5.

CHEMICAL FUELS

Introduction, Classification, Calorific value and its determination Bomb calorimeter

and Boys calorimeter, Coal and its analysis -proximate and ultimate, Brief introduction to
liquid and gaseous fuels
Learning objectives
Define calorific value and describe how to classify fuels
Perform simple calculations involving NCV and GCV
Describe the procedures to obtain calorific value of solid, liquid and gaseous fuel
Demonstrate an understanding of the working principle of Bomb and Boys
calorimeter
Demonstrate an understanding of proximate and ultimate analysis.
Understand the cracking and reforming of petroleum
Know about merits and demerits of gaseous fuels.
5 Introduction
Chemical fuel is a carbonaceous material which on proper combustion in air releases
large amount of heat which can be used for both domestic and industrial purposes
economically. Eg. Wood, charcoal, coal, kerosene, petrol, diesel, producer gas, water gas,
natural gas etc. The main elements invariably present in chemical fuels are C and H.
During combustion, C and H of the chemical fuel combine with oxygen of air to form
CO2 and H2O respectively. Chemical fuels relaease heat during combustion as the heat
content of combustion products (CO2 & H2O) are lower than that of reactants (C, H of
fuel). The combustion process can be explained in terms of the three components -
temperature, time and turbulence.
Temperature To have good combustion, the temperature must be high enough to ignite
the fuel constituents and all the gases that are released during the process.
Time The time (reaction period) must be sufficient to complete the combustion process.
Turbulence There should be sufficient turbulence to allow complete mixing of
combustible elements, fuel and oxygen. The sustainability of fire depends upon a
favorable fuel-oxidant ratio and the maintenance of temperature above ignition

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temperature. The three components of fire involve a fuel such as wood, kerosene or gas,
energy sufficient to support combustion and an oxidizing agent like air.
5.1 Classification of fuels
Fuels may be classified generally in two ways as follows;
a) based on occurrence Primary (natural) and secondary (derived/man made/synthetic)
fuels.
b) based on the physical state solid, liquid and gaseous fuels.
A primary fuel is the one which occurs naturally and requires no chemical processing
before use. Eg. Wood, Coal. Secondary fuels are produced from naturally occurring
substances by subjecting them to treatments which alter their chemical composition and
often improve their quality. Eg. Coke, Kerosene. The various types of fuels are tabulated
in Table 1.
Table 1. Classification of Fuels
_____________________________________________________________________
Physical state Primary fuel Secondary fuel
Solid Wood, Peat, Lignite, Coal Charcoal, Coke
Liquid Crude petroleum Petrol, Kerosene, Diesel,
Synthetic petrol
Gas Natural gas Producer gas, Coal gas,
Water gas, biogas, LPG
_____________________________________________________________________
5.2 Calorific value and its determination
The calorific value is the amount of heat or energy produced when the substance is
allowed to undergo combustion. It is an important property of a fuel and is defined as
the amount of heat liberated when unit mass (or unit volume in gaseous fuel) of fuel is
completely burnt with pure oxygen. In the case of solid or liquid fuels the weight
sufficiently defines the quantity of the fuel present. However, in the case of gaseous
fuels, it is necessary to specify both temperature and pressure to define this quantity. The
calorific value is generally expressed in calorie per gram (cal/g), kilo calorie per kilo
gram (kcal/kg) or joule per kilogram (J/kg) in case of solid and liquid fuels. In case of
gaseous fuels, the units used are kilocalorie per cubic meter (kcal/m3) or joules per cubic

