MODULE-6

FUELS AND COMBUSTION

1
 OUT LINE OF THIS MODULE
❑ Calorific value - Definition of LCV, HCV

❑ Measurement of calorific value using

❑ Bomb calorimeter and
❑ Boy’s calorimeter
❑ Numerical problems.

❑ Calculation of minimum quantity of air by volume and by weight-

Numerical problems

❑ Knocking and chemical structure, octane number and cetane number

and their importance

2
❑ Biodiesel-synthesis, advantages and commercial applications
 Outline of this unit

Classification of fuels

Calorific value (CV) of fuel

Characteristic of a good fuel

Determination of CV of a fuel - Bomb and Boy’s Calorimeter

Numerical problems based on Bomb and Boy’s Calorimeter

3
 Fuel

Fuel – a combustible substance, upon burning in air or O2 gives large

amount of heat. Eg. wood, charcoal, kerosene, petrol, LPG, biogas, etc.

Combustion - a process in which a substance burn in air or O2 with

evolution of heat. A substance which is burnt is called combustible
substance.

Fuels contain C and H as main constituent, during combustion C and H

combine with O2 and produce CO2 and H2O with simultaneous release of
heat at rapid rate.
4
 Fuel
CO2 and H2O has low energy than the compound from which it is
formed.

Thus energy released during the combustion process is the difference in

the energy of the reactant and that of products formed.

5
 Classification of fuels
Fuels classified based on their 1) Origin and 2) Physical state

Classification based on physical state a) Solid b) Liquid and c)

Gaseous fuel.

Classification based on origin is of two types

Natural or Primary fuels - found in nature as such eg. coal, petroleum etc.

Artificial or Secondary fuels - are those which are derived from primary
fuels eg. kerosene, diesel, etc.
6
 Calorific Value (CV) of a fuel

Efficiency of a fuel is judged based on their CV

CV of fuel - quantity of heat evolved by complete combustion of unit

quantity of fuel in air or O2.

Units of heat is generally expressed in Calories (cal), Kilo calories (kcal),

British Thermal Units (BTU), Centigrade Heat Unit (CHU)

a) 1 Calorie (cal) – quantity of heat required to raise the temp. of 1 g of

H2O by 1 °C
1 cal = 4.185 Joules
7
 Calorific Value (CV) of a fuel

Unit of CV of solids and liquids

Generally expressed in calories/gram (cal/g) or kilocalories/kilogram

Unit of CV of gas
Expressed in kcal/m3 or cal/cm3 at given T and P. Heat quantity per unit
volume of gas is CV of gaseous fuel.

Since volume of gas varies with T and P. CV of gaseous fuel includes T

and P.

8
 Calorific Value (CV) of a fuel

CV of fuel generally expressed in two ways

Calorific Value
(CV)

Gross/High Calorific Value Net/Low Calorific Value

(GCV/HCV) (NCV/LCV)

9
 Gross/Higher Calorific Value (GCV/HCV)

Quantity of heat evolved by complete combustion of unit mass of fuel in

air or O2 and the products of combustion are brought down to normal
temperature.

Hydrocarbon fuel is mostly used. During combustion, carbon is oxidized

to CO2 and H2 to steam. When products of combustion are cooled to
room temperature, latent heat of condensation of steam released
includes to heat of combustion of fuel.

GCV = Heat of combustion of fuel + latent heat of condensation of steam

10
 Net/Lower Calorific Value (NCV/LCV)

Quantity of heat evolved when unit mass of fuel is burnt completely and
the products are permitted to escape.

In practice when fuel is burnt, the water vapour, and moisture are not
condensed and they escape along-with hot combustion gases. Thus
heat corresponds only to combustion and does not include latent heat of
condensation of steam. The quantity of heat so measured is called
net/low calorific value

NCV = GCV – latent heat of steam

11
 Characteristics of a good fuel
High calorific value

Moderate ignition temperature

Low moisture content

Low non-combustible matter

Combustion should be easily controllable

Products of combustion should not be harmful & easy to transport,

store and handle.
12
Determination of Calorific Value of Fuel by
Bomb Calorimeter

13
Determination of Calorific Value of Fuel by Bomb Calorimeter
Calorific value of solid and non-volatile liquid fuel can be determined
by Bomb Calorimeter

14
 Apparatus-Bomb Calorimeter
Apparatus consists of…….

Strong cylindrical stainless steel bomb

inside which the combustion of fuel made to
take place.

