APPLIED CHEMISTRY

CALORIFIC VALUE

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 MUST DO TOPICS!!
Calorific value
Octane number and cetane number
Sweating of petrol
Synthetic petrol
Power petrol
Coke
knocking and Antiknocking
Unleaded alcohol
Coal gas, Water gas and Natural gas
CNG and LPG
Petroleum fractions
Caking and Coking of coal
Thermal and catalytic cracking
GCV and NCV
Moving bed and Fixed bed catalytic
cracking Otto Hoffman Coke Oven
Bomb Calorimeter and Boy's Calorimeter
CHEMISTRY NOTES
Unit 1
CALORIFIC VALUE is the amount of heat energy
present in food or fuel and which is determined by
the complete combustion of specified quantity at
constant pressure and in normal conditions. It is
also called calorific power. The unit of calorific
value is kilojoule per kilogram i.e. KJ/Kg.

OCTANE NUMBER is the measure of the resistance

of gasoline against detonation or preignition of the
fuel in the engine. It is measured relative to the
mixture of iso-octane (2,2,4 trimethylpentane) and
n-heptane.
Higher octane fuel has a greater resistance to
autoignition under higher combustion pressure and
heat.

While CETANE NUMBER is the measure of

combustion quality of diesel oil or it is the measure
of the ignition delay, the higher the cetane number
of diesel the shorter the ignition delay, and the
greater the fuel quality, and vice versa. A short
delay affords more time for diesel fuel to burn
completely.

SWEETENING OF PETROL: Sweet crude refers to

crude oil that is extracted that is found to contain very
low amounts of sulfur. It is considered a valuable
and efficient source of crude oil due to the fact that
sulfur lowers the yield of various refined petroleum
products such as gasoline, diesel fuel, and even
plastics.

Sweet crude can be contrasted with the less

desirable sour crude, which has a high level of
sulfur content.

Now syngas is a mixture of hydrogen and carbon

monoxide. SYNTHETIC PETROL is mainly obtained
from a process called Bergius process. In the
Bergius process, hydrogen gas and coal are heated
together which produces a mixture of hydrocarbons
through the process of hydrogenation.
Ethyl alcohol is called POWER ALCOHOL as it is used
to generate power. It is also used as an additive to
motor fuels to act as fuel for internal combustion
engine. The mixture has generally 80% petrol and
20% alcohol.

COKE, solid residue remaining after certain types of

bituminous coals are heated to a high temperature
out of contact with air until substantially all of the
volatile constituents have been driven off. The
residue is chiefly carbon, with minor amounts of
hydrogen, nitrogen, sulfur, and oxygen.

KNOCKING (also knock, detonation, spark

knock, pinging or pinking) in spark ignition
internal
combustion engines occurs when combustion of
some of the air/fuel mixture in the cylinder does
not result from propagation of the flame front
ignited by the spark plug, but one or more pockets
of air/fuel mixture explode outside the envelope of
the normal combustion front.

Branched alkanes and cycloalkanes burn more

evenly than straight-chain alkanes. Short alkanes

burn more evenly than long alkanes

. Alkenes burn more evenly than alkanes.

An ANTI KNOCKING is an additive that is used to

reduce engine knocking and increase the fuel's
octane rating.

The best example of an anti-knocking agent is

Tetraethyl lead (T.E.L).

Tetraethyl lead:

Tetraethyl lead is that it is used to enhance the

octane number of fuel like gasoline.
The more the octane number, the higher the
efficiency of the fuel and the lower probability to
produce a knocking sound.

COAL GAS is also obtained as a by product while

producing coke, and again, just like tar, its smell is
not very pleasant. It is a highly flammable gas as
the main component of it is methane. Thus, if not
regulated carefully, it can form mixture with air
resulting in explosions.
Coal gas, also known as a gaseous mixture, is a
fuel made up of hydrogen, methane, and carbon
monoxide produced by destructive distillation
(continuous heating in the absence of air) of
bituminous coal. Coal is mostly made up of carbon,
with varying proportions of additional elements
such as hydrogen, sulphur, oxygen, and nitrogen.
Coal is generated when dead plant matter decays
into peat, which is then transformed to coal over
millions of years by the heat and pressure of deep
burial.