2
tmeter (J/m3). It is measured either as gross or net calorific value; the difference is given
by the latent heat of condensation of the water vapour produced during the combustion
process.
Gross or Higher calorific value (GCV /HCV)
The Gross or Higher calorific value is defined as the amount of heat liberated when unit
mass / volume of the fuel is burnt completely in oxygen and the products of combustion
are cooled to room temperature. When a fuel containing carbon and hydrogen is burnt, C
and H are converted into CO2 and water vapour. Latent heat of steam is released and
water vapour condenses to form water when the combustion products are cooled to room
temperature. GCV is higher than NCV as it includes latent heat of condensation of steam.
Net or Lower calorific value (NCV / LCV)
Net or Lower calorific value is defined as the amount of heat produced when unit
mass/volume of fuel is completely bunt in air and the products of combustion are allowed
to escape into the atmosphere. In actual practice the combustion products (steam) are not
cooled to room temperature but simply let off into the atmosphere. Hence, a lesser
amount of heat is available. Since this calorific value does not include the latent heat of
condensation of steam, net calorific value is always lower than gross calorific value.
NCV = GCV Latent heat of condensation of steam
= GCV Mass of hydrogen 9 latent heat of steam
= GCV 9 x % of hydrogen latent heat of steam
100
NCV = GCV 0.09 % H 587
[Note: Because1g hydrogen gives 9g of water.
If H = Percentage of hydrogen in fuel, then,
Water formed by combustion of 1g of fuel = 18 x H = 9 x % of hydrogen
2 100 100
Latent heat of steam is 587cal/g.]
[Water equivalent of calorimeter: The amount of water that would absorb the same
amount of heat as the calorimeter per degree temperature increase.]

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The calorific value of a chemical fuel is determined experimentally using Bomb and
Boys calorimeter. The bomb calorimeter is used for the determination of calorific value
of solid and liquid fuels whereas Boys calorimeter is used for liquid and gaseous fuels.
5.2.1 Determination of calorific value of solid fuel by Bomb calorimeter
Bomb calorimeter (Fig. 1) consists of a stainless steel air tight sealed cylindrical bomb
provided with two stainless steel electrodes and an oxygen inlet valve in which the fuel is
made to undergo combustion. To one of the electrodes, a small ring is attached and over
which a nickel or stainless steel crucible can be supported. The bomb is kept in a copper
calorimeter, which is surrounded by an air-jacket and water-jacket. This prevents the heat
loss due to radiation. The copper calorimeter is provided with an electrically operated
stirrer and Beckmanns thermometer (reads temperature difference accurately up to
1/100th of a degree).

Fig. 5.1 Schematic diagram of Bomb calorimeter

Principle: A known mass of the fuel sample (solid or liquid fuel) is burnt completely in
excess of oxygen. The liberated heat is absorbed by water and calorimeter. Thus the heat

4
lost by burning fuel is the heat gained by water and calorimeter. The calorific value of the
fuel is calculated from the measured data.
Procedure: A known mass (approximately 0.5 - 1.0g) of the given fuel is taken in a clean
nickel or stainless steel crucible. The crucible is placed over the ring, attached to one of
the electrodes. A thin magnesium wire is then stretched across the electrodes, touching
the fuel sample. The bomb lid is tightly screwed and filled with oxygen to 25 atm
pressure. It is placed in a copper calorimeter containing known mass of water, stirrer is
started and initial temperature of water is recorded. The circuit is completed by
connecting the electrodes to a 6V battery. The sample undergoes combustion and heat is
liberated. Finally the maximum temperature attained by water 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 C
Final temperature of water = t2 C
Heat liberated by burning of fuel = Heat absorbed by water and calorimeter
m x GCV of fuel = (W + w) (t2 - t1)
or GCV of fuel = (W + w) (t2 - t1) cal/g
m
= (W + w) (t2 - t1) 4.184 103 J/kg
m
NCV = GCV Latent heat of water formed
If H = Percentage of hydrogen in the fuel, then:
Water formed by combustion of 1g of fuel = 18 x H = 0.09H g
2 100
Latent heat of water formed = 0.09 H 587 cal/g
NCV = GCV 0.09 H 587 cal/g
NCV = GCV 0.09 H 587 cal/g
Numerical problems
1. On burning 0.83 g of a solid fuel in a bomb calorimeter the values of GCV and NCV
are 12638 cal/g and 12601 cal/g. Latent heat of steam 587 kcal/kg. Calculate the
percentage of hydrogen in the fuel.

