MODULE 6

Fuels and Combustion

 Definition
• Fuel - combustible substance having carbon as major
constituent.

• Reacts with oxygen leading to the formation of the

product with the evolution of heat at a rapid rate.

• The energy content of the products is less than the

reactants.

• The excess energy is liberated as heat energy.

 Fuels and Combustion
• Fuel is a combustible substance, which on combustion
produces a large amount of heat, which can be used for
various domestic and industrial purposes.

• 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".
 Classification
• Primary fuels: Natural fuels

• Solid
• Liquid
• Gas

• Secondary fuels: Derived

• Solid
• Liquid
• Gas
Classification of fuels
 Calorific value of fuels

• The most important property of fuel to be taken into

account is its calorific value or the capacity to supply
heat.

• The calorific value of a fuel can be defined as "the total

quantity of heat liberated when a unit mass or volume
of the fuel is burnt completely".
 Units of heat
1. Calorie - Calorie is the amount of heat required to
raise the temperature of one gram of water through
one degree centigrade.

2. Kilocalorie (or) kilogram centigrade unit - This is

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.
 Units of heat

3. British thermal unit (B. Th. U.) - This is defined as

"the quantity of heat required to raise the
temperature of one pound of water through one
degree Fahrenheit". This is English system unit.
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.) - This is the

"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.
 Units
Amount of heat required to raise the temp. of

• Calorie: 1g of water through 1oC

• Kilocalories : 1Kg of water through 1oC
• British Thermal
Unit (B. Th. U) : 1pound of water through 1oF
• Centigrade Heat Unit (C.H.U) : 1pound of water
through 1oC
 GCV/HCV
– Gross / Higher calorific value
• Amount of heat produced, when unit
mass/volume of the fuel is burnt completely
and the products of combustion have been
cooled to room temperature.

• If the products of combustion are condensed to

room temp., the latent heat of condensation of
steam also gets included in the measured heat.
Hence higher or gross calorific value
 NCV/LCV
- Net / Lower calorific value
• In practice, water vapor are not condensed but
allowed to escape. Hence lesser amount of
heat is available.

• LCV is the net heat produced, when unit mass

of the fuel is burnt completely and the products
are permitted to escape.

• LCV = HCV – Latent heat of water vapor produced

= HCV – Mass of hydrogen x 9 x Latent heat of steam
Determination of Calorific Value
Bomb calorimeter
Determination of Calorific Value of Fuel (Liquid
and Solid) by Bomb Calorimeter
Principle:

 The HCV (Calorific Value) of a substance is measured by burning it in

a controlled environment.

 The resulting heat released by this combustion i.e. the net

temperature rise, is proportional to the calorific value of the fuel.

 The experiment is carried under adiabatic so that no energy is lost or

gained.

 To achieve this state, the Calorimeter Vessel (bomb) and bucket are
surrounded by a water jacket which is strictly temperature controlled by
a system of circulators, heaters and coolers, so that it has the same
temperature as the inner bucket.
 Calculation of Calorific Value of Fuel (Liquid
and Solid) by Bomb Calorimeter
• Weight of fuel sample = x (g)
• Initial tempt. of water = T1 (0C)
• Final tempt. of water = T2 (0C)
• Weight of H2O in copper calorimeter = W1 (g)
• Wt. of bomb calorimeter, stirrer & thermometer = W2 (g)
• Calorific value of fuel (HCV) = L
Heat produced by burning m (g) of fuel = m.L
Heat gained by water = (W1 + W2) (T2 – T1)

Calorific value of fuel (L) = (W1 + W2) (T2 – T1) S / x

Where S is specific heat of water = 4.187 J/ g0C (or) 1 cal/g0C

Note: Here, the calorific value (L) corresponds to HCV i.e. GCV
 Corrections
• Fuse wire correction. Heat liberated during sparking should be
subtracted from heat liberated.

• 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).

• Cooling correction. The rate of cooling of the calorimeter from

maximum temperature to room temperature is noted. From this rate of
cooling (i.e., dt°/min) and the actual time taken for cooling (t min) then
correction (dt × t) is called cooling correction and is added to the (t2 .
t1) term.
Corrections
 Bomb Calorimeter - Problems

When 1 g of a fuel on complete combustion in excess of oxygen,

increases temperature of water in a calorimeter containing 500 g
of water to 4.50C. Calculate the gross (higher) calorific value of
the fuel if the weight of the calorimeter setup is 150 g.
(2925 cal/gm)

