SINHGAD ACADEMY OF ENGINEERING, KONDHWA (BK)

(2019- Pattern)
Engineering Chemistry
FACULTY- Dr.S.P.SAPTALE

Model Answer Set

Time: 03 hrs. Max. Marks: 70

1. Engineering Materials
1. What is the structural requirement for a polymer to show conductive
property? Give structure, doping and applications of polyacetylene? (7M)

Marking scheme- structural requirement - 2marks, structure -1mark,

doping-2marks, applications -2marks.

Answer-
Structural requirement-

If alternate double bonds are present in the polymer chain then the polymer
conducts electricity on its own. Such a system is called as conjugated system.

the other is a weak µ bond.)

In these systems (polymers) there is overlapping of conjugated
the entire polymer chain. This leads to formation of conduction bond (CB)
and valence bond (VB). If the excitation of µ electrons present in the VB is
done by either supplying heat or exposing to light, then the polymer
conducts electricity.

Structure –

(a) P-type Doping or Oxidative Doping:

A suitable oxidizing agent (e.g. halogen molecules) is added to conjugated

and makes it a positively charged cation.

Delocalization of positive charge (hole) takes place over the whole polymer
chain and it becomes conducting. e.g. polyacetylene + I 2.

(Delocalization of µ electrons to fill the ‘hole’)

This is called as oxidative doping because the polymer chain has actually lost
the µ electrons to halogen molecule.

(b) N-type Doping or Reductive Doping:

A suitable reducing agent (e.g. Alkali metal atoms like Na, K, Li) are added to
conjugated polymer chain which donate a pair of electrons to polymer chain.
This makes the polymer chain a negatively charged anion (i.e. electron rich)
and it becomes conducting.
e.g. Polyacetylene + Na

(Delocalization of µ electrons to accommodate extra electrons)

Applications
In rechargeable light weight batteries
In telecommunication system.
In electronic devices such as transistors, diodes

2 Give the structure, properties and applications of Polycarbonate

Marking scheme- structure - 1mark, properties -1mark, applications -1mark.

Structure-
Properties:
It is crystalline thermoplastic.
It shows very good mechanical properties like high impact strength, even at
low temperature.
It has low moisture absorption.
High heat resistance (140C).
High thermal and oxidation stability in molten state.
It is transparent and self extinguishing.

Applications:
All types of housing or casing for electrical appliances, home appliances,
Computer peripherals.
Automobile head and tail light casing and lenses.
Telephone and cell phone casings.
Unbreakable crockery and glazing glass substitutes.
As a bulletproof material, helmets, covers of vehicle lights Also used for
making CD and DVD.

3. Define electroluminescence. Give the structure with mechanism and

applications of polyphenylenevinylene (PPV)

Marking scheme- Definition - 1mark, structure -1mark, mechanism -2mark.

Applications-1mark
Definition

The property in which a material produces bright light of different colours

when stimulated electronically is known as electroluminescence and the
material which shows electroluminescence is called as electroluminescent
material.

(Structure of PPV or polyphenylene vinylene)

Mechanism-

Anode injects a hole towards a transport layer and then electrons injected by
cathode layer into the emitter layer. Then hole and electron recombine in the
emitter layer causing emission of light, during return of excited emitter to
ground state.

Applications-
In photovoltaic cells
Electroluminescent night lamps

In flat panel displays

In light decoration.
Light strips for decorative buildings.

4. Define polymer composites. What is the role of matrix phase in

composites? Give properties and applications of composites?

Marking scheme- Definition - 1mark, role -2marks, properties -1mark.

Applications-2marks

Polymer composites-The addition of external materials to the polymer is

called as reinforcement and the polymer formed after reinforcement are
called as polymer composites.
Role/functions of matrix phase-

1. Bind reinforcing particles/fibres strongly

2. Acts as a medium for disperse phase

3. Keep the reinforcing fibres in proper orientation for high strength

development.

Properties-

1. High strength, stiffness and thermal stability.

2. Cheap and easily fabricate

3. High impact strength and abrasion resistance

Applications-

1. Automobile body and parts

2. Sport goods (rackets) toys musical instruments

3. In rocket, aircraft, helicopters (light in weight)

4. Marine applications (shaft, hulls etc.)

5. Define and give the classification of composites.

Marking scheme- Definition - 1mark, classification -4marks

Polymer composites-The addition of external materials to the polymer is

called as reinforcement and the polymer formed after reinforcement are
called as polymer composites.

Classification of composites-

Based on reinforcement forms, composites can be classified as

i) Fiber reinforced composites-

These are composed of fibers embedded in the matrix material. These mainly
includes
a) Glass fibers-Glass fibers are popular reinforcing material. It provides high
tensile strength, thermal stability, high toughness and impact strength to the
polymer matrix.

20-40 percent glass fibers filled in the polymers.

b) Carbon fibers-These fibers are strong and stiff even at high temp.

c) Aramid fibers- These are aromatic polyamides ex.Nomex, Kevlar. These are
liquid crystal polymers property. These fibers have very high tensile strength.
impact resistant and thermal stability. Some other fibers are silicon carbide
and aluminum oxide.

ii) Particle reinforced composites- It mainly includes metal powder, metal

oxides, carbon black, mica and silica powder can be mixed with the polymer
matrix to make the composite.

These particles offer high mechanical strength, better performance at high

temp.

6. What is biodegradable polymer? Give the structure of PHBV with its

applications.

Marking scheme- Definition - 1mark, structure -1mark, applicatioms-1marks

Biodegradable polymer-

A polymer which can degrade easily and can be converted to harmless

gaseous products by action of microorganisms and water is known as
biodegradable polymer.

Structure of PHBV
Applications-

i) PHBV is useful for packaging, lamination and for molded articles.

ii) Useful in medical and vetarnary applications.

iii) Also used in surgical, organ transplant and orthopaedic operations.

