe + O2 + H2O→2Fe+2 + 4(OH)-→ 2Fe(OH)2

The Fe+2 ions and OH ions diffuse and form ferrous hydroxide precipitate when they meet with each
other.
Now depending on the availability of oxygen in the environment, two types of corrosion
productsare formed.

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 in excess supply of O2- yellow rust is formed.
4Fe(OH)2 +2H2O +O2 →4 Fe(OH)3 →2Fe2O3. xH2O
Yellow rust

in limited supply of oxygen- black rust is formed.

6 Fe(OH)3→ Fe2O3. FeO. 6H2O
Black rust
Figure: Oxygen absorption mechanism
[4 Marks]
With an increase in supply of oxygen to metal surface corrosion is promoted. Less oxygenated
parts act as anodes and more oxygenated parts act as cathode. This results in the formation of
concentration cells. [1 Mark]

2. Proper designing-important designing principles are-

• Avoid the contact of two dissimilar metals with a large difference of reduction potential.
• In galvanic cells, use large anodic area as compared to cathodic area.
• Proper drainage of water (avoid sharp edges).

Fig: Corrosion prevention by proper design

[2 Marks]
5(b) Discuss the differences between anodic and cathodic metallic coatings. Explain the
processes of Galvanizing and Electroplating? What will happen if an iron ship
travelling in the sea is attached through an insulated metallic wire to a small
sheet of magnesium?
Ans. Metallic coatings:
ANODIC COATING / SACRIFICIAL COATING
1 Base metal is coated with a metal which is more reactive in its comparison.
2 Protects the underlying base metal sacrificially.
3 Known as anodic coating as the reduction potential coating metal is less than that of base metal.
4 If there are pores, cracks, or breaks in such a coating base metal is not corroded till all the coating
metal is consumed.
5 Zn, Cd, Al are generally used as sacrificial coatings.
6 E.g. galvanized iron (coating of Zn on Fe)

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 CATHODIC COATING / NOBLE COATING
1 Base metal is coated with a metal which is less reactive (more noble) in its comparison.
2 Protects the base metal due to its noble character.
3 Also known as cathodic coating as reduction potential of coating metal is more than that of base metal.
4 If there are pores, break, etc corrosion takes place because of small anodic area and large cathodic
area.
5 Ni, Ag, Cr, Pb, etc are used generally for noble coating.
6 E.g. coating of Sn on Fe. [4 Marks]

Galvanization or galvanization (or galvanizing as it is most commonly called) is the process of

applying a protective zinc coating to iron or steel, to prevent rusting. The most common
method is hot dip galvanizing, in which steel sections are submerged in a bath of molten zinc.
Electroplating is a process by which metal ions migrate via a solution from a positive electrode
to a negative one. An electrical current passing through the solution causes objects in the cathode
to be coated by the metal in the solution. [2 Marks]
Blocks of magnesium are often strapped to steel hulls of ocean-going ships as magnesium causes
cathodic protection of iron. Magnesium is more reactive than iron. [1 Mark]

(1) Attempt any one part of the following: 7x1=7

6(a) Explain the zeolite process of water softening. What are the advantages and limitations
of this process? Calculate the amount of lime and soda required for the treatment of 10,000
litres of water whose analysis is as follows (in mg/L): Mg(HCO3)2=73; CaSO4=102; MgCl2=95;
MgSO4=24; Ca(HCO3)2=121.5;NaCl= 55.
Ans. Zeolite is micro-porous mineral which is used as catalyst in many industrial purposes such as
water purification and air purification. The zeolites are hydrated alumino silicates and general
composition Na2O, Al2O3, nSiO2, xH2O. These are used as ion exchanger and odor removal in water
softener. Permutit are more porous, glassy, and have higher softening capacity than greensand.
Zeolites are characteristically soft to moderately hard, light in density, insoluble in water but can act
as base exchangers in contact with water containing cations. Hence these can remove Ca2+ and
Mg2+ ions from water when hard water is passes through.

Zeolite process for water softening

Zeolite process for water softening has become a commercial success for the reason that zeolite can
be easily regenerated. When Ca2+ and Mg2+ ions containing hard water pass through a bed of
sodium zeolite, the sodium ions are replace by the calcium and magnesium ions.

Na2Ze + Ca(HCO3)2 → 2NaHCO3 + CaZe

Na2Ze + Mg(HCO3)2 → 2NaHCO3 + MgZe
Na2Ze + CaSO4 → Na2SO4 + CaZe
Na2Ze + MgSO4 → Na2SO4 + MgZe

When all sodium ions are replaced by calcium and magnesium ions, the zeolite becomes inactive.
Then the zeolite needs to be regenerated. Brine solutions are passing through the bed of inactivated
zeolite. The following reactions are taken place and form Na2Ze.

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 CaZe + 2NaCl → Na2Ze + CaCl2
MgZe + 2NaCl → Na2Ze + MgCl2

The softening water by this process is used for laundry process and cannot be used for
boiler purpose. Because this water softening system contains NaHCO3 in the water; when
this water is heated, it produces CO2 which is corrosive for boilerplates.

