Unit 5 Fuels

Unit Objectives:

At the end of unit, you should be able to:

1. define fuels
2. describe the properties of fuels
3. discuss as to how fuels are classified
4. discuss calorific value and its importance
5. distinguish solid fuels from liquid and gaseous fuels

Lesson 5.1 Definition

Chemical fuel is a combustible carbonaceous material which on proper burning in air
gives large amount of heat that can be used economically for domestic and industrial
purposes
Ex. wood, charcoal, coal, kerosene, petrol, diesel, producer gas, water gas,
natural gas, etc.

During the process of combustion, C and H of the fuel combine with oxygen of air to
form CO2 and H2O respectively.

Since the heat content of combustion products (CO2, H2O, etc.) being lower than that
of reactants (C, H, etc. of fuel), the chemical fuel release heat during their combustion
process

Classification

A. On the basis of occurrence, fuels are classified as primary and secondary fuels

1. Primary fuels occur in nature and are used without processing.

2. Secondary fuels are obtained by chemical processing of primary
fuels.

B. On the basis of physical state, fuels are classified as solid, liquid and gaseous
fuels
Lesson 5.2 Characteristics of a Good Fuel
• High calorific value.
• Moderate ignition temperature.
• Low moisture content
• Low content of non-combustible matter.
• In case of solid fuel, the ash content should be less and the size should be
uniform.
• Readily available in bulk at low cost.
• Products of combustion should not be harmful.
• Combustion should be easily controllable.
• It should be safe, convenient and economical for storage and transport

E.g. Coal Crude oil Natural gas Charcoal Petrol Coal gas Wood (Petroleum) Coke
Diesel Water gas

Lesson 5.3 Calorific Value

It is defined as “the amount of heat liberated when unit mass (or unit volume in the
case of a gaseous fuel) of fuel is completely burnt in air or oxygen” The quality of a
fuel is determined by the amount of energy released per unit mass or volume referred
to as calorific value.

Fuels generally contain hydrogen in addition to carbon. During combustion,

the hydrogen is converted to steam.

In the determination of calorific value of the fuel if the products of

combustion are cooled to ambient temperature (room temperature), the latent
heat of steam is also included.
This is referred to as gross calorific value (GCV) or higher calorific value.

In practice, the products of combustion are allowed to escape and the

amount of heat realized is lesser than the GCV (since the latent heat of vaporization
is not released). This is net calorific value (NCV) or lower calorific value.

GCV = NCV + latent heat of steam

Units

Solid or Liquid fuels - cal/g or kcal/kg or J/kg

Gaseous fuels – kcal/m3 or J/m3
Fuels generally contain hydrogen in addition to carbon. During combustion, the
hydrogen is converted to steam.

In the determination of calorific value of the fuel if the products of combustion are
cooled to ambient temperature (room temperature), the latent heat of steam is also
included. This is referred to as gross calorific value (GCV) or higher calorific value.

Gross or Higher 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”

In practice, the products of combustion are allowed to escape and the amount
of heat realized is lesser than the GCV (since the latent heat of vaporization is not
released). This is net calorific value (NCV) or lower calorific value.

Net or Lower calorific value (NCV)

It is defined as “the amount of heat produced when unit mass/volume of fuel

is completely burnt in air and the products of combustion are allowed to escape into
the atmosphere”
GCV = NCV + latent heat of condensation of steam

NCV = GCV – 9 × Mass of hydrogen × Latent heat of steam

NCV = GCV – 0.09 × % of hydrogen × Latent heat of steam

Determination of Calorific Value of a Solid Fuel using Bomb Calorimeter

Principle

A known mass of the fuel sample is burnt completely in excess of oxygen.

The liberated heat is absorbed by water and calorimeter.
The heat lost by burning fuel is the heat gained by water and calorimeter.
The calorific value of the fuel is calculated from the measured data.
Construction

➢ The bomb calorimeter (shown in the fig.) consists of an outer cylindrical

steelvessel (bomb) with an airtight screw and an inlet for oxygen.
➢ The bomb has a platinum crucible with a loop of wire. The ends of the
wire project out and can be connected to a source of electric current.
➢ The bomb is immersed in a rectangular vessel (calorimeter) containing
water, which is continuously stirred.
➢ A Beckmann thermometer is introduced into the calorimeter.

Process
➢ A known mass of the fuel is made into a pellet and taken in the crucible.
➢ Oxygen is passed through the bomb.
➢ A known mass of water is taken in the calorimeter and is closed with the lid.
➢ The initial temperature of water is noted.
➢ The ends of the wire are connected to an electric source so as to ignite the fuel.
➢ The heat released is absorbed by water. The temperature of water rises.
➢ The final temperature is noted.

