Module-6

Fuels and Combustion

Calorific value - Definition of LCV, HCV. Measurement of calorific
value using bomb calorimeter and Boy’s calorimeter including
numerical problems.
Controlled combustion of fuels - Air fuel ratio – minimum
quantity of air by volume and by weight-Numerical problems-
three way catalytic converter- selective catalytic reduction of
NOX; Knocking in IC engines-Octane and Cetane number -
Antiknocking agents.
Fuel is substance, which on combustion produces a large
amount of heat, which can be used for various domestic and
industrial purposes

Combustion
The process of combustion involves oxidation of carbon,
hydrogen etc. of the fuels to CO2, H2O, and the difference in the
energy of reactants and the products are liberated as large
amount of heat energy which is utilized.

Fuel + O2 Products + Heat

The primary or main source of fuels are coal and petroleum

oils, the amounts of which are dwindling day by day. These
are stored fuels available in earth's crust and are generally
called "fossil fuels".
The term combustion refers to the exothermal
oxidation of a fuel, by air or oxygen

FUEL

OCCURENCE PHYSICAL STATE

3
 Classification of Fuels
On the basis of occurrence
Primary or Natural Secondary or Derived

On the basis of state

Solid Liquid Gaseous Solid Liquid Gaseous

Wood Crude Natural Coke Tar Coal gas
Coal oil gas Charcoal Kerosene Water gas
Dung Diesel Oil gas
Petrol Biogas
Fuel oil Coke oven
LPG gas
Synthetic Blast
gasoline furnace gas
4
Does the efficiency of the same quantity of different kind of fuels
are the same?
For example

Answer is No!
Calorific Value or the capacity to supply heat
"the total quantity of heat liberated when a unit
mass or volume of the fuel is burnt completely".
5
Units of heat
1. Calorie
The amount of heat required to raise the temperature of
one gram of water through one degree centigrade
2. Kilocalorie (or) kilogram centigrade units
the unit of metric system and is equal to 1000 calories.
This may be defined as
"the quantity of heat required to raise the temperature
of one kilogram of water through one degree
centigrade".
Thus 1 kcal = 1000 cal
6
Units of heat continued
3. British thermal unit (B. Th. U.)
“the quantity of heat required to raise the temperature of one
pound of water through one degree Fahrenheit”

1 B. Th. U. = 252 cal = 0.252 k cal.

1 k cal = 3.968 B. Th. U.

4. Centigrade Heat Unit (C. H. U.)

"quantity of heat required to raise the temperature of one pound
of water through one degree centigrade".

Thus, 1 k cal = 3.968 B. Th. U. = 2.2 C. H. U.

7
 Higher or Gross Calorific Value (HCV or GCV)
Most of the fuels contain some hydrogen and when the calorific
value of hydrogen containing fuel is determined experimentally,
the hydrogen is converted to steam

If the products of combustion are condensed to room temperature

(15C or 60F), the latent heat of condensation of steam also gets
included in the measured heat, which is then called "higher or
gross calorific value"
So gross or higher calorific value may be defined as…
"the total amount of heat produced when one unit mass/volume
of the fuel has been burnt completely and the products of
combustion have been cooled to room temperature"

8
9
 Lower or Net Calorific Value (LCV)
In actual case of any fuel, the water vapour and moisture etc are not
condensed and escapes as such along with hot combustion gases. Hence
a lesser amount of heat is available. So, net or lower calorific value may
be defined as…
“The net heat produced when unit mass / volume of the fuel is burnt
completely and the products are permitted to escape."
Net or lower calorific value can be found from GCV value
NCV = GCV - Latent heat of water vapour formed
= GCV - Mass of hydrogen × 9 × latent heat of steam
1 part by mass of hydrogen produces 9 parts by mass of water.

