Energy sources

Module -V
Dr. Saurav Prasad
Department of Chemistry
VIT Bhopal University
 Module V- An Insight
Fuels-Definition. Calorific value - Definition of LCV, HCV.
Measurement of calorific value using Bomb and Boy’s calorimeter
– problem solving.

Coal analysis-proximate and ultimate analysis and significance.

Stoichiometric combustion reactions of C, CH4 etc. 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;

Alternate fuels and Fuel additives. Biodiesel-synthesis,

advantages and commercial applications;
 Fuels and Combustion

“For many years to come, the greatest portion of the world’s power will
come from the combustion of fuels”
 Definitions
 Fuels: Combustible substance (may be solid, liquid or gas) having carbon as major
constituent gives energy while burning.
Energy: Heat or Light

 Reacts with oxygen leading to the formation of the product with the evolution of heat
at a rapid rate.
Fuel + O2  Products + Heat

 The energy content of the products are less than the reactants and the excess
energy is liberated as heat energy.
 Heat and Temperature
Heat is the thermal energy transferred from hotter to cooler system that are in
contact.
Temperature is a measure of avg. kinetic energy of the atoms or molecules in
the system.

q= m X C X T 3
 Characteristics of a good fuel
• Easily available
• Ease of storage, transportation and handling
• Moderate ignition temperature
• Smoke emission should be less
• Should have low combustion rate
• Higher calorific value
• High suitability.
• Low combustion residue
• Low moisture content
• Size and Price
 Classification of fuels

a) On the basis of
their occurrence

b) On the
basis of
physical state
of
aggregation
 Units of heat
• Calorie: It is defined as the total amount of heat required to
raise the temperature of 1 gm of water through 1º C.
1 cal = 4.187 Joules

• Kilocalorie: It is defined as the total amount of heat required

to raise the temperature of 1 Kg of water through 1º C.
1 Kcal = 1000 cal

• British Thermal Unit (B.Th.U.): It is defined as the total

amount of heat required to raise the temperature of 1 pound of
water through 1º F.

• Centigrade Heat Unit (C.H.U.): It is defined as the total

amount of heat required to raise the temperature of 1 pound of
water through 1º C.
1 Kcal = 3.968 B.Th.U. = 2.2 C.H.U
 Calorific value of fuels
• Total quantity of heat liberated when a unit
mass of fuel is burnt completely is known as
Calorific Value.

• Units: cal/g or J/g

• For gases, cal/cm3 or J/cm3
 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”.

• Hydrogen is present in all most all the fuels & when the calorific
value of the fuel is determined experimentally, hydrogen is
converted into steam.

• If the product of combustion are condensed to the room

temperature, the latent heat of condensation of steam also gets
included in the measured heat, which is then called Gross
Calorific Value or Higher Calorific Value.

• Bomb Calorimeter: Calorific value determination gives

GCV/HCV.
 LCV/NCV– Low / Net calorific value
It is the net heat produced when unit mass or volume of
fuel has been burnt completely and the products of
combustion are allowed to escape.

In actual use of any fuel, the water vapour and moisture

etc. escape as such along with hot combustion gases.
Since they are not condensed. Hence a lesser amount of
heat is available.

LCV = HCV – Latent heat of water vapour formed

 LCV/NCV– Low / Net calorific value
1
𝐻2 + 𝑂2 → 𝐻2 𝑂
2
2 kg 18kg
1g 9g

(1 part by mass of hydrogen produces 9 part by mass of water)

LCV = HCV – 9 x Percentage of Hydrogen x Latent Heat of steam

LCV = HCV – 0.09 * %H * 587

Latent Heat of steam= 587 cal/g

 Determination of Calorific Value by Bomb calorimeter

A known mass of the fuel is burnt and the quantity of heat

produced is absorbed by water & measured, then the
quantity of heat produced by burning unit mass of fuel is
calculated.
 Determination of Calorific Value by Bomb calorimeter

Beckmann’s
thermometer Oxygen
valve

Electrically
operated stirrer
Electrodes to
which Mg
wire is
attached Copper
calorimeter

Mg fuse wire Stainless

steel bomb

Weighed pellet Stainless steel

of a fuel sample crucible
 Construction
1. Steel Bomb

Stainless steel bomb in which the combustion of

fuel takes place
Two holes for 2 electrodes and one oxygen inlet
valve.
small ring is attached where a Nickel/steel crucible
is kept
fuse wire of Magnesium is connected to both the
electrode.
A cotton thread is tied at one end of the fuse wire
while other end remain in contact with fuel in the
stainless crucible.