Observations and Calculations

Mass of the fuel sample taken - m=g

Mass of water taken in the copper calorimeter – W=g
Water equivalent of calorimeter – w= g
Initial temperature of water - t1 = 0 C
Final temperature of water - t2 = 0 C
Specific heat of water - S

Heat liberated by burning of fuel = Heat absorbed by water and calorimeter

m x GCV = (W + w) x(t2 - t1)xS

GCV = (W + w) (t2 - t1) cal/g

m

GCV = (W + w) (t2 - t1) × 4.184 × 103 J/kg

m
Calculation

Let
m = mass of fuel
W = mass of water
w = water equivalent of calorimeter
t1 = initial temperature of water
t2 = final temperature of water
s = specific heat of water

GCV ( solid fuel) = (W+w) x (t2-t1) x s

m

If the fuel contains x% hydrogen, NCV of the fuel is calculated as follows

2 atoms of hydrogen produce one molecule of water,
2g of hydrogen produce 18 g of water
x g of hydrogen produce 9 g of water

x %Hydrogen =( 9) ( x g of water) =0.09

100

NCV = GCV - latent heat of steam formed

= GCV - 0.09 x latent heat of steam

Latent heat of steam = 2454 kJ kg-1

1 calorie = 4.187 kJ kg-1

The calorific value of a liquid fuel can be determined using bomb calorimeter.
Calculation of NCV

If H = Percentage of hydrogen in fuel, then

Water formed by combustion of 1g of fuel = 18 x H
2 100

= 0.09H g

Latent heat of water formed = 0.09H × 587 cal/g

NCV = GCV – Latent heat of water formed

= GCV – 0.09H × 587 cal/g

Determination of Calorific Value of a Gaseous Fuel - Boy’s Calorimeter

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 the calculated from these data.

Construction
Boy’s calorimeter consists of a combustion chamber surrounded by water tube with
two thermometers T1 and T2 attached.

There is a burner in the chamber, which is connected to a gas tube

Process

A known volume of water is passed through the tubes.

The initial temperature is noted when two thermometers show the same constant
temperature
A known volume of gas is passed through the tube and burnt in the combustion
chamber.
The heat liberated is absorbed by the water in the tubes.
The final temperature of water is noted.
The gaseous products are cooled and condensed into a measuring jar.

Observations and Calculations

Volume of fuel burnt at STP in time, t V = m3

Mass of cooling water circulated in time, t W= kg
Steady temperature of incoming water t10 = C
Steady temperature of outgoing water t20 = C
Rise in temperature (t2 - t1) = 0 C
Mass of water produced from steam condensation m = kg
Specific Heat of Water = S
Heat released by combustion of fuel = Heat absorbed by water

V x GCV = W (t2 - t1) x

GCV = W (t2 - t1) kcal/m3

V

= W (t2 - t1) × 4.184 kJ/m3

V

Latent heat of steam per m3 of fuel sample = m × 587 kcal

V

NCV = W (t2 - t1) - m ×587 kcal

V V

= [W (t2 - t1) - m ×587 ] 4.184 kJ/m3

V V

Calculation:
Let
V = volume of gas burnt
W = mass of water
t1 = initial temperature of water
t2 = final temperature of water
s = specific heat of water
v = volume of water collected in the measuring jar

GCV( gaseous fuel) = W s (t2- t1)

V

NCV ( gaseous fuel) = GCV - latent heat of steam formed

= GCV - latent heat of steam x volume of water collected

Formulae for Solving Numerical Problems:

.

GCV (solid fuel) = (W+w) (t2-t1) s

m

NCV (solid fuel) = GCV - latent heat

= G.C.V. - (0.09 % of H) latent heat

GCV( gaseous fuel) = W s (t2- t1)

V

NCV ( gaseous fuel) = GCV – latent heat

= G.C.V. – amount of water collected x latent heat
V
= G.C.V. – v latent heat
V

3
(1 cm of water 1 g of water)

Numerical Problems

Problem 1: Calculate the gross calorific value and net calorific value of a sample of
coal 0. 5g of which when burnt in a bomb calorimeter, raised the temperature of 1000g
of water from 293K to 301.6K. The water equivalent of calorimeter is 350 g. The specific
heat of water is 4.187 kJ kg- , latent heat of steam is 2457.2kJkg-1. the coal sample
1

contains 93% carbon, 5% hydrogen and 2% ash.

m = mass of the fuel =0.5g
W = mass of water taken =1000g
w = water equivalent of calorimeter =350g
t1 = initial temperature of water =293K
t2 = final temperature of water = 296.4 K
-1 -1
s = specific heat of water = 4.187 kJ kg K

GCV (solid fuel) = (W+w) (t2-t1) s

m
= (1000 +350) g (296.4 -293)K 4.187 kJ kg- K-
1 1

0.5g
= 1350 g 3.4 K 4.187 kJ kg- K-
1 1

0. 5g

= 3 8437 kJ kg-1

NCV (solid fuel) = GCV - latent heat

= G.C.V. - (0.09 % of H) latent heat
= 38437 kJ kg-1 - (0.09 5) 1105.7 kJ kg-1
= 38437 kJ kg-1 – 1106 kJ kg-1

