Part - A

1.Distinguish between sludge and scale with an example

S.No Sludge Scale

1 Sludge is a loose, slimy and non- Scale is a hard, adherent coating

adherent precipitate
2 The main sludge forming The main scale forming substances are
substances are MgCO3, MgCl2, Ca(HCO3)2, CaSO4, Mg(OH)2
MgSO4 and CaCl2
3 Disadvantages: Sludges are poor Disadvantages: Scales act as thermal
conductors of heat. Excess of insulators. It decreases the efficiency of
sludge formation decreases the boiler. Any crack developed on the scale
efficiency of boiler leads to explosion

Prevention: Prevention:
Scale formation can be prevented by
Sludge formation can be dissolving using acids like HCl, H2SO4
prevented by using softened water

Sludges can also be removed by Scale formation can be removed by

4 “blow-down operation” (a)external treatment (b)internal treatment

Blow –down operation is a They can also be removed by applying

process of removing a portion of thermal shocks, scrapers, wire brush, etc.,
concentrated water by fresh water
frequently from the boiler during
steam production.
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2.What is calgon conditioning ?

 Calgon is sodium hexa meta phosphate Na2 [Na4 (PO3)6].
 This substance interacts with calcium ions forming a highly soluble complex and thus
prevents the precipitate of scale forming salt.

2CaSO4 + Na2 [Na4 (PO3)6] → Na2 [Ca2 (PO3)6] + 2Na2SO4

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3.Write any two difference between physical and chemical adsorption.
S.No Physisorption Chemisorption

1 Caused by intermolecular Vander Caused by chemical bond formation

Waal’s forces (weak) (strong)

2 Heat of adsorption is low (0 – 40 k.cal / Heat of adsorption is high (40 – 400 k.cal
mol) / mol)

3 Adsorption decreases with increase in Adsorption increases with temperature

temperature

4 Multiplayer adsorption occurs Only monolayer adsorption occurs

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4.What is meant by catalytic poisoning ?

 It refers to the partial (or) total deactivation of a catalyst caused by exposure to a
range of chemical compounds (or) substances.
 Thus, substances which destroy the activity of the catalyst are known as catalytic
poisons.

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5.Define the term alloy and its significance with an example.

 An alloy is defined as “homogeneous solid solution of two or more different elements,
one of which at least is essentially a metal”.

Significance:

 To increase the hardness of the metal.

 To resist the corrosion of the metal.

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6.What is meant by eutectic point ?

 It is the temperature at which two solids and a liquid phase are in equilibrium.

Solid A + Solid B Liquid

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7.Write the classification of fuels with an example.

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8.Define the term spontaneous ignition temperature with an example.

 The minimum temperature at which the fuel catches fire (ignites) spontaneously
without external heating.

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9.Mention any two examples for secondary cells.

1. Lead acid battery

2. Nickel cadmium battery

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10.What are fast breeder reactors ?

 Breeder reactor is the one which converts non-fissionable material (U238, Th232) into
fissionable material (U235, Pu239).
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11.b.i Define hardness of water and explain the experimental determination of

hardness of water by EDTA method.

Principle
pH 8 - 10
2+ 2+
[ Ca , Mg ] +EBT -------------> [Ca,Mg EBT]
pH 8 - 10
[ Ca, Mg EBT] +EDTA -------------> [Ca,Mg EDTA] + EBT
Solution preparation
 EDTA solution → 4 gm EDTA in 1000 ml of distilled water
 Std.hard water → 1gm CaCO3 + min HCl + 1000 ml of distilled water
 EBT indicator → 0.5 gm EBT in 100 ml of alcohol
 Buffer solution → 67.5 gm NH4Cl + 570 ml NH3 + made upto 1000 ml using distilled
water

Experimental methods
Standardization of EDTA
EDTA
50 ml std.hard water + 10 ml buffer solution + 5 drops of EBT -----------> colour change from
wine red to steel blue
Volume of EDTA consumed be V1 ml

Estimation of total hardness of water sample

EDTA
50 ml given.hard water + 10 ml buffer solution + 5 drops of EBT --------> colour change from
wine red to steel blue
Volume of EDTA consumed be V2 ml
Estimation of permanent hardness of water sample.
∆
100 ml of given hardwater -------> temporary hardness removed
15 min
Cool and filter the solution and take upto to 100 ml in a standard flask by adding distilled water.