Bomb has a lid, which can be screwed to

the body of bomb to make a perfect gas-
tight seal.

The lid is provided with two stainless steal

electrodes and an oxygen inlet valve
15
 Apparatus-Bomb Calorimeter
To one of the electrode a small ring is
attached, which supports a nickel or stainless
steel crucible, where the fuel is placed & burnt.

Bomb is placed inside a copper calorimeter

which is surrounded by an air-jacket and
water-jacket to prevent heat loss due to
radiation.

Calorimeter provided with an electrically

operated stirrer and Beckmann’s thermometer,
which can read accurately temperature
difference up to 1/100th of a degree
16
 Working Procedure-Bomb Calorimeter
Working procedure…..

A known mass (0.5 to 1 g) of given fuel is

taken in crucible.

A fine Mg wire (0.75 mm) bent into loop and

made to touch the fuel sample, is then
stretched across the electrodes.

Bomb lid is tightly screwed and bomb filled

with O2 to 25 atm.

Bomb is lowered into copper calorimeter,

containing a known mass of water. 17
 Working Procedure-Bomb Calorimeter
Calorimeter vessel is then placed in the
insulating jacket.

Stirrer is operated and initial temperature of

the water is noted

Electrodes are connected to 6V battery to

ignite the sample. Sample burns and heat is
liberated

Heat liberated rises the temperature of water

in the calorimeter. Uniform stirring of water is
continued and maximum temp. attained is
noted. 18
 Heat Capacity-Bomb Calorimeter
Specific heat capacity (SHC): Amount of heat needed to increase the
temperature of 1 g of a substance by 1 °C

SHC of water = 1 cal/g per 1 °C rise.

Heat capacity = W x SHC W = mass of water

Heat capacity - amount of heat that W g of substance (which has certain

SHC) absorbed to bring about 1 °C rise in temperature.

19
 Calculation-Bomb Calorimeter
Heat liberated by fuel = Heat absorbed by water, calorimeter etc.
mθ = (W+w) (t2-t1) x SHC
g. cal/g = g. °C. cal/g °C

GCV of fuel (θ) = (W+w) (t2-t1) x SHC of H2O

cal/g (or kcal/kg)
m

Note: Heat quantity calculated above is GCV because the products of

combustion remain inside the calorimeter and brought down to ambient
temperature.

20
 Calculation-Bomb Calorimeter
Calculation
Weight of the fuel sample taken = m g
GCV of the fuel = θ cal/g
Weight of the water taken in the calorimeter = W g
Water equivalent of calorimeter, bomb, thermometer, bomb etc. = w g
Initial temperature of water in calorimeter = t1
Final temperature of water in calorimeter = t2

Heat liberated by combustion of fuel = mθ

Heat absorbed by water and calorimeter etc. = (W+w) (t2-t1)

21
 Water Equivalent in Bomb Calorimeter

Water Equivalent - It is the amount of water which is thermally

equivalent to the given body.

In other words, it is the mass of water which has the same heat capacity
that of the body itself.

Eg. Lets assume, to bring about 1 °C rise in temperature of calorimeter

is 570 cal. So, this same amount heat (570 cal) can bring about 1 °C
rise in 570 g of water (we know that specific heat capacity of water is
1 cal/g °C). Thus calorimeter is thermally equivalent to 570 g of water or
simply its water equivalent is 570 g.
22
 Water equivalent in Bomb Calorimeter

Since water and bomb calorimeter are in thermal equilibrium during the
experiment, the temperature noted in Beckmann’s thermometer is also
the temperature of bomb calorimeter.

The observed rise in temperature be t2-t1

Heat absorbed by W g of water in calorimeter and water

equivalent w g is = (W+w) (t2-t1)

23
 Calculation-Bomb Calorimeter
Heat liberated by fuel = Heat absorbed by water, calorimeter etc.
mθ = (W+w) (t2-t1) x SHC

GCV of fuel (θ) = (W+w) (t2-t1) x SHC of H2O

cal/g (or kcal/kg)
m

24
 Calculation Correction-Bomb Calorimeter
Corrections: For accurate results, the following correction are applied.

Fuse wire correction (tF): Heat liberated, as measured above, includes

the heat given out by ignition of the fuse wire used, which actually has to
be excluded from GCV.