-1
= 37331 kJ kg

Problem 2: Calculate the gross calorific value and net calorific value of a gaseous fuel,
0.012m3 of which when burnt raised the temperature of 3.5kg of water by 8.2K.
Specific heat of water is 4.2 kJ kg K . Latent heat of steam is 2.45 kJ kg . The volume
-1 -1 -1

of water collected is 6.5cm . Latent heat of steam is 2457.2kJ kg-1

3

V = volume of the gas burnt = 0.012 m3

W = mass of water = 3.5 kg
t2- t1 = rise in temperature =8.2 K
s = specific heat of water = 4.2kJ kg-1K-1
v = volume of water collected = 6.5 cm3

GCV( gaseous fuel) = W x s x (t2- t1)

V
 =3.5kg x 4.2 kJkg-1K-1 x 8.2K
0.012 m3

= 10045 kJm-3

NCV( gaseous fuel) = GCV – latent heat

= G.C.V. - amount of water collected x latent heat
V
= 10045 kJm-3 – 6.5 10-3 kg x 2457.2kJkg-1
0.012 m3
(1 cm3 of water 1 g of water)

= 10045 kJm-3 – 6.5 10-3 kg x 2457.2kJkg-1

0.012 m3

= 10045 kJm-3 – 1331 kJm-3

= 8714 kJm-3

Lesson 5.4 Solid Fuels

Coal

Coal is a highly carbonaceous matter that has been formed as a result of alteration of
vegetable matter (e.g., plants) under certain favorable conditions.

It mainly composed of C, H, N, and O, besides non-combustible inorganic matter

Wood → Peat → Lignite → Bituminous coal → Anthracite

Carbon content, calorific value and hardness

Moisture content, C,O,N and S content, volatile matter

Analysis of coal and its significance

The proximate analysis involves the determination of moisture, volatile matter, ash,
and fixed carbon.
This gives quick and valuable information regarding commercial classification and
determination of suitability for a particular industrial use.

The ultimate analysis involves the determination of carbon, hydrogen, sulphur,

nitrogen, oxygen and ash.

The ultimate analysis is essential for calculating heat balances in any process for
which coal is employed as a fuel.

Proximate analysis

1. 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. The crucible is cooled first in air then in
a desiccator and then weighed.

% moisture = Loss in weight × 100

Wt. 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.

2. 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 950 0 C. The crucible is taken out
after 7 minutes of heating. It is cooled first in air then in a desiccator and finally
weighed.

% Volatile matter = Loss in weight × 100

Wt. of coal taken

• A high volatile matter content means that a high proportion of fuel will
distill over as vapour and a large portion of which escapes un burnt. So,
higher % of volatile matter in coal is undesirable.
• 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.

3. Ash:
 The residual coal left in the crucible in step (ii) is then heated without lid in a
muffle furnace at 700-7500 C, until a constant weight of residue is obtained.

% Ash = Wt. of ash left × 100

Wt. 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.

4. 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.

• Higher the percentage of fixed carbon, greater is its calorific value and
better is the quality of coal.
• Greater the percentage of fixed carbon, smaller is the percentage of
volatile matter. It is the fixed carbon which burns in the solid state.
• Information regarding the percentage of fixed carbon helps in
designing of the furnace and the fire-box.

ULTIMATE ANALYSIS

1. Carbon and Hydrogen:

An accurately weighed coal sample (1-2g) is burnt in a current of oxygen in

combustion apparatus. As a result C and H of the coal are converted into CO 2 and
H2O respectively. These are absorbed respectively in KOH and CaCl 2 tubes of
known weights. The increase in the weights of KOH and CaCl 2 tubes corresponds
to the amount of CO2 and H2O formed respectively.

C + O2 → CO2
12 44
2 KOH + CO2 → K2CO3 + H2O

H2 + 1/2O2 → H2O
2 18
CaCl2 + 7 H2O → CaCl2 .7 H2O

% Carbon = Increase in wt .of KOH tube × 12 × 100

 Wt. of coal taken ×44

% Hydrogen = Increase in wt. of CaCl tube × 2 ×100

2

Wt. of coal taken ×18

• C and H in coal directly contribute towards the calorific value of the coal.
• Higher the percentage of C and H, better is the quality of the coal and
higher is its calorific value.

2. Nitrogen:

Determined by digesting a known quantity (1g) of powdered air-

dried coal sample in a kjeldhal’s flask with conc. H 2SO4 and HgSO4 in
the presence of K2SO4 as a catalyst. After the solution becomes clear, it is
treated with excess of NaOH.

The liberated ammonia is distilled into a known volume of

standard acid solution. The volume of unused acid is then determined
by back titration with standard NaOH solution.From the volume of acid
used by ammonia liberated, the percentage of nitrogen is calculated.