EDTA
50 ml boiled water + 10 ml buffer solution + 5 drops of EBT --------> colour change from wine
red to steel blue
Volume of EDTA consumed be V3 ml
Calculations
Standardization of EDTA
1 ml of Std hard water = 1 mg of CaCO3
50 ml of Std hard water = 50 mg of CaCO3
50 ml of Std hard water contains = V1 ml of EDTA
V1ml of EDTA = 50 mg of CaCO3
1 ml of EDTA = 50 / V1 mg of CaCO3

Estimation of total hardness

50 ml of the given hard water sample consumes = V2 ml of EDTA = V2 X 50/V1 mg of
CaCO3
1000 ml of the given hard water sample = V2 X 50 / V1 X 1000 / 50 = 1000 X V2 / V1 mg of
CaCO3
Total hardness = 1000 X V2 / V1 ppm
Estimation of permanent hardness
50 ml of the given hard water sample after boiling consumes = V3 ml of EDTA = V2 X 50/V1
mg of CaCO3
1000 ml of the given hard water sample = V3 X 50 / V1 X 1000 / 50 = 1000 X V3 / V1 mg of
CaCO3
Permanent hardness = 1000 X V3 / V1 ppm
Temporary hardness
Total hardness – permanent hardness = 1000 X V2 / V1 – 1000 X V3 / V1
Temporary hardness = 1000 / V1 X (V2 – V3) ppm
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12.a.1.What are adsorption isotherms ? Explain the five different forms of

adsorption isotherms with suitable examples.
Definition:

 Adsorption isotherm is a relationship between magnitude of adsorption with pressure

at constant temperature.

Type I:

 As postulated by Langmuir, it corresponds to monomolecular adsorption.

 The volume of the gas adsorbed approaches a limiting values Ps, which is just enough
to complete monolayer, even when the gas pressure is low.
 Further increase in pressure will not increase the amount of adsorption.

Ex: adsorption of N2 (or) H2 on charcoal at -180°C

Type II and III:

 These isotherms show large deviations from Langmuir model.

 The amount of adsorption, in each type, is going on increasing with increase in
pressure.
  This is due to the formation of additional layers over the monolayers by Vander waals
forces of attraction.
 It has been suggested that, the gas molecules adsorbed in the first layers may hold a
second layers of gas molecules by weak Vander waals forces (Physical bond), which
in turn, may hold a third layer and so on.

Ex:

 Type II : adsorption of N2 on Fe (or) Pt catalyst at -195°C

 Type III : adsorption of Br2 on silica (or) alumina gel at 80°C

Type IV and V:

 These isotherms indicate a possibility of condensation of gases in the minute capillary

pores of the adsorbent at the pressures even below the saturation pressure ‘Ps’.

 This is not only due to formation of multi molecular adsorption layers of the gas
molecules but also due to condensation of some of the gas molecules with in the
capillary pores of the adsorbent.
 This is known as capillary condensation of the gas.

Ex:

 Type IV : adsorption of benzene on silica gel at 50°C

 Type V : adsorption of H2O vapour on activated carbon at 100°C

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12.a.ii) Write informative notes on Langmuir adsorption isotherm

 Langmuir derived an equation based on some theoretical considerations.

Assumptions (or) Postulates:

1. Valencies at the surface of adsorbent are not fully satisfied.

2. The adsorbed gas layer on the solid surface is only one molecule thick.
3. The surface of the solid homogeneous, so the adsorbed layer is uniform all over the
adsorbent.
4. There is no interaction between the adjacent adsorbed molecule.
5. The adsorbed gas molecule do not move around on the surface.