Can withstand a pressure up to 50 atm

Lined with platinum to resist acid corrosion

 Construction
2. Copper calorimeter

The bomb is kept in a copper calorimeter having

known quantity of water.

The copper calorimeter is provided with an

electrical stirrer and a Beckmann’s thermometer.

3. Air-jacket and water-jacket

The copper calorimeter is surrounded by air-

jacket and water-jacket to prevent loss of heat due
to radiation.
 Working
• Known amount of fuel is taken.
• Bomb is filled with Oxygen at 25 atm.
Pressure.
• Kept inside the calorimeter having known
amount of water.
• Start the stirring and Initial temperature
of water is noted (t1º C).
• Then electrodes are connected to 6 V
battery.
• Sample burns and heat liberated which is
transferred to water.
• Stirring is continued and maximum
temperature attained is noted (t2º C)
 Calculation:
m = mass of fuel pellet
w1 = mass of water in the calorimeter
w2 = water equivalent of calorimeter and others
w1+w2= total weight
t1 = initial temperature of calorimeter
t2 = final temperature of calorimeter
t2-t1 = Increase in temperature
Heat lost by ‘m’ mass of fuel = heat gained by system
m * HCV/GCV = (w1+w2) * Sp. heat * (t2-t1)

HCV /GCV = {(w1+w2) * (t2-t1)} / m cal/g or kcal/kg

LCV of Fuel (L) = HCV – 0.09 * %H * 587 (cal/g or

kcal/kg)
 Corrections:
i) Fuse wire corrections, FC: Heat liberated & measured includes heat given
by the ignition of fuse wire due to short circuit. Hence it should be
deducted.

ii) Acid corrections, AC: Fuel containing Sulphur, Nitrogen are oxidised
under high pressure. Formation of acid is exothermic reaction so,
measured heat also includes the heat given out during acid formation.
Hence it should be deducted.

iii) Cotton Thread corrections, CtC: Cotton thread is used for the ignition of
fuel, so its burning also generates heat & it should be deducted.

iv) Cooling corrections, CC: Time taken to cool the water in calorimeter from
maximum temperature to room temperature is noted. From the rate of
cooling (dT/minute) and actual time taken for cooling (t min.) the cooling
correction of (dT*t) is added to the rise in temperature.
HCV /GCV = {(w1+w2) * (t2-t1)} / m

{(w1+w2) *(t2-t1 +CC) – FC- AC – CtC} /m

 Problems:
• Calculate the GCV and NCV of a fuel from the following data:
– Mass of fuel burnt= 750 mg
– Water equivalent = 350 g
– Mass of water taken =1.15 kg
– Initial temperature= 16 0C
– Final temperature = 19.02 0C
– Percentage of hydrogen in fuel = 2.8

ANS: HCV : 6040 cal/g

LCV: 5892 cal/g
 Problems:
A Coal sample contains C= 92%; H= 5% and ash = 3%. When
this coal sample was tested in the laboratory for its CV in a
bomb calorimeter, the following data were obtained.

Mass of coal burnt= 0.95 g

Water equivalent = 700 g
Mass of water taken = 2 kg
Initial temperature= 16 0C
Final temperature = 18.48 0C
Acid correction = 60 cal
Fuse wire correction = 10 cal
Cooling correction = 0.02 0C

Calculate the GCV and NCV

Ans: GCV= 7031.57 cal/g

NCV= 6767.43 cal/g
 Boy’s gas calorimeter
The calorific value of gaseous or volatile liquid fuels is measured
by Boy’s Calorimeter.

