Module 3

CHEMICAL FUELS
Chemical fuel is a combustible substance which when burnt in air or
oxygen produces large amount of heat which can be economically
used for domestic and industrial purposes.

Fuel + Air → CO2↑ + H2O↑ + heat

Combustion products are CO2 and H2O (steam) with liberation of

heat.
Since the fuels contain carbon and hydrogen as major elements they
are known as hydrocarbon fuels.
Examples are wood, coal, petrol, diesel, kerosene, natural gas,
producer gas, coal gas, water gas, etc.
 Classification of fuels

Fuels are mainly classified as solid, liquid and gaseous fuels.

Further they are classified as

(i) Natural or primary fuels and (ii) Derived or secondary fuels

Natural or primary fuels: These fuels are obtained directly from

nature.

Derived or secondary fuels: These fuels are derived from natural

fuels
Type Primary fuel Secondary fuel
(natural fuel) (derived fuel)
Wood,coal,peat, Charcoal,coke,
Solid lignite, etc. etc.
Petroleum Petrol, diesel
Liquid (crude oil) kerosene, etc.
Producergas,
Gaseous Natural gas watergas,coalgas
biogas,LPG, etc.
 Calorific value of a fuel (CV)

It is a measure of capacity of a fuel to supply heat. Higher the CV

of a fuel, higher is the efficiency.
It is defined as the amount of heat released when unit quantity of
a fuel is completely burnt in excess of air or oxygen.

Calorific value is of two types: (i) Gross CV or Higher CV and (ii)

Net CV or Lower CV

Gross calorific value (GCV): It is the amount of heat released

when unit quantity of a fuel is completely burnt in excess of air or
oxygen and the combustion products are cooled to room
temperature.

GCV includes latent heat of steam.

Net calorific value (NCV): It is the amount of heat released when
unit quantity of a fuel is completely burnt in excess of air or oxygen
and the combustion products are let off into the atmosphere.
NCV does not include latent heat of steam.
NCV = GCV – latent heat of steam
GCV is always greater than NCV because GCV includes latent heat of
steam.
For solid and liquid fuels the CV is expressed as kJ/kg and for
gaseous fuels it is expressed as kJ/m3
Characteristics of a good fuel
▪High calorific value
▪Moderate ignition temperature
▪Low moisture content
▪Low ash content
▪No harmful combustion products
▪Easily available with minimum cost
▪Easy storage and transportation
Determination of calorific value of solid and
liquid fuels using Bomb calorimeter
The bomb calorimeter consists of a stainless steel cylindrical
vessel known as bomb, which is provided with air tight lid. The
lid is fitted with two stainless steel electrodes and an inlet valve
for oxygen used for combustion.
A stainless steel crucible is attached to one of the electrodes. A
known weight of the fuel sample is placed in the crucible. A
magnesium fuse wire touching the fuel sample is stretched
across the electrodes. Oxygen gas for combustion of fuel is filled
in the bomb and lid is tightly screwed.
The bomb is placed in a copper calorimeter containing known
weight of water.
The calorimeter consists of a Beckmann’s thermometer and an
electrical stirrer. The calorimeter is surrounded by an air jacket
and water jacket.
The water is stirred using stirrer and the initial temperature of water is
noted.
The electrodes are connected to a battery and current is passed.
The fuel sample burns completely liberating heat and the heat is
absorbed by the calorimeter and water.
The water is again stirred and the final temperature of water is noted.
Calculation:
Weight of fuel sample taken = m gms
Weight of water taken in calorimeter = w1 gms
Water equivalent of calorimeter = w2 gms
Initial temperature of water = t1 oC
Final temperature of water = t2 oC
Specific heat of water = 4.187 kJ/ kg / oC
If Q is the GCV of the fuel, then, the heat liberated by burning m gms
of fuel = m x Q
Heat absorbed by the water and calorimeter = (w1+w2) x (t2-t1) x 4.187
If Q is the GCV of the fuel, then, the heat liberated by burning m gms of
fuel = m x Q
Heat absorbed by the water and calorimeter = (w1+w2) (t2-t1) 4.187

Since, Heat liberated = Heat absorbed

m x Q = (w1+ w2) x (t2-t1) x 4.187

Therefore, Q (GCV) = (w1+ w2) x (t2-t1) x 4.187 kJ/ kg

m x 10-3
Water equivalent w2 can be determined by burning a fuel of known
calorific value and using the above equation.