% Nitrogen = Wt. of nitrogen × 100

Wt. of coal taken
Where,
Wt. of nitrogen = Vol. of acid used × Nacid × 14
1000
Thus, % Nitrogen = Vol. of acid used × Nacid ×1.4
Wt. of coal taken

• Nitrogen in the coal does not contribute any useful value to the coal.
• Since it is generally present in small quantities (~ 1%) its presence is not
of much significance.
• A good quality coal should have very little nitrogen content

3. Sulphur:

A known amount of coal sample is burnt completely in a bomb

calorimeter. Sulphur present in coal is oxidized to sulphates. The ash left
after combustion from the bomb calorimeter is extracted with dil. HCl. The
acid extract is then treated with barium chloride solution to precipitate
sulphate as barium sulphate. The precipitate is filtered, washed, ignited and
weighed.

% Sulphur = Wt. of BaSO4 obtained × 32 × 100

 Wt. of coal taken × 233

Sulphur containing coal is not suitable for the preparation of metallurgical

coke as it adversely affects the properties of the metal.

Oxides of sulphur pollutes the environment and leads to corrosion.

4. Ash:

The ash content of coal sample is determined as described under proximate

analysis.

5. Oxygen:

% Oxygen = 100 – % (C + H + N + S + Ash)

The lower the oxygen content, the more is the maturity of coal and greater
is its calorific value

Lesson 5.5 Liquid Fuels

Petroleum (Crude oil)

• An important primary liquid fuel.

• It is a dark colored viscous oil found deep in the earth’s crust.
• It is believed to have been formed millions of years ago by anaerobic
decay of marine plant and animal life under the influence of high
temperature and pressure.
• It is mainly a complex mixture of hydrocarbons (like straight-chain
paraffins, cycloparaffins, olefins and aromatics) with small amounts of
other organic compounds containing N, O and S, and traces of inorganic
compounds.
• The average composition of crude oil is:

C: 83 - 87%; H: 11 - 15 %; S, N and O: 0.1- 5%.

Petroleum refining

“It is the process of separation of crude oil into different useful fractions on the basis
of their boiling points”

• The crude oil, freed from water and sulphur, is first heated in a pre-heater (350-
4000 C). The vapors are then fed into a specially designed large bubble cap
fractionating column.
• The volatile components condense on the upper plates of the fractionating
column while the less volatile fraction is collected on the lower plates.
 • The various fractions condensed and collected at different heights of the column
are Gases (Boiling range, below 300 C), Petroleum ether (30-700 C), Gasoline or
petrol (40-1200 C), Naphtha (120-1800 C), Kerosene (180-2500 C), Diesel or fuel
oil or light gas oil (250-3200 C), Heavy oil (320-4000 C), Paraffin wax, Asphalt,
etc., (above 4000 C).

Cracking

Heavy oil is a major fraction of petroleum refining. It is converted to petrol by

cracking.

• The objective of cracking is to obtain greater yields of improved gasoline by

thermal decomposition of the surplus heavier fractions.
• Gasoline obtained by cracking gives better engine performance (less knocking)
than straight-run gasoline (obtained from fractional distillation of crude oil).

Cracking is defined as the process of decomposition of higher molecular

weight hydrocarbons (higher boiling) into lower molecular weight
hydrocarbons (low boiling).

• Cracking process involves breaking of C-C and C-H bonds.

• It produces low boiling alkanes and alkenes.
• A small amount of carbon and hydrogen are also produced.

Cracking

C10H12 C5H12 + C5H10

Decane Pentane Pentene

Advantages of catalytic cracking

• The octane number of gasoline produced is high.

• The yield of gasoline is also high.
• The process can be better controlled.
 • The product contains a very little amount of undesirable sulphur.
• There is a saving in production costs since high temperatures and high
pressures are not needed.
• In catalytic cracking, external fuel is not required. The necessary heat is
obtained by burning off the coke deposited on the catalyst itself, during
the regeneration process.
• The gasoline formed contains much less gum and gum forming
compounds.
• Catalysts are selective in their action, and therefore, they permit cracking
of only high boiling hydrocarbons.

Catalytic Cracking methods

Fixed-bed catalytic crackling:

The catalyst (Al2O3 + SiO2) in the form of powder or pellets is placed on the
grid in the catalytic chamber. The vapours of the feed stocks (Heavy oil, gas oil, etc.)
are passed through the bed of catalyst maintained at 450-500 0C. About 50% of the feed
stock is converted into gasoline together with elemental carbon which gets deposited
on the surface of the catalyst. Cracked vapours are next subjected to fractionation in a
fractionating column wherein gasoline is separated from un-cracked heavy oil. The
catalyst loses its activity because of the deposition of carbon and also due to the
adsorption of oil vapours. Accordingly, the catalyst requires regeneration after 8-10
hours. During regeneration time, the cracking process is interrupted and the adsorbed
oil is stripped off by passingsteam while deposited carbon is burnt off by a hot air
blast.