7. How nanomaterials are classified on the basis of dimensions. Give its

applications.arking scheme- Classification- 4marks, applicatioms-2marks

Classification of nanomaterials –

Nanomaterials are classified according to their dimensions.

i) Zero dimensional nanomaterials (0D)-

The nanomaterials have all dimensions are measured within nanoscale range
i.e.no dimension are larger than 100 nm.

Ex.Particles, quantum dots, hollow spheres.

Quantum dots are used in LED, solar cells, lasers.These are either crystalline
or amorphous exist indidually or in a matrix.

Fig.

ii) One dimensional nanomaterials (1D)-

These materials having two of three dimensions are measured within

nanoscale. I.e.no dimension are larger than 100 nm.

Ex.Nanowire, nanorod, nanotube and nanofilms.

Fig.

Silicon IC industry depends upon thin films for their operations. Monolayer is
used in fuel cell.

iii) Two dimensional nanomaterials (2D)-

These materials having two of three dimensions are measured within

nanoscale. (2 dimensions outside the nanoscales)
Ex. Carbon nanotubes, nanosheets, nanofilms,

These are in the form of layers and can be used as single layer or multilayred.

Fig.

iv) Three dimensional nanomaterials (3D)-

These are the materials having all the three dimensions not measured within
the nanoscale i.e.no dimension are larger than 100 nm.These are also known
as bulk nanomaterials.

Ex.fuiierene, bundles of nanowires, bundle of nanotubes.

Fullerene C60,C70 are important for miniature ball bearing to lubricate

surface, drug delivery vehicles and in electric circuits.

Fig.

8. What are carbon nanotubes? Discuss the different types of carbon

nanotubes with respect to their structure. Give any three applications of it.

Marking scheme- Definition-1mark, Types-3marks applications-2marks

Carbon nanotubes-

Carbon nanotubes are the members of fullerene family and can be imagined
as a cylinder forms by rolling of graphite sheet.

Depending on number of times rolling the graphite sheet, nanotubes are

devided into two types.

SWCNT-Single wall carbon nanotubes

MWCNT-Multi wall carbon nanotubes

SWCNT further subdivided into 3 types zigzag, armchair and helical or chiral
(Depending on the folding line passes through the axis X-Y line)

Applications-

i) Filtration- CNT can be used to separate particle size greater than diameter
of CNT .CNT can also used to trap smaller sized ion from a solution.

ii) As a nanocylinders-Hydrogen gas can be safely stored in CNT

iii)Stereospecific reactions- Some organic reactions can be carried out inside

CNT

iv)Preparation of mask

v) Catalyst for reactions

vi) Drug delivery system

vii) Body part implants

ix) Coatings

9. Explain the structure of graphene with the help of a diagram .Give its
applications.

Marking scheme- Structural information-3mark, applications-2marks

Graphene is a single layer of graphite, it is two dimensional network of
carbon atoms bounded within the plane by strong bonds into a honeycomb
array comprised of six membered rings.

Structural information-

Formation of graphene involves sp2 hybridisation, having three hybrid

orbitals at 1200 angle in one plane (forming sigma bond with 3 such carbons)
C-C bond length is 1.420

The two sheets like graphene molecules are at the distance of 3.4A0 in
graphite and there is a weak Vander Walls force between them. Graphene
has high chemical reactivity due to presence of double bond.

Applications-

i) Sensor in gas detection

ii) In integrated circuits

iii) Solar cells, batteries

iv) As adsorbent for gas storage

v) In IR detectors, composite material

vi) LCD, organic photovoltaic cells.

10. What are quantum dots? Give its properties and applications.

Marking scheme- Definition-1mark, properties -1mark applications-2marks

Quantum dots-

Quantum dots are semiconductor nanocrystals that glow a particular colour

after being illuminated by light.

Properties-

i) The tiny nanoparticles have diameters that range from 2 nanometers to 10

nanometers.

ii) The particles differ in colour depending on their size.

iii) They are able to ‘tune’ the wavelength of the emitted light to a specific
colour.

Applications-

i) Solar cells, transistors

ii)LED, medical imaging

iii) QPD-quantum dot photodetectors

iv) Optical-LED, soild state lightning

v) Biological applications- biosensors

vi) Lasers in communication devices

 4. FUELS
Define – Gross and net calorific value and justify the relationship between
GCV and NCV of the fuel. (3M)

Marking scheme- Definition-1mark each, relation -1mark

Gross calorific value (GCV)-

It is defined as “the amount of heat liberated when unit mass / volume of the
fuel is burnt completely in air and the products of combustion are cooled to
room temperature”

Net calorific value (NCV)-

It is defined as “the amount of heat liberated when unit mass / volume of the
fuel is burnt completely in air and the products of combustion are allowed to
escape into the atmosphere”

Relation between GCV and NCV

NCV = GCV – (0.09 × H × 587) Cal/gm.

Q2.Give construction, working and calculation for finding gross calorific value
of a solid fuel by Bomb Calorimeter. (7M)

Marking scheme- construction-2mark, working and calculation-4 marks,

formula-1mark

Construction- Bomb calorimeter consist of

I) Bomb pot II) calorimeter III) Water and air jacket

Accessories - a) pellet press b) Oxygen cylinder

The gross calorific value of solid and liquid fuels can be determined by Bomb
calorimeter.
WORKING:-

Weigh the pellet of solid fuel or liquid capsule and keep it in crucible. Keeps
the crucible in the ring of electrode keep the resistance wire touching to the
fuel?
Add about 10 ml distilled water at the bottom of bomb pot and fix the lid
tightly to bomb pot by screwing.

Fill the bomb with oxygen at the pressure 25kg/cm2.

Place the bomb in calorimeter .Add known volume of water in the

calorimeter so the bomb gets immersed in the water.

Place the calorimeter in the water jacket over the plastic studs keep the
thermometer and stirrer in the water calorimeter.

