ii.

Chemical Energy Sources

Introduction to energy: Energy is an important aspect of human activity. A

large number of energy sources such as animal waste, firewood, coal, oil etc.
are now available. As these sources are depleting in nature. After some
years the availability of fossil fuels may come to an end. Hence scientists
and engineers have been trained to develop new sources of energy
alternative to fossil fuels. Solar energy and nuclear energy are possible
alternatives which can replace fossil fuels.
Fuels:
Definition: A substance which is used to produce heat, light and electricity
by combustion is called a fuel.
Classification of fuels: Chemical fuels are classified into two types whether
they are in solid, liquid or gaseous state.
a) Primary fuels: The naturally occurring fuels are called primary fuels.
b) Secondary fuels: Artificially prepared fuels are called secondary
fuels.
State Primary Secondary
Solid Coal, wood, peat Charcoal, Coke etc.,
lignite, bituminous
coal
Liquid Petroleum Petrol, diesel, kerosene, alcohol,
LPG
Gas Natural gas Bio gas, water gas (CO + H2),
Producer gas (CO+ N2),
Coal gas
Importance of Hydrocarbons as fuels: The petroleum is a complex mixture of
hydrocarbons. The hydrocarbons may vary from low molecular weight into
high molecular weight. Crude petroleum is a mixture of alkanes, alkenes,
alkynes, cycloalkanes, aromatic hydrocarbons along with a small percentage
of heterocyclic compounds. Some of hydrocarbons present in the liquid
fuels are as follows:
Hydrocarbons Examples
Alkanes Methane, ethane, propane, butane etc.,
Alkenes Ethane, propene, butane, etc.,
Cycloalkanes Cyclo propane, cyclo butane etc.,
Aromatic hydrocarbons Benzene, toluene etc.
Heterocyclic compounds Pyridiene, thiopene, pyrol etc.

Calorific value of a fuel:

Definition: The quality of a fuel is expressed in terms of calorific value.
Calorific value is defined as the total quantity of heat produced when unit
mass or unit volume of the fuel is burnt completely in the presence of excess
of air or oxygen.
Units of calorific value:
(a)Calorie: It is the amount of heat required to rise the temperature of 1 gm
of water through 1° C. In SI units, calorific value is expressed in Joule
1 calorie = 4.183 J
(b) British thermal unit: It is the amount of the heat required to rise the
temperature of one pound of water by 1° F. It is called British system unit.
1 BTU = 252 cal.
(c) Centigrade Heat Unit (CHU): It is the quantity of heat required to rise the
temperature of 1 pound of water 1° C.
1 K cal = 2.2. CHU
Types of calorific value: Calorific value have been classified into 2 types
1) Gross calorific value
2) Net calorific value
1. Gross calorific value [higher calorific value, HCV or GCV]:
Chemical fuels usually contain H2. During combustion H2 present in the
fuel is converted into steam during the determination of calorific value in the
bomb calorimeter. Steam is condensed to H2O in the bomb calorimeter and
hence the latent heat of steam gets included in the measured quantity of heat.
Therefore Calorific value will be a little higher than the normal value.
Hence it is called Gross Calorific value.
Gross calorific value is defined as the quantity of heat produced when 1
gm of fuel is burnt completely and the products of the combustion are cooled
to room temperature.
2. Net calorific value (Lower calorific value, NCV or LCV):
During the actual use of fuel combustion products are not condensed to
room temperature. Water vapour etc. are allowed to escape into the
atmosphere along with other hot combustible gases. Therefore calorific
value will be a little less than the gross calorific value. Hence it is called net
calorific value.
Net calorific value is defined as the quantity of heat produced when one
gram of fuel is burnt completely and the products are permitted to escape.
Net calorific value = (Gross calorific value) – (Latent heat of steam)

Comparative survey (Advantages and disadvantages) of solid, liquid and

gaseous fuels:

Solid Liquid Gas

1. Not very clean, because
both smoke and air are
produces
2.Transportation is difficult
and much labour is involved
3. Large excess of air is
required for combustion.
4. Rate of combustion cannot
be controlled and a lot of heat
is wasted during the process
5. They cannot be used in IC
Engines
6. Calorific value is least.
7.Thermal efficiency is least
and burn with clinker
formation
8. Storage is easy and there
will be no risk of fire hazards
Only smoke is produced and
no ash is left behind. Hence
liquid fuels are clean
Transportation is easier and
can be easily transfer through
pipes
Less air is sufficient
Rate of combustion can be
controlled easily which gives
economy of the fuel.
They can be used in IC
engines
Calorific value is higher
Thermal efficiency is higher
than solid fuels.
Highly inflammable and
volatile and there will be a
risk of fire hazards.
Neither smoke not ash is
produced. Hence gaseous
fuels are very clean.
Can be distributed through
pipelines from storage tanks.
Hence transportation is easier.
Less air is sufficient
Rate of combustion can be
controlled and combustion
takes place more efficiently.
They can be used in IC
engines
Calorific value is higher
Thermal efficiency is highest
Highly inflammable and
chances of fire hazards is
highest.
 d) It should contain lesser amount of non-combustible gases like CO2 , N2
etc.,
e) It should not produce harmful gases like SO2, SO3, H2S, PH3, oxides of
nitrogen etc.,
f) A good chemical fuel should be readily available at cheaper rate.
Experimental determination of calorific value of the given solid fuel
or liquid fuel using Bomb calorimeter
Principle:
The Calorific Value of solid and liquid fuels can be determined by
burning a known weight of fuel in oxygen under pressure in Bomb
calorimeter. The heat produced and absorbed by a known weight of H2O.
By measuring the rise in temperature of H2O the calorific value of a fuel can
be determined.

Procedure: The bomb calorimeter consists of a strong steel vessel fitted

with a valve for pumping O2. Known weight of the fuel is taken in the
platinum crucible and it is placed in the steel vessel. Two copper wires are
the introduced into the steel vessel for ignition of the fuel. O2 is filled into
the steel vessel at a pressure of 25 – 30 atmospheres. The steel vessel is
placed in the copper calorimeter enclosed in insulating material to prevent
the loss of heat due to radiation. A known weight of water is placed in the
calorimeter. Calorimeter is fitted with a mechanical stirrer and a Beckmann
thermometer. The initial temperature of H2O in the calorimeter is noted.
The fuel is ignited by passing electric current. Rapid combustion takes
place. H2O in the calorimeter is stirred continuously using mechanical
stirrer. The maximum temperature attained by the water is noted.
Calculation:
Weight of the fuel taken = xg
Weight of water taken in the calorimeter = W g
Water equivalent of calorimeter = wg
 Initial temperature of water = t1 °C
Final temperature of water = t2 °C
Rise in temperature = (t2 – t1)°C
Let the gross calorific value =L
Heat produced by the fuel = xL
Heat gained by water and apparatus = ( W + w) (t2 – t1)

Heat lost by the fuel= heat gained by the H2O

xL = (W + w) (t2 – t1)
L = (W + w) (t2 – t1) cal/gms------------------------------------(1)
x
L = (W + w) (t2 – t1) 4.2 J/kg ----------------------------------(2)
x x10 -3
Net Calorific Value = L – latent heat of steam
Net Calorific Value = L – 0.09 H x 587 ------------------------------- (3)
Where H = % of hydrogen within the fuel.

Determination of water equivalent (w) of calorimeter: A known weight

of the fuel of known calorific value is burnt in the Bomb calorimeter. The
rise in temperature of water is determined. The water equivalent of
calorimeter can be calculated from the equation (1).

Experimental determination of calorific value of a gaseous fuel

using Boy’s calorimeter

Principle:

A known volume of the fuel is burnt in Boy’s calorimeter at STP in

the presence of air. The heat produced is absorbed by circulating water. By
measuring the rise in temperature of the circulating water, the calorific value
of the given gaseous fuel can be calculated.
Procedure:

A known volume of the gaseous fuel whose calorific value is to be

determined is introduced into the burner under pressure at uniform rate in a
known interval of time. The combustion products are passed through spiral
tube over which H2O flows at a constant rate. During the process flowing
H2O absorbs all the heat produced in the burner. The steam formed during
the combustion is condensed to liquid. It is collected and weighed. The
weight of H2O used for cooling during the same interval of time is also noted.

Calculations:
The following readings are noted when steady conditions are established.
Volume of gas burnt @ STP in a particular interval of time = V cm3
Mass of water used for cooling in the same interval of time = W kg
Temperature of incoming water = t1°C
Temperature of outgoing water = t2°C
Mass of water condensed in the same interval of time = m
Let gross cal value = L
Heat produced by the fuel = heat grained by the water
VL = W(t2-t1)
L= W(t2 – t1) cal/m3
V
Mass of water condensed/m3 of the fuel = m/v kg
Latent heat of steam/m3 of the fuel = m/v x 587
Net Calorific Value = L – LHS
Net Cv = L – m/v x 587 cal /cm3

Fractionisation of crude petroleum:

Refining of petroleum: The crude petroleum consists of a mixture of

hydrocarbons boiling between a wide ranges of temperature. Hence crude
petroleum is not suitable for technical purposes. The process of fractional
distillation of petroleum into different useful fraction and the removal of
undesirable impurities is called Refining of petroleum. The crude petroleum
is brought to the surface of the earth by bore wells and by means of
pumping. The crude petroleum is washed with the dilute H2SO4 to remove
basic impurities and then with dil NaOH to remove acidic impurities. It is
then heated with steam coils. The emulsion breaks into two types. The
upper layer is taken out and subjected to fractional distillation with tall
fractionating column. The following fractions are collected.

Fractions Length of carbon BP range Uses

Gas C1 – C4 < 40°C Domestic gas fuel
Gasoline (petrol) C5 –C10 40 – 120 °C Fuel for IC engine
Kerosene C10 – C15 160 -250 °C Domestic fuel
Diesel C16 – C20 250 – 300 °C Fuel for diesel engines
Heavy oils C20- C25 300 -350 °C To produce petrol by
cracking
Pitch ( asphalt) > C25 Residue For surfacing roads
Several useful products are obtained by processing crude petroleum.
They include petroleum ether Benzene, lubricating oil, paraffin wax,
petroleum cakes etc.,
Cracking of petroleum: The process of cracking up of higher hydrocarbons
into more volatile lower hydrocarbons is known as cracking of petroleum.
There are two types of cracking
a) Thermal cracking
b) Catalytic cracking

a) Thermal cracking: The heavy oil is subjected to high temperature and

pressure. The bigger hydrocarbons are broken down to given smaller
molecules of alkanes, alkenes, alkynes, hydrogen etc. The thermal cracking
may be carried out either in liquid phase or in vapour phase.
 In liquid phase thermal cracking, the heavy oil is heated to 500 – 600°C
under a pressure of about 100 atmospheres. After cracking, the products are
separated by fractional distillation.
Ex: C8H18 C5 H12 + C3H5
Ocatane pentane propene
C10 H22 C5 H12 + C5 H10
Decane pentane pentne
BP = 174° C BP= 34° C
In vapour phase thermal cracking, the heavy oil is vapourised and then
heated to about 600 to 650°C under pressure of 10 to 50 atmospheres.
Vapour phase cracking method require less time than liquid phase cracking.
Petrol obtained by vapour phase cracking has better antiknock properties.
Catalytic cracking: In this process the vapours of high boiling fraction are
heated in the presence of catalysts such as Silica, Alumina, Thoria (ThO2),
Zirconium Oxide (ZrO), MnSO4 etc.
Types of catalytic cracking
a) Fixed bed catalytic cracking
b) Fluidized (moving) bed catalytic cracking

Fluidized (moving) bed catalytic cracking: In this process, the solid catalyst
is finely powdered so that it behaves as a fluid which can be circulated along
with the vapors of heavy oil. The vapors of heavy oil are mixed with finely
divided catalyst and this mixture is passed into the reactor maintained at
500°C. Cracking of heavy oil occurs. A centrifugal separator called cyclone
is provided in the reactor which allows only cracked vapours to pass into the
fractionating column. The catalyst gets separated in the reactor, is collected,
regenerated and reused. The different fractions like gasoline kerosene,
diesel etc. are collected in the fractionating column.

Advantages of catalytic cracking:

a) Catalytic cracking takes place at lower temperature and pressure.
a) The yield of petrol is high
 b) The process can be controlled easily and the desired products can be
obtained.
c) The products contain higher amount of aromatic hydrocarbons.
Hence possess better antiknock characteristics.
d) Catalysts are specific in their action and therefore they permit
cracking of high boiling hydrocarbon.

Reformation of petroleum: Gasoline used in automobiles mainly consists

of a mixture of hydrocarbons; namely alkanes, cycloalkanes and aromatics.
Branched chain hydrocarbons and aromatic hydrocarbons possess good
combustion characteristics. Whereas straight chain hydrocarbons have got
poor combustion characteristics because former have higher octane number
and later compounds have lower octane number.

Octane number of gasoline is the percentage of Isooctane (Octane

Number = 100) (v/v) in a mixture of isooctane and n- heptane (ON= 0).
Higher the octane number least is its tendency for knocking (rattling sound
in IC engines). IC engines require gasoline of octane number above 90 (in
USA) and 75 -85 (in India). But gasoline obtained from primary distillation
of crude oil contains mainly straight chain hydrocarbons having octane
number lessthan 60. Octane number of this gasoline can be improved by
structural modification i.e., by converting straight chain hydrocarbons into
cyclic, branched chain and aromatic hydrocarbons. This is done by catalytic
reforming.
Reforming is