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 NCV = GCV [ 0.09 x H 587 cal/g ]
12601 = 12638 [0.09 x H x 587]
H = 0.7 %
2. Temperature of 3.5 kg of water was raised from 26.5 to 29.2 0C when 0.83 g of a solid
fuel was burnt in a bomb calorimeter. Water equivalent of calorimeter and latent heat of
steam are 385 g and 587 cal/g. If the fuel contains 0.7 % hydrogen calculate GCV and
NCV.
GCV = (W + w) (t2 - t1) cal/g
m
GCV = (3500+ 385) (29.2-26.5)
0.83
= 12638 cal/g
= 52877.4 kJ/kg
NCV = GCV 0.09H 587 cal/g
= 12638 (0.09 0.7 587)
=12601 cal/g
= 52722.6 kJ/kg
5.2.2 Determination of C.V of liquid and gaseous fuel using Boys calorimeter
Boys calorimeter (Fig. 2) used for measuring the calorific value of gaseous fuels and
liquid fuels (which get vaporized easily) consists of a combustion chamber. A known
volume of fuel sample is burnt at constant rate by using a suitable burner kept inside the
combustion chamber. The outer and inner walls of the chamber are coiled by copper
tubings through which cooling water is circulated at a constant rate. Water enters the
outer coil from the top of the chamber, moves down to the bottom and then goes up
through the inner coil to the exit at top. The circulated water is collected in a measuring
jar. The thermometers T1 and T2 record the steady temperature of the incoming and
outgoing water respectively. The steam produced during combustion is condensed and
collected in a trough placed at the bottom. The whole assembly is enclosed in an
insulated container.
Principle: A known volume of fuel sample is burnt in the combustion chamber of Boys
calorimeter. The released heat is quantitatively absorbed by cooling water, circulated
through copper coils surrounding the combustion chamber. The mass of cooling water

6
and its rise in temperature are noted. The mass of water produced by condensation of
steam is recorded. The calorific value of the fuel sample is then calculated from these
data.

Fig. 5.2 Schematic diagram of Boys calorimeter ( Ref: Engg. Chem.; Gadag & Shetty)
Procedure: The fuel sample whose calorific value is to be determined, is burnt at the
burner at constant flow rate of the burner and simultaneously cooling water is circulated
at a constant rate. The process of burning of the gas and circulation of water at constant
rate are continued for some time to establish steady conditions. After attaining the steady
state, the following observations are recorded and the calorific value of the fuel sample is
calculated.
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 = t 10 C
Steady temperature of outgoing water = t 20 C
Rise in temperature = (t2 - t1) 0 C
Mass of water produced from steam condensation = m kg
Heat released by combustion of fuel = Heat absorbed by water
V x Gross calorific value of the fuel = W (t2 - t1)

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or Gross calorific value of the fuel = W (t2 - t1) k cal/ m3
V
= W (t2 - t1) 4.184 k J/ m3
V
Latent heat of steam per m3 of fuel sample = m 587 k cal
V
Net calorific value = W (t2 - t1) - m 587 k cal
V V
= [W (t2 - t1) - m 587 ] 4.184 k J/ m3
V V
Numerical problems
1. On burning 2.9 cm3 of a gaseous fuel in a Boys calorimeter the values of GCV and
mass of condensed steam were found to be 12500 cal/g and 0.8 g. Calculate NCV of the
fuel. [Latent heat of steam 587 kcal/kg]
NCV = GCV - [ m 587 ] kcal/m3
V
= 12500 [0.8 587 ]
2.9
= 12338.1 kcal/m3
= 51622.6 kJ/m3
2. Calculate GCV and NCV of a gaseous fuel from the following data obtained in Boys
experiment:
Volume of gaseous fuel burnt at STP = 0.08 m3
Weight of water used for cooling = 24 Kg
Temperature of inlet water = 26C
Temperature of outlet water = 40C
Weight of water produced by steam condensation = 0.03 kg
Latent heat of steam = 587 4.187 kJ/Kg
GCV = W (t2-t1) S
V
= 24(40-26) 4.187 kJ/m3
0.08
= 17585.4 kJ/m3
NCV = GCV m 587 4.187 kJ/m3
0.08
= 17585.4 0.03 587 4.187 kJ/m3
0.08
3
= 16663.73 kJ/m