Typical composition of the Coal gas is as follows:

Hydrogen 50%

Methane 35%

Carbon monoxide 10%

Ethylene 5%
A mixture of CO + H2 is called WATER GAS. WATER
GAS IS USED WITH PRODUCER GAS FOR THE
PRODUCTION OF FUEL GAS. IT IS USED TO
REMOVE CARBON MONOXIDE FROM FUEL CELL
APPLICATIONS. IT IS USED TO GET PURE
HYDROGEN FOR SYNTHESIS OF AMMONIA.

NATURAL GAS is a mixture of gases which are rich

in hydrocarbons. All these gases (methane,
nitrogen, carbon dioxide etc) are naturally found in
atmosphere. Natural gas reserves are deep inside
the earth near other solid & liquid hydrocarbons
beds like coal and crude oil.
CNG is actually a compressed form of pure
Methane gas. It is useful to create clean fuel
without doing any pollution and also it is almost
clean to the atmosphere. Therefore CNG is also
popular as “clean fuel”. Here compression is done
at less than 1% of the volume at the standard
atmospheric pressure. Its storage and distribution
are being done in hard containers. Normally such
containers are cylindrical or spherical in shapes.

LPG is referring to Liquified Petroleum Gas. It is a

mixture of light gaseous hydrocarbons like propane,
butane, and some other light petroleum products. It
is further converted into a liquid by applying much
high pressure. Its bulk production is being done
during the oil refining. This gas is filled in cylinders
at high pressure. Then further its transportation, as
well as storage, is easy and safe. To identify any
leakage from the pressurized cylinders, a slight
quantity of mercaptans is being added to it. This is
because it has a foul smell.

PETROLEUM FRACTIONS: The four fractions

obtained from petroleum which are used as fuels are
Gasoline, Diesel Oil, Kerosene and Petrol. Note:
Fractional distillation is also used for various other
miscible liquids, which have very less difference in
their boiling points.

CAKING COAL: Coal that softens and

agglomerates on heating and after volatile matter
has been driven
off at high temperatures; produces a hard gray
cellular mass of coke. All caking coals are not good
coking coals.

COKING COAL: These coals, when heated in the

absence of air, form coherent beads, free from
volatiles, with strong and porous mass, called coke.

These have coking properties

Mainly used in steel making and metallurgical

industries
Also used for hard coke manufacturing

THERMAL CRACKING is a chemical process used

to
convert large hydrocarbons into smaller molecules,
or to break down a large molecule into smaller
molecules. Thermal cracking is used to produce
gasoline, diesel fuel, and other petroleum products.
The process involves heating a petroleum product
to a high temperature in the presence of a catalyst.
The catalyst causes the large molecules to break
down into smaller molecules.

CATALYTIC CRACKING is a refinery process that

breaks down large, complex molecules into smaller,
more useful molecules. It does this by using a
catalyst, which is a substance that speeds up a
chemical reaction without being consumed by the
reaction.
In catalytic cracking, a reactor is heated to a very
high temperature. The catalyst is then added, and
the reaction begins. The large molecules are
broken down into smaller molecules,
including gasoline, diesel fuel, and other
products.

Net calorific value (NCV) = Gross calorific

value
(GCV) - Latent heat of water vapors

Gross calorific value(GCV) = Net calorific

value + Latent heat of water vapors

OTTO HOFFMAN'S PRODUCT OVEN:

Thebeehive ovens have been replaced by chamber
ovenswhich works on regenerative principle of
heateconomy. All the valuable products are
recoveredfrom the outgoing flue gases.
Construction:

It consists of no. of narrow rectangularchambers

made of silica bricks.