(NCV) = GCV – 0.09 x H x latent heat of steam

H = percentage of hydrogen in the fuel.

Latent heat of steam = 587 cal/g = 587 x 4.187 kJ / kg
 Numerical problems

1). When 0.75gm of a coal sample with 2.5% hydrogen is burnt in a bomb
calorimeter, the temperature of 2 Kg of water is increased by 3 0C . Compute GCV
and NCV of the coal sample. Given that, the water equivalent of calorimeter is
470g, specific heat of water is 4.187 KJ/Kg/ 0C and latent heat of steam is 587
cal/gm.

GCV = (W1+W2) x( t2-t1) x 4.187

m
= (2+ 0.470) x 3x 4.187
0.75x10-3
= 41367.5 kJ / kg

NCV = GCV - 0.09H x latent heat of steam

= 41367.5 - 0.09 x 2.5 x 587x 4.187
= 41367.5 - 552.9 = 40814. 6 kJ / kg
2). When 0.7x10-3 Kg of a solid fuel with 5% hydrogen is burnt in a bomb
calorimeter, the temperature of 2500gms of water is increased by 2.6 0C .
Compute GCV and NCV of the fuel sample. Given that, the water equivalent of
calorimeter is 450g, specific heat of water is 4.184 KJ/Kg/ 0C and latent heat of
steam is 2455 KJ/Kg.

GCV = (W1+W2) x( t2-t1) x4.184

m
= (2.5+ 0.450) x 2.6x 4.184
0.7x10-3
= 45844.7 kJ / kg

NCV = GCV - 0.09H x latent heat of steam

= 45844.7 - 0.09 x 5 x 2455
= 45844.7 – 1104.7 = 44740 kJ / kg
3). 0.80gm of coal sample (carbon-91.8%, hydrogen-6% and ash-2%) was
subjected to combustion in a bomb calorimeter. Mass of water taken in the
calorimeter was 1800gm and the water equivalent of calorimeter was 250gm.
The rise in temperature was found to be 4.2 0C. Compute the GCV and NCV of
the coal sample. Latent heat of steam = 2457 kJ/kg and specific heat of water =
4.187kJ/kg/ 0C.

m=0.0008kg, W1 =1. 8kg, W2 =0.25kg, t2 – t1 = 4.2, %H = 6

specific heat of water = 4.187kJ/kg/ 0C , latent heat of steam = 2457 kJ/kg

calculate GCV and NCV

 Cracking
The petrol obtained by fractional distillation of petroleum
(crude oil) is called as straight run gasoline. In this process the
yield and quality of gasoline is low. The petrol yield can be
increased by chemical process like cracking.
Cracking is a process in which high molecular weight
hydrocarbons in petroleum fractions are split into low
molecular weight hydrocarbons.
The petroleum fractions such as heavy oil can be subjected to
cracking to produce petrol or gasoline.

C10H22 → C8H18 + C2H4

Decane Octane

C15H32 → C8H18 + C7H14

 Catalytic cracking
▪ It is carried out using a suitable catalyst.
▪The advantage in this process is it gives high yield of petrol.
▪Heavy oil fraction is subjected to cracking and it is carried out in vapour phase.
▪It is necessary to have good contact between the vapour and the catalyst.
▪The catalyst is taken in the form of pellets or powder.
▪The catalyst used is Aluminium silicate which consists of Alumina and Silica (Al2O3 +
SiO2).
▪Fluidised catalytic cracking is one of the types of catalytic cracking.

Fluidised catalytic cracking

Feed stock : Heavy oil vapour
Catalyst : Al2O3 + SiO2 (Fluidised)
Temperature : 550oC
Pressure : Little above normal
Yield : 106 gallons per day
In this process, a mixture of heavy oil vapour and powdered catalyst aluminium
silicate(Al2O3 + SiO2) in a fluidised state is sent into a cracking chamber.
The heavy oil undergoes cracking at a temperature of 550oC and the cracked
products are sent into a fractionating column in which the gasoline is separated
and collected. The uncracked heavy oil is again subjected to cracking.

