VARDHAMAN COLLEGE OF ENGINEERING, HYDERABAD

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MODULE IV: ENERGY SOUCES

Introduction:

 Energy is a part of life. Better energy sources are status symbol of country.
 A fuel is a substance which provides energy on combustion for industry and domestic
purposes.
 The combustion is the process of oxidation that provides heat energy with light.
 Every combustion is an oxidation but every oxidation is not combustion.
Ex: combustion of wood, petrol, kerosene gives heat energy.

oxidation
Fuel ----------------- heat energy + light + combustion products (CO2 + H2O etc.)

Fuels and Classification of Fuels:

Fuels are broadly classified as Primary fuels (or) natural fuels and Secondary fuels (or) artificial
fuels.
Fuels

Primary fuels (or) natural fuels secondary fuels (artificial fuels)

The natural and artificial fuels can be further classified based on the state of fuels:

Primary fuels (or) natural fuels

Solid fuels liquid fuels gas fuels

Ex: wood petroleum natural gas

Secondary fuels (or) artificial fuels

Solid fuels liquid fuels gas fuels

Ex: charcoal petrol, diesel etc L.P.G, C.N.G etc

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Comparisons among Solid, Liquid and Gaseous Fuels:

Solid fuels liquid fuels gaseous fuels

1. Slow combustion and easy 1. Quick combustion and 1. Combustion is rapid and
to control it. cannot be controlled. burning can be controlled.
2. Transportation is difficult. 2. Transportation is easy 2. Transportation is easy
through pipe lines. through pipe line and
3. Storage is safe. 3. There is risk in storing containers.
4. Calorific value is 4. Calorific value is 3. There is risk in storing
comparatively low. comparatively higher. 4. Calorific value is
5. Slow combustion. 5. Quick combustion. comparatively highest.
6. More ash content. 6. No ash content. 5. Very fast combustion.
7. Causes more pollution. 7. Least pollution. 6. No ash content.
8. More oxygen is required for 8. Less oxygen is required for 7. Least pollution.
combustion. combustion 8. Least oxygen is required for
9. It cannot be used as fuels in 9. Mainly used in vehicles as combustion.
vehicles (but coal is used as fuel. 9. Mainly used in vehicles as
fuel in trains). fuel.

Characteristics of Good Fuel:

 It should possess high calorific value and naturally carbon content.
 It should have lower moisture content as well as lower volatile matters since these will
affect heating value of the fuel.
 It should possess low ash content since the ash formation will affect the heating value of
the fuel.
 It should be easily transportable, otherwise cost of fuel will increase.
 It must have high calorific value.
 It must have moderate ignition temperature. Low (burning)/ignition temperature can
cause fire accident. (ignition temperature is the lowest temperature to which the fuel
must be pre – heated for a smooth burning process).
 It should not give poisonous gasses after combustion.
 Its handling should be easy.
 It should not burn spontaneously to avoid fire hazards.
 Combustion of good fuel can be easily controlled.
 It should be cheap.
 It should be easily available.

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Calorific Value:
The Calorific value of the fuel can be defined as the total quantity of heat liberated when a unit
mass of the fuel is completely burnt in air or oxygen.
The calorific value is measured in several units of heat; they are calorie, kilo calorie, British
Thermal Unit (B.T.U) and centigrade Thermal Unit (C.T.U).
1 k.cal = 1000 cal = 3.968 BTU = 2.2 CHU
1 cal =4.18 joule (joule is also unit of energy).

There are two types of calorific values of a fuel:

Gross Calorific Value (GCV) (Or) High Calorific Value (HCV):

Gross (or) higher calorific value (HCV) is defined as the total amount of heat produced when
unit mass/ volume of the fuel has been burnt completely and products of combustion have
been cooled to room temperature & reused.
Net calorific value (NCV) (or) low calorific value (LCV):
Net (or) low calorific value is the net (or) actual heat produced when unit mass/ volume of the
fuel is completely burnt and the products are permitted to escape i.e. HCV includes the latent
heat of water (587 k.cal/kg).

Relationship between HCV & LCV:

LCV = HCV – Latent heat of water vapour formed.
 Since 1 part by mass of hydrogen produces 9 parts by mass of water as given by
the equation below.
H2 + ½ O2 ----------------------- H2O

LCV = HCV – mass of hydrogen Χ 9 Χ latent heat of water vapour formed.