Working:
Coal is charged into the chamber.The coke ovens
are heated to 1200oC by burninggaseous fuels.The
process of carbonization takes place layer bylayer
in the coal charge. As the coal adjacent to the oven
walls gets heated, a plastic zone is formed which
moves away from thewalls towards the central
zone. As the coal is converted into coke, there is
decreasein volume. This is because of the removal
of volatilematter in the form of tar and gas at about
500oC. At further high temperature, the plastic
mass solidifies into hard and porous mass called
coke.

BOMB CALORIMETER: The calorimeter used to

determine the energy change during a reaction
accurately is known as a bomb calorimeter. The
modern Bomb calorimeter is a development of the
original calorimeter of Berthelot. The modern bomb
calorimeter is made of corrosion resisting steel in
which the combination Bomb Calorimeter.
The bomb calorimeter is an instrument used to
measure the heat of reaction at a fixed volume and
the measured heat which is called the change of
internal energy (ΔE). In chemistry, the changes of
heat of a reaction can be measured at fixed
pressure or volume.
Working of Bomb Calorimeter

The bomb calorimeter is a type of constant-volume

calorimeter used to measure the combustion heat
of oxygen-burnable samples. Four critical parts are
needed in every bomb calorimeter.
The bomb calorimeter is a laboratory instrument
used to measure the amount of a sample’s
combustion heat or heat power when excess
oxygen combustion occurs. The purpose of this
research is to determine the effect of using the
bomb calorimeter on the ability of physics students
to process science. Influences involve the efficacy
of using the devices and learning how to develop
the abilities of the scientific method of students
before and after using materials.
If the heat capacity of the calorimeter is known,
then one can determine the heatchange during a
chemical reaction by noting the change in the
temperature in the process.
The heat

Q = Cv(Tf –Ti)

where, q is the amount of heat according to the

change in temperature measured in joules
Cv is the heat capacity of the calorimeter

Tf is the final temperature

Ti is the initial temperature

Construction of Bomb Calorimeter
The bomb calorimeter is used to determine the
calorific values of solid and liquid fuels. It consists
of a strong steel shell known as a bomb.
It consists of a base which supports the platinum
crucible and is screwed to the body of the bomb.
The top of the bomb carries an oxygen supply
connection and a valve to release the product. One
gram of powdered sample coal is taken for the test
and the calorimeter is filled with 2000cm3 of
water. The sample is placed in the platinum
crucible. The iron fuse wire which surrounds the
sample of coal, is connected to the lower end of the
two
electrodes. The electrodes extend through the base
of the bomb and connect the fuse wire to an
electric circuit. The coal can be ignited by closing
the electric circuit.
The bomb is placed inside a copper vessel which
contains water. There is a stirring device for
agitating the water within the calorimeter. The
calorimeter containing the bomb is placed in
another container which acts as a heat insulator.
The temperature of water in the calorimeter is
measured by a thermometer.

The oxygen cylinder is coupled to the bomb and

oxygen is admitted to the bomb through the value
until the pressure gauge in the cylinder indicates a
pressure of 25 atmospheres. The fuel is ignited by
passing a current through the fuse wire. The
temperature of both starts increasing and the
readings on the thermometer are taken at one
minute intervals for 10 minutes, after the maximum
intervals for 10 minutes, after the maximum
temperature is reached. Thereafter the
temperature starts falling slowly. When the
temperature fall shows a steady rate the readings
are taken at regular intervals for an additional five
minutes.
Heat given by the combustion of coal + Heat given
by the combustion of fuse wire = Heat taken by the
water and calorimeter.

BOY'S GAS CALORIMETER:

This calorimeter is used for determining the
calorific value of gaseous and volatile liquid
fuels.

Principle: The calorific value of gaseous fuels is

determined by burning a known volume of gas
sample in a combustion chamber. The released
heat is quantitatively absorbed by cooling water,
circulated through the copper coils surrounded the
combustion chamber. The mass of the cooling
water and its rise in temperature are noted. The
mass of water produced by
condensation of steam is also recorded. The
calorific value of the gas sample is then
calculated from these data.