The latent heat of steam is 587 k cal / kg or 1060 B. Th. U. / lb of

water vapour formed at room temperature. (ie 15C)
10
 Characteristics of a good fuel
1. High Calorific Value
2. Moderate Ignition Temperature
3. Low Moisture Content
4. Low non-combustible matter content
5. Moderate velocity of combustion
6. Products of combustion should not be harmful
7. Low Cost
8. Easy to transport
9. Combustion should be easily controllable
10.Should not undergo spontaneous combustion
11.Storage cost in bulk should be low
12.Size should be uniform (solid fuel) – Combustion is regular

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12
Determination of Calorific Value
Bomb calorimeter

13
• What is a Bomb- or Combustion Calorimeter?
A Bomb-Calorimeter is used to measure the heat created by a
sample burned under an oxygen atmosphere in a closed vessel,
which is surrounded by water, under controlled conditions.

• The measurement result is called the Combustion-, Calorific- or

BTU-value

• 1g of solid or liquid matter is weighed into a crucible, and placed

inside a stainless steel container (the “Decomposition vessel”)
filled with oxygen. Then the sample is ignited through an ignition
wire inside the decomposition vessel and burned

• The reaction is carried out in insulated container, where the heat

evolved by the reaction causes the temperature of the contents to
change
• All organic matter is burned under these conditions, and oxidized.
Even inorganic matter will be oxidized to some extend 14
• The heat created during the burning process can be
determined in different ways

• By measuring the temperature increase

• The heat created by the combustion process is transferred to

known amount of water

15
16
 Calculations

x = mass of fuel pellet (g)

W = mass of water in the calorimeter (g)
w = water equivalent of calorimeter (g)
t1 = initial temperature of calorimeter.
t2 = final temperature of calorimeter.
L= Higher calorific value of fuel in cal/g.

(W+w) (t2-t1)
L= Cal/g
x
17
 Water Equivalent of the calorimeter is determined by burning a fuel
of known calorific value (benzoic acid (HCV = 6,325 kcal/kg) and
naphthalene (HCV = 9,688 kcal/kg)

If H is the percentage of hydrogen in fuel, the mass of water produced

from 1 g of fuel = (9/100) × H
= 0.09 H
Heat taken by water in forming steam = 0.09 H× 587 cal
(latent heat of steam = 587 cal/kg)

LCV = HCV – Latent heat of water formed

LCV or NCV = [HCV or GCV – 0.09 H × 587]

1. 0.72 gram of a fuel containing 80% carbon, when burnt in a
bomb calorimeter, increased the temperature of water from 27.3o
to 29.1oC. If the calorimeter contains 250 grams of water and its
water equivalents is 150 grams, calculate the HCV of the fuel.

Solution.

Here x = 0.72 gm -- C 80%----0.576 gm,

W = 250 g, w = 150 g
t1 = 27.3oC, t2 = 29.1oC.

HCV of fuel (L) = (W + w) (t2 – t1) cal/gm

x
= (250 + 150) × (29.1-27.3) = 1250 cal/gm
0.576
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2. On burning 0.83 gm of a solid fuel in a bomb calorimeter , the
temperature of 3500 g of water increased from 26.5oC to 29.2oC.
Water equivalent of calorimeter and latent heat of steam are 385 g
of and 587 cal/g respectively. If the fuel contains 0.7% hydrogen,
calculate its Gross and Net Calorific value.
Solution. Here wt. of fuel (x) = 0.83 g of ; wt of water (W) = 3500 g;
water equivalent of calorimeter (w) = 385 g ;
(t2 – t1) = (29.2oC - 26.5oC) = 2.7oC ; percentage of hydrogen (H) = 0.7% ;
latent heat of steam = 587 cal/g
Gross calorific value = (W + w) (t1 - t2) cal/g
x
= (3500 +385) × 2.7 = 12638 cal/g
0.83
NCV = [GCV – 0.09 H × 587]
= (12638 – 0.09 × 0.7 × 587) cal/g
= (12638 – 37) cal/g = 12601 cal/g 20
1. Fuse wire correction
2. Acid correction
3. Cooling correction

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 Corrections

Fuse wire correction:

Heat liberated during sparking should be _????????_
from calorific value

22
Acid correction:
Fuels containing Sulphur and Nitrogen if oxidized, the heats of
formation of H2SO4 and HNO3 should be subtracted (as the acid
formations are exothermic reactions)

23
24
Cooling correction:
The rate of cooling of the calorimeter from maximum
temperature to room temperature is noted.