Figure: Zeolite method for water softening [3 Marks]

Amount of Lime and ||Soda Required:

Conversion to CaCO3 equivalent

Constituents Amount (ppm) Multiplication CaCO3 equivalents Lime/Soda
factor
Mg(HCO3)2 73 mg /L 100/146 50 2L
Ca(HCO3)2 121.5 mg/L 100/162 75 L
CaSO4 102 mg/L 100/136 75 S
MgSO4 24 mg/L 100/120 20 L+S
MgCl2 95 mg/L 100/111 85.58 L+S
NaCl 55 mg/L Does not react with -- --
lime and soda
[2 Marks]

Lime Requirement= 75/100(2x50+75+20+85.58)10000

=1729350 mg = 1.729 kg
106
Amount of soda (S) required for softening

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 Soda requirement=106/100(75+20+85.58) 10000

=1913300 mg = 1.913 kg
106
[2 Marks]

6(b) Explain the different parameters that are determined in the proximate analysis
of coal. On burning 0.92g of a solid fuel in a bomb calorimeter, the temperatureof
3300g of water increased by 2.42℃. Water equivalent of calorimeter and latent heat
of steam are 385.0g and 587.0cal/g, respectively. If the fuel contains 0.7% hydrogen,
calculate its GCV and NCV.

Ans Proximate analysis: In the proximate analysis, fixed carbon (C) moisture (M), Ash
(A) and volatile matter (VM) are determined.
Fixed carbon (FC) is obtained from the following equation:
FC= 100 – (%M + %A + %VM) ……... (1)
Moisture is determined by drying 1gm of sample at 100- 110 °C for 1hr. Weight loss is
expressed in the %of initial weight of sample, i.e.
%M = (weight loss/weight of sample) ×100 …… (2)
Volatile matter is the weight loss obtained on heating 1 gm sample of coal at 950°C for 7
minutes in the absence of air.
VM = (weight loss due to VM/ weight of sample) ×100. …… (3)
Ash is the weight of residue obtained after complete combustion of 1 g of coal at 700‐750 °C
upto half an hour or till a constant weight is obtained.
Ash in % is A= (weight of residue/weight of sample) ×100 ……. (4)
Fixed carbon can be calculated by eq. 1. [4 Marks]

The following data are obtained in a Bomb Calorimeter experiment are.

Weight of coal burnt = 0.92g

Weight of water taken = 3300g
Water equivalent of calorimeter = 385g
Increase in temperature = 2.42°C
Latent heat of condensation = 587 cal/g

H =0.7%.
(𝑊+𝑤)(𝑇2−𝑇1+𝐶𝑜𝑜𝑙𝑖𝑛𝑔 𝑐𝑜𝑟𝑟𝑒𝑐𝑡𝑖𝑜𝑛)−(𝐴𝑐𝑖𝑑 𝑐𝑜𝑟𝑟𝑒𝑐𝑡𝑖𝑜𝑛+𝑓𝑢𝑠𝑒 𝑤𝑖𝑟𝑒 𝑐𝑜𝑟𝑟𝑒𝑐𝑡𝑖𝑜𝑛)
GCV = 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑓𝑢𝑒𝑙

NCV=GCV-0.09 H587
(3300+385)(2.42))
GCV = 0.92

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GCV= 9693.15 cal/gm
NCV= GCV-0.09 H587
NCV=9693.15- 0.09 0.7 587
NCV =9656.169 cal/gm [3 Marks]

7. Attempt any one part of the following: 7 x 1 = 7

7 (a) (i) Differentiate between Chain Growth and Step Growth polymerization.

[3 Marks]
7(a)(ii) Outline the process of vulcanization of rubber. Describe the preparation,important
properties and uses of Butyl rubber or Kevlar.

Ans. Vulcanisation of rubber: Natural rubber becomes soft at high temperature (>335 K) and

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brittle at low temperatures. On vulcanization, Sulphur forms cross links at the reactive sites of
double bonds and thus the rubber gets stiffened.
In the manufacture of tyre rubber, 5% of sulphur is used as a crosslinking agent. The probable
structures of vulcanized rubber molecules are depicted below:

Advantages of vulcanization.