After 10 hours of cracking the catalyst becomes inactive because of the

deposition of carbon and oil drops on its surface, and it is called as spent
catalyst. The spent catalyst has to be regenerated.

The spent catalyst is transferred by air blast into the regeneration chamber in
which hot air and steam is introduced.
The hot air burns the carbon and the steam removes oil drops from catalyst
surface.
The regenerated catalyst becomes active again and by air blast it is sent back to
cracking chamber and mixed with heavy oil for further cracking.
The advantage of this process is that, higher yield of petrol is obtained because
of good contact between heavy oil vapour and catalyst.
 Reformation of petrol
It is the process of carrying out structural modifications in the components of petrol
to increase its octane rating.

The quality of petrol increases with increase in octane number. The straight run
gasoline obtained from fractional distillation of petroleum contains mainly straight
chain hydrocarbons which have low octane number.
If the percentage of branched chain hydrocarbons, cyclic hydrocarbons and
aromatic hydrocarbons is increased in petrol its octane number increases.

Some of the examples of reformation reactions are :

1). Isomerization : n - alkanes are converted into branched alkanes.

2). Dehydrogenation : Cyclo alkanes are converted into aromatic compounds
3). Dehydrocyclisation : n - alkanes are converted into cyclo alkanes
4). Hydrocracking : n - heptane reacts with hydrogen in presence of platinum
catalyst and undergoes cracking to produce lighter alkanes.
Write the reactions for each
 Knocking in IC engines
A mixture of petrol vapours and air is used as a fuel in Internal combustion
engines. Normally smooth combustion occurs in IC engines.
If the petrol has low octane rating the fuel-air mixture undergoes spontaneous and
explosive combustion producing rattling sound in the engine. This is called
knocking.
Knocking is the rattling sound produced in IC engines due to spontaneous
combustion of fuel-air mixture.

Compression Ratio : It is the ratio of gaseous volume (V1) in the cylinder at the end
of suction stroke to the volume (V2) at the end of compression stroke of the piston.
Compression ratio is always greater than one because V1 > V2 .
Compression ratio = V 1 / V2 > 1

Efficiency and power output of engine increases with increase in compression ratio
upto certain value.

Due to knocking the power output and efficiency of the engine decreases
 Adverse effects of knocking

▪ Undesirable rattling noise

▪ Power output decreases
▪ Engine efficiency decreases
▪ Fuel consumption increases

Prevention of knocking

Antiknocking agents:The substances added to the fuel to reduce

knocking in IC engines are called antiknocking agents. These
compounds improve the quality of fuel.
The important antiknocking agent used for petrol is TEL (Tetra
Ethyl Lead (C2H5)4Pb) and TML(Tetra Methyl Lead).
The petrol containing TEL or TML is called as leaded petrol. About 0.5 ml of TEL
per litre is added for petrol in automobiles.

TEL is a colourless liquid. During combustion of petrol in IC engines the TEL is

converted into PbO which reduces knocking.

PbO is non-volatile and its deposition damages the cylinder wall. By adding
dibromo ethane(C2H4Br2) along with TEL the non volatile PbO2 can be converted
into volatile PbBr2 which escape with other gases through the exhaust.
Lead is toxic and harmful to environment. Therefore, nowadays the use of leaded
petrol is avoided.

Unleaded petrol:The petrol containing antiknocking agents without lead is called

as unleaded petrol.

For example Methyl tertiary butyl ether MTBE or Ethyl tertiary butyl ether ETBE is
used as antiknocking agents in unleaded petrol.

MTBE is a colourless liquid and it reduces knocking and petrol becomes more
antiknocking.
Leaded petrol cannot be used in automobiles attached with catalytic converter
because the lead poisons the catalyst.
Therefore, the advantage of using unleaded petrol is that it is free from harmful
effects of lead. Further it allows the use of catalytic converter attached to the
exhaust in automobiles. The catalytic converter contains a rhodium catalyst
which converts the toxic gases such as CO and NO to harmless CO2 and N2.