The Boys gas calorimeter is a simple and effective means of

measuring the calorific values of gaseous fuels.

The principle is to burn the gas at a constant rate in a

vessel & the entire amount of heat produced is absorbed
by water which is also flowing at constant rate.

From the volume of gas burnt, the volume of water

collected and mean rise in temperature of water, the
calorific value of gaseous fuel can be calculated.
 Construction
A burner situated in chimney which is the
centre of the annual vessel.

A tank where the water condensate from

the product

The product of combustion moves

upwards to the chimney and deflected
downward by water cooled head.

A gasometer measures volume of gas

burning per unit time.

Water: The water flows from outer coil to

the inner coil and the temperature of inlet
and outlet water are measured with
different thermometers.

Outer Jacket: Prevents heat loss by

radiation.
Working of Boy’s Calorimeter :-
Start burning the gas at suitable pressure and adjust the rate of
water flow such that the temperature of outgoing water remains
constant.

Burn the gas for 5-10 minutes to have the steady temperatures
of outgoing water.

After the steady conditions of outgoing water temperature, constant

water circulation and gas flow rate reached, simultaneously note the
following :

a) Volume of gas burnt at given temp. & pressure in certain time period.
b) Quantity of water passed through coil during this period.
c) Mass of water condensed from product gas during the period.
d) The steady rise in temperature of water (t2 – t1).
 Calculation:
• Volume of gas burnt = V m3
• Mass of the water = W kg

• Temperature of inlet water = t1

• Temperature of outlet water = t2

• Specific heat of water S = 1 kcal/kg/oC

• Heat absorbed by circulating water = W(t2-t1)×S

= W(t2-t1)

• HCV = W(t2-t1)/V kcal/m3

If ‘m’ kg of steam condensed from V m3 of the fuel

Then, mass of condensation per 1 m3 of the fuel == m/v kg
So, Latent heat of steam= 587* m/V kcal

LCV = HCV- (587* m/V )

 Problem
• Following data were obtained in a Boy’s calorimeter
– Volume of gas burn = 0.1 m3
– Mass of the water = 25 kg
– Temperature of inlet water = 20 0C
– Temperature of outlet water = 330C
– Weight of steam condensed = 0.025 kg
Calculate GCV and LCV

ANS: GCV= 3250 kcal/m3

LCV= 3103 kcal/m3
 Problem
The following data were obtained in the Boy’s gas calorimeter
experiments

Volume of gas used = 0.5 m3 at NTP

Weight of water heated = 20 Kg
Temp. of inlet water = 22˚C
Temp. of outlet water = 35˚C
Weight of steam condensed = 0.021 kg
Calculate the gross and net calorific value per m3 at NTP.
The heat liberated in condensing water is 587 kcal/kg
 Coal
Coal is a fossil fuel found under the earth crust
commonly known as coal beds or coal seams. It is formed
from the dead plants by a process called coalification.

Dead plants are first converted into peat which in turn is

converted into lignite, after that bituminous coal and
then anthracite.

Coal is classified on the basis of % of carbon which is

known as “Rank of Coal”.
S.No. Coal % Carbon Rank
1 Peat 57 Low
2 Lignite 67
3 Bituminous Coal 83
4 Anthracite 93 High
 Analysis of Coal
The analysis of coal done to determine the coal’s energy
value. It is a important factor for deciding the usage of
coal.

Analysis of coal done by two methods:

a) Proximate Analysis
b) Ultimate Analysis (Elemental Analysis)

(A) Proximate analysis

It involves the determination of percentage of,

 Moisture content
 Volatile matter
 Ash content
 Fixed carbon in coal
 Proximate Analysis - Moisture content
Moisture content quenches the fire and it evaporates during
the burning of coal & takes the liberated heat in the form of
latent heat evaporation & reduces the effective calorific
value.

Procedure:

About 1gm of powdered air-dried coal sample is taken in a

crucible and heated at 100-105oC in an electric hot-air oven for 1
hour. The loss in weight of the sample is found out and the % of
moisture is calculated as,
 Proximate Analysis - Volatile content
The volatile matter may be combustible gases (like H2, CO, CH4 &
other lower hydrocarbons) and non-combustible gases (like CO2 &
N2).