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5.3 Solid fuels
Solid fuels are primarily classified into two;
Natural fuels- wood & coal
Manufactured fuels- charcoal & coke.
Advantages
(a) Easily transportable.
(b) Conveniently stored without risk of any spontaneous explosion.
(c) Low production cost.
(d) Possess moderate ignition temperature.
Disadvantages
(a) High ash content.
(b) Wastage of large proportion of heat.
(c) Clinker formation when they burn.
(d) Combustion process cannot be easily controlled.
(e) High handling cost.
The main solid fuels include wood, peat, lignite, coal and charcoal.
Applications:
Used since many years to create fire.
Coal - fuel source that aided the industrial revolution
Wood - used to run steam locomotives.
Peat and coal Currently used in generation of electricity
5.3.1 Proximate analysis of coal
(i) Moisture: About 1 g of air-dried finely powdered sample of coal is weighed into a dry
silica crucible and heated for about one hour at 110 0 C in an electric hot air-oven. The
crucible is cooled first in air, then in a desiccator and weighed. Loss in weight is noted.
% of moisture = Loss in weight 100
Wt. of coal sample
During burning of coal, moisture in it evaporates by taking some liberated heat in the
form of latent heat of evaporation, thereby lowering the effective calorific value of coal.
Hence, lesser the moisture content better is the quality of coal as a fuel. But, presence of
up to 10% moisture creates more uniform fuel-bed and less of fly-ash.

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(ii) Volatile matter: The dried coal sample left in the crucible in step (i) is then covered
with a lid and placed in a muffle furnace, maintained at 950 200 C. The crucible is taken
out after 7 minutes of heating. It is cooled first in air further in a desiccator and finally
weighed.
% of volatile matter = Reduction in weight due to loss of volatile matter 100
Wt. of coal sample
Higher % of volatile matter in coal is undesirable as high proportion of fuel will distill
over as vapour and a large portion of which escapes unburnt. Coal sample with high %
volatile matter burns with a long flame, high smoke and has low calorific value. Coal is
ranked good if the volatile matter is less.
(iii) Ash: The residual coal left in the crucible in step (ii) is heated without lid in a muffle
furnace at 700-7500 C, until a constant weight of residue is obtained.
Percentage of ash = Wt. of ash left 100
Wt. of coal sample
The mineral matter originally present in the vegetable material from which the coal was
formed, consists of oxides of K, Mg and Ca and is called intrinsic ash. Non-essential
mineral matters such as clay, gypsum or other inorganic matters, give rise to extrinsic
ash. The intrinsic ash content rarely exceeds 1 to 2% whereas extrinsic ash content is
relatively higher.
Ash-forming constituents in coal are undesirable for the following reasons: (i) the
calorific value of the coal is decreased; (ii) the removal and disposal of ash poses
problems; (iii) the ash deposited in the fire bars interferes with circulation of air, and (iv)
if the ash fuses to form a clinker on the fire bars, it hinders air circulation and also
promotes corrosion of the fire bars. However, some ash is desirable since it serves to
protect the grates from direct contact with incandescent coal, which might lead to
oxidation of the grate bars.
(iv) 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.
Calorific value and quality of a coal sample increases with the percentage of fixed
carbon. Greater the percentage of fixed carbon, smaller is the percentage of volatile
matter. It is the fixed carbon which burns in the solid state. Hence information regarding
the percentage of fixed carbon helps in designing of the furnace and the fire-box.

10
Significance: Grading of a coal or coke sample to determine moisture, volatile matter,
fixed carbon, and ash is done by proximate analysis which is important to both the
suppliers and users to have a speedy, precise, and consistent procedure. It also helps to;
i) Rank coal
ii) show the quantity of combustible and non-combustible constituents
iii) provide the basis for buying/selling,
iv) identify appropriate coal for different purposes.
5.3.2 Ultimate analysis of coal
(i) Carbon and hydrogen: An accurately weighed coal sample (1-2 g) is burnt in a
current of oxygen in a combustion apparatus. As a result carbon and hydrogen of the coal
are converted into CO2 and H2O respectively. These are absorbed respectively in weighed
KOH and CaCl2 tubes. The rise in the weights of KOH and CaCl2 tubes corresponds to
the amount of CO2 and H2O formed respectively.