25
 (W+w) (t2-t1+Cooling Correction) – (Acid + Fuse Correction)
GCV =
Mass of the fuel (x)

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3. A sample of coal contains C =93%; H =6% and ash = 1%. The following
data were obtained when the above coal was tested in bomb
calorimeter. Wt. of coal burnt = 0.92 g, Wt. of water taken = 550 g
Water equivalent of calorimeter =2200 g, Rise in temperature = 2.42 oC
Fuse wire correction = 10 cal. Acid correction = 50 cal.
Calculate gross and net calorific value of the coal, assuming the latent
heat of condensation of steam as 580 cal/g.

Solution: Wt. of coal sample (x) = 0.92 g; wt. of water (W) =550 g;
Water equivalent of calorimeter (w) = 2200 g;
Temperature rise (t2-t1) = 2.42 oC;
Acid correction = 50 cal;
Fuse wire correction = 10 cal;
Latent heat of steam = 580 cal/g;
Percentage of H =6%
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GCV = (W + w) (t1 - t2) – [acid + fuse corrections]
x
= (550 + 2200) × 2.42 – [50 + 10] cal
0.92g
= 7168.5 cal/g.

NCV = [GCV – 0.09 H × latent heat steam]

= (7168.5 – 0.09 × 6 × 580) cal/g
= 6855.3 cal/g

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 Boy’s Calorimeter
It is used for measuring the calorific value of gaseous (or) liquid fuels.
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 then calculated
from these data.
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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.

Working :
 A known volume of water is passed through the tubes.
 The initial temperature is noted when the two thermometers
show the same constant temperature.
 A known volume of the gas (measured using a meter) 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.
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31
Calculations:
Let V = Volume of the gas burns at STP in certain time, t;
W = mass of the cooling water used in time, t,
T1= Temperature of inlet water;
T2 = Temperature of the outgoing water;
m = mass of steam condensed in time ‘t ‘in a graduated cylinder;
L = Higher calorific value of fuel.
Then, heat absorbed by circulation water = W (T2-T1)
And heat produced by the combustion of fuel = VL
Assuming no heat loss we get: VL = W (T2-T1)
Or HCV (or GCV) L = W (T2-T1)/V
Mass of H2O condensed per m3 gas = m/V Kg
Latent heat of steam per m3 of gas = m × 587/V kcal
LCV (or NCV) = [L- (m × 587/V)] kcal/ m3
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1. The following data were obtained in a boy’s gas calorimeter experiment
Volume of the gas used = 0.1 m3 at STP
Wt. Of water heated = 25kg
Temperature of inlet water = 20oC
Temperature of outlet water = 33oC
Wt. of steam condensed = 0.025 kg
Calculate the higher and lower calorific value per m3 at STP. Take the heat
liberated in condensing vapour cooling the condensed as 580 kcal/kg.

Solution:
Here V = 0.1 m3; W = 25 kg; T1 = 20oC; T2 = 33 oC; m = 0.025kg
HCV (L) = W (T2-T1)/V
= 25(33-20)/0.1 = 3,250 kcal/m3
LCV (or NCV) = [L- (m /V× 580)]

= 3,250 kcal/m3–[(0.025kg/0.1/m3) × 580 kcal/kg

= 3,250 kcal/m3 – 145kcal/m3 = 3105 kcal/m3.
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 COMBUSTION Calculations
• Atmospheric Air contains approximately 21% oxygen
(O2) by volume. The other 79% of "other gases" is
mostly nitrogen (N2), so we will assume air to be
composed of 21% oxygen and 79% nitrogen by volume.
• Thus each mole of oxygen needed to oxidize the
hydrocarbon, is accompanied by 79/21 = 3.76 moles of
nitrogen.
• Using this combination the molecular mass of air
becomes 28.94 [kg/kmol].
• Note that it is assumed that the nitrogen will not
normally undergo any chemical reaction.
COMBUSTION Calculations-
Theoretical calc. of calorific value of a fuel using Dulong’s formula:
The theoretical or minimum mass (or volume) of oxygen required for
complete combustion of 1 kg of fuel may be calculated from the
chemical analysis of the fuel. In order to obtain maximum amount of
heat from a fuel, the adequate supply of oxygen is very essential for the
complete combustion of a fuel.