Derivation:

 According to langmuir’s assumptions, when the gas molecules strike a solid surface,
some to the molecules are adsorbed and some of these are desorbed.
 Thereby dynamic equilibrium is established between adsorption and desorption.
If A is gas molecule and M is surface then,

k1
A(g) +M(surface) AM
k2

Let,

Fraction of the total of the surface covered by the adsorbed molecule = θ

Fraction of uncovered (vacant area) area = (1 – θ)

Rate of desorption is proportional to number of adsorbed molecules = Rd  kd

kd : rate constant for desorption

Thus the rate of adsorption is proportional to available uncovered area = Ra  ka (1   ) P

ka = rate constant for adsorption

At equillibrium;

Rate of desorption ≡ Rate of adsorption

 k d  k a (1   ) P  k a  k a P
k d  k a P  k a P
 (kd  ka P )  ka P
ka P
 
(kd  ka P )

Dividing (1) by kd : 
 ka / kd  P or =
KP
(2)
1   ka / kd  P 1+KP
Where

ka / kd  K = Equillibrium constant (Absorption coefficient )

But, the amount of gas adsorbed per gram of the adsorbent is proportional to θ .  x   --
-- (3)

KP KP
Comparing (2) & (3) : x  xK' (4)
1+KP 1+KP

Where, K’ is a new constant

(4) gives the relation between the amount of gas adsorbed to the pressure of the gas at
constant temperature and is known as Langmuir Adsorption Isotherm

K'KP 1 KP P 1 K P
Eqn. (4) can be rewritten as 1+KP= ;   ; + P (5)
x K'K K'K x K'K K'K x

The equation (5) is similar to an equation for a straight line (ie., y = c + mx). If the graph is
plotted between P / x Vs P, we should get a straight line with slope K / K’K
and the intercept 1 / K’K.

The equation is found valid in all cases.

The graph between P/x Vs
Slope P should be a straight line
K/K'K
with slope K/K’K and
P/x Intercept
1/K'K intercept 1/K’K
P

Case (i) : At low pressure

K 1 K
At low P, P is negligeble; i.e.,  P
K'K K'K K'K

1 P
Hence Eqn (5) becomes : i.e.,  ; x= PK'K (or) 𝑥 ∝ 𝑃 -------------------(6)
K'K x
Amount of adsorption per unit weight of adsorbent is directly proportional to P at low P

Case (ii) : At high pressure

1 K 1
At high P, is negligeble ; i.e., P 
K'K K'K K'K

K P
Eqn (5) becomes: P (or) x=K' (constant) (or) 𝑥 = 𝐾 ′ 𝑃° -----------------(7)
K'K x

Ie., extent of adsorption is independent of pressure of the gas, because the surface becomes
completely covered at high pressure.

Case (iii) : At normal pressure

If the pressure (P) is normal (intermediate) the equation (7) becomes

x=K'P n Where n lies between 0 and 1

Eqn (8) is Frendlich Adsorption Isotherm

Limitations (or) merit and demerit

 Langmuir adsorption isotherm holds good at lower pressure but fails at high pressure.
 According to langmuir’s adsorption theory, the adsorption is monolayer, but
multilayer adsorption is also possible.

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13.a.Explain the heat treatment of steel in detail.

HEAT TREATMENT OF ALLOYS (Steel)

 Heat treatment is defined as, “the process of heating and cooling of solid steel article
under carefully controlled conditions,”
 During heat treatment certain physical properties are altered without altering its
chemical composition.
Types of Heat Treatment of Alloys (Steel)

The main characteristics and the relevant heat-treatment processes are

1. Annealing 4. Normalizing

2. Hardening 5. Carburizing

3. Tempering 6. Nitriding

1. Annealing

 Annealing means softening.

 This is done by heating the metal to high temperature, followed by slow cooling in a
furnace.
 The approximate annealing temperatures of various grades of carbon steel are
1. mild steel = 840 − 870° C

2. medium-carbon steel = 780 − 840° C

3. high-carbon steel = 760 − 780° C

Purpose of annealing

(i) It increases the machinability.

(ii) It also removes the imprisoned gases

2. Hardening (or) Quenching

 It is the process of heating steel beyond the critical temperature and then suddenly
cooling it either in oil or brine-water or some other fluid.
 Hardening increases the hardness of steel. The faster the rate of cooling harder will be
the steel produced.

