MUST DO TOPICS

UNIT-1
• 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

CALORIFIC VALUE: It 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: It 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.

CETANE NUMBER: It is the measure of combustion quality of diesel oil or it is the measure of
the ignition delay, the higher the cetane number of diesels 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.

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 byproduct 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:

The beehive ovens have been replaced by chamber ovens which works on regenerative principle
of heat economy. All the valuable products are recovered from the outgoing flue gases.

Construction:

It consists of no. of narrow rectangular chambers made of silica bricks.

Working:
Coal is charged into the chamber. The coke ovens are heated to 1200oC by burning gaseous
fuels. The process of carbonization takes place layer by layer in the coal charge. As the coal
adjacent to the oven walls gets heated, a plastic zone is formed which moves away from the
walls towards the central zone. As the coal is converted into coke, there is decrease in volume.
This is because of the removal of volatile matter 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 heat change 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:
MUST DO QUESTIONS
UNIT-1
•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
Otto-Hoffmann 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 principals 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 calorific 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?
•Calculate 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)