Put the plastic cover on the top and make electrical connections from battery
to electrodes.

Operate the stirrer for 5 min. and note the initial temp. of water.

Pass the current for 5-10 seconds to heat the wire so that the fuel catches
fire. If the fuel contains S and N elements, they get converted to SO3 and
N2O5 . These gases get dissolves in the distilled water in bomb to form H2SO4
and HNO3 (along with liberation of little heat.)

Note the maximum temp.reached. After that note the rate of fall of temp.per
min.and the time taken for reaching to initial temp. are noted.

Open the bomb pot and wash the contents as its bottom into beaker to find
out the amount of H2SO4 and HNO3 formed.
Observations and Calculations

Mass of the fuel sample taken = X g

Mass of water taken in the copper calorimeter = W g
Water equivalent of calorimeter = w g
Initial temperature of water = t10 C

Final temperature of water = t20C

Rise in temp. Of water = (t2- t1)

Gross calorific value of fuel = L Cal/gm

Heat liberated by burning of fuel = Heat absorbed by water and calorimeter

Fuel mass × CV = (mass of H2O× H2O eq. Bomb) x temp. rise x sp. Heat of H2O

XL = (W + w) (t2 - t1) sp. Heat of water= 1cal/gm

(W + w) (t2 – t1)
GCV = L = ----------------------------- cal/gm
X

After taking all corrections into account, the final formula for GCV is

(W + w) (t2 – t1 + tc)- (a + f +)
GCV = L = ------------------------------------- cal/gm
X
(Same question in different format 3M)

Draw neat labelled diagram of Bomb calorimeter. Give the formula to

calculate GCV with and without corrections.

3. How calorific value of gaseous fuel is determines by using Boy’s

calorimeter. (7M)

Marking scheme- construction-2mark, working and calculation-4 marks,

formula-1mark
Principle

A known volume of gaseous fuel sample is burnt in the combustion chamber

of a Boy’s calorimeter the released heat is quantitatively absorbed by cooling
water, circulated through copper coils surrounding the combustion chamber.
The mass of cooling water and its rise in temperature are noted. The mass of
water produced by condensation of steam is calculated. The calorific value of
the fuel sample is then calculated from these data.

Construction:-

Gas burner ii) combustion chamber (chimney) iii) thermometers

Insulating cover.

A) GAS BURNER:-

There is a gas burner in which a known volume of gas is burnt at a known

press. The gas is burnt at the rate of 3-4 lit. Per min.

B) Combustion chamber:-

Around the burner there is a combustion chamber which has copper tubing
coiled inside as well as outside of it. Water enters from the top of outer coil
moves to the bottom of chimney and then goes up through the inner coil exit
at the top.

C) Thermometers:-
There are two thermometers to measure temp. Of inlet water and outlet
water.

D) Insulating cover:-

The assembly is covered with by an insulator to detach combustion chamber

from atmosphere. There are three holes for exhaust gas, water inlet and
condensed steam.

WORKING:-

Start burning the gas at suitable pressure and adjust the rate of water flow
such that the temp. Of outgoing water remains constant.

Burn the gas for 5-10 min. To have the steady temp. in and around the
combustion chamber.

After the steady conditions of outgoing water temp., Constant water

circulation and gas flow reached, simultaneously note the following.

Volume of gas burnt at given temp. and pressure in certain time period.

Quantity of water passed through coil during this period.

Mass of water condensed from product gas during the period.

The steady rise in temp. Of water.

CACULATIONS:-
Volume of fuel (gas) burnt at STP.
Let this STP vol.be = Vm3
Mass of cooling water in kg. = W
Mass of water condensate in kg = m
GCV of fuel = L
Steady temperature of incoming water = t1 OC
Steady temperature of outgoing water = t2 0C
Rise in temperature = (t2 - t1 )0 C
Heat released by combustion of fuel = Heat absorbed by water
V x L = W (t2 - t1)
The mass of condensate water per m3 of gas will be m/v kgm3

If this water had left as steam in product gases would have taken away heat=

M/v x 587 kcal/m3

NCV = GCV – m/v X 587

Therefore

4. What is proximate analysis? Explain the procedure for determination of

each of constituents with its formula. (6M)

Marking scheme- 4 constituents with its formula- 1.5 Marks each

i) Moisture:

An air-dried coal sample is weighed in to a dry silica crucible and heated for
about one hour at 1100 C in an electric hot air-oven for 1 hour. The crucible is
cooled first in air then in desiccators and then weighed.

Weight of moisture
% moisture = -------------------------- X 100
Weight of coal taken
Moisture in coal evaporates during the burning of coal and it takes some of
the liberated heat in the form of latent heat of evaporation.

Moisture lowers the effective calorific value of coal.

Lesser the moisture content better is the quality of coal as a fuel.

ii) Volatile matter:

The dried sample of coal left in the Crucible in step (i) is then covered with a
lid and placed in a muffle furnace, maintained at 9500C. The crucible is taken
out after 7 minutes of heating. It is cooled first in air then in desiccators and
finally weighed.

Weight of V.M.
% Volatile matter = -------------------------- X 100
Weight of coal taken
A high volatile matter containing coal burns with a long flame, high smoke
and has low calorific value.

Lesser the volatile matter better is the rank of coal.

iii) Ash:

The residual coal left in the crucible in step (ii) is then heated without lid in a
muffle furnace at 700-7500C, for 30 min. until a constant weight of residue is
obtained.

Weight of ash formed

% Ash = --------------------------- X 100
Weight of coal taken

Ash-forming constituents in coal are undesirable for the following reasons:

The calorific value of the coal is decreased. The removal and disposal of ash
poses problems. The ash deposited in the fire bars interferes with circulation
of air. If the ash fuses to form a clinker on the fire bars, it hinders air
circulation and also promotes corrosion of the fire bars.

iv)Fixed carbon:

It is reported as the difference between 100 and the sum of the percentages
of moisture, volatile matter and ash content of a coal sample.