C(s) +O2 (g) CO2 (g)

12 32 44

The mass of oxygen, required by each of the constituents of the fuel,

may be calculated from the chemical equations given in previous topic
about "combustion of fuels". Now consider 1 kg of a fuel.
We know that 1 kg of carbon requires 8/3 kg of oxygen for its
complete combustion.

Similarly, 1 kg of hydrogen requires 8 kg of oxygen and 1 kg of

sulphur requires 1 kg of oxygen for its complete combustion

Total oxygen required for complete combustion of 1 kg of fuel is given

as:
• If some oxygen (say O2 kg) is already present in the fuel, then total
oxygen required for the complete combustion of 1 kg of fuel is:

• It may be noted that the oxygen has to be obtained from the

atmospheric air, which mainly consists of nitrogen and oxygen.

The composition of air is taken as:

Nitrogen (N2) = 77% ; Oxygen (O2) = 23% (By Mass)
and
Nitrogen (N2) = 79%; Oxygen (O2) = 21% (By Volume)

It is thus obvious, that for obtaining 1 kg of oxygen, amount of air

required:

• Theoretical or minimum air required for complete combustion of 1 kg of

fuel (Dulong’s formula):
 Problem
• A coal sample was found to contain the following:
• C-81%
• H2-4%
• N2- 1%
• Remaining being ash
• Estimate the minimum quantity of air required for the complete
combustion of I kg of coal .

Minimum quantity of air

= 4.35 [ (8 / 3) 81 + 8 (4)]
= 4.35 [ 2.66 X 81 + 32]
= 4.35 X 248
= 1078.8 Kg
 Knocking – IC engine
Maximum power derived from the
gasoline when it burns silently and
uniformly in an internal combustion
engine
The ratio of the gaseous volume in
the cylinder at the end of the suction-
stroke to the volume at the end of
compression-stroke of the piston is
known as the ‘Compression Ratio'
(CR).

After the initiation of combustion reaction by spark in

the cylinder, the flame should spread rapidly and
smoothly through the gaseous mixture, thereby the
expanding gas drives the piston down the cylinder
 V1 being greater than V2, the CR is >1

 The CR indicates the extent of compression of the fuel-air-

mixture by the piston

 However, successful high compression ratio is dependent on the

nature of the constituents present in the gasoline used

 In certain circumstances, due to the presence of some

constituents in the gasoline used, the rate of oxidation becomes
so great that the last portion of the fuel-air mixture gets ignited
instantaneously producing an explosive violent reaction, known
as 'knocking‘

 The knocking results in loss of efficiency, since this ultimately

decreases the compression ratio.
 Chemical structure and knocking
The tendency of fuel constituents to knock is in the
following order
Straight-chain paraffins > branched-chain paraffins
(iso-paraffin) > olefins > cyclo paraffins (naphthenes)
> aromatics
Octane number
 Knocking characteristics of a fuel - expressed by
'octane number'
 A measure of resistance of fuels towards autoignition
 n-heptane, knocks very badly and hence, its anti-
knock value = 0
 Iso-octane (2, 2, 4-trimethyl pentane) gives very little
knocking, so its anti-knock value = 100
 Octane number or rating

Octane number is equal to the percentage by volume of iso-

octane (2,2,4-trimethyl pentane) in a mixture of n-heptane
and iso-octane having the same knocking tendency
compared to the sample of gasoline being tested
CH 3
H H H H H H H