𝐇
LCV = HCV – 9 Χ Χ587
𝟏𝟎𝟎
LCV = HCV – 0.09 Χ H Χ 587
Where H is the % of hydrogen in the fuel.

 Dulong proposed a formula for the calculation of the calorific value from the
chemical composition.

𝟏 𝐎
I.e. HCV = (8080 C+ 34,500 (H- ) +2240 S) K cal/kg
𝟏𝟎𝟎 𝟖

(c – carbon, H – hydrogen, O – oxygen, S – Sulphur are percentages of these elements in

coal.)

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1. Calculate the gross and net calorific value of a coal sample having the following
composition
C = 80 %, H = 7 %, O = 3 %, S = 3.5 %, N = 2 %, and ash = 5 %.

Solution: GCV (or) HCV = [8080 C + 34,500 (H- ) +2240 S]

= [8080 Χ 80 + 34,500 (7- ) +2240 Χ3.5]
= 8828 k.cal / kg
NCV (or) LCV = GCV – 0.09 Χ H Χ 587
= 8828 – 0.09 Χ 7 Χ587 = = 8458 k.cal / kg

2. Calculate the gross and net calorific value of a coal sample having the following
composition
C = 85 %, H = 8 %, S = 1 %, N = 2 %, and ash = 4

Solution: GCV (or) HCV = [8080 C + 34,500 (H- ) +2240 S]

= [8080 Χ 85 + 34,500 (8- ) +2240 Χ1]
= [6,86,800 + 2,76,000 +2240]
= [6868 + 2760 +22.4]
= 9650.4 K cal/ kg
NCV (or) LCV = GCV – 0.09 Χ 8 Χ 587
= 9650.4 – 0.09 Χ 8 Χ587
= 9650.4 – 422.64 = 9227.76 kcal/kg

3. On analysis, a coal sample has the following composition by weight; C = 85 %, O = 3

%, S = 0.5% and ash = 3 %. Net calorific value found to be 8400 k cal/kg. calculate the
percentage of hydrogen and gross calorific value of coal
Solution:
GCV= [NCV + 0.09H Χ587] kcal/kg
= [8400+ 0.09H Χ587] kcal/kg
= [NCV + 52.8 H] kcal/kg---------------(1)

GCV (or) HCV = [8080 C + 34,500 (H- ) +2240 S] kcal/kg

= [8080 Χ 85 + 34,500 (H- ) +2240 Χ0.5]
= [686800 + 34500H – 12937.5 +1120]

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= [6868 + 345H – 129.37 +11.2]

=6749.8+345 H kcal/kg------------- (2)
From (1), (2)
6749.8+345 H = 8400+52.8 H
345H -52.8H = 8400-6749.8
292.2H =1650.2
H = 5.647
% of H = 5.647 -------------------(3)

From (1), (3)

GCV = (8400+(52.8 Χ5.647))= 8698.16kcal/kg

SOLID FUELS:

 The main solid fuels are wood, peat, lignite, coal and charcoal.
 In addition to these certain agricultural and industrial wastes such as rice husk, coconut
and nut shells etc. employed as fuels.
/
Wood > coal
 Wood contains higher carbon percentage in the form of cellulose, lingo – cellulose, they
are transformed into the form of coal.
Dry wood has composition as Carbon ⇒ 40 – 50 %
Oxygen ⇒ 42 – 44 %
Hydrogen ⇒5 – 6 %
 The calorific value of wood is 4000 – 4500 k.cal / kg
 Wood can be converted into a charcoal is used as adsorbent of gasses and for
decolourisation of cane sugar.
Wood ----- peat --------lignite ------------- bituminous --------- anthracite

Coal, Analysis of Coal:

The analysis of coal is helpful in its ranking. The assessment of the quality of coal is carried
out by two types of analysis.
1. Proximate analysis
2. Ultimate analysis

Proximate Analysis: Proximate analysis is the simplest form of analysis of coal and gives
information which is useful in the practical utilization of coal. In this analysis, the percentage of