F.C = 100 – (% moisture + % ash + % Volatile matter)

Higher the percentage of fixed carbon, greater is its calorific value and better
is the quality of coal.

5. Explain in brief the process with diagram for distillation of crude

petroleum. Give composition, boiling range and uses of any three fractions
obtained. (6M)

Marking scheme- Process with explaination-3Marks, any three fractions-

3Marks.

Process with explanation- The crude oil is piped through the pipe still and
heated to a temperature of 316oc.The hot vapours are passed through a 30
meter high fractionating column i.e. bubble tower and get cooler and cooler.
Due to the gradual cooling the vapours condensed over the plates i.e. at
intermediate points. Heavy oil condensed at lower plate has a higher boiling
point than the oils on upper parts.

The lowest fraction at a base is passed through heat exchanger where it is

cooled to produce lubricating oil, greases and wax.

The fractions at with lowest temperature rise at the top pass through a
condenser and then gas separator. As a result gas and gasoline are separately
obtained.

Sr. Name of Boiling range Composition Uses

No fraction
1 Gases Below 40 OC C1-C4 Domestic and
industrial fuel as LPG
2 Petrol 60-120 OC C5-C8 In IC engine, dry
cleaning as a solvent
3 Naphtha 120-180 OC C7-C10 As a solvent,
chemicals
4 Kerosene 180-250 O C C10-C16 Domestic fuel, fuel
of jet engine
6. What is power alcohol? Give its manufacturing and any two merits and
demerits of power alcohol.

Marking scheme-Def.1Mark, Reactions-2Marks, advantages-1Mark.

Disadvantages-1Mark.
Power alcohol- When ethyl alcohol is used as fuel in internal combustion
engine, it is called as "power alcohol". Generally ethyl alcohol is used as its 5-
25% mixture with petrol.

Manufacturing of ethyl alcohol

Ethyl alcohol is mainly manufactured by fermentation of molasses by using

invertase and zymase enzymes.

Invertase
i) C12H22O11 C6H12O6 + C6H12 O6
H2O Glucose Fructose
Sucrose in (fermentation)
Molasses
Zymase
ii) C6H12O6 2C2H5OH + 2CO2
Advantages of power alcohol

i) Ethyl alcohol has good antiknocking property and its octane number is 90,
while the octane number of petrol is about 65. Therefore, addition of ethyl
alcohol increases the octane number of petrol.

ii) Alcohol has property of absorbing any traces of water if present in petrol.

ii) Ethyl alcohol contains 'O' atoms, which helps for complete combustion of
power alcohol and the polluting emissions of CO, hydrocarbon, particulates
are reduced largely
Disadvantages of power alcohol

i) Ethyl alcohol has calorific value 7000cal/gm much lower than calorific value
of petrol 11500cal/gm. Use of power alcohol reduces power output up to
35%.
ii) Ethyl alcohol has high surface tension and its atomisation, especially at
lower temperature, is difficult causing starting trouble.

iii) Ethyl alcohol may undergo oxidation reaction to form acetic acid, which
corrodes engine parts.
7. Write chemical reactions for production of Biodiesel and give its
advantages.

Marking scheme- Reaction-2Marks, advantages- 1Mark.

Reaction-

ADVANTAGES:-

i) It has high cetane no. and high calorific value

ii) Biodiesel is cheaper

iii) It is environmental friendly

iv) It reduces on dependent on diesel on foreign countries saving currency.

8. Explain manufacturing of hydrogen gas by steam reforming of methane
and coke. (5M)

Marking scheme- 2.5Marks each

Steam reforming of methane.

i) Steam reforming: In the step steam is reached with materials containing

hydrocarbons such as natural gas, naphtha, at high temperature in presence
of Ni as catalyst to obtain hydrogen and carbon monoxide.

Ni
CH4 + H2O (steam) CO + 3 H2
8000C
ii) Shift reaction: In this step the products of steam reforming process
combine with steam at low temperature in presence FeO as catalyst. This
increases the hydrogen yield through conversion of CO (which is toxic) to
CO2.

FeO

CO + H2O (steam) CO2 + H2

3500C
Then mixture of CO2 and H2 gas is compressed and cooled to get liquid CO2
and H2 gas. From liquid mixture CO2 liquid can be removed by alkali solution
and pure Hydrogen gas can be obtained.

Coal/Coke gasification

It is the second most common method used for producing hydrogen gas. It is
Similar to that of steam reforming of hydrocarbons except the raw material
which is coal. In steam reforming step the steam reacts with carbon in coal,
thereby forming Carbon monoxide and hydrogen
 (Steam)

C (coal) +H2O CO+H2 while in shift reaction

CO reacts with steam and thereby increasing the hydrogen yield.

(Steam)

CO + H2O CO2 + H2

9. What is CNG? Give the composition, properties and applications of CNG.

Compressed Natural Gas: (C.N.G)

“After scrubbing out CO2, NH3, and H2S from the natural gas, it is filled under

Pressure in cylinder, and is known as compressed natural gas”. It mainly

contains CH4 along with CO and C2 - C4 hydrocarbons.

Composition

CH4 = 88%

C2 to C4 = 10%

CO = 0.5 to 1 %

Properties

i) C.N.G. on combustion produces little CO and reactive hydrocarbons thus

does not cause air pollution.

ii) C.N.G. burns very clearly and hence reduces maintenance cost as well as
wear and tear of engine.

iii) Calorific value of C.N.G. is 13,000 cal/litre.

Applications

i) C.N.G. is used as excellent fuel for domestic purposes.

ii) It is used as automobile fuel.

iii) It is a good industrial fuel also.

iv)It is also used as a raw material for carbon black and hydrogen
gas.