 Medium and high-carbon steels can be hardened, but low-carbon steels cannot be
hardened.

Purpose

1. It increases its resistance to wear, ability to cut other metals and strength, but steel
becomes extra brittle.
2. It increases abrasion-resistance, so that it can be used for making cutting tools.

3. Tempering

 It is the process of heating the already hardened steel to a temperature lower

than its own hardening temperature and then cooling it slowly.
 In tempering, the temperature to which hardened steel is re-heated is of great
significance and controls the development of the final properties.
Thus

(i) For retaining strength and hardness, reheating temperature should not exceed
400°C.
(ii) For developing better ductility and toughness, reheating temperature should be
within 400 − 600°C.

Purpose

 It removes any stress and strains that might have developed during quenching.
 It reduces the brittleness and also some hardness but toughness and ductility
are simultaneously increased.
 Cutting-tools like blades, cutters, tool-bites always require tempering.

4. Normalising

It is the process of heating steel to a definite temperature (above its higher critical
temperature) and allowing it to cool gradually in air.

Purpose

 It recovers the homogeneity of the steel structure.

 It refines grains.
 It removes the internal stresses.
 It increases the toughness.

5. Carburizing

 The mild steel article is taken in a cast iron box containing small pieces of charcoal
(carbon material).
 It is then heated to about 900 to 950°C and allowed to keep it as such for sufficient
time, so that the carbon is absorbed to required depth.
 The article is then allowed to cool slowly within the iron box itself.
 The outer skin of the article is converted into high-carbon steel containing about 0.8
to 1.2% carbon.

Purpose:

To produce hard-wearing surface on steel article.

6. Nitriding

Nitriding is the process of heating the metal alloy in presence of ammonia at a

temperature to about 550°C. The nitrogen (obtained by the dissociation of ammonia)
combines with the surface of the alloy to form hard nitride.

Purpose:

To get super-hard surface.

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14.a.1Explain how is metallurgical coke manufactured by Otto-Hoffman
methods.
METALLURGICAL COKE

 When bituminous coal is heated strongly in the absence of air, strong, porous mass is
obtained which is called Metallurgical Coke.

MANUFACTURE OF METALLURGICAL COKE

 There are so many types of ovens used for the manufacture of metallurgical coke.
 But the important one is Otto-Hoffman’s by product oven.

Otto-Hoffman’s by-product oven

Inorder to

 increase the thermal efficiency of the carbonization process and,

 recover the valuable by products (like coal gas, ammonia, benzol oil, etc.)

Otto-Hoffman developed modern by product coke oven.

 The oven consists of a number of silica chambers.

 Each chamber is about 10 − 12 m long, 3 − 4 m height and 0.4 − 0.45 m wide.
 Each chamber is provided with a charging hole at the top.
 It is also provided with an iron door at the bottom for discharging coke.
 Coal is introduced into the silica chamber and the chambers are closed.
 The chambers are heated to 1200°C by burning the preheated air and the
producer gas.
 The air and gas are preheated by sending them through 2nd and 3rd hot regenerators.
 Hot flue gases produced during carbonization are allowed to pass through 1st and 4th
regenerators until the temperature has been raised to 1000°C.
 While 1st and 4th regenerators are heated by hot flue gases, the 2nd and 3rd regenerators
are used for heating the incoming air and gas mixture.
  For economical heating, the direction of inlet gases and flue gases are changed
frequently.
 The above system of recycling the flue gases to produce heat energy is known as the
regenerative system of heat economy.
 When the process is complete, the coke is removed and quenched with water.
 Time taken for complete carbonization is about 12-20 hours. The yield of coke is
about 70%.
 The valuable by products like coal gas, tar, ammonia, H2S and benzene, etc. can be
recovered from flue gas.

Tar

 The flue gases are first passed through a tower in which liquor ammonia is sprayed.
 Tar and dust get dissolved and collected in a tank below.

Ammonia

 The gases are then passed through another tower in which water is sprayed.
 Here ammonia gets converted to NH4OH.

Naphthalene

 The gases are again passed through a tower, in which cooled water is sprayed.
 Here naphthalene gets condensed.