After the analysis of moisture content, the crucible with

residual coal sample is covered with a lid and it is heated at
950  20oC for 7 minutes in a furnace. The loss in weight of
the sample is found out and the % of volatile matter is
calculated as,
 Proximate Analysis - Ash content
Ash is a non-combustible & useless which is left behind
when all the combustible substance is burnt off &
reduces the calorific value

After the analysis of volatile matter, the crucible with

residual coal sample is heated without lid at 700  50oC
for 1 hour in a furnace. The loss in weight of the sample is
found out and the % of ash content is calculated as,
 Proximate Analysis – Fixed Carbon
After the determination of moisture, volatile
content and ash content the remaining matter is
Fixed Carbon. Higher % of Fixed carbon, greater is
the calorific value.

% Fixed Carbon = 100 - %(moisture + volatile + ash)

 Significance of Proximate Analysis
Moisture content
> High percentage lesser will be the calorific value of coal
> Moisture in coal consumes more heat in the form of
latent heat of evaporation. Hence more heat is to be
supplied to the coal.
Volatile matter
High percentage of volatile matter is undesirable because
a) It reduces the calorific value of coal.
b) Large proportion of fuel on heating will distill over as vapour
which escapes unburnt.
c) Coal with high percentage of volatile matter burns with long
flame with high smoke.
d) Coal containing high percentage of volatile matter do not coke
well.
34
Ash content
High percentage of ash content is undesirable because,
 It reduces the calorific value of coal,
 Ash causes hindrance to heat flow as well as produces clinkers, which
blocks the air supply through the fuel,
 It increases the transporting, handling, and storage costs. It involves
additional cost in ash disposal.

Clinker : A stony residue 

Fixed Carbon

High percentage of fixed carbon is desirable because higher the percentage

of fixed carbon in a coal, greater is its calorific value.
The percentage of fixed carbon helps in designing the
furnace and the shape of the fire-box.
 Problem
A sample of coal was analyzed as follows. Exactly 2.5 g was weighed into
silica crucible. After heating for an hour at 110 0C, the residue was
weighed 2.415 gm. The crucible was then covered and strongly heated
for 7 to 10 minutes at 950 0C. The residue weighed 1.528 g. The crucible
was then heated without cover until a constant weight was obtained.
The last residue was found to weigh 0.245 g. Calculate the % of
moisture, volatile matter, ash and fixed carbon in the coal sample.

ANS:
Moisture = 3.4 %; Volatile = 36.7%; Ash= 9.8%; Carbon= 50.1%
 Ultimate Analysis
Elemental Analysis of Coal

It involves the determination of percentage of,

 Carbon and hydrogen contents
 Nitrogen content
 Sulphur content
 Ash content
 Oxygen content
 Determination of Carbon & Hydrogen
A known quantity of coal (about 1-2 gm) is burnt in the current of dry oxygen
when carbon and hydrogen in coal are oxidised to CO2 & H2O respectively.
C + O2  CO2
H2 + ½ O2  H2O
A gaseous product of combustion are passed through CaCl2 tube and potash
bulbs.

The CaCl2 tube contains weighted amount of anhydrous CaCl2 absorbs water.
CaCl2 + 7 H2O  CaCl2.7.H2O

The Potash tube contains weighted amount of KOH absorbs CO2.

2KOH + CO2  K2CO3 + H2O
 Determination of Carbon & Hydrogen

Increase in weight of KOH ∗ 12 ∗ 100

%C=
Weight of Coal sample taken ∗ 44

Increase in weight of CaCl2 ∗ 2 ∗ 100

%H=
Weight of Coal sample taken ∗18
 Determination of Nitrogen
Nitrogen in coal is determined by kjeldhal’s method
• 1 gm of accurately weighed powdered coal is heated with conc. H2SO4 along with
K2SO4 (Catalyst) in a long necked flask (Kjeldahl’s flask).
• Nitrogen in the coal is converted into ammonium sulphate.
• It is heated with 50% NaOH and it produce NH3
• The liberated NH3 is distilled over and absorbed in a known volume of std 0.1N HCl
• NH3 + HCl  NH4Cl
• The volume of unused acid is determined by back titration with std. NaOH
(0.1N)
Digestion:
Sample (N)+
Conc. H2SO4 +
K2SO4