10. Numericals on -

Bomb calorimeter

Boy’s calorimeter

Proximate analysis

Ultimate analysis

Unit 5 Spectroscopic Techniques

1. Give principle and instrumentation and applications of UV-visible
spectrophotometer. (6M)

Marking scheme- Principle-1Mark, Instrumentation-4Marks, Applications-1

Mark

Principle- The absorbance of monochromatic light from UV-visible region is

proportional to concentration of the solution, for the constant path length.

Mono- Photo Readout

Source chroma Amplifier device
tor detector
Instrumentation-

1. Source of radiation- Source of radiation should provide sufficient intensity

over the wavelength region (300-1000nm). Ex. Tungsten filament lamp.

2. Monochromator- Monochromator consists of entrance slit, grating or

prism. A good monochromator provides very narrow wavelength. Ex. Glass
prism, quartz prism.

3. Sample holder- There is a special glass tube (cuvette) which does not
absorb light from UV-visible spectrum and the sample solution is kept in it.
Ex. Quartz glass cuvette.

4. Detector- A detector is a transducer that converts electromagnetic

radiations into an electron flow and the current or voltage produced thereby.
The photocurrent is amplified if necessary. Then there is a recorder or digital
display device. Ex. Photovoltaic cells, phototubes.

5. UV-Spectrum- Sample to be tasted is dissolved in an inert solvent and filled

in sample holder. The absorbance is noted for the solution at various
wavelengths in UV region. The graph is plotted with absorbance versus
wavelength.

Applications-

i) Qualitative analysis of organic compounds.

ii) Detection of impurities.

iii) Quantitative analysis

iv) Chemical kinetics

v) Structural information

vi) Dissociation constant of weak acid, bases.

2. Give the theory of electronic excitation in UV-visible spectroscopy. (6M)

Marking scheme- Theory-2Marks, Excitation- 1Mark each (1*4)

Theory- Energy absorbed from the uv region causes excitation of electrons in
a bond to higher energy state. This transition consists of excitation of
electrons from occupied molecular orbital to next high energy orbital.

Types of Electronic excitation/Transitions-

1.  transition- These transitions occurs in such compounds in

which all the electrons are involved in single bonds and there is no lone pair
of electrons.Ex-Saturated hydrocarbon, alkanes. As the energy required for
the transition is large, 100-135nm.

2. n  transition- These transitions occurs in unsaturated molecules

contain atoms like oxygen, nitrogen,halogen. The transition exhibit very
weak band absorption i.e.10 to 100.In aldehydes and ketones the transitions
occur due to excitation of electron from p-orbital to antibonding orbital.

3. n transition- saturated compounds with atoms having lone pair

of electrons can undergo this transition, and the bands are observed in the
near uv region 180-225nm.This transition shifts to the longer wavelength.Ex-
oxygen,nitrogen,halogen.

4 transition-compounds containing isolated double bond where

absorption is large and in the range160-175nm (E band). Compounds having
conjugated double bond like in butadiene, where absorption is large and in
the range 210-280nm (K band).

3. State and derive Lamberts, Beers law of absorption of wavelength. (3M)

Marking scheme- Statement-1Mark, derivation-2 Mark.

Statement-

Beers law- The rate of decrease in intensity of radiation is directly

proportional to the concentration of solution, when the monochromatic light
passes through a solution, for a fixed thickness.

-dI/Io ∝ dc

Lambert’s law- The rate of decrease in intensity of radiation is directly

proportional to path length of solution, when the monochromatic light
passes through a solution of constant concentration.

-dI/Io ∝ dx

Where Io= Intensity of the incident radiation

dx=small thickness of solution or path length

dI=small decrease in intensity of light=Io-It

4. What are the applications of UV spectroscopy?

Marking scheme- Four applications -1Mark each.

1. Qualitative Applications

2. Quantitative Applications

3. Analytical determination of metals and non-metals

4. Analytical determination of organic compounds

5. Determination of dissociation constants of organic acids and dyes

6. Determination of metal-ligand formation constants

7. Determination of kinetic stability of complexes

5. Define the following terms with examples

(i)Bathochromic shift (ii) Hypsochromic shift (iii) Auxochrome

(iv) Chromophore (v) Hyperchromic effect (vi) Hypochromic effect

Marking scheme- 1Mark for each definition

(i)Bathochromic shift-

“A shift of absorption to a longer wavelength or less energy is known as

bathochromic shift”.

ii) Hypsochromic shift-

“A shift of absorption to a shorter wavelength or high energy is known as

hypsochromic shift”.

(iii) Chromophore-

“Chromophore is a covalently unsaturated group responsible for electronic

transition in UV region”. Ex. C =C, C=O, C=N

(iv) Auxochrome-

“Saturated group with lone pair of electrons, when attached to chromophore

changes both wavelength and intensity of absorption”.

Ex.NH2, OH, CH3, Cl groups.

(v) Hyperchromic shift-

“An increase in absorption intensity”

(vi) Hypochromic shift-

“A decrease in absorption intensity”

6. What are the conditions of absorption of IR radiations by the molecule?
Marking scheme- 2Marks for each condition

Even though a molecule ca vibrate in number of ways, each and every

vibration does not absorb IR.The absorption of IR radiations takes place only
if following two conditions are fulfilled.

i) Correct frequency radiation-

A molecule absorbs radiations only when the natural frequency of vibration

of some part of a molecule (atoms/group of atoms) is same as the frequency
of radiation.

“When the frequency of vibration of a bond and frequency of IR radiations

used for excitation match perfectly, then only the IR energy is absorbed”.

ii) Electric dipole-

Only those vibrations which result in change in dipole moment of the

molecule absorb IR radiations. Such vibrations are said to be IR active.

Ex. Symmetrical stretching of acetylene does not result in change in dipole

moment and hence does not absorb IR region. Such vibrations are said to be
IR inactive (other diatomic molecules like H2, Cl2, O2)

7 Give principle of IR spectroscopy. Explain modes of vibrations with

stretching and bending vibrations.