Fig. 5.3 Schematic diagram of % C & % H analysis

C + O2 CO2 H2 + O2 H2O
12 44 2 18
2 KOH + CO2 K2CO3 + H2O CaCl2 + 7 H2O CaCl2 .7 H2O
Percentage of carbon = Increase in weight of KOH tube 12 100
Weight of coal taken 44
Percentage of hydrogen = Rise in weight of CaCl2 tube 2 100
Weight of coal taken 18

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Carbon and hydrogen in coal directly contribute towards the calorific value of the coal.
Greater the percentage of C and H, better is the coal quality and higher is its calorific
value.
ii) Nitrogen: The percentage of nitrogen is determined by digesting a known quantity (1
g) of powdered air-dried coal sample with conc. H2SO4 and HgSO4 in a Kjeldahls flask
using K2SO4 as a catalyst. After the solution becomes clear, excess NaOH is added and
the ammonia liberated is distilled into a known volume of acid solution of known
strength. The volume of unused acid is determined by back titration using standard NaOH
solution. The percentage of nitrogen is calculated from the volume of acid neutralized by
ammonia liberated, The Kjeldahls apparatus is shown in Fig. 5.4.

Fig. 5.4 Schematic diagram of Kjeldahl apparatus

Nitrogen in the coal does not contribute any useful value to the coal and since it is
generally present in small quantities (~ 1%) its presence is not of much significance.
However,nitrogen content is less in good quality coal.
Percentage of nitrogen = Weight of nitrogen 100
Weight of coal taken

Where, Weight of nitrogen = Volume of acid used Normality of acid 14

1000
Thus, Percentage of nitrogen = Vacid Nacid 1.4
Wt of coal taken

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(iii) Sulfur: Weighed coal sample is allowed to undergo complete combustion in a bomb
calorimeter by which sulphur present in coal is oxidized to sulphates. The ash left after
combustion from the bomb calorimeter is extracted with dil. HCl. Barium chloride
solution is added to the acid extract barium sulphate, which is then filtered, washed,
ignited and weighed. From the weight of barium sulphate obtained the sulphur present in
the coal is calculated.
Percentage of sulphur = Wt. of BaSO4 obtained 32 100
Wt. of coal taken 233
Sulfur present in coal adds to the calorific value of the coal but its combustion products
(SO2 and SO3) have corrosive effects on equipments, particularly in the presence of
moisture. Further, the oxides of sulphur are undesirable from the atmospheric point of
view. Sulphur containing coal is not suitable for the preparation of metallurgical coke as
it adversely affects the properties of the metal.
(iv) Ash: The ash content of coal sample is determined as described under proximate
analysis.
(v) Oxygen: The oxygen content is calculated by difference as follows:
Percentage of oxygen = 100 Percentage of (C + H + N + S + Ash)
Oxygen content of coal is generally associated with moisture. The lower the oxygen
content, the more is the maturity of coal and greater is its calorific value. As the oxygen
content increases, the capacity of the coal to hold moisture increases and the coking
power decreases.
Significance
To evaluate the chemical composition of coal in terms of various elements present
(C, H, O, N, S) and ash
To predict the suitability of coal for purpose of heating
For combustion calculations
To determine the composition of flue gases
Numerical problems
1. About 0.6 g of a coal sample was allowed to undergo combustion in a bomb
calorimeter. The calorific value of the sample was found to be 8600 cal/g. The ash
formed was extracted with acid and this was heated with BaCl2 solution. The weight of