Benzene

 The gases are passed through another tower, where petroleum is sprayed.
 Here benzene gets condensed to liquid.

Hydrogen Sulphide

 The remaining gases are then passed through a purifier packed with moist Fe2O3.
 Here H2S is retained.
 The final gas left out is called coal gas which is used as a gaseous fuel.

Advantages of Otto Hoffman’s Process

 Valuable by products like ammonia, coal gas, naphthalene etc., are recovered.
 The carbonization time is less.
 Heating is done externally by producer gas.

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14.a.ii)Differentiate between gross and net calorific value with an example.
Calorific value:

 The total amount of heat liberated, when a unit mass of a fuel is burnt completely.

Calorie:

 It is defined as the amount of heat required to raise the temperature of 1 gram of water
through 1°C (15 to 16°C).

HIGHER AND LOWER CALORIFIC VALUES

 Higher (or) Gross calorific value (GCV)

 Lower (or) Net Calorific Value (NCV)

Higher (or) Gross Calorific Value (GCV)

 It is defined as the total amount of heat produced, when a unit quantity of the fuel is
completely burnt and the products of combustion are cooled to room temperature.
 When a fuel containing hydrogen is burnt, the hydrogen is converted into steam.
 If the combustion products are cooled to room temperature, the steam gets condensed
into water and latent heat is evolved.
1 𝑂
𝐺𝐶𝑉 = [8080𝐶 + 34500 [𝐻 − ] + 2240𝑆] 𝑘. 𝑐𝑎𝑙/𝑘𝑔
100 8
Lower (or) Net Calorific Value (NCV)

 It is defined as the net heat produced, when a unit quantity of the fuel is completely
burnt and the products of combustion are allowed to escape.
9
𝑁𝐶𝑉 = 𝐺𝐶𝑉 − [ 𝐻 𝑋 587] 𝑘. 𝑐𝑎𝑙/𝑘𝑔
100

 Where, H = % of H2 in the fuel.

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 15.b.i)Write informative notes on the following :
Lithium ion battery and its working mechanism with a neat diagram.
*Secondary battery

Anode Negative electrode (layers of porous carbon)

Cathode Positive electrode (layers of lithium – metal oxide)

Electrolyte Polymer gel (separator)

Diagram

Charging LiCoO2 + C → Li1-XCoO2 + CLiX

Discharging Li1-XCoO2 + CLiX →LiCoO2 + C

Advantages  High voltage and light weight batteries

 Smaller in size
 Produces three times the voltage of Ni – Cd batteries
Uses  Cell phone, note PC, portable LCD TV, semiconductor driven audio etc.,

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 15.b.ii)H2O2 fuel cell and its working mechanism with a neat diagram.
*simplest and most successful cell

*converts the chemical energy of the fuels directly into electricity without combustion.

Anode Carbon porous electrode (Pt,Pd,Ag) by passing H2 gas

Cathode Carbon porous electrode (Pt,Pd,Ag) by passing O2 gas

Electrolyte NaOH (or) KOH (25%)

Diagram

Anode reaction

Cathode reaction

Overall reaction

Emf of the cell 0.8 to 1.0 V

Applications  It used as auxiliary energy source in space vehicles, submarines or other

military vehicles.
 It produces water which is valuable source for astronauts.
Advantages  It emits only water vapour and no other harmful chemicals to the
environment
 Efficiency is more than 75% and take less time for operation
 As hydrogen is the lightest element, it can be transported easily from
one place to another
 Pollution free technique
 It produces electric current directly from the reaction of a fuel and an
oxidiser
 It causes less noise pollution.

Disadvantages  Hydrogen gas is explosive

 It is very expensive to be carried out
 As hydrogen is a gas, it is difficult to compress into liquid form
 Hydrogen is not present as it is, but always present in combined form
with either oxygen or some other element, so it must be separated first
 While using H2 – O2 fuel cell in an automobile, a high pressure must be
created inside the engine, which is risky
 It can not store electric energy
 Electrodes are expensive and short lived
 Storage and handling of hydrogen gas is dangerous

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