Marking scheme- principle- 1Mark, stretching-1Marks, and bending-3Marks.

Principle-

Atom in molecules are not stationary, they vibrate in different ways. Each
vibration requires different energy.

If molecule absorbs IR radiations, it gets excited to higher vibrational energy

levels. The type of IR wavelength absorbed by the molecule depends upon
type of atoms and chemical bond in the molecule.

A) Stretching vibrations-
These are characterized by change of internuclear distance. The vibration in
which distance between two atoms increases or decreases, but atoms remain
along the same bond axis are called as stretching vibrations.

Stretching vibrations further divided into 2 types.

i) Symmetric stretching-

In this type of stretching bond length increase or decrease symmetrically (in

same direction). Two bonds vibrate in and out together.

ii) Asymmetric stretching-

In this type of stretching, length of one bond increase and other one decrease
or we can say some bonds are getting shorter and others are getting longer
at same time.

B) Bending vibrations-

These are characterized by change of angle between two covalent

bonds.(due to the change in the position of atoms relative to the original
axis)

Bending vibrations are of 2 types in plane and out of plane bending.

i) Scissoring (in plane bending)-

Scissoring in which bond angle decreases. The movement of two atoms
towards and away from each other in the same plane.
ii) Rocking (in plane bending)-

Rocking in which bond angle is maintained, but both bonds moves within the
same plane. The movement of atoms forward and backward.

i) Wagging (out of plane bending)-

In which both atoms move to one side of the plane .Movement of atoms up
the plane or below the plane with respect to central atom.

ii) Twisting ((out of plane bending)-

These involve the movement of one atom up and other atom down the plane
with respect to central atom.
8. Draw a block diagram of IR spectrophotometer. Explain the components of
IR spectrophotometer with their functions.

Marking scheme- block diagram - 1Mark, explaination-5Marks.

Block diagram-

i)Source-

Source for the IR radiation is obtained from nichrome wire, Nernst filament
(zirconium oxide)

ii) Monochromator-

Prism or grating is used as monochromators. They used to select desired

radiation frequencies. Prisms are normally made of halides like NaCl, KBr.

iii) Detectors-

Thermal detectors are used in IR spectroscopy.

a)Thermocouple-

Made from metals like Bi, Sb or semiconductor alloy as a thin film on support
material. This material is kept in evacuated chamber. The incident radiation
is absorbed by junction of two metals. This gives rise in emf.in proportion of
intensity of radiation.

iv) Sampling-

a) Solid sampling can be done by deposition of solid film by evaporation of

solvent on KBr plate. Sometimes solid sample is pasted with oil.

b) Liquid sample is directly taken and kept in cell of KBr.

c) Gas sample is taken in long tube provided with IR instrument.

v) Amplifier and recorder-

Amplifier amplifies the signals from the detector and send to

recoder.Sophisticated recorders give IR spectrum of a compound as a graph.

9. Explain any five applications of IR spectroscopy.

Marking scheme- Any five applications - 1Mark each.

i) Identification of functional group-

Various functional groups have characteristic absorption in IR region,

therefore they can be identified in the organic compound.

ii) Strength of bond-

Stronger bond absorb IR at greater wave number, strength of various bonds

in the molecule can be understood.

iii) Detection of impurities-

IR spectra of impure sample will show extra absorption bands. By comparing

with IR spectra of pure compound, presence of impurity can be detected.

iv)Hydrogen bonding-

IR spectroscopy gives information regarding the hydrogen bonding .Bands

due to hydrogen bonding appears at lower frequency.

v)Identification of organic compound-

Matching the IR spectra of an unknown sample and a known compound. It is

possible to identify the unknown organic compound.

iv)Quantitative estimation-

Determining concentration of solution in terms of functional group, on the

basis of extent of absorption by the group is useful for quantitative
estimation technique.

10. Explain Functional group region and finger print region in IR spectrum.

Marking scheme- Functional group and finger print region-2.5marks each

i) Functional group region-

This group extending from 4000-1500 cm-1 (2.5-6.5µ) is called functional

group region. This part of IR spectrum contains absorption bands due to
stretching vibrations of functional group such as O-H, N-H, C-H etc.

Common functional groups show absorption bands in this region.

i) Finger print region-

The region 1500-909 cm-1 is called finger print region. This is the most
complex part of the IR spectrum and contains number of absorption bands.
This band appears due to stretching and bending vibrations.

6. Corrosion Science
1. Define oxidation corrosion. Explain the general mechanism of oxidation
corrosion with diagram.

Marking scheme-Definition-1mark, mechanism with reactions-4marks,

diagram-1mark

Oxidation corrosion-

When metal comes in the contact with the dry atmospheric gases such as
oxygen and undergoes corrosion is known as oxidation corrosion.

Mechanism-

Formation of oxide film and their growth is a stepwise process. At the initial
stage, oxygen gas is adsorbed on the metal surface. Van der Waal's forces are
responsible for this adsorption. After adsorption, oxygen molecules
dissociate into atoms or ions. These oxygen ions combine with metal by
electron transfer or electron sharing between oxygen and metal atoms.

M Mn+ + ne– (oxidation)

O2 + ne– 2On– (reduction)
i.e. Mn+ + 2On–MO2
(a) Adsorption:
When surface of a metal is exposed to oxygen, it gets adsorbed on the
surface. Initially, there is no chemical bond between the metal surface and
oxygen but they are held together by secondary forces of attraction such as
weak van der Waal's forces.
(b)Chemisorption:
After adsorption, actual process of corrosion starts. Oxygen is an
electronegative element and metals are electropositive in nature. So slowly
electrons from metal get transferred to oxygen. Due to such electron transfer
oxygen acquires negative charge and the metal surface becomes positively
charged. Hence, there is a chemical bond formation between the metal atom
and oxygen.
This type of adsorption is called chemisorption, it continues till unimolecular
oxide layer covers the metal surface.
(c) Film Formation:
When chemisorption complete, a strong adhering film of metal oxide is
formed on the surface and the metal is corroded.
2.Define Wet corrosion. Explain the mechanism of wet corrosion by hydrogen
evolution with suitable example. (5M)

Marking scheme-Def.1mark, explanation, diagram, reaction-4marks

Wet corrosion-

Corrosion of a metal by aqueous conducting medium, with the formation of

anodic and cathodic areas is known as wet corrosion.