Fluidized (moving) bed catalytic cracking:

The finely divided catalyst bed (Al 2O3 + SiO2) is fluidized by the upward
passage of feed stock vapours (Heavy oil, gas oil, etc) in a cracking chamber (called
Reactor) maintained at 5500 C. Near the top of the reactor, there is a centrifugal
separator (called cyclone), which allows only the cracked oil vapours to pass onto the
fractionating column but retains the catalyst powder in the reactor itself. The catalyst
powder gradually becomes heavier due to the deposition of carbon and settles to the
bottom, from where it is forced by an air blast to the regenerator (maintained at 600 0
C). After cracking, the products are fractionated into gases, gasoline, gas oils and
residual oils. The heavier oil fractions may be cracked in a second-stage cracking.

In regenerator, the spent catalyst is stripped of the adsorbed oil by passing

steam and then decarbonized by a hot air blast, under controlled conditions. The
heat liberated during this regeneration is used to raise steam and to preheat the
catalyst.

Regeneration of Catalyst
After some time, the catalyst gets deactivated due to the deposition of carbon and oil
on its surface. Steam is passed through the riser column. The deactivated catalyst is
led into a regenerator through which air is passed. Air oxidizes C to CO 2 and steam
removes the oil.

Advantages of fluidized-bed cracking

A high degree of mixing is achieved and consequently a good contact is established

between the catalyst and the feed stock vapours. This results in a higher yield. The
regeneration of the inactive catalyst can be carried out continuously without
interrupting the production of gasoline unlike in fixed-bed catalytic cracking.

Reforming of petrol

Catalytic Reforming: It is the process of upgrading gasoline (increasing its octane

number) in presence of a catalyst

• The increase in octane number of straight run gasoline occurs through

structural modifications such as conversions of straight hydrocarbons into
branched, cyclic and aromatic hydrocarbons.

Reforming Process: The feed stock (straight run gasoline) is preheated to remove S
and N content to acceptable limits to avoid platinum catalyst being poisoned. The
vapours of the feed stock is mixed with hydrogen and preheated to 500 0 C. The
mixture is compressed (15-50 atmosphere) and then fed into a series of three
cylindrical reactors containing the platinum catalyst supported on alumina-silica
base. The reformed products are fractionated to get stabilized gasoline

Reforming reactions

Reforming is a process carried out to improve the octane number of petrol by

bringing about changes in the structure of hydrocarbons.
The changes in structure could be isomerization, cyclization or aromatization..

Isomerization straight chain hydrocarbons are converted to branched hydrocarbons

H3C (CH2)4 CH3 H3C CH CH2 CH2 CH3

CH3

n-hexane 2-methyl petane

Cyclization straight chain hydrocarbons are converted to cyclic compounds CH3 -

CH2 - CH2 - CH2 -CH2-CH2 - CH3 -CH3
n- heptane methyl cyclohexane

Aromatization cyclic compounds are dehydrogenated.

- CH3 - CH3

methyl cyclohexane toluene

Knocking in IC Engines

The power output and efficiency of an IC engine depends on the

Compression ratio which is the ratio of the volume of the cylinder at the end of the
suction stroke to the volume of the cylinder at the end of the compression stroke.

Compression ratio = Volume of cylinder at end of suction stroke

Volume of cylinder at end of compression stroke

Under ideal conditions, in an IC engine the petrol-air mixture drawn into the
cylinder of the engine undergoes compression and then ignited. The hydrocarbons in
petrol undergo complete combustion and the flame propagates smoothly. Sometimes,
due to deposits of carbon on the walls of the cylinder the hydrocarbons in petrol form
peroxy compounds.
The accumulated peroxides decompose suddenly and burst into flames producing
shock waves.
The shock wave hits the walls of the engine and the piston with a rattling sound. This
is knocking. The reactions that take place in an IC engine are given below (taking
ethane as an example for the hydrocarbon pre sent in petrol):

1. 2. 3.

Note that the overall reaction is the same under both the conditions. One
molecule of ethane reacts with 7/2 molecules of oxygen forming carbon dioxide and
water with the release of energy. Under ideal conditions, the energy is released at a
uniform rate. Under knocking conditions, the energy is released slowly at first
followed by a lag (formation of peroxides) and finally the energy is released at a very
fast rate (decomposition of peroxides).