Power alcohol

When ethyl alcohol is used as an additive to petrol to act as a fuel for IC engines
it is called as power alcohol.

About 25% of alcohol with petrol are used as fuel. It is called as alcohol petrol
blend.
 Advantages of power alcohol

▪Addition of alcohol to petrol increases the octane number and antiknock

properties.

▪Because of high octane number it can be used in engines with higher

compression ratio.

▪Lubrication in case of alcohol- petrol blend and pure petrol is the same.

▪Power output is good.

▪Emission of carbon monoxide is reduced.

 Synthetic petrol
Production of synthetic petrol has become a necessity because of the fast
depleting of petroleum resources.

Bergius process
This method involves hydrogenation of coal. The coal dust is mixed with heavy
oil and made into a paste. Iron oxide (FeO) or Nickel catalyst is added. The
mixture is sent into a reactor and hydrogen gas is passed through it at a
temperature of 500oC and pressure 250 atmosphere. The product obtained is a
mixture of hydrocarbons which is sent into a fractionating column to separate
the petrol. Write a Diagram

SLE PORTION
Octane Number: It is the percentage of Iso-octane in a mixture of Iso-octane
(O.N.=100) and n – heptane (O.N.= 0.0) which has same knocking as the petrol
sample under test.
Cetane Number: It is the percentage of n-cetane in a mixture of n-cetane
(C.N.=100) and α-methyl naphthalene (C.N.=0.0) which has the same knocking
as the diesel under test.
 Solar energy
Photovoltaic cell(PV cell): It is a semiconductor device which converts sunlight into
electricity.
It produces direct current. The PV cell produces current as long as sunlight is
available. In the absence of sunlight it stops producing current. PV cells need no
recharging like batteries. They operate at ambient temperature and are environment
friendly, no wear and tear, silent operation and no corrosion. Silicon is the
semiconductor material used in PV cells.

Importance of PV cells
Use of photovoltaic cells will avoid problems associated with present electricity
production techniques such as burning of fossil fuels and nuclear fission reactions.
PV cells can generate electricity for a wide variety of applications. PV cells provide
power for space craft and satellites.
Using PV cells electricity can be generated in rural areas, which are far away from
electric grid connection and remote areas such as mountains. PV cells ensure
pollution free energy production. In homes, they are used for lighting and heating.
They are used in community services and communication systems. Used in health
sectors and agricultural sectors.
 Production of solar grade silicon by chemical vapour deposition
method ( c v d method)
In this method trichlorosilane is prepared by hydrochlorination of metallurgical
grade silicon at 350oC

Si + 3HCl → SiHCl3 + H2
The trichlorosilane is double purified by fractional distillation. High purity SiHCl3
is then vaporised, diluted with hydrogen and sent into the deposition reactor
containing heated silicon seed rods.

The SiHCl3 vapour is decomposed on the surface of heated silicon seed rods at
1100oC to produce silicon.

2SiHCl3 → SiH2Cl2 + SiCl4

SiH2Cl2 → Si + 2HCl
SiHCl3 + H2 → Si + 3HCl
SiHCl3 + HCl → SiCl4 + H2
 Working of PV cell
PV cell is composed of a thin wafer consisting of an ultrathin layer of n-type
silicon on top of the p-type silicon, and a p-n junction is formed. A metallic grid
forms one of the electrical contacts of the diode and allows light to fall on the
semiconductor between the grid lines.
An antireflective layer between the grid lines increases the amount of light
transmitted to the semiconductor. Another metallic layer forms electrical
contact.
When light radiation falls on the p-n junction diode, electron-hole pairs are
formed by the absorption of radiation. The electrons start moving and collected
at the n-type end and holes start moving and collected at p-type end.
When these two ends are electrically connected, there is a flow of current
through the external circuit. Thus, photo electric current is produced.

Write a Diagram
 SLE
Purification of silicon by zone refining technique

Principle: Impurities are more soluble in the melt than in

the solid material.
Write a Diagram and explain