Acid correction (tA): Fuel containing S and N are oxidized to H2SO4 and
HNO3, under high pressure and temperature of ignition.

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 Calculation Correction-Bomb Calorimeter

Formation of these acids are exothermic reactions. So, the measured heat
also includes the heat given out during the acid formation.

The amount of these acids is analyzed from washing of bomb by titration.

H2SO4 alone is determined by reacting with BaCl2 or Ba(OH)2 to
precipitate as BaSO4 (correction for 1 mg of S is 2.25 cal). If it does not
form precipitate with Ba(OH)2, means H2SO4 absent. May only nitric acid is
present. Which can be determined by titration against a base (eg. NaOH).

For each ml of N/10 H2SO4 formed, 3.6 cal. should be subtracted

For each ml of N/10 HNO3 formed, 1.43 cal. should be subtracted
26
 Calculation Correction-Bomb Calorimeter

Cooling correction (tC): Time taken to cool the water in calorimeter from
maximum temperature to room temperature is noted, let it be (u) and
rate of cooling dt°/min, then cooling correction = u x dt° This should be
added to the observed raise in temperature.

GCV of fuel (θ) = (W+w) (t2-t1 + tC) x SHC of H2O – (tA + tF)
cal/g (or kcal/kg)
m

27
 Calculation-Bomb Calorimeter
NCV can be calculated if the % of hydrogen in the fuel is known. Let the
% of hydrogen be n

1 g of hydrogen produce 9 g of steam. So “n” gram of hydrogen produce

9n gram of steam.
If hydrogen is given in percentage (%). Divide the hydrogen percentage
𝟐
by 100 to convert to grams, ex. 2% hydrogen = = 0.02 g of hydrogen.
𝟏𝟎𝟎
Latent heat of condensation of steam = 587 cal/g.
𝐇
NCV = GCV – 9 x X 587 cal
𝟏𝟎𝟎
28
 Problems in Bomb Calorimeter
1)Calculate the CV of a fuel sample of coal 0.6 g. Water equivalent of
calorimeter 2200 g. Increase in temperature = 6.52 °C

Ans: GCV = 23906 cal/g

2)Calculate GCV and NCV of a fuel from the following data: Mass of fuel
burnt = 0.75 g, water equivalent of calorimeter = 350 g, mass of water
taken = 1150 g, rise in temperature = 3.02 °C, % of hydrogen in fuel = 2.8.

Ans: GCV = 6040 cal/g

NCV = 5892.1 cal/g 29
 Problems in Bomb Calorimeter
3)0.6 g of a coal sample with 92% C, 5% hydrogen, and 3% ash, caused a
rise in the temperature of 2000 g water by 3.2 °C in a bomb calorimeter
experiment. Calculate the GCV and NCV of coal, given. Water equivalent
= 200 g.
Ans: GCV = 11733.3 cal/g
NCV = 11469.2 cal/g
4)On burning 0.75 x 10-3 kg of a solid fuel in a bomb calorimeter, the
temperature of 2.5 kg water is increased from 24 °C to 28 °C. The water
equivalent of calorimeter is 0.485 kg and the latent heat of steam is 587
kcal/kg. If the fuel contains 2.5% hydrogen, calculate its GCV and NCV.
Ans: GCV = 15920 kcal/kg
NCV = 15787.9 kcal/kg
30
 Problems in Bomb Calorimeter
5)Determine the water equivalent of the bomb calorimeter apparatus which
gave the following data in an experiment:
GCV of benzoic acid = 6324 cal/g
Wt. of benzoic acid taken = 1.364 g
Wt. of calorimeter = 1025 g
Wt. of calorimeter + water = 3025 g
Initial temperature = 11.872 C
Final temperature = 14.625 C
Cooling correction = 0.015 C
Heat from fuses = 22 cals
Washing of the bomb on analysis indicate the presence of 3.5 ml of N/10 HNO3
and there is no H2SO4 formed.
Ans: Water equivalent of calorimeter = 1126 g
31
Determination of Calorific
Value of Gas Fuel by Boy’s
Calorimeter

32
 Boy’s Calorimeter-Description
Chimney
Apparatus to measure CV of
gaseous and volatile liquid fuel

Water enters from top of outer Cu

coil, moves to bottom of chimney
and then goes up through the inner
coil to the exit at top

Gas burner
(known volume of gas can
be burnt at known pressure)
33
 Boy’s Calorimeter-working principle

Circulation of H2O and gaseous fuel

at constant rate for 15 min –
warming up period.