Ill Effects of Knocking

1. Decreases life of engine

2. Causes Piston wrap
 3. Consumption of fuel is more

Octane Number

• Graham Edger proposed an arbitrary scale, octane rating, in order to express

the ant-knock properties of gasoline's.
• The resistance to knocking offered by petrols is expressed in terms of an
arbitrary scale called octane number
• Octane number is the percentage by volume of isooctane present in a mixture
of isooctane and n – heptane which has the same knocking characteristic as the
petrol under test.
• Among alkanes, n-heptane knocks severely, while under identical conditions,
2,2,4-trimethyl pentane (iso-octane) has a high resistance to knocking.
• For the scale proposed to indicate the anti-knock properties of gasoline, n-
heptane was arbitrarily assigned an octane number of zero and iso-octane was
arbitrarily assigned a value of 100.
• By blending these two hydrocarbons in various proportions, primary
reference fuels were prepared.
• In the same engine under the same set of conditions and the same critical CR,
various blends of the n-heptane and iso-octane are burnt and the percentage of
iso-octane by volume in blend that knocks under these conditions is the octane
number of the gasoline.
• The compression ratio of the fuel under test is determined under the same
conditions.
Suppose the compression ratio of the fuel is same as that of 80 :20 mixture, the
octane number of the fuel is 80.

Cetane Number:

The resistance to knocking offered by diesels is expressed in terms of an arbitrary

scale called cetane number
It is the percentage by volume of cetane present in a mixture of cetane and ∝- methyl
naphthalene which has the same knocking characteristic as the diesel under test.

Adverse effects of gasoline knock

• It increases the fuel consumption.

• It results in decreased power output.
• It causes mechanical damage by overheating of the cylinder parts.
• The driving becomes rather unpleasant.

The knocking in IC engines can be minimized through the following measures:

• By a suitable change in engine design.

 • By using critical compression ratio.
• By using high rating gasoline.
• By using anti-knocking agents.

Prevention of Knocking

Addition of lead tetraethyl (TEL) to Petrol:

Lead tetraethyl decomposes the peroxides formed and prevents knocking. In

the process, lead gets deposited on the inner walls of the engines and at spark plugs.
Hence dichloroethane and dibromoethane are added along with tetraethyl lead.
These convert the lead into lead halides, which are volatile and escape with exhaust
gases.

The release of lead compounds pollutes the atmosphere. Catalytic converters

(rhodium catalyst) are used in IC engines to convert CO in the exhaust to CO 2. Lead
tetraethyl used as anti knocking agent poisons the catalyst and hence leaded petrol is
not advisable in such IC engines.

Addition of MTBE:

Methyl tertiary butyl ether (MTBE) is added to petrol (unleaded petrol) to boost its
octane number. The oxygen of MTBE brings about complete combustion of petrol
preventing peroxide formation and hence knocking is prevented.

MTBE can be used as antiknocking agent in IC engines with catalytic converter.

Power Alcohol:

• This is alcohol-blended petrol.

• Gasohol is a blend of 10 – 85% of absolute ethanol and 90 – 15% of petrol by
volume and is used as a fuel in the United States. Absolute alcohol is used in
the preparation of Power alcohol to prevent phase separation.
• Alcohol contains higher percentage of oxygen than MTBE and hence brings
about complete oxidation of petrol more effectively.
• Therefore power alcohol has better antiknocking characteristics than
unleaded petrol.

Advantages of power alcohol

 • power output is high does not release CO, causes less pollution.
• alcohol is obtained from molasses, a agricultural product and hence
renewable. biodegradable.

Lesson 5.6 Gaseous Fuels

• Gaseous fuels are obtained either naturally or by the treatment of solid or liquid
fuel.
• Among the naturally occurring gaseous fuels, natural gas and liquefied
petroleum gas are most important.
• These gases have high calorific value.
• The calorific value (CV) and specific gravity (Sp. gr.) of a gaseous fuel
determine the thermal output of a heating appliance.

Gas v/s Fuel

• Gaseous fuels have lower energy content than liquid fuels such as, petrol or diesel.

• Gaseous fuels are potentially more deserved fuel as they produce very low
greenhouse gas upon burning and hence air quality benefits are obtained compared
to conventional and petrol and diesel products.

1. Manufactured Fuel gases

• Manufactured fuel gases are those produced through an artificial process, usually
gasification, at a location known as a gasworks. Eg; Biogas, Producer gas.

BIOGAS • A mixture of methane and carbon dioxide 𝐶𝐻4 , 𝐶𝑂2

How its made?

Biogas is produced by the breakdown of organic waste by bacteria without

oxygen (anaerobic digestion or fermentation).

From sources:-

Leftover food from houses, shops, restaurants and factories

Leftover meat and blood from abattoirs

Cow, sheep and chicken manure

Leftover straw and crops from farming

• Biogas can be used as a fuel.

• It can be used for any heating purpose, such as cooking. It can also be used in a gas
engine to convert the energy in the gas into electricity and heat.