(NH4)2SO4
 Determination of Nitrogen

1.4 ∗ Normality of used HCl∗ Volume of used HCl

%N=
Weight of Coal sample ta𝐤𝐞𝐧
 Determination of Sulphur
Presence of sulphur is undesirable in coal as on oxidation
it produces harmful and corrosive SO2 and SO3

A known amount of coal (W 1gm) is burnt completely in bomb

calorimeter in the current of oxygen, by which sulphur is oxidised to
sulphates.

The ash from the bomb calorimeter is extracted with dil. HCl. The acid
extracted is treated with BaCl2 to precipitate sulphate as BaSO4.

The BaSO4 is filtered, washed, dried and heated to constant weight.

S + O2  SO42-  BaSO4
weight of BaSO4 ppt formed ∗ 32 ∗ 100
%S=
Weight of Coal sample taken ∗ 233
 Determination of Oxygen
Oxygen is present in combined form with hydrogen in
coal and thus hydrogen available for combustion is
lesser than the actual one.

High Oxygen content coals have high moisture & low

calorific value. Thus a good quality coal should have low
% of oxygen.

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

43
 Importance of Ultimate Analysis
 Carbon
Higher the % of carbon, better is the quality of coal and higher is its
calorific value

The % of carbon is helpful in classification of coal.

Higher % of carbon in coal reduces the size of combustion chamber

required.

Oxygen Content:
Lower the % of oxygen higher is its calorific value.
As the oxygen content increases its moisture holding capacity increases,
and the calorific value of the fuel is reduced.
 Nitrogen content:
Nitrogen does not have any calorific value and its presence in coal is
undesirable.
Good quality coal should have very little nitrogen content.

 Sulphur content:
Though Sulphur increases its calorific value its presence in coal is
undesirable because
the combustion products of Sulphur are harmful and have corrosion
effects on equipment.

The coal containing Sulphur is not suitable for the preparation of

metallurgical coke as it affects the properties of the metal.
 Theoretical Calorific Value: Dulong’s Formula
The approximate calorific value of a fuel can be determined by knowing the amount of
constituents present:
Gross or higher calorific value (HCV) from elemental constituents of a fuel.
H = 34500 kcal/kg; C = 8080 kcal/kg; S = 2240 kcal/kg
Oxygen present in the fuel is assumed to be present as water (fixed
Hydrogen).

Available Hydrogen = Total hydrogen - Fixed hydrogen

= (Total hydrogen - 1/8 mass of oxygen in fuel).

LCV = HCV – 0.09 * H * 587

46
 Problem
Calculate the GCV and NCV of coal having following composition:
Carbon= 85%; Hydrogen= 8%; Sulphur= 1%; Nitrogen= 2% and
Ash= 4%

Ans: GCV : 9650 kcal/kg

LCV: 9227 kcal/kg
A coal has following composition by weight: C= 90%; O= 3%; S= 0.5%; N= 0.5% and
Ash= 2.5%. NCV of coal = 8490.5 Kcal/kg. Calculate the % of H and HCV.

%H= 4.575
HCV= 8731.8 kcal/kg
Combustion
 Combustion
Combustion ( burning) is a chemical process in which fuel reacts with
an oxidant to give out heat. The release of heat can produce light in
the form of flame.
 Rapid Combustion: Combustion in which a substance burns
rapidly and produces heat & light with the help of external heat.
Burning of LPG

 Spontaneous Combustion: Combustion in which a substance

burns spontaneously and produces heat & light without the help
of external heat.
Phosphorous burns spontaneously at RT.

 Explosion: Combustion in which a substance burns suddenly and

produces heat, light and sound with the help of heat/pressure.
Explosion of Crackers on applying heat/pressure.
 Basic Stoichiometry
Specific amount of oxygen is required for perfect
combustion.