A sample of coal contains 90% C; 4% H; 2% ash. When this fuel

sample is tested in the bomb calorimeter for finding the calorific
value, the following results are obtained. Calculate the gross and
net calorific values of the fuel based on the data given below.
Weight of the coal burnt = 0.5 g; Weight of water taken = 500 g
Weight of calorimeter = 500 g; Rise in temperature = 4.85 0C
Cooling correction = 0.05 0C; Fuse wire correction = 15.0 Cal;
Acid correction = 75.0 Cal (GCV=9620, NCV=9408.68 cal/gm)
 Calculation of Calorific Value of Fuel
(Gas) by Boy’s Calorimeter
• Volume of fuel sample burnt = V (m3)
• Initial tempt. of water = T1 (0C)
• Final tempt. of water = T2 (0C)
• Weight of H2O in spiral glass container= W (g)
• Mass of condensed water = m gm
• Calorific value of fuel = L
• Heat produced by burning V (m3) of fuel = V.L
• Heat gained by water = (W) (T1 - T2) x s

Calorific value of fuel (HCV) = (W) (T2 – T1) S / V

Where S is specific heat of water = 4.187 J/ g0C (or) 1 cal/g0C
Mass of water condensed per m3 of gas= m/V kg
Latent heat of steam per m3 of gas= m x 587/V kcal/m3
LCV / NCV = GCV- m x 587 / V
Calculation of Minimum amount of Air
Requires for complete combustion of Fuel

The amount of air required for complete combustion of

a fuel can be calculated by following the various steps
given below

Step 1: Write the equation for the

combustion reaction.

Step 2: From the equation calculate the

amount of oxzygen required for
the elements or compounds
present in the fuel.
Step 3: If oxygen is mentioned in the
problem, subtract the weight or
volume of oxygen already
present in the fuel from the total
volume of oxygen required by the
other elements or compounds.
Step 4: Since N2, CO2 and H2O are non-
combustible, they do not require
any oxygen (air). Therefore, their
values, if mentioned in the
problem, can be ignored.
Step 5: Finally calculate the amount of air
required by the fuel by
multiplying 100/21 (if volume %)
with total amount of oxygen
required, and 100/23 (if weight %)
with total amount of oxygen
required.

Step 6: Excess amount of air for combustion

Excess amount of air is necessary
than the theoretical amount of air
to achieve complete combustion.
 The excess air required is expressed in
percentage of theoretical air as

100  Excess air

= Theoretica l air x
100
Combustion reactions: For Solid Samples
• C + O2 CO2
12 Kg of C requires 32 Kg of O2 for complete combustion to CO2
Therefore …… Kg of C requires 32/12 x …… Kg of O2 for complete combustion

• H2 + O1/2 H2O
2 Kg of H requires 16 Kg of O2 for complete combustion to H2O
Therefore …… Kg of H requires 16/2 x …… Kg of O2 for complete combustion

• S + O2 SO2
32 Kg of S requires 32 Kg of O2 for complete combustion to CO2
Therefore …… Kg of S requires 32/32 x …… Kg of O2 for complete combustion

Theoretical amt. of O2 required = Total amt. of O2 required to combust C, H and S

Note: In case O2 % value is also provided in the problem, then it has to be
substrated from the total amount of O2 inorder to calculate the theoretical
amount of O2 required for combustion
 Points to remember
• Minimum amt (Kg) of air required for complete
combustion of a given coal sample =
(C * 32/12 + H * 16/2 – O + S) * 100/23
23 Kg of O2 is present in 100 Kg of air

• Convert % wt. into wt (Kg) by dividing the

constituent (%C, %H, %S, %O & sometimes
%CH4, %CO) values by 100

• If it is for gaseous samples then convert % vol.

into vol. (m3) by dividing the constituent (%C,
%H, %S, %O, %CH4, %CO) values by 100
 For Gases Samples
• Additional constituents that can be observed are CO
(%) and CH4 (%)
• Combustion reaction
• CO + O1/2 CO2
28 kg of CO requires 16 Kg of O2 for combustion
Therefore …. Kg of CO requires 16/28 * ---- Kg of O2
• CH4 + 2O2 CO2 + 2H2O
16 Kg of CH4 requires 64 Kg of O2 for combustion
Therefore …. Kg of CH4 requires 64/16 * ---- Kg of O2
• Add the above O2 required amounts for CH4 and CO to
the total amount of O2 required for calculating the
theoretical O2 required
Note: In case CO2 and N2 % values are provided in the problem, it should
not be taken into account while calculating the theoretical amount of O2
required for combustion
 Conversion from Kg (wt.) to m3 (vol.)
After the calculating the theoretical O2 required amount (Kg), for
converting into volume (m3) at NTP, use the below procedure