H C C C C C C C H CH 3 C CH 2 CH CH 3
H H H H H H H
CH 3 CH 3
n-heptane Isooctane
• The fuel which has same knocking tendency with the
mixture having 80 % iso-octane has octane number 80
Improvement of anti-knock characteristics of a fuel
 The octane number - raised by the addition of tetra ethyl lead
(C2H5)4Pb or TEL and diethyl telluride (C2H5)2Te. In motor spirit
(Motor fuel) about 0.5 ml and in aviation fuel 1.0 - 1.5ml of TEL are
added per litre of petrol.
 TEL is converted into a cloud of fine lead and lead oxide (litharge)
particles in the cylinder and these particles react with any peroxide
molecules formed, slow down the chain reaction and decrease the
chances of explosion
 However deposit of lead oxide is harmful to the engine life. In
order to help the simultaneous elimination of lead oxide formed from
the engine, a small amount of ethylene dibromide (or ethylene
dichloride) is also added to petrol.
 Ethylene dibromide + lead oxide lead bromide (volatile). TEL is
more effective on saturated hydrocarbons than on unsaturated ones.
Alternative methods
Addition of high octane compounds like isopentane,
isooctane, ethyl benzene, isoprpopyl benzene, methyl
tertiary butyl ether (MTBE)

Other additives

• Oxidation inhibitors - 2,4-ditertiary butyl-4-methyl

phenol.
• Rust inhibitors - Organic compounds of
phosphorus or antimony.
• Ignition control additives - tricresyl phosphate
which suppresses pre-ignition of the fuel due to
glowing deposits on spark plug or a hot spot on the
cylinder wall.
 Diesel Engine Fuels
Characteristics of an ideal diesel oil
• It should have low spontaneous ignition temperature
• It should have very little sulphur, aromatic and ash content
• The ignition lag should be short
Cetane Number:
 There is a delay between the injection of diesel fuel and its ignition.
This delay period if becomes large, too much fuel accumulates
in the cylinder and burns very rapidly and causing “diesel
knock”.
 This delay period is connected to the type of hydrocarbons
present in the diesel.
 n-alkanes < naphthalenes < alkenes < branched alkanes <
aromatics
The suitability of a diesel fuel is determined by its cetane
value, which is the percentage of hexadecane in a mixture of
hexadecane and 2-methyl naphthalene, which has the same
ignition characteristics as the diesel fuel sample, under the
same set of conditions.
H H H CH3

H C C C H

H H H
14
n-hexadecane 2-Methyl naphthalene
(cetane No.=100) (cetane No.=0)

The cetane number of a diesel fuel can be raised by the

addition of small quantity of certain "pre-ignition dopes" like
alkyl nitrites such as ethyl nitrite, buytl nitrite, diteritiary butyl
peroxide.
Ignition quality decreases among hydrocarbons is as
follows

n-alkanes > naphthalenes > alkenes >

branched alkanes > aromatics

 Ignition delay increases

 Diesel knock increases
 Ignition quality decreases
 Cetane number decreases
Three-way catalytic converter
 Components
• 3-way catalyst is generally a multi-component material containing
precious metals like Rhodium, Pt, and (to a lesser extent) Pd, Ceria
(CeO2), γ-Alumina (Al2O3), and other metal oxides.
• It typically consists of a ceramic monolith of cordierite
(2Mg.2Al2O3.5SiO2) with strong porous walls enclosing an array of
parallel channels.
• Cordierite is used because it can withstand the high temperatures in
the exhaust and the high rate of thermal expansion encountered
when the engine first starts. Typically, the exhaust gas temperature can
reach several hundred degrees in < 1 min.
• The reduction catalyst is made of Pt and Rh while the oxidation
catalyst is made of Pt and Pd. Both the catalysts have a ceramic
honeycomb structure.
 Working of 3-way Catalytic Converter
A three-way catalytic converter makes use of two catalysts to
convert harmful gases to harmless gases. They are: Reduction
Catalyst & Oxidation Catalyst
Stage 1: Reduction Catalyst:
• The exhaust gases are first sent over the reduction catalyst (which
is made of Pt and Rh).
• It converts oxides of nitrogen (NOx) to N2 and O2.
2NO → N2 + O2
2NO2 → N2 + 2O2
Stage 2: Oxidation Catalyst:
• Exhaust gases that are free of oxides of nitrogen (NOx) are then
sent over the oxidation catalyst (made of Pt and Pd).
• The oxidation catalyst coverts CO and hydrocarbons (HC) in the
gases into CO2 and H2O.
2CO + O2 → 2CO2
HC + O2 → CO2 + H2O