A fuel may contain C, H, O, N & S. During combustion

these elements combine with oxygen.

If the % of Carbon, Hydrogen, Oxygen, Nitrogen &

Sulphur is known the quantity of oxygen/air required
for combustion can be calculated.
 Basic Stoichiometry
Oxygen required for combustion of Carbon
C + O2  CO2
12Kg 32 Kg 44 Kg
12 kg Carbon Requires = 32 kg of oxygen
32 𝑥
x Kg of Carbon requires = = 2.67 𝑥 Kg of Oxygen
12

Oxygen required for combustion of Hydrogen

H2 + 1/2O2  H2O
2Kg 16 Kg 18 Kg
2 kg Hydrogen Requires = 16 kg of oxygen
16 𝑦
y Kg of Hydrogen requires = = 8 𝑦 Kg of Oxygen
2

Oxygen required for combustion of Sulphur

S + O2  SO2
32Kg 32 Kg 64 Kg
32 kg Sulphur Requires = 32 kg of oxygen
32 𝑧
z Kg of Hydrogen requires = = 1 𝑧 Kg of Oxygen
32
 Basic Stoichiometry
Quantity of oxygen required for combustion of 1 Kg of Fuel

= (2.67 * C + 8 * H + S) Kg

If oxygen is already present in the fuel then this should be

reduced.
Quantity of O2 required = (O2 required - O2 present in the fuel)

Minimum Quantity of O2 or Theoretical amount of O2 required

for complete combustion
= (2.67 * C + 8 * H + S - O) Kg
 Air Required
By weight
Air contains 23% of O2 and 77% of N2 by weight.
𝟏𝟎𝟎
Hence Air required = * (2.67 * C + 8 * H + S - O) Kg
𝟐𝟑
By Volume
Air contains 21% of O2 and 79% of N2 (by volume).
𝟏𝟎𝟎
Hence Air required = * (2.67 * C + 8 * H + S - O) m3
𝟐𝟏

Non combustible substances like Nitrogen, Ash, CO2

etc. don’t require any oxygen for combustion.
 Problem-1
• Calculate the mass of air needed for complete combustion of 5kg of
coal contain C=80%, H= 15%, O= rest. Find out HCV and LCV.
ANS: Mass of Air= 71.43 Kg, HCV= 11423 kcal/kg, NCV= 10630 Kcal/Kg
5 Kg coal contains C= 5*80/100 = 4kg
H= 5* 15/100= 0.75 Kg
O= 5*5/100= 0.25 Kg

𝟏𝟎𝟎
Mass of the Air = 𝟐. 𝟔𝟕𝑿𝟒 + 𝟖𝑿 𝟎. 𝟕𝟓 − 𝟎. 𝟐𝟓 = 71.43 kg
𝟐𝟑

𝟏 𝑶
GCV = 𝟖𝟎𝟖𝟎 %𝑪 + 𝟑𝟒𝟓𝟎𝟎 𝑯 − + 𝟐𝟐𝟒𝟎 𝑺 𝒌𝒄𝒂𝒍/𝒌𝒈
𝟏𝟎𝟎 𝟖
𝟏 𝟓
= 𝟖𝟎𝟖𝟎𝑿 𝟖𝟎 + 𝟑𝟒𝟓𝟎𝟎 𝟏𝟓 − =11423 kcal/kg
𝟏𝟎𝟎 𝟖

LCV = GCV-0.09HX587
= 11423-0.09X15X587 = 10630 kcal/kg
 Problem-2
A sample of coal was found to have the following % composition C = 75%, H = 5.2%, O =
12.1%, N = 3.2%, & ash = 4.5%. (1) Calculate the minimum amount of air necessary for
complete combustion of 1 kg of coal. (2) Also calculate the HCV & LCV of the coal sample.
Composition Composition in Combustion Weight of O2 needed for
(%) 1 kg of coal Reaction combustion of 1 kg of coal
C = 75% 0.75 C + O2  CO2 32*0.75/12 = 2 kg
H = 5.2% 0.052 H2 + ½ O2  H2O 16*0.052/2 = 0.416 kg
O = 12.1% 0.121 No Reaction -
N = 3.2% 0.032 No Reaction -
ASH = 4.5% 0.045 No Reaction -
Total O2 needed 2.416