• 32 Kg of O2 amount is equivalent to 22.4 m3 of

O2 volume
• Therefore, …. Kg of O2 = 22.4/32 x …. m3 of O2

21 m3 of O2 is present in 100 m3 of air

 Knocking
• It is a kind of explosion due to rapid rise of pressure in an internal
combustion (IC) engine.
• Gasoline and air(1:17) mixture is compressed and ignited by a
spark where oxidation of HC takes place.
• Products of oxidation drives the piston down in cylinder, if
combustion is uniform and regular.
• Sudden oxidation takes place and mixture detonates resulting an
explosive sound called knocking which leads to loss of power.
• Compression ratio= Gaseous vol. in the cylinder at the
end of suction stroke/ volume at the end of
compression stroke.
• Compression ratio depends on the nature of constituents of the fuel.
Efficiency of IC engine increases with compression ratio
• Knocking tendency depends on the chemical structure
of fuel, which decreases in the following order.
• Straight chain paraffins > Branched chain paraffins >
Cycloparaffins > Olefins > Aromatics
• Knocking results in loss of efficiency of the engine
• Knocking characteristics of a combustion engine fuel
(petrol) – octane number or rating
• Antiknock quality of a fuel is expressed as its octane
number
• It is defined as the % of isooctane in a mixture of n-
heptane and isooctane which has the same knocking
characteristics of the petrol under the same set of
conditions.
 Octane number
Isooctane – best antiknocking properties and
assigned O.N of 100

• n-heptane – poor antiknocking property and

assigned O.N. of 0

• Most effective antiknock agent is tetraethyl lead

(TEL) along with ethylene dibromide which prevents
deposition of lead by forming volatile lead halides
• Others are tetramethyl lead, tertiary butyl acetate,
diethyl telluride
• Greater the octane number, greater is the resistance of
knocking
 Diesel knock
• Long ignition delays lead to accumulation of more vapours in
the engine and when ignited an explosion results as the
combined effect of temperature and pressure. This is
responsible for diesel knock.

• Diesel Index: Specific gravity (API) X Aniline point (oF)/100

• API – American Petroleum Institution
 Cetane number

• Long ignition delays lead to accumulation of more vapours in

the engine and when ignited an explosion results as the
combined effect of temperature and pressure. This is
responsible for diesel knock.

• There is a delay period between injection of diesel fuel

 Cetane number
• There is a delay period between the injection of diesel fuel and its ignition.
If this delay period is large, too much fuel accumulates in the cylinder and
burn very rapidly and causes diesel knock.

• Increasing delay period occurs in the series : n-paraffin < Olefins <
naphthenes < isoparaffins < aromatics.

• Order is the reverse for gasoline antiknock quality.

• n-hexadecane ; Cetane number 100
• α – methyl naphthalene ; cetane number 0

• A given fuel matches in quality with the blend having 40/60 blend of
cetane and methyl naphthalene, it is assigned a cetane number 40

• Cetane number of diesel can be improved by adding amyl/butyl nitrite,

carbamates, ditertiary butyl peroxide and metal organic compounds.
 Structures

CH3-CH2-CH2-CH2-CH2-CH2-CH3 –n-heptane (O.N = 0)

CH3-C(CH3)2-CH2-CH(CH3)-CH3 – 2,2,4 – trimethylpentane (O.N. =100)

CH3-(CH2)14-CH3 – n-hexadecane (C.N = 100)

CH3

2-methyl naphthalene (C.N. = 0)

 Biodiesel
 Biodiesel refers to a vegetable oil or animal fat based
diesel fuel consisting of long-chain alkyl esters.
 It is made by chemically reacting lipids (eg.
Vegetable oil, animal fat) with an alconol.
 It is meant to be used in standard diesel engines and
is thus distinct from the vegetable and waste oils
used to fuel converted diesel engines.
 Biodiesel can be used alone, or blended with
petrodiesel.
 Biodiesel can be produced from vegetable oil via
transesterification process.
 It is produced by base-catalyzed transesterification.
 The reaction scheme is as follows :
 i) Transesterification
Rapeseed oil + Alcohol → Mixed ester + Glycerol35
Ii) Neutralisation : Unavailable side reaction in the
presence of free fatty acids.

Block diagram is as follows :

Vegetable oil→Transesterification
→Neutralization
• Transesterification gives byproduct glycerine
and oilcake. Oilcake is a good source of organic
manure which contains about 30% protein.
• Biodiesel contains no petroleum, it can be
blended at any level with petroleum diesel.
• A pure 100% biodiesel fuel is referred as B 100.
• Biodiesel blends are referred as BXX, where
XX indicates the amount of biodiesel in the
blend ex.
• B20 blend is 20% by volume biodiesel and 80%
by volume petrodiesel.
• In USA, biodiesel is made from soyabean oil.
• In Europe, biodiesel is made from rapeseed oil.
• In India, it is produced from seeds of plant
Jatropa curcas and Karanja (Non edible oil).
• In India, Jatropa plant is grown in marginal and
poor soil with minimum cultural practices.
Biodiesel has higher cetane number. This oil
reduces emission of CO2 by 78%, CO by 44%,
Sulphate 100%, polycyclic aromatic
hydrocarbon (PAA) by 75-85% and particulate
matter.