Construction: It consists of a suitable gas burner in

which a known volume of gas can be burnt at a
uniform rate. Around the burner, there is a chimney
or combustion chamber having copper tubing coiled
inside as well as outside it. Water at a constant
rate enters at the top of the outer coil, moves to the
bottom of the chimney and then goes up through
the inner coil to
the exit at the top. The thermometers T1 & T2 gives
the temperature of the incoming and outgoing
water respectively. The whole assembly is enclosed
in an insulated chamber.
During the process of down and up movement
through coil, the flowing water takes away
practically all the heat of burner and any steam
formed during combustion is condensed back as
water, which can be collected.

Working: The gas is tuned on and ignited. The

water is turned on and rate of flow is so
adjusted that the rise in temperature of water in
passing through the calorimeter is about 20°C.
After 45 minutes, the following readings are noted.
The volume of gas burnt at a given
temperature and pressure during a certain
time interval, t= V
· The amount of water passed through the coil
during the same time interval, t = w
· Temperature of incoming water = t1 °C

· Temperature of outgoing water = t2 °C

· The amount of water condensed during the

experiment = m
Calculations:

Total heat liberated = V.θ

Total heat absorbed = w (t2 t1)

Now, heat liberated = heat absorbed

V.θ = w (t2 t1)

Therefore, G.C.V., θ = w (t2 t1)/V

The amount of water condensed by 1m3 of gas =

m/V
The latent heat of steam per m3 of gas at 15 °C =
587 Kcal
Therefore, N.C.V., = θ m x 587/ V
DU LONG'S FORMUALE:
MOST REPEATED QUESTIONS
•Define the terms cetane number and octane
number.(2.5) OR
Explain cetane number and octane number by
chemical structure.(3)
•Distinguish between producer gas and water gas
(2.5)
•Differentiate between Proximate and Ultimate
analysis of coal. How is coke manufactured by
OttoHoffmann Oven?(6.5)
•A sample of coal was found to contain the
following:C=81%, H = 4%, O = 2%, N = 1.0% the
remaining being ash.Estimate the quantity of
minimum air required for complete combustion of 1
kg of the sample. find the composition of dry flue
gas by volume, if 40% excess air is required.(6)
•Describe the bomb's calorimeter used for the
determination of calorific value of fuels. Also,
outline the principles involved in refining of
petroleum and name of chief components
separated?(6.5) OR Explain how the calorific value
of a fuel can be determined by BOMB calorimeter
with the help of a neat diagram.(6.5)
•Calculate the HCV (in kJ/kg) of 0.75 g of a fuel containing
85% of carbon, when burnt in a bomb calorimeter, increased
the temperature of water from 27.5 to 29.3C. The calorimeter
contains 250 g of water and its water equivalent is 150 g.(6)
•Define the terms thermal cracking and anti knocking
agents.
•Explain what is ultimate analysis of coal? How one can fine
the Composition of C, H, N & S using it?
•How the calorfic value of a fuel can be determined by Boy's
gas calorimeter? Explain with the help of a neat diagram. OR
Explain the determination of calorific value by Boy's
calorimeter.
•2.16 g of coal was kjeldalized and NH3 gas thus evolve was
absorbed in 25 ml of O.INH2S04.After absorption, the excess
acid required 12.5 ml of 0.1N NaOH for exact neutralization.
Determine the percentage of N in sample Of coal.
•What is synthetic petrol?(2.5)
•Define HCV and GCV.
• Fixed and Fluidized bed catalytic cracking. •What is
sweetening of petrol?
•Calcuate GCV and NCV Of a gaseous fuel from the following
data obtained from calorimeter experiment. Volume of
gaseous fuel burnt at STP 0.08m3 Temperature of inlet water
= 260C Temperature of Outlet water = 320C Weight of water
produced by steam condensation = 0.01 kg. Late heat of
steam = 587 Kcal/kg (6)
 FFT15

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