Net O2 required = Total O2 needed – O2 present = 2.416 – 0.121 = 2.295 kg

O2 Required = 2.67* 0.75+ 8*0.052-0.121= 2.295
weight of air = 100 * Net O2 / 23 = 100 * 2.295/23 = 9.9782 kg
GCV = 1/100 [8080 %C + 34500 (%H- %O/8) + 2240% S] = 7332.1875 kcal/kg

LCV = GCV – 0.09 * H * 587 = 7057.47 kcal/kg

 Problem
Problem 3
The composition of petrol by weight was found to be C = 84% & H = 16%,
Calculate
a. Min. air required for complete combustion of 1kg of petrol.
b. Calorific value of fuel.
Problem 4
1 kg of a fuel oil has the following composition on analysis C = 90%, H =
6%, S = 2.5%, O2 = 1%, ash = 0.5%. Calculate the quantity of the air
required for the complete combustion of 1kg of fuel by weight.
Knocking
 Knocking
 In a petrol engine, combustion is triggered by a spark.
(Fuel+Air+Spark)
 Under certain temperature and pressure, the fuel can
ignite spontaneously even before sparking.
 When this happens there is a very rapid reaction occurs
to the fuel-air mixture in the engine and produces shock
waves.
 The shock waves dissipates its energy by hitting the walls
of cylinder and the piston.
 Piston strikes the wall of cylinder of Internal combustible
engine & produce hammering sound known as Knocking.
 The compression ratio at which Knocking takes place is
known as Critical Compression Ratio.
Self-Study: Compression Ratio
It is the ratio of gaseous volume ‘V1’ at the
end of suction stroke to the gaseous
volume at the end of compression stroke
‘V2’ of the piston.

𝑉1
Compression Ratio = >1
𝑉2
 Knocking
Knocking depends on

(a) Engine Design

(b) Running condition
(c) Chemical Structure of the fuel hydrocarbon

Knocking tendency depends on the chemical structure of fuel, which

decreases in the following order.
n-alkanes > mono-substituted alkanes > cyclo alkanes
> alkenes > poly substituted alkenes > aromatic
 Octane Number
Is a measure of its ability to resist knocking.

It is defined as the % of Iso-octane present in the

mixture of iso-octane & n-heptane which has same
knocking characteristic as that of fuel under test under
same set of conditions.
n-heptane knocks very
quickly hence its Octane
No. = 0

Isooctane has high

resistance to knocking
hence its Octane No. =
100
 Obtaining High Octane Compounds
• Additives
Knocking can be prevented by using a high-octane compounds
in petrol manufacture.
Methyl tert. Butyl ether (MTBE) –Octane number 118

• Conversion from low-octane to High-octane compound

– Isomerization
Pentane to 2-methyl butane

– Dehydrocyclization
Hexane to cyclohexane

– Catalytic Cracking
Large molecules breakdown into smaller ones
 Anti-knocking Agent
• Knocking of petrol reduced by adding some organo-lead compound.
Tetraethyl lead (TEL)- (C2H5)4Pb
Tetramethyl lead (MEL)- (CH3)4Pb
Mixture of TEL and MEL

• TEL and MEL produces free radicals and combine with fuels
to check the knocking
• Pb or PbO2 gets deposited on engine part and causes damage.
• If ethylene bromide is used along with TEL/MEL, PbBr2 formed in
this process is volatile it escapes into atmosphere and pollutes the
environment.
 Unleaded Petrol
Petrol whose octane number is increased without
adding lead is known as unleaded petrol.

Octane number can be increased by-

 Reforming- The process of increasing branched & aromatic

hydrocarbon in the petrol.