13
dried barium sulphate obtained was found to be 0.05 g. Calculate the % of S in the coal
sample.
% of S = Wt. of BaSO4 obtained 32 100
Wt. of coal 233
= 0.05 32 100
0.6 233
= 1.14 %
2. About 1.6 g of coal sample was kjeldahlised and NH3 gas thus evolved was absorbed in
50 mL of 0.1 N sulphuricacid. After absorption, the excess of acid required 6.5 mL of 0.1
N NaOH for neutralisation. Calculate the % of nitrogen in the sample.
% Nitrogen = Vol. of acid used Nacid 1.4
Wt. of coal taken
% Nitrogen = 43.5 0.1 1.4
1.6
= 3.8 %
5.4 Liquid fuels
Liquid fuels are combustible molecules that can be harnessed to create mechanical
energy. They are predominantly used in industries. Most liquid fuels used currently are
made from crude petroleum. Gasoline is the most widely used liquid fuel. Liquid fuels
have the advantage of higher calorific value per unit mass compared to solid fuels, burn
without dust, ash & clinkers and are easy to transport through pipes. But liquid fuels are
costlier than solid fuels and possess greater fire hazard risks (especially highly
inflammable & volatile liquid fuels).
Petroleum
Petroleum was formed in nature by anaerobic decay of marine plant and animal life under
high temperature and pressure millions of years ago. It is a complex mixture of organic
crude oil and natural gas which consists of hydrocarbons like paraffins, cycloparaffins,
olefins and aromatics with small quantities of nitrogen, oxygen and sulphur containing
organic compounds and traces of inorganic compounds. The process of separation of
crude oil into different useful fractions on the basis of their boiling points using an
efficient bubble cap type fractionating column is called petroleum refining.
5.4.1 Cracking
An average grade crude oil on fractionation yields about 20-30 % gasoline, 30-45 %
intermediate oils and 25-50 % residual fuel oils. Cracking of the surplus heavier fractions

14
gives greater yields of improved gasoline and better engine performance than that
obtained from fractional distillation of crude oil. Cracking is defined as the process of
decomposition of hydrocarbons with higher molecular weight into that of lower
molecular weight by breaking C-C and C-H bonds producing low boiling alkanes and
alkenes.
Cracking
C10H12 C5H12 + C5H10
Decane (high b.p) Pentane Pentene (low b.p)
The main advantages of catalytic cracking are as follows;
The octane number and yield of gasoline produced is high.
The process can be better controlled.
There is a saving in production costs as high temperatures and high pressures are
not required.
External fuel is not required. The necessary heat is obtained by burning off the
coke deposited on the catalyst itself, during the regeneration process.
Catalysts are selective in their action, and therefore, they permit cracking of only
high boiling hydrocarbons.
Fluidized (moving) bed catalytic cracking:

Fig. 5.5: Schematic diagram of fluidized bed catalytic cracking

The finely divided catalyst bed (Al2O3 + SiO2) is fluidized by the upward passage of feed
stock vapours (heavy oil, gas oil) in a cracking chamber (reactor) maintained at 550 0C.
Near the top of the reactor there is a centrifugal separator (cyclone), which allows only
15
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 0C). 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, thereby increasing the overall yield of the cracked products. 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.
5.4.2 Catalytic Reforming: Process of upgrading gasoline by increasing its octane
number in the presence of a catalyst. The main reactions taking place during catalytic
reforming process are:
i) Isomerisation: Conversion of straight chain hydrocarbons into branched chain
hydrocarbons.
H3C (CH2)4 CH3 H3C CH CH2 CH2 CH3
CH3

n-hexane 2-methyl petane

ii) Dehydrogenation: Dehydrogenation of cycloalkanes to produce aromatic

compounds.

Methyl cyclohexane Toluene

iii) Cyclisation and dehydrogenation: Straight chain hydrocarbons undergo
cyclisation followed by dehydrogenation to produce aromatic hydrocarbons.