1. The tensile strength of vulcanized rubber is very good, about 10 times the tensile strength
of raw rubber (strength(2000 kg/cm2).
2. It has a broader useful temperature range is -40 to 1000C.
3. It has excellent resilience (After removal of deforming force, the articles made from
vulcanized rubber regain theiroriginal shape).
4. It has better resistance to moisture, oxidation and abrasion.
5. It is resistant to organic solvents like CCl4, benzene, petrol etc. but it swells in them.
6. It has low elasticity.
7. It has only slight tackiness. [2 Marks]

ButylRubber(GR-I)Preparation:

Properties:
1. Amorphous: Polyisobutylene or butyl rubber is amorphous under normal conditions but crystallizes
on stretching.
2. Resistance to Attack by Oxygen and Ozone: It exhibits outstanding resistance to attack by oxygen
and ozone due to low concentration of double bonds. It is less sensitive to oxidative ageing as
compared to other Elastomers except silicon’s.
3. Oxidative degradation: Butyl rubber becomes soft on oxidative degradation.
4. Ozone and Acid Resistance: It has high ozone and acid resistance.
5. Soluble: It is soluble in hydrocarbon such as benzene
Application:
• Tyre tubes: It is used for making inner tubes for tyres because of its impermeability to gases.
• Wire and cable insulation: It is used for wire and cable insulation.
• Lining of Tanks, Housings: It is used for lining of tanks, housings.
OR

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 Kevlar
Kevlar is synthesized in solution from the monomers 1,4-phenylene-diamine (para-
phenylenediamine) and terephthaloyl chloride in a condensation reaction yielding
hydrochloric acid as a byproduct. The result has liquid-crystalline behavior, and mechanical
drawing orients the polymer chains in the fiber's direction.

Application:
Kevlar is a type of aramid fiber.
It is woven into textile materials and is extremely strong and lightweight, with
resistance toward corrosion and heat.
It is used in vast applications such as aerospace engineering (such as the body of the aircraft),
body armor, bulletproof vests, car brakes, and boats. [2 Marks]

OR
7(b) (i) Differentiate between Thermosetting and Thermoplastic polymers.

Ans.
[3 Marks]

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7(b)(ii) Giving examples write a brief note on conducting polymers.

Ans. A polymer which can conduct electricity is termed as conductivity polymer.

Classification of conducting polymer

A) Intrinsically Conductivity polymer. These polymers have extensive conjugation in

the backbone which isresponsible for conductance.

(a) Conducting polymers having conjugated π-electrons in the backbone. Such polymers contain
conjugated π- electrons in the backbone which increases their conductivity to a large extent. This
is because, overlapping of conjugated π-electrons over the entire backbone results in the
formation of valence bands as well as conduction band,which extends over the entire polymer
molecule. The valence band and conduction bands are separated by a significant band gap. Thus,
electrical conduction could occur only after thermal or photolytic activation of electronsto give
them sufficient energy to jump the gap and reach into the lower levels of the conduction band.
Examples:
(i) Polyacetylene

(ii) Polypyrrole

(iii) Polyaniline

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 (b) Doped conducting polymer. The conducting polymers of type (a) can be easily oxidized or
reduced as they have low ionization potentials and high electron affinities. Their conductivity
can be increased by creating positive or negative charge on polymer backbone by oxidation or
reduction.
p-doping It is done by oxidation process. Conductivity polymer of type (a) is treated with
Lewis acid or with iodine vapour or iodine in CCl4.
(CH)x + A (Lewis acid) ↔ x (CH) +A- (oxidation process)
Ex.
(CH)x+2FeCl3 x (CH) +FeCl4- + FeCl2

n-doping It is done by reduction process. For this, conducting polymer of type (a) is treated
with lewis bases like sodiumnaphthalide

(CH)x + B (Lewis base) ↔ x (CH) -B+ (reduction process)

(CH)x + Na+(C10H8)- x (CH) -Na+

+(C10H8)-C10H8

Conducting polymer Polyaniline Polypyrrole Polythiophene

Dopants HCl BF4- Tosylate
Conductivity(Scm-1) 1000 500-7500 1000

B) Extrinsically conducting polymer. In this, the polymer owes their conductivity due to the
presence of externally added ingredients in them. These are of following two types:
(a) Conductivity element filled polymer. In this, the polymer acts as the binder to hold the
conducting element (such as carbon black, metallic fibre, metallic oxides) together in the solid
entity.
The minimum concentration of conductive filler which should be added so that polymer starts
conducting is known as percolation threshold. Because at this concentration of filler a
conducting path is formed in polymeric material. Generally, Carbon black is used as filler
which has very high surface area, more porosity.

(b) Blended conducting polymer. These polymers are obtained by blending a conventional
polymer with a conducting polymer. Such polymers possess better physical, chemical,
electrical and mechanical properties. For example, up to 40% of polypyrrole will have little
effect on tensile strength and also give a much impact strength than obtained with a carbon
black filled compound at only 10% loading.

Applications of Conducting Polymer

1. In Rechargeable lithium-ion batteries

2. In analytical sensors: For making sensors for pH, O2, NOx, SO2, NH3 and glucose.
3. For making ion exchangers
4. In electrochromic displays and optical filters: conducting polymers can be used as
electrochromic material (i.e. thematerials which change color reversibly during the
electrochemical charge and discharge)
5. In electronics: In LED’s and Data storage
6. In photovoltaic devices: ex Al/conducting polymer/Au photovoltaic cell.
7. Polypyrrole is used in smart windows: smart windows can change their color in response to
change in temperatureor amount of sunlight. [4 Marks]

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