 Methyl tertiary butyl ether (MTBE) is added to improve the

octane number.
 Diesel Engine

air is drawn air is Compressed Fuel injected

Temp reaches to 500 0C Auto ignition
 Diesel Knocking
The combustion of the fuel in diesel engine does
not takes place instantaneously, the interval
between the start of fuel injection and attainment
of ignition temperature is called Ignition Delay.

Due to Ignition delay, accumulation of diesel in

vapour state takes place in the engine. When
ignited, an explosion takes place as a combined
effect of increased temperature. This is called
Diesel Knock.
 Cetane Number
To grade the diesel fuel, Cetane rating is employed.

It is the measure of the ease with which a fuel will ignite under
compression.

It is defined as the percentage of Cetane by volume in a mixture of

Cetane(n-hexadecane) and α-methyl naphthalene which has same
ignition properties as that of fuel under test.

Cetane α-methyl naphthalene

(Ignite Quickly) (Long Ignition Lag)
Cetane Number = 100 Cetane Number = 0
 Alternative Fuel
 Alternative fuel defines as a product that is substantially
nonpetroleum which yields energy security and environmental
benefits.
 These are non-conventional fuels. Any substance other than
conventional fuels which can be used as fuel is known as Alternative
fuel.
 Natural gas (compressed or liquefied) mainly methane,
 Liquefied petroleum gas (propane, butane)
 Hydrogen
 Coal-derived liquid fuels
 Fuels derived from biological materials
 Electricity (including electricity from solar energy)
 100% Biodiesel (B100)
 Source Gas
Biodiesel Vegetable oil, Soybean oil Liquid
animal fats, or
recycled restaurant grease
Compressed Methane Under- Gas
Natural Gas ground
(CNG) reserves
Ethanol (E85) Denatured Corn, grains, or Liquid
ethanol and agricultural
gasoline waste
Liquefied Methane that Underground Liquid
Natural Gas is cooled reserves
(LNG) cryogenically
Liquefied Propane, butane A by-product of Liquid
Petroleum petroleum
Gas (LPG) refining or
natural gas
processing
Methanol Methanol and Natural gas, Liquid
(M85) gasoline coal, or woody
biomass
 ALTERNATIVE FUEL VEHICLES
Biodiesel Ethanol Methanol
LNG LPG
(B20) CNG Electricity (E85) Hydrogen (M85)
Any vehicle Many types of Electric Light-duty No vehicles are Medium and Light-duty Mostly Heavy-
that runs on vehicle classes. vehicles, vehicles, available for heavy-duty vehicles, which duty buses are
diesel also bicycles, light- medium and commercial trucks and can be fueled available.
compatible duty vehicles, heavy-duty sale yet buses. with propane
with up to 20% medium and trucks and or gasoline,
blends. heavy-duty buses medium and
trucks and heavy-duty
buses. trucks and
buses that run
on propane.
 Biodiesel
Biodiesel is a alternative, renewable and biodegradable fuel
derived from vegetable oils, animal fats and Soybeans
having same vehicular performance as Diesel.

Biodiesel can also be used in its pure form but it may

require certain engine modification to avoid maintenance
& performance problem.

Its not suitable for winter time use.

 Biodiesel
A typical molecule of biodiesel looks like the structure below.

Biodiesel

Mostly it is a long chain of carbon atoms, with hydrogen atoms

attached, and at one end is what we call an ester functional group

Diesel
Biodiesel-Synthesis

Vegetable Oil Triglycerides

 Biodiesel-Synthesis
Biodiesel can be produced by the base transesterification of
vegetable oil, palm oil, sunflower oil, cotton oil etc.
Triglyceride present in these oils on reaction with methanol in the
presence of catalyst yield monomethyl esters or monoethyl ester of
long chain fatty acid & glycerol.
The mixture is allowed to settle so that the glycerol
being heavy will settle down at the bottom and its
separated by gravity separation method.

Excess amount of methanol is separated by fractional

distillation by flash evaporation method.

Biodiesel has low toxicity, high flash point, don’t emit

SO2 .
Process flow diagram of Biodiesel production
Advantages of Biofuels
Advantages of Biofuels
Thank you!