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carbon indirectly determined and includes percentage of moisture, volatile substance and ash
content.
a. Moisture content: A known mass of finely powdered coal is taken in a crucible. It is
heated up to 1100c for an hour and cooled to room temperature in desiccators. The
moisture is removed as water vapour and the process is repeated till the constant
weight is obtained.
𝐥𝐨𝐬𝐬 𝐢𝐧 𝐰𝐞𝐢𝐠𝐡𝐭 𝐨𝐟 𝐜𝐨𝐚𝐥
Percentage of moisture = Χ100
𝐰𝐞𝐢𝐠𝐡𝐭 𝐨𝐟 𝐜𝐨𝐚𝐥
Significance:
 High percentage of moisture content is undesirable.
 It increases the transport costs and reduces the calorific value.
 Considerable amount of heat is wasted in evaporating the moisture during combustion.

b. Volatile matter: the above sample (moisture free coal) taken and heated at 950 0c in the
absence of air for 7 minutes. It is then cooled to room temperature and weighed. The
loss of weight is noted as volatile matter and is removed from coal at 950 0c.

𝐥𝐨𝐬𝐬 𝐢𝐧 𝐰𝐞𝐢𝐠𝐡𝐭 𝐝𝐮𝐞 𝐭𝐨 𝐫𝐞𝐦𝐨𝐯𝐚𝐥 𝐨𝐟 𝐯𝐨𝐥𝐚𝐭𝐢𝐥𝐞 𝐦𝐚𝐭𝐭𝐞𝐫

Percentage of volatile matter = Χ100
𝐰𝐞𝐢𝐠𝐡𝐭 𝐨𝐟 𝐜𝐨𝐚𝐥

Significance:
 A coal containing high volatile matter
 Burns with long flame.
 High smoke
 Low calorific value.

c. Ash content: coal, free from moisture and volatile matter is heated in a crucible at 700 –
7500c for half an hour. It undergoes cooled to room temperature and weighed.
𝐦𝐚𝐬𝐬 𝐨𝐟 𝐚𝐬𝐡
Percentage of ash = Χ100
𝐦𝐚𝐬𝐬 𝐨𝐟 𝐜𝐨𝐚𝐥
Significance:
 Reduces the calorific value of coal.
 Decreasing the efficiency.
 Increases transporting, handling, storage and disposal costs.
 Hence lesser the % of ash the better is the quality of coal.

d. Fixed carbon: Fixed carbon means the quantity of carbon in coal that can be burnt by a
primary current of air drawn through the hot bed of fuel. The sum (total) of the
percentages of moisture, volatile matter and ash subtracted from 100 gives the fixed
carbon.
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= 100 – (% of moisture + % of volatile matter + % of ash)

Significance:
 The higher the fixed carbon in a coal, the greater is the calorific value.

Ultimate Analysis: This is the elemental analysis and often called as qualitative analysis of
coal. This analysis involves the determination of carbon and hydrogen, nitrogen, sulpher and
oxygen.

a. Determination of carbon and hydrogen:

 A known mass of coal is taken and burnt in a steam of pure oxygen in a combustion
apparatus. The carbon changes to CO2 and hydrogen changes to H2O.
 The vapors of CO2 and H2O are taken passed through KOH and CaCl2.
 The CO2 absorbed by KOH in the tube while H2O is absorbed by CaCl2. Because of the
absorption the weight of KOH and CaCl2 increases, which is then measured.

C + O2 ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ CO2
12 44
H 2 + ½ O2 ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ H2O
2 18

KOH + CO2 K2CO3 + H2O

𝐢𝐧𝐜𝐫𝐞𝐬𝐞 𝐢𝐧 𝐰𝐞𝐢𝐠𝐡𝐭 𝐨𝐟 𝐊𝐎𝐇 𝟏𝟐

Percentage of carbon = Χ Χ 100
𝐰𝐞𝐢𝐠𝐡𝐭 𝐨𝐟 𝐜𝐨𝐚𝐥 𝟒𝟒
𝐢𝐧𝐜𝐫𝐞𝐬𝐞 𝐢𝐧 𝐰𝐞𝐢𝐠𝐡𝐭 𝐨𝐟 𝐂𝐚𝐂𝐥𝟐 𝟐
Percentage of hydrogen = Χ Χ 100
𝐰𝐞𝐢𝐠𝐡𝐭 𝐨𝐟 𝐜𝐨𝐚𝐥 𝟏𝟖
Significance: The higher the percentage of carbon and hydrogen the better is the quality of coal
and higher the calorific value.

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b. Nitrogen percentage:
 Nitrogen is determined by the kjeldahl method. About 1 gm of finely powdered
coal sample with K2SO4 (catalyst) and conc.H2SO4. Nitrogen in coal converted to
(NH4) SO4.

The Kjeldahl method is divided into three main steps. The method has to be carried out in
proper sequence. The steps include digestion, distillation, and titration.
1. Digestion: In this method, a certain substance or sample is heated in the presence of
sulphuric acid. The acid breaks down the organic substance via oxidation and reduced
nitrogen in the form of ammonium sulphate is liberated. Potassium sulphate is usually
added to increase the boiling point of the medium. Catalysts like mercury, selenium,
copper, or ions of mercury or copper are also used in the digestion process. The sample
is fully decomposed when we obtain a clear and colourless solution.

2 N2 + 3 H2 + H2SO4 -------------------- (NH4)2SO4.

2. Distillation: The distillation of the solution now takes place and a small quantity of
sodium hydroxide is added to convert the ammonium salt to ammonia. The distilled
vapours are then trapped in a special trapping solution of HCl (hydrochloric acid) and
water.

(NH4)2 SO4 + 2 NaOH ------------------- 2 NH3 + Na2SO4 + 2 H2O

3. Titration: The amount of ammonia or the amount of nitrogen present in the sample is
then determined by back titration. As the ammonia dissolves in the acid trapping solution
some HCl is neutralized. The acid that is left behind can be back titrated with a standard
solution of a base such as NaOH or other bases.
NH3 + H2SO4 -------------------- NH4)2SO4.

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Formula for Calculation:

𝐯𝐨𝐥𝐮𝐦𝐞 𝐨𝐟 𝐇𝐂𝐥 𝚾 𝐧𝐨𝐫𝐦𝐚𝐥𝐢𝐭𝐲 𝐨𝐟𝐇𝐂𝐥 𝟏𝟒
Percentage of Nitrogen = Χ Χ 100
𝐰𝐞𝐢𝐠𝐡𝐭 𝐨𝐟 𝐜𝐨𝐚𝐥 𝟏𝟎𝟎𝟎

Significance: Nitrogen has no significance.

c. sulpher percentage : Sulpher is estimated gravimetrically in terms of BaSO4

S +2 O2 + 2 e- ------------------- SO42-
SO42- +BaCl2 -----------------BaSO4 + 2 Cl-

𝐰𝐞𝐢𝐠𝐡𝐭 𝐨𝐟𝐁𝐚𝐒𝐎𝟒 𝟑𝟐
Percentage of sulpher = Χ Χ 100
𝐰𝐞𝐢𝐠𝐡𝐭 𝐨𝐟 𝐜𝐨𝐚𝐥 𝟐𝟑𝟑

Significance:
 increase calorific value
 SO2, SO3 have corrosive effect on equipment and cause air pollution

d. Ash content: The coal sample is ignited and the weight of ash is measured at room
temperature.
𝐰𝐞𝐢𝐠𝐡𝐭 𝐨𝐟 𝐚𝐬𝐡
Percentage of ash = Χ 100
𝐰𝐞𝐢𝐠𝐡𝐭 𝐨𝐟 𝐜𝐨𝐚𝐥

e. Oxygen percentage: The % of oxygen is determined by subtracting the sum of

percentage of C, H, S and ash from 100.
Percentage of oxygen = 100 – (% of C + H + N + S + ash)
Significance:
 High oxygen content
 High inherent moisture
 Low calorific value

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LIQUID FUELS:

 Petroleum is one of the best primary liquid fuels. It is also known as crude oil. Petrol,
diesel, kerosene are main liquid fuels. They are secondary fuels derived from petroleum.
 The word meaning of petroleum is rock oil (petra = rock , oleum = oil), it is a mixture of
number of hydrocarbons (paraffines, olefins, aromatics and naphthalene), nitrogen,
sulpher, oxygen contain practically active compounds along with traces of compounds
of heavy metals like Fe, Co, Ni and V.
 Composition of petroleum is
C = 79.5 – 87.1 % , H2 = 11.5 – 14.8, S = 0.1 % N2 &O2 = 0.1 – 0.5%

Classification and Theories of Petroleum

There are mainly three types of Petroleum.
1. Paraffinic base type crude oil mains consist of the saturated hydrocarbons from CH 4 to
C35H72 and littile naphthalene and aromatics.
2. Asphaltic – base type crude mainly consists cyclo paraffins, naphthalenes and aromatics.
3. Mixed – base crude mainly consists both paraffins and asphaltic hydrocarbons.

Refining Of Crude Oil (Petroleum):

 The crude oil as impure i.e. a lot of soluble and insoluble impurities are present.
 Refining can be defined as the process by which petroleum is made free of impurities,
division of petroleum into different fractions having different boiling pints and their
further treatment to impart specific properties. Refining of petroleum is done in
different stages.
1. Separation of water (Cortell process):
 The crude oil will always mix with the brine water forming emulsions. The crude oil is
allowed to flow through two highly charged electrodes.
 The colloidal emulsion of oil and water separates out to larger water areas which
separated from the oil.

2. Removal of harmful sulpher compounds:

After the removal of water the oil is treated with copper oxide. The copper sulphide can
be separated out by filtration.

3. Fractional distillation:
 The crude oil or crude petroleum is heated to about 400 0c in an iron retort where all
volatile constituents evaporate except the asphalt residue.
 The fractionating column is a tall cylindrical tower containing a number of horizontal
stainless steel tray one over another of a fixed distance.

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 Each tray is provided with short chimney covered with loose cap. As the vapors go
up they touch chimney cap and get condemned at different heights of the trays.

The lower boiling fractions can travel more height without getting condensed even at the
lower trays. The different fractions obtained at different trays,
They are:
Petroleum ether (C5 – C7): It is the highly volatile lower molecular weight and its boiling
range is between 30 – 700c, it is mainly used as solvent.
Gasoline or petrol (C5 – C9): The boiling range of this fraction is between 40 – 120 0c. its
approximate composition is C = 84 %, H = 15 % , N + S + O = 1 %. It has a calorific value
11250 k.cal/ kg it is highly volatile and mainly used in internal combustion engines. Most
of the automobiles making use of this fuel only.
Solvent naphtha (C9 – C10): The boiling range of this fraction is between 120 – 1800c. It is
mainly used as solvent in various industries.
Kerosene (C10 – C16): the boiling range of this fuel is between 180 – 2500c. Its calorific
value is 1,100 k.cal/ kg. It does not vaporize easily. It is mainly used as domestic fuel in
stoves and lamps. It is also jet engine fuel and for making oil gas.
Diesel oil (C15 – C16): The boiling range of this fuel is between 300 – 3500c. It is used as
fuel in ships and used in metallurgical furnaces.
Heavy oil or residual oil (C18 –C30): The boiling range of this fuel 350 – 4000c. It is used a
fuel for ships and used in metallurgical furnaces. Heavy oil on further fractionation gives;
i) Lubricating oil ii) paraffin wax iii) Petroleum jelly (Vaseline)
iv) Greases.

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Cracking of Fuels:
Cracking is the process of conversion of bigger hydrocarbon molecules into smaller
hydro carbons of lower molecular weights.
Small saturated hydro carbons
Higher hydro carbons (saturated) > +
/
Small unsaturated hydro carbon
C12H26 ⎯⎯⎯⎯ C7H16 + C5H10
Alkane alkene
The process of cracking is mainly of two types.
1. Thermal Cracking: In this process heavier hydrocarbon molecules are converted into
light hydrogen – rich molecules at higher temperature.
2. Catalytic Cracking: In this process heavier hydrocarbon molecules are converted into
light hydrogen – rich molecules in the presence of catalyst.
Catalytic cracking is also of two types.
Fixed – bed cracking 2. Fluid – bed (moving - bed) cracking.

Fluid – bed (moving - bed) cracking:

In fluidized-bed catalytic cracking, the finely divided catalyst is kept agitated by gas
streams (feed stock vapour) so that it can be handled like a fluid system i.e., it can be pumped
as a true liquid. The advantage of fluidized-bed cracking process is that a high degree of mixing
is achieved and consequently a good contact is established between the catalyst and the feed
stock vapours. This results in a higher yield. The regeneration of the inactive catalyst can be
carried out continuously without interrupting the production of gasoline unlike in fixed-bed
cracking method.

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Process:

 The finely divided catalyst bed (Al2O3 + SiO2) is fluidized by the upward passage of feed
stock vapours (Heavy oil, gas oil, etc) in a cracking chamber (called Reactor) maintained
at 5500 C.
 Near the top of the reactor , there is a centrifugal separator (called cyclone), which
allows only the cracked oil vapours to pass onto the fractionating column but retains the
catalyst powder in the reactor itself.
 The catalyst powder gradually becomes heavier due to the deposition of carbon and
settles to the bottom, from where it is forced by an air blast to the regenerator
(maintained at 6000 C).
 After cracking, the products are fractionated into gases, gasoline, gas oils and residual
oils (unconverted).
 The heavier oil fractions may be cracked in a second-stage cracking, thereby increasing
the overall yield of the cracked products.
 In regenerator, the spent catalyst is stripped of the adsorbed oil by passing steam and
then decarbonized by a hot air blast, under controlled conditions.
 The heat liberated during this regeneration is used to raise steam and to preheat the
catalyst.

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Knocking:

The efficiency of engine depends on the compression ratio.

Compression ratio =
.

 Compression ratio is directly proportional to efficiency of an engine. More the CR, better
will be engine, CR depends on the type of constituents in the gasoline.
 Compression in the cylinder produces shock waves, it results in rattling sound in the
engine called knocking and knocking decreases the efficiency of engine.
 The tendency of knocking depends on the chemical structure of hydrocarbons.
Ease of combustion reaction:
Aromatic > olefins > cyclo alkenes > chain
Knocking: chain > cyclo alkenes > olefin > aromatic
Knocking is measure of octane number. Hence,
For n – heptanes, octane number = 0
Iso octane, octane number = 100
 The anti-knocking value of fuel can be increased by adding tetra ethyl lead (TEL). The
oxides of lead formed as combustion products inhibits free radical chain reaction
responsible for knocking.
 Small quantity of methyl cyclo penta dienyl manganese tetra carbonyl is also used in
Canada & European countries in place of TEL which also results in Mn pollution in air &
soil.
Prevention of Knocking: To improve the antiknock value of the petrol sample, Tetraethyl
lead (TEL) and diethyl telluride [(C2H5)2Te] are added
Octane number (or) octane rating:

 The maximum knocking is from n – heptanes and hence its octane number is zero, while
iso octane knocks minimum (0) its octane number has been given 100.
 Hence octane number of gasoline is the % of iso octane in the mixture of iso octane and
n – heptanes. Therefore octane number 60 of a gasoline sample means
 The mixture contains 60 % iso octane & 40 % n – heptanes.
 Gasoline has higher octane number, lower knocking.
 The cetane number decreases in the following order.

Aromatic > olefins > cyclo alkenes > chain

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Cetane number (or) Cetane rating:

 Cetane number is a measure of the ignition value of a diesel fuel.
 It is introduced to express the knocking characteristics of diesel.
 Cetane has a very short ignition lag and hence its cetane number is taken as 100.
 On the other hand 2-methyl naphthalene has a long ignition lag and hence its cetane
number is taken as zero.
 The percentage of hexa decane present in a mixture of hexa decane and 2-methyl
napthalene, which has the same ignition lag as the fuel under test".
 The cetane number decreases in the following order.
n-alkanes > Cycloalkanes > alkenes >branched alkanes >aromatics

Cetane(n-hexa decane)
Cetane Number = 0

Octane Number Cetane Number

1. Performance indicator of petrol or

1. Performance indicator of diesel
gasoline

2. Delay self ignition of fuel 2. Speed up ignition of fuel

3. Percentage of iso-octane is the 3. Percentage of nhexacetane is the

benchmark benchmark

4. Fuel with high octane number has 4. Fuel with high cetane number has low
low cetane number octane number

5. Octane number of petrol can be 5. Cetane number diesel can be increased

increased by adding benzene or by adding by adding ethyl nitrate or
toluene acetone peroxide

6. Octane number for good petrol 6. Cetane number for good diesel is about
should be about 85-90 45-50

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SYNTHETIC PETROL:
Petrol is mainly obtained from crude oil from oil wells but can also be obtained by synthetic
processes.

1) Fisher – tropsch process 2) Bergius process

Fisher – Tropsch process:

 In this process water gas (CO + H2) is mixed with hydrogen gas (H2) in the presence of
catalyst maintaining a temperature of about 200 – 300 0c and pressure of about 5 – 25
atm.
 The catalyst used consists of mixture of 100 parts Co, 5 parts Ni, 8 parts MgO and 200
parts kieselguhr earth.
n CO + 2n H2 ------------------ CnH2n + n H2O
n CO + (2n +1) H2 ------------------ CnH2n+1 + n H2O
CO + H2o ------------------ CO2 + H2

 First the water gas & hydrogen gas mixture is purified by Passing through Fe 2O3 and
Fe2O3 + Na2CO3.
 After that the pressure is maintained to 5 -25 atm and passed through the converter
where the catalyst and temperature are maintained 200 – 300 0c.
 in the converter the polymerization takes place and the hot gasses are passed
through a cooler where the crude oil is produced.
 The crude oil is fractioned in a fractionating column and gasoline fraction is
produced in the top fraction.
 The high boiling heavy oil is obtained at the bottom can be used for cracking to get
more gasoline.

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GASEOUS FUELS.

Gaseous fuels are classified into two types.

 Primary fuels: Ex: natural gas
 Secondary fuels: Ex: coal gas, producer gas, water gas, oil gas etc.
Natural gas:
Natural gas always found above the oil in the oil wells. It can be found under earth
without any liquid petroleum below it natural gas which is known as fire damp.
Composition of natural gas: (methane) CH4 = 88.5 %
(ethane) C2H6 = 5.5 %
(propane)C3H8 = 3.7 %
(butane) C4H10 = 1.8 %
Pentane, H2, CO, CO2 and higher hydrocarbons ⇒0.5 %
The calorific value of natural gas 8000 – 1400 k.cal / m3
Applications:
 It is an excellent domestic fuel which can carry to long distances in pipelines as town
gas U.S, U.K And Mumbai.
 It is also an industrial fuel.
 It also used for manufacturing of chemicals like CH3OH, carbon black, HCHO etc.
 Natural gas also used as a source of H2 gas.
Hence ammonia can be made by reacting N2 with H2 (H2 obtaining from natural gas).

Liquefied Petroleum Gas (LPG):

 LPG is also known as autogas because it is used as a fuel in automobiles.

 LPG is a mixture of hydrocarbon gases and is flammable. It has a high heating value and
is therefore popular in the heating industry as well.
 Liquid petroleum gas is very flammable
 LPG has a high calorific value and, therefore, is best suited for cooking purposes.

Chemical Composition:
 The main constituents: n – butane, iso butane, butylene and propane, negligible
amount of propene & ethane.
Characteristics:
 LPG is obtained as byproduct during refining of crude oil or from natural gas
 It mainly contains n-butane, isobutane, butylene and propane
 It has high calorific value: 27800 kcal/m3
 It gives less CO and least un-burnt hydrocarbons. So, it causes least pollution
 It gives moderate heat which is very useful for cooking

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 It has a tendency to mix with air easily

 Even though it is toxic, on combustion it gives no toxic gases
 It neither gives ash or smoke content
 It is cheaper than gasoline. Hence used as motor fuel
 It is dangerous when leakage is there. It is highly knock resistant
 LPG is used as domestic fuel and as a fuel in internal combustion engines
 It is used as fuel in some industries

Applications:
 LPG is used in various sectors like health, industrial, construction, transportation, and
residential use.
 It is used for cooking because it is cheaper than other fuels and thus makes it beneficial
economically. In many countries, it’s commonly used for domestic cooking.
 Liquid Petrol Gas is used for heating purposes. People use electricity, kerosene, or
natural gas to heat their homes, but LPG is a great alternative.
 LPG is also used as dual fuel in many new technologies to produce heat and electricity,
like in CHP (combined heat and power) systems.
 Liquid petroleum gas is used as a vehicle fuel, hence it gets the name “autogas.” In
comparison with petrol, LPG burns cleaner and is more economical. It has some
problems. It is not as efficient as other fuels used in cars, so it is not as popular. But still,
there are some modified cars in which Liquid Petrol gas acts as a bi-fuel and can be used
in conjunction with petrol.
 It is also used in refrigeration applications as a refrigerant.

Compressed Natural Gas: (CNG)

 It is a fuel gas as Petrol/Diesel.

 When natural gas compressed at 100 atm pressure (or) cooled to -165 0C converted into
C.N.G.
 Natural gas offers a lower risk in the case of a leak, as compared to other liquid.
 Naturally occurring natural gas was discovered and identified in 1626, America. William
Hart, in 1821 dug the first successful natural gas well in New York, U.S.

Characteristics:

 CNG is odorless, tasteless and non-toxic, and made up of methane, nitrogen, carbon
dioxide, propane, and traces of ethane.
 Methane is the main component in CNG.
 It is an environmentally clean alternative fuel.
 CNG provides less risk in case of leakage, as it dispenses fast in the air.
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 CNG has an energy density of 53.6 MJ/kg (or) 9 MJ/L.

 The gas has a high calorific value because it is free of any kind of toxicity.
 It is a highly combustible gas and a fossil fuel. It has a low flammability range and high
ignition temperature.

Applications:

 As you already know CNG is widely used by the transportation sector for powering cars,
trains, ships, and other vehicles.
 The gas is used by end consumers for cooking and heating.
 Dryers use CNG for drying clothes. It is 50% more cost-effective than electricity.
 Some countries also use CNG for generating electricity.
 Manufacturing a huge range of chemicals like acetic acid, ammonia, methanol, butane,
propane, ethane, etc. Even fertilizers are made using CNG.
 It is heavily used as chemical feedstock for manufacturing plastic and other
commercially important organic chemicals.
 CNG is used in the production of glass, fabric, steel, paint, etc.
 Protein-rich animal and fish feed is produced by feeding CNG.

Biodiesel:

 Biodiesel is a renewable and clean-burning fuel that is made from waste vegetable oils,
animal fats, or recycled restaurant grease for use in diesel vehicles.
 Biodiesel produces less toxic pollutants and greenhouse gases than petroleum diesel.
 It can be used in pure form (B100) or can be blended with petro-diesel in the form of B2
(2% biodiesel, 98% petroleum diesel), B5 (5% biodiesel, 95% petroleum diesel), B20
(20% biodiesel, 80% petroleum diesel) and B100 (pure biodiesel).

Chemistry of biodiesel production: Transesterification:

 The process takes place in the following steps.

 The first step is to mix the alcohol for reaction with the catalyst, typically a strong base
such as NaOH or KOH.
 The alcohol/catalyst is then reacted with the fatty acid so that the transesterification
reaction takes place.

Preparation of the catalyst with the alcohol:

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 Methanol and base are combined; NaOH separates into ions in methanol.
 The OH- reacts with the H+ of methanol to take H2O, leaving OCH3- to react with fatty
acid.

 The catalyst is prepared by mixing methanol and a strong base such as sodium
hydroxide or potassium hydroxide.
 During the preparation, the NaOH breaks into ions of Na+ and OH-. The OH-
abstracts the hydrogen from methanol to form water and leaves the CH3O-
available for reaction.
 Methanol should be as dry as possible.
 When the OH- ion reacts with H+ ion, it reacts to form water.
 Water will increase the possibility of a side reaction with free fatty acids (fatty
acids that are not triglycerides) to form soap, an unwanted reaction.
 Enzymatic processes can also be used (called lipases); alcohol is still needed and
only replaces the catalyst.
 Lipases are slower than chemical catalysts, are high in cost, and produce low
yields.
 The triglyceride will react with 3 mols of methanol, so excess methanol has to be
used in the reaction to ensure complete reaction.
 The three attached carbons with hydrogen react with OH- ions and form
glycerin, while the CH3 group reacts with the free fatty acid to form the fatty acid
methyl ester.
 Glycerol is formed and has to be separated from the biodiesel. Both glycerol and
biodiesel need to have alcohol removed and recycled in the process.
 Water is added to both the biodiesel and glycerol to remove unwanted side
products, particularly glycerol, that may remain in the biodiesel.
 The wash water is separated out similar to solvent extraction (it contains some
glycerol), and the trace water is evaporated out of the biodiesel. Acid is added to
the glycerol in order to provide neutralized glycerol.

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Schematic of the biodiesel process using trans esterification:

Advantages:
 Produced from Renewable Resources
 Can be Used in existing Diesel Engines
 Less Greenhouse Gas Emissions
 Grown, Produced and Distributed Locally
 Biodegradable and Non-Toxic
 Positive Economic Impact
 Reduced Foreign Oil Dependence
 More Health Benefits

Disadvantages:
 Variation in Quality of Biodiesel
 Not Suitable for use in Low Temperatures
 Food Shortage
 Increased use of Fertilizers
 Water Shortage
 Fuel Distribution
 Slight Increase in Nitrogen Oxide Emissions

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