Hydrogen evolution-

At anode (oxidation)- Metal atoms on the surface of anode pass into

conducting medium forming metal ions, leaving behind electrons.

Fe → Fe ++ +2e-

At cathode (reduction) - The electrons left on anodic part, flow to cathodic

part instantly.

If the corroding medium is acidic then H+ ions from the medium capture
electrons from cathode and there is libration of the H2 gas by following
equation.

2 H+ +2e- → 2H→ H2↑

Net reaction- Fe + 2 H+ → Fe ++ + H2↑

Mechanism of wet corrosion by hydrogen evolution

3. Explain oxygen absorption mechanism of wet corrosion with diagram and
reactions

Marking scheme- Explanation, diagram, reaction-4marks

Mechanism-

The surface of iron is, usually coated with at thin film of iron oxide. However,
if this iron oxide film develops some cracks, anodic areas are created on the
surface; while the well-metal parts act as cathodes. It follows that the anodic
areas are small surface parts; while nearly the rest of the surface of the metal
forms large cathodes. Such type of metal comes in contact with alkaline or
neutral electrolyte; the following reactions will be takes place.
Reactions-
At Anode: Fe Fe2+ + 2e- ------- (Oxidation)
At cathode: ½ O2 + 2e- + H2O 2 OH-
Fe2+ + 2 OH- Fe (OH) 2
4 Fe (OH)2 + O2 + 2H2O 4 Fe (OH)3
2 Fe (OH)3 Fe2O3.xH2O (Yellow rust)
2 Fe (OH)2+½ O2 Fe3O4 (Black rust) + 3H2O

Mechanism of wet corrosion by oxygen absorption

4. Explain any six factors affecting corrosion on the basis of nature of metal.

Marking scheme- Explanation of six factors -1mark each.

1. Position of metal in galvanic series: higher the position in galvanic series

(position towards the anodic end) it is more reactive and less corrosion
resistant. Lower the position of metal in galvanic series (position towards the
cathodic end) it is noble and more corrosion resistant.

2. Relative areas of cathode and anode: If the ratio of cathode area to anodic
area is greater than the rate of corrosion is faster.

Relatively large cathode area has high demand of electrons and it can be met
by smaller anode by undergoing rapid corrosion. Hence better design by use
of 2 metals is the one which anodic area is much larger than cathodic area.

3. Impurity/Heterogeneity in chemical composition: Because of impurity or

difference in composition some of the areas of same piece becomes anodic
with respect to others and corrode by galvanic type of corrosion.

4. Nature of oxide film: If the oxide film is non-porous, protective and

strongly adhered then further corrosion stops.

But if the film is porous, loosely adhered then corrosion takes place until the
complete destruction of metal.

5. Physical condition of metal surface: Rough surface corrode faster than

smooth surface. This is due to the differential aeration corrosion. The O 2
concentration is more at the hills (crest) and less at the valleys. The areas
where O2 concentration is less becomes anodic with respect to the other
areas and corrode by galvanic type of corrosion.

6. Solubility of corrosion products:

In electrochemical corrosion, if the corrosion product is soluble in the
corroding medium, then corrosion proceeds at a faster rate. On the contrary,
if the corrosion product is insoluble in the medium or thereby suppressing
further corrosion.
7. Volatility of corrosion products:
If the corrosion product is volatile (MoO3), it volatilizes as soon as it is
formed, thereby leaving the underlying metal surface exposed for attack of
environmental conditions. This causes rapid and continuous corrosion.
5. Explain any four factors affecting corrosion on the basis of nature of an
environment.

Marking scheme- Explanation of four factors -1mark each.

(i) Temperature:
The rate of corrosion increases with increase in temperature of environment,
because both the attacking gas as well as metal activated at higher
temperature, the reaction as well as diffusion rate increase, thereby
corrosion rate is generally enhanced.
(ii) Humidity of air:
The metal gets more corroded in humid atmosphere because atmospheric
gases like CO2, SO2 etc.gets dissolved in water and produced a medium which
sets an electrochemical cell in metal. The rate of corrosion increases with
increase in humidity.
(iii) Presence of impurities in atmosphere: Atmosphere, in the vicinity of
industrial areas, contains corrosive gases like CO2, SOX (formation of H2SO4).
Presence of these gases, the acidity of the liquid, adjacent to the metal
surfaces, increases and its electrical conductivity also increases. This
consequently, results in an increase of corrosion.
(iv) Influence of pH:
Generally, acidic media (i.e., pH <7) are more corrosive than alkaline and
neutral media.
(v) Conductivity:
If the electrical conductivity of medium or soil is higher, then the rate of
corrosion will be faster
Eg. Rusting of iron part in underground structures.
6. What is pilling-Bedworth ratio? Give four types of oxide films formed on
surface of metal with suitable example. (5M)

Marking scheme- PBR-1mark, four types of films-1 mark each.

Pilling-Bedworth ratio-

1. Porous film: if the oxide film is porous, then through the pores oxygen
molecules penetrate and corrosion continues until whole metal get
consumed. Ex. Oxide of iron, magnesium, sodium.

2Fe + O2 → 2FeO

2Mg + O2 → 2MgO

2. Non-porous film: if the oxide film is stable, non-porous, well adhered to

metal surface, then further corrosion stops. Ex. film of chromium, tin, zinc,
lead, aluminium.