• The biogas is a renewable energy that can be used for heating, electricity, and many
other operations that use a reciprocating internal combustion engine.
PRODUCER GAS
A combustible mixture of nitrogen, carbon monoxide, and hydrogen,
generated by passing air with steam over burning coke or coal in a furnace and
used as fuel. Also called air gas. Typical components of producer gas Producer
gas is usually a mixture of mainly carbon monoxide (CO), hydrogen (H2),
methane. (CH4), and the inert species carbon dioxide (CO2), nitrogen (N2),
water steam (H2O) small amounts of Argon (Ar). Apart from the main species,
the gas contains various
2. NATURAL GAS - CNG
• The main constituent is methane.
• It is a fuel gas substitute for gasoline(petrol), diesel or propane/(LPG).
• It is more environmentally clean alternative to those fuels and its much
safer than other fuels in the event of spill.
• It is made by compressing natural gas(which is mainly composed of
methane), to less than 1% of the volume it occupies at standard atmospheric
pressure.
• Used in cars and locomotives
3. PETROLEUM GAS- LPG

• Also called liquified petroleum gas or bottled gas or refinery gas

• It is obtained as a byproduct, during the cracking of heavy oils or from
natural gas. A non-renewable source of energy.
• extracted from crude oil and natural gas
 • The main composition of LPG are hydrocarbons containing three or four
carbon atoms. The main constituents of LPG are n-butane,
isobutene,butylenes and propene.
• It can be easily condensed, packaged, stored and utilized, which makes it an
ideal energy source for a wide range of applications.
• LPG is non-toxic, its abuse – (like that of solvents) – is highly dangerous.
LPG should always be treated with respect and kept away from children
whenever possible.
• It has the calorific value of about 25000 kcal /m3.
•LPG is widely used as a domestic fuel. Used as an alternative fuel for IC
engines, since it permits the attainment of high compression ratios without
producing knocking The main reason for converting to LPG is its superb
portability and convenience: it can be used in remote places where ordinary
gas supplies are unavailable.
• The two big disadvantages of LPG are safety and cost.

Advantages of LPG over gasoline as a motor fuel

• It is cheaper than gasoline.

• It readily mix with air.
• It is highly knock resistant,
• Residue and oil contamination is less, as it burns cleanly.

Disadvantages of LPG over gasoline as a motor fuel

• Handling has to be done under pressure.

• LPG is advantageous only in engines working under high compression ratio.
• Its octane number is quite low.
• Its response to blending is very poor.

Water gas

• It is essentially a mixture of combustible gases, CO and H 2.

• It is also known as blue gas because it burns with a blue flame due to the
combustion of carbon monoxide.
• The calorific value of water gas is about 10000 -11000 KJ/m3.
• The average composition of water gas is as follows:

CO: 40 – 45% ; H2 : 45 – 50% ; CO2 : 4% ; N2 : 4%

Manufacture:

It is produced by passing alternatively steam and little air through a bed of

red hot coke maintained at10000 C.
 Principle:

When steam is blown through a bed of hot coke (10000 C) water gas is
produced.

C + H2O (steam) → CO + H2 ∆H = 131.4 KJ

• The reaction being endothermic in nature, the temperature of the coke bed
gradually decreases with continuous passage of steam and the drop in
temperature must be prevented. For this the steam supply is temporarily cut
off and air is blown in.

The over all reaction during air blow is the formation of CO.

2C + O2 → 2CO ∆H = - 221.9 KJ

This reaction being exothermic increases the temperature of the coke bed to
about 10000 C. Thus by blowing steam and air alternatively, the temperature
of the coke bed can be maintained at 10000 C.

Uses

• It is used for the production of hydrogen.

• It is extensively used for the manufacture of methyl alcohol and synthetic
petrol.
• It is used as a fuel in glass and ceramic industries.
• Enriched water gas (mixed with hydrocarbons), which burns with luminous
flame is used as illuminating agent

Biofuels

1. Biomass

Plants convert solar energy to biomass and this can be used as fuel. Thus wood is a
biomass and has been used as a fuel. Trees such as pine, eucalyptus, aquatic plants
like algae and wastes such as manure are biomass.

Advantages:

Renewable High energy content Less polluting Cheap

2. Algae

Algae are small green plants. These are, dried , powdered and can be used in IC
engines.
Advantages:

– Can be grown in both land and water.

– Can be grown even if the soil quality is poor and the water is alkaline.
– Does not release CO2 on burning and hence does not contribute to atmospheric
pollution.
– Energy produced is cheaper

3. Water hyacinth

– It is a weed and grows wildly on the surface of water bodies.

– It is dried, powdered and heated with Klebseills oxytoca in the presence of
NaOH.
– Butanediol is obtained which is distilled and is used to boost the octane number
of aviation fuel.

4. Rapeseed oil ( biodiesel)

– Rapeseed is crushed and the oil is treated with NaOH and methanol to 50oC.
A mixture of diester and glycerol is obtained.
– The diester is separated.
– This has properties same as diesel and is called biodiesel.

Advantages of biodiesel

– Energy output is high

– Renewable
– Does not cause pollution
– No change in the engine design is needed. Non toxic.

5. Biophotolysis

• Breaking of water to hydrogen and oxygen is called photolysis

• Algae containing the enzyme alcohol dehydrogenase produce hydrogen form
water.
• The hydrogen can be used as a fuel.