CH 3 (CH 2)4 CH 3 + H2

n-Hexane Cyclohexane

+ 3H2

Cyclohexane Benzene

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iv) Hydrocracking: n-Paraffins undergo cracking in the presence of hydrogen and
catalyst to produce light gases that are removed from gasoline fraction.
Cat
CH3 (CH2)8 CH3 + H2 2 CH3 (CH2)3 CH3
n-Decane n-Pentane
5.4.3 Knocking in internal combustion engines
Premature combustion of a portion of compressed air and fuel mixture in the cylinder of
an internal-combustion engine giving rise to sharp sounds is called knocking.
The adverse effects of gasoline knock are as follows:
It increases the fuel consumption
It reduces the power output
It causes damage to mechanical parts due to overheating of the cylinder parts
The driving becomes rather unpleasant
The knocking in IC engines can be minimized through the following measures:
A suitable change in engine design
By using critical compression ratio
By using high rating gasoline
By using anti-knocking agents.
Octane Number: The percentage by volume of iso-octane in a mixture of iso-octane and
n-heptane blend, which has identical knocking characteristics as the gasoline sample,
under the same set of conditions.
5.5 Gaseous Fuels
The main advantages of gaseous fuels are:
It is easier to handle gaseous fuels than solid fuels.
It can be transported easily through pipelines.
They do not leave any residue after burning.
They have higher calorific values than the solid fuels.
They produce little or no smoke, whereas most of the solid fuels burn with
smoke.
They have relatively low ignition temperature and hence they burn more
easily.

17
The main disadvantages of gaseous fuels are:
Very large storage tanks are needed for storing gaseous fuels.
The chances of fire hazards in case of leakages are high as they are highly
inflammable.
They are more expensive than solid or liquid fuels.
Water gas
Water gas is a mixture of mainly two combustible gases, CO and H2. It is also known as
blue gas because it burns with a blue flame due to the combustion of carbon monoxide. It
requires careful handling because of the risk of carbon monoxide poisoning. The calorific
value of water gas is about 10000 to 11000 KJ /m3. The composition of water gas is as
follows:
CO: 40 45 %; H2 : 45 50 %; CO2: 4 %; N2 ; 4 %.
The water gas plant is made up of steel and lined inside with refractories. The plant is
charged with coke at the top using a cup and cone feeder. Inlet pipes for passing steam
and air are provided at the base. Steam and air is passed alternatively through a red hot
coke bed which is maintained at 1000 0C. The charge inside the plant is first heated to
1000 0C and then steam is blown in through an inlet provided for some time.
C + H2O (steam) CO + H2 H = 131.4 KJ
During the steam passage, water gas is produced which is withdrawn through an outlet
near the top of the plant. 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 overall reaction during air blow is the formation of carbon monoxide.
2C + O2 2CO H = - 221.9 KJ
This reaction being exothermic increases the temperature of coke bed to about 1000 0C.
Thus by blowing steam and air alternatively, the temperature of the coke bed can be
maintained at 1000 0C.

18
 Fig.5.6 Schematic diagram of water gas plant (Ref. Engg. Chemistry, Jain & Jain)
Uses of water gas:
For the production of hydrogen, manufacture of methyl alcohol and synthetic
petrol.
As a fuel in glass and ceramic industries.
Enriched water gas (mixed with hydrocarbons), which burns with luminous flame
is used as an illuminating agent.

5.6 Summary
In this chapter, the types of fuels based on their origin and physical state and their
characteristics are discussed. Any fuel has carbon and hydrogen as the main constituents.
The fuel is a material that stores chemical energy in forms that can be practically released
and used as thermal energy. The calorific value of a substance is the amount of heat
released when its specific amount undergoes combustion. The method to determine GCV
and NCV of chemical fuels using bomb and boys calorimeter are described in detail. The
energy value of coal is the amount of chemical energy in coal that can be converted into
useful energy or work. The use of coal as fuel requires it to be graded by proximate or
ultimate analysis. The calculated values can be compared with different grades of coal.
Crude petroleum is processed and refined into more useful fractions such as gasoline,
diesel fuel, kerosene and liquefied petroleum gas. The rating of gasoline using octane
number and the need of antiknock agent are discussed. Quality of gasoline is upgraded

19
through reforming and cracking processes. Water gas (CO+H2 mixture) is made by
passing steam over a red hot carbon fuel such as coke.

20