4Al + 3O2 → 2 Al2O3

2Cu + O2 → 2 CuO

3. Unstable oxide film: When the oxide film is unstable i.e.it decomposes
back into metal and oxygen the net corrosion is zero.

Ex. Metals like gold, platinum and silver.

4Ag + O2 ↔ 2 Ag2O

4. Volatile oxide film: When oxide film is volatile, it vaporize as soon as it is

formed, the underlying metal surface is exposed for further attack of oxygen
and cause further corrosion.

4MO + 3O2 → 2MO2O3↑

7. What is principle of cathodic protection? Discus Sacrificial anodic

protection method. (4M)
Marking scheme- Principle-1mark, any one type-3mark

Cathodic protection- Principle of this method is, the metal to be protected is

force to behave as cathode.

Sacrificial anodic protection:

Sacrificial anodic protection method

The metallic structure to be protected from corrosion is connected to anodic
metal by an insulated wire. The active metals like Zn, Al, Mg etc. acts as
anode, and gets corroded hence it is called as sacrificial anode. For the
purpose of increasing electrical contact the active metal is placed in back fill
(coal+NaCl).When the sacrificial metal consumed completely. It is replaced by
fresh piece.

Applications- Buried steel pipelines, ship hull, and hot water tank.

8. What is principle of cathodic protection? Discus impressed current

protection method. (4M)

Marking scheme- Principle-1mark,Explination with diagram-3marks

Cathodic protection- Principle of this method is, the metal to be protected is

force to behave as cathode.

Impressed current protection method-

In this method, an impressed current is applied in an opposite direction to

nullify the corrosion current and converting the corroding metal from anode
to cathode. This can be accomplished by applying sufficient amount of direct
current from a battery to an anode buried in the soil and connected to the
corroding metal structure which is to be protected. The anode is in a backfill
(composed of gypsum) so as to increase the electrical contact with the soil.
Since in this method current from an external source in impressed on the
system, this is called impressed current method.
This type of protection is given in the case of buried structures such as tanks
and pipelines.

Impressed current cathodic protection method

9. What is anodic cathodic and coating? Which is more protective? Why. (4M)

Marking scheme-Def.2mark, reason with explaination-2mark.

Anodic coating- If the coating metal is higher placed in galvanic series than
base metal is called anodic coating.Ex.Zn, Al, Cr on steel.

Cathodic coating- If the coating metal is lower placed in galvanic series than
base metal is called cathodic coating.Ex.Sn on steel.

Reason- in zinc any porous or breaks occur in such coating, and then galvanic
cell is set up between base metal and coating metal, as coating metal higher
placed acts as anode and start corroding and the base metal gets protected.
As long as coating of tin is uniform on base metal, the base metal protected.
But if the coating ruptures base metal acts as anode and gets corroded.

That’s why anodic coating is better than cathodic coating.

10. What is electroplating? Explain process of electroplating and give
applications. (5M)

Marking scheme-Def.1mark, process-3marks, applications-1mark.

Electroplating- In this method coating metal is coated on base metal on the

basis of electrolysis.

Process- The article to be plated is cleaned well. A tank containing solution of

salt of coating metal. The article is connected to negative terminal of DC
supply to make cathode .Anode is coating metal in the form of rod/strip.
After adjusting PH and current electroplating begins.

Diagram-

Reactions- anode- Cr→ Cr+3 +3e-

Ag→ Ag++ e-

Metal ions migrate towards article and capture e- on reaching there to get
discharged as metal atom.

Cathode- Cr+3+3e- → Cr chromium plating

Ag++ e- → Ag silver plating

Applications- i) Dual purpose corrosion protection and decoration, ii) surface

of plastic, glass also plated iii)coating metals-Cu,Ni,Cr,Ag,Au and base metal-
iron ,steel, glass.

11. How steel is galvanized? Explain the process with the help of diagram.
(4M)
Marking scheme- Galvanizing-1mark, process-3mark

Galvanizing- Coating of zinc on iron or steel, is called as galvanizing.

Process- The article is cleaned well with dil.H2SO4, washed with water and
then dried. Then it is dipped in the molten bath of zinc maintained at 425-
4500C.Surface of the bath is covered with the flux like NH4Cl.After taking it
out, the article is rolled to make coating of uniform thickness and to remove
any excess of zinc. Then it is cooled slowly.

Diagram-

Applications- G.I.sheets used for wires, pipes, buckets, screws. G.I.sheets is

commonly used for roofing of industrial sheds.

12. Explain the metal cladding and cementation method of applying metallic
coating on base metal.

Marking scheme- metal cladding and cementation -2marks each.

i) Metal cladding-

The process by which a dense, homogeneous layer of coating metal is

bonded firmly and permanently to the base metal on one or both sides.
Corrosion resistant metals like silver, chromium, nickel, (clad metals) This
is done on the base metals like Aluminium, copper etc.
Cladding is done by performing a sandwich of protecting layer and the
base metal, which are passing through the rollers and bonded under the
action of pressure and heat.
Applications:
i) A clad sheets widely used in aircraft industry are made by this
ii) Ni and Ni cladded steel is used in making equipments for use in
chemical, petroleum, rubber and soap industry.
iii) Copper cladded steel wires are made by forcing steel wires in to closely
fitting copper tubes, which are widely used in electrical conductors method
by sandwiching duralumin between two layers of pure Aluminium.
ii) Cementation-

This is a process of applying coating of metal on base metal by means of

diffusion of coating metal in base metal at elevated temp. In this method a
uniform surface coating is obtained by heating the base metal in a powder
of coating metal. Diffusion of coated metal powder s into the base metal
takes place resulting in the formation of layer of alloy of varying
composition and forms protective coating to the base metal.
Applications-
The process is suitable for coating small articles of uneven surfaces and
intricate shapes. (Screws, bolts, threaded parts etc.)