Fuel burning and water circulation

controlled - exit water at atmospheric
pressure.

Readings taken after – steady

condition reached.

34
 Boy’s Calorimeter-working principle

Readings are taken simultaneously of

Volume (V) of gas burnt at given temp.

and pressure in a certain time period.

Quantity (W) of water passing through

the coil, during the same time.

Steady rise in temperature, i.e T2-T1

Mass of water (m) condensed during

this time.
35
 Boy’s Calorimeter Calculation
Heat absorbed by circulating water = W(T2-T1)
Heat produced by combustion of fuel = VL
VL = W(T2-T1) x SHC

L = W(T2-T1)
V
Calorific value of gas or volatile liquid fuel = L
Mass of H2O condensed per m3 of gas = m/V kg
Latent heat of steam per m3 of gas = m x 587 kcal
V
LCV or NCV = [ L - m x 587]
V
36
 Boy’s Calorimeter Calculation
Volume of gas burns at STP in a certain time (t) = V

Mass of cooling water used in time (t) = W

Temperature of the inlet water = T1

Temperature of outlet water = T2

Mass of steam condensed in time (t) in a

graduate cylinder = m

High Calorific value = L

37
 Boy’s Calorimeter-numerical problem
During the determination of CV of a gaseous fuel by Boy’s calorimeter,
the following results were recorded:
Volume gaseous fuel burnt at STP = 0.093 m3
Weight of water used for cooling = 30.5 kg
Weight of steam condensed = 0.031 kg
Temperature of inlet water = 26.1 °C
Temperature of outlet water = 36.5 °C
Determine the GCV and NCV per m3. Heat liberated during latent heat of
condensation of steam is 587 Kcal/kg.

Ans: 3214.3 kcal/m3

38
 Calculation of minimum quantity of air by
volume and by weight-Numerical problems

39
 Combustion
Combustion - exothermic chemical reaction accompanied by increase of
heat eg.

The main gaseous product of combustion are CO2, SO2, H2O, CO, N2,
O2 – flue gases

For proper combustion, the substance must be brought to its ignition

temperature.

Ignition temperature – min. temp. at which the substance ignites and

started to burn without further addition of heat.
40
 Calculation of air quantities
Elementary principle - to find the amount of O2 and air required for
combustion of a unit quantity of a fuel.

Combustion of carbon

12 g of carbon requires 32 g of O2.

Hence, C g of carbon in fuel requires = 32/12 x C amount of O2 is

required for complete combustion.
41
 Calculation of air quantities
Combustion of hydrogen

4 g of hydrogen requires 32 g of O2 for complete combustion

Hence, H g of hydrogen in fuel requires = 32/4 x H or 8H amount of O2

required for complete combustion.
H = mass of hydrogen
42
 Calculation of air quantities
A part of total amount of hydrogen in fuel exist in combined form i.e
water. This part of hydrogen is a non-combustible.

It is taken that O2 available in fuel, exist as water.

We know that 1 part of hydrogen combines with 8 part of O2. So, the
number of hydrogen in combined form is O/8 (O = mass of oxygen)

So amount of hydrogen available for combustion is = (H-O/8)

Hence O2 required for combustion of hydrogen = 8(H-O/8)

43
 Calculation of air quantities
Combustion of sulphur

32 g of Sulphur requires 32 g of O2 for complete combustion

Hence, S g of sulphur in fuel requires = 32/32 x S or S amount of O2 for
complete combustion.

Theoretical amount of O2 required for the complete combustion of 1 kg of

fuel

44
 Calculation of air quantities
Air contains 21% of O2 by volume or 23% by weight of O2

This means 1 kg of O2 is supplied by 100/23 = 4.35 kg of air

Similarly 1 m3 of O2 is supplied by 100/21 = 4.76 m3 of air

Minimum weight of air

required for combustion

Minimum volume of air

required for combustion
45
 Calculation of air quantities

1 gram mol of any gas at STP (i.e 0 °C and 1 atm) occupies 22.4 L (or
dm3) of volume or 1 kilogram mole occupies 22.4 m3

Molecular mass of air is taken as 28.95 g/mol

The problems are generally based on calculating

The wt. or vol. of air theoretically required or used for the combustion of
1 kg of fuel.