Advantages

– High calorific value

– Does not cause pollution
– The product of combustion is water, which is again used for photolysis.
6. Hydrocarbons

Organic wastes contain polymers like carbohydrates, lipids and proteins.

These can be broken down by bacteria into amines, acids and alcohols.
These are further converted to esters and hydrogen and oxygen. And further
converted to hydrocarbons, which can be used as sources of energy.
Thus acetogenic bacteria act on organic wastes and form acetates and H2 and O2.
methanogenic bacteria convert the acetates to methane. Methane can be used as
afuel.

Advantages

Renewable
High energy content Less polluting

7. Biofertilizers

These are fungi, aquatic plants or bacteria which help in nitrogen fixation and
improve the quality of soil to increase crop production. They are:
a. Symbiotic nitrogen fixers:
Rhizobia in combination with leguminous plants can convert atmospheric nitrogen
into ammonia.
Ammonia is released into the soil, converted to ammonium compounds and thus
quality of the soil is improved.

b. Asymbiotic nitrogen fixers:

Azatobacter produces enzymes which can form ammonia from atmospheric
nitrogen.

8. Algal fertilizers:

These are blue green algae which when used in combination with certain
cultures such as Anabena, Nostoc are useful as fertilizers for paddy.
Algae are cheap, resistant to pesticides, and can be grown in saline water and poor
quality soil.

9. Phosphate solubilizers:

These convert insoluble phosphates in the soil into soluble phosphates so that
plants can easily absorb them for their growth. There are certain type of rhizobia
which can form complexes with iron in the soil and make iron unavailable to weeds.
Thus weeds are destroyed and the growth of the plant is promoted by Mycorrhizae:
 These grow with the plant. They absorb from the soil, substances (that cannot
be taken in by the plant directly) and release them to the plant.
In return, they take certain nutrients from the host plant for their own growth.
Example, azatobacter.

9. Biosurfactants:

Surfactants have a lyophobic and a lyophilic group in their molecule. They

increase the solubility of organic compounds present in the soil. They remove non
aqueous wastes from the soil. Rhamnolipids and Trehalose are biosurfactants which
are commonly used. They are more advantageous than chemical surfactants
because:

1. they are biodegradable

2. they themselves do not add to the contaminants in the soil
3. they are nontoxic.
4. 4. they can be grown at the site.
Questions
1. Give the classification of fuels with examples. (5 points)
2. Explain the process of fluidized bed catalytic cracking of petroleum (5 points)
3. Calculate the calorific value of coal sample from the following data: (10 points)
Mass of coal: 1g, water equivalent of calorimeter: 2 Kg
Specific heat of water: 4.187 KJKg-1C-1 and rise in temperature: 4.8oC

Describe how the calorific value of a gaseous fuel is determined using

Boy‘s calorimeter. (5 points)
4. What is meant by cracking? Describe fluidized bed catalytic cracking. (5 points)
5. On burning 0.83 x 10-3Kg of a solid fuel in a bomb calorimeter, the temperature
of 3.5Kg of water increased from 26.5 oC to 29.2 oC. The water equivalent
of calorimeter and latent heat of steam are 0.385Kg and 4.2 x 587
KJ/Kg respectively. If the fuel contains 0.7% hydrogen, calculate its gross
and net calorific values. (10 points)
6. What is reforming of petroleum? Give any three reactions involved in
reforming.
7. Calculate the gross and net calorific values of a gaseous fuel at STP given
0.03m3 of the gas at STP raised the temperature of 6 Kg of water by 16K and
13.8 cm3 of water was collected. Specific heat of water is 4.18 KJKg -1C-1 and
latent heat of steam at STP is 2.45 KJkg-1 (10 points)
8. What is power alcohol? Give its advantages as a fuel. (5 points)
9. Define Gross and Net calorific values. Explain Bomb‘s calorimetric method
of determining calorific value of a solid fuel. (5 points)
10. Calculate Gross calorific and Net calorific values of a coal sample from
the following data: (10 points)
Weight of coal sample taken: 8.5 x 10-4 Kg

Weight of water taken in the calorimeter:3.5 Kg

Water equivalent of calorimeter 0.5 Kg
Initial temperature of water 25 oC
Final temperature of water 27.5 oC
Percentage of H2 in the coal sample 2.5
Latent of Heat of steam
 2455
kJ/Kg

11. What is octane number? Explain with equations how reformation of

gasoline enhances its octane rating. (10 points)
12. Calculate Gross calorific value of a coal sample from the following data: (10
points)
Weight of coal sample taken 5.5 x 10-3 Kg

Weight of water taken in the calorimeter: 2.5 Kg

Water equivalent of calorimeter 0.5 Kg

Initial temperature of water 24 oC

Final temperature of water 28 oC
13. What is knocking? What are its ill effects? Give the mechanism of knocking.
How can knocking be prevented? (10 points)