(2019- Pattern)

Engineering Chemistry

Model Answer Set

Time: 03 hrs. Max. Marks: 70

3. 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. (It should be noted that
out of these two bonds, one is a strong  bond and the other is a weak µ bond.)
In these systems (polymers) there is overlapping of conjugated  bonds over 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 polymer chains.
The oxidizing agent extracts a pair of  electrons from chain 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 + I2.
 (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 = Vm 3
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 OC 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
 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

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. σ σ* 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 π* 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 π* orbital.

3. n σ* 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 O2 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 Al 2O3

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 Ag 2O

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 P H 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.)