Composition of solid or liquid fuel is usually expressed on wt. basis

whereas the composition of a gaseous fuel is expressed on vol. basis.
46
 Numerical problems-Combustion and air quantities
1) Calculate the weight and volume of air required for combustion of 3 kg of
carbon. (Ans: Wt. = 34.783 kg; Vol. = 26.92 m3)

2) A sample of coal was found to contain: C = 80%, H = 5%, O = 1%, N =

2%. Calculate the minimum amount of air required for complete combustion
of 1 kg of coal sample. (Ans: 10.97 kg)

3) The % composition of sample of coal is C = 90%, H = 4%, O = 3%, N =

0.5%, S = 0.5%. a) Calculate the min. wt. of air requires for combustion.
(Ans: Wt. = 11.71 kg)
4) Calculate the minimum of air by weight required for the complete
combustion of fuel having the following composition by weight. C = 85%, H
= 10%, O = 3%. (Ans: 13.16 kg)
 Numerical problems-Combustion and air quantities

6) A coal sample has the following composition: C = 87%, H = 4.5%, O =

3%, S = 0.5%, N2 = 0.5%. a) calculate min. wt. and vol. of air.
(Ans: Wt. = 11.54 g, Vol. = 8.91 m3)

7) A gas used in an internal combustion engine had the following

composition by volume: H = 45%, CH4 = 36%, CO = 15%, N = 4%. Find
the volume of air required for the combustion of 1 m3 of the gas.
(Ans: 4.857 m3)

8) A fuel gas has the following composition by volume: H = 22%, CH4 =

4%, CO = 20%, CO2 = 6%, O = 3%, N = 45%. If 25% excess air is used,
find the wt. of air supplied per m3 of the gas. (Ans: Wt. = 2.21 kg)
48
Knocking and chemical structure, octane
number and cetane number
 Knocking

Knocking – simply refers to metallic sound in combustion engine

‘Knocking’ a type of noise in internal combustion engine (ICE) of a

motor during combustion of fuel
 Knocking

Gasoline(petrol)- complex mixture of hydrocarbons(100 different

compounds) ranging from C5 to C9. Most of these- branched-chain alkanes
and some are aromatic compounds. Its boiling range is 40-120 °C.

Diesel is a mixture of hydrocarbons ranging from C10 to C18 and boiling

range is 250-320 °C.

Diesel is hard to vaporize than petrol. This is why the two are not
interchangeable in car engines.

51
 Knocking
Gasoline - fuel in motors. Inside internal combustion engine (ICE) number
things happen to gasoline…

Compression of gasoline generates fine droplets

of gasoline vapor
Gasoline vapor is mixed with air and transfer to ICE
Petrol-air mixture is compressed
Petrol-air mixture, ignited by spark and it burns
Gases produced by combustion - expands
Expansion causes, piston to move i.e K.E is produced
The essential chemical reaction is oxidation of HCs
52
 Knocking
Normal combustion
To run the engine smoothly combustion of fuel- spark plug
air mixture inside ICE should proceed in
controlled fashion.
flame front

piston
Normal combustion
After ignition flame spread rapidly and
smoothly through gas mixture. The expanding
gas drives the piston down the cylinder.

In a properly functioning engine, the fuel burns

with the flame front progressing smoothly from
the point of ignition across the combustion
chamber. 53
 Knocking
Abnormal combustion
Last unburnt fuel-air mixture outside flame front may
get spontaneously ignited and combusted, rate of
oxidation is so great producing an explosive violence
sound - ‘knocking’ . It results in loss of efficiency.
or
At high compression ratio, some of the last
unburned fuel-air mixture may spontaneously ignite
ahead of the flame front and burn in an uncontrolled
manner, producing intense high-frequency pressure
waves. These pressure waves force parts of the
engine to vibrate, which produces an audible ‘knock’.
54
Rough representation of knocking

55
 Knocking

Compression ratio =

Efficiency of ICE depends on CR. Efficiency of ICE increases with

increase in CR.

Explosive reaction inside cylinder cause combustion

to stop before the optimum timing, causing a
decrease in performance.

CR depend on type of fuel and nature of constituent

present in gasoline used. Eg benzol has high CR.
56
 Knocking

Knock occurs after the passage of the spark

ignition.

While pre-ignition is the spontaneous

combustion of fuel-air mixture before the spark.

Knocking cause – damage to engine parts and

spark plug, decrease in efficiency, increase in fuel
consumption, undesirable rattling sound etc.

It can be avoided by adjusting CR, burning time, using high octane

number fuel and using anti-knocking agents. The most common method
to avoid knocking is to burn gasoline of higher octane number.
57
 Octane number
Knocking characteristics of gasoline is usually expressed in terms of
‘octane number’ higher the octane number – lesser is the knocking
tendency
Octane number of a fuel is measure of its ability to resist knocking.

Iso-octane has very little knocking, hence its anti-knock value (octane
number) is arbitrarily taken as 100.

58
 Octane number

n-heptane knocks very readily, hence its anti-knock value (octane

number) is arbitrarily taken as 0.

Octane number of any fuel is just comparison of its knocking value with
knocking value of iso-octane - n-heptane mixture.

Eg. 80-octane fuel is one which has the same combustion

characteristics as a 80:20 mixture of iso-octane and n-heptane.
59
 Chemical structure and knocking

Knocking tendency of gasoline…..

Hydrocarbons with branched-chains are more resistant to knocking than

the corresponding straight-chain paraffins.

Knocking tendency decrease with presence double bonds and cyclic

structure.
Eg. Olefins of same carbon-chain length posses better anti-knocking
property than the corresponding paraffins. Anti-knocking tendency
increase as the position of double bond approaches the center of chain.
60
 Chemical structure and knocking
Aromatic hydrocarbons (eg. benzene, toluene, xylene) have high octane
number.

Alcohols have high octane number

Naphthenes have high octane number than normal paraffins

Gasolines obtained by cracking have higher octane number than straight

run gasolines.

Alternately octane number of fuel can be increased by adding anti-

knocking agents. 61
 Anti-knocking agents
Substances added to control knocking is called anti-knocking agents eg.
tetra ethyl lead (TEL, (C2H5)4Pb)), tetra methyl lead (TML, (CH3)4Pb)),
diethyl telluride (C2H5)2Te.

They are added to motor fuel eg. about 0.5 ml/L of TEL is added to
gasoline as anti-knocking agent.

Mechanistic action of TEL

TEL converted into cloud of finely divided PbO particles, which reacts
with any hydrocarbon peroxides formed, thereby slowing down the chain
oxidation and decreasing the chances of any early detonation.

62
 Anti-knocking agents
Disadvantage of TEL
PbO formed is harmful to engine life. In order to eliminate PbO from the
engine a small amount of C2H4Br2 is also added with TEL in gasoline.

C2H4Br2 removes PbO as volatile PbBr2 with the exhaust gases. These
lead halides are poisonous to human beings and animals.

Also leaded gasoline cannot be used in automobiles equipped with

catalytic convertor because Pb present in exhaust gas poisons the
catalyst. 63
 Anti-knocking agents
Unleaded gasoline
Alternative methods of increasing octane number of gasoline is to add
high octane compounds like iso-pentane, iso-octane, ethyl benzene,
isopropyl benzene, methyl tertiary butyl ether (MTBE).

MTBE is preferred over the others because it contains oxygen in the

form of ether and supplies oxygen during combustion thereby reducing
the extent of peroxy compound formation.

Major advantage of unleaded gasoline is that it permits the use of

catalytic converter attach to the exhaust in automobiles.
64
Cetane Number

65
 Cetane number
Working of diesel engine
Diesel is a mixture of hydrocarbons ranging from C10 to C18 and boiling
range is 250-320 °C

In diesel engine, air is only first compressed to about 30-50 kg/cm2, its
temp. raises to 500-600 °C.

At this stage diesel is injected in the form of spray in to the hot air. Diesel
vapourises, attains self-ignition temp.

Pressure is further increased to about 70 kg/cm2. Diesel oil starts burning.

66
 Cetane number
Whole process of combustion of fuel in diesel engine may be consider to
take place in the following steps .
Oil droplet shot into the very hot compressed air in the cylinder, it get
vaporized
Ignition of hot vapor occurs with consequent increase in temp. and
pressure.
Oil spray still entering burns like jet flame, supplying heat and hot
gaseous combustion products to keep up the push on the piston.

All these steps completed within small fraction of second.

67
 Cetane number
In high speed diesel engine (HSD) combustion takes place in about
1/500th of a second.
Fuel used must have self-ignition temp. at least 30 °C below the temp. of
the compressed air.

Usually there is time lag between vaporization and combustion called

Ignition lag or diesel lag.

Ignition lag should be as brief as possible for smooth working.

When there is long ignition lag there occurs diesel knock.

68
 Cetane number

Long ignition lag cause large portion of fuel to get injected and
accumulated into the cylinder in vapour state before ignition is initiated.

This result in diesel vapor and air to get ignited with explosion and
violent combustion and sudden increase in temp. and pressure causing
rough and bumpy run – diesel knock.

Longer the ignition lag – greater will be the diesel knock

Straight-chain paraffins give less diesel knock than aromatic and

branched hydrocarbons.
69
 Cetane number
Knocking characteristics of diesel oil are expressed in terms of ‘cetane
number’.
Cetane number indicates readiness with which a given diesel oil
undergoes compression ignition.

Cetane a straight-chain saturated hydrocarbon (n-hexadecane, C16H34)

is chosen as reference to express the knocking characteristics of diesel
oil because it has very short ignition lag, so knocking is almost nil so its
anti-knocking value is taken as 100 i.e cetane number 100.

70
 Cetane number
2-methyl naphthalene has very long ignition lag as compared to any
commercial diesel oil. So it has very bad knocking. Hence, its cetane number is
taken as 0

CN is just comparison of knocking characteristics of fuel under test with

knocking characteristics of cetane - 2-methyl naphthalene mixture %.

Cetane number (CN) - % by volume of cetane in a mixture of Cetane - 2-

methyl naphthalene which exactly matches in its knocking characteristics with
the oil under test.

CN of high speed, medium speed and low speed diesel engine should be at
least 45, 35 and 25 respectively. 71
 Cetane number
CN of an oil can be improved by adding substances (called dopes) like
EtNO2, EtNO3, isoamyl nitrite and acetone peroxide.

Dopes are added only in small amounts (2%) and they are not effective
on low CN fuels.

Knocking in petrol engine - due to sudden spontaneous ignition

Knocking in diesel engine - due to delayed ignition

An oil of high octane number has low CN and vice versa i.e
hydrocarbons which are poor gasoline fuel are good diesel fuels. 72
Biodiesel - synthesis, advantages
and commercial applications

73
 Biodiesel
Diesel (fossil fuel) - is a mixture of hydrocarbons ranging from C10 to C18.

Biodiesel - is a mixture of alkyl ester of long-chain fatty acids, since

these are biodegradable and its spills cause little or no threats they
referred as bio-diesel.

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 Biodiesel
Biodiesel can be prepared from vegetable oils or from animal fats via
base-catalyzed transesterification.

Transesterification process gives alkyl ester (biodiesel), glycerol and

oilcake. Glycerol and oilcake are byproducts. Oilcake is good source of
organic manure. 75
 Biodiesel
Biodiesel contains no petroleum, it can be blended at any level with
petroleum diesel.

A pure biodiesel fuel is referred as B100. Biodiesel blends are referred as

BXX where XX indicates the amount of biodiesel in the blend, eg. B20
refers to 20% by volume of biodiesel and 80% by volume of petro-diesel.

Biodiesel is made from…..

Soyabean oil – US
Rapeseed oil – Europe
Seed of Jatropa curcas and Karanja – India

Biodiesel has high CN and it reduce emission of CO 44%, sulphate

100%, polyaromatic hydrocarbon 75-85% and particulate matter. 76
Block diagram of biodiesel preparation

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 Undesirable side reaction during biodiesel preparation
Esters may get hydrolyzed to the corresponding acids and it reacts with
base to form sodium salt of long-chain fatty acid (soap).

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 Advantages of biodiesel
Advantages of biodiesel - alternate fuel for conventional diesel, it can
also be used as an additive for diesel and diesohol, has high CN,
renewable, can be used in diesel engines, environmental friendly
(because there is substantial reduction of unburned hydrocarbons, CO
and particulate matter when used in conventional diesel engine), it is
biodegradable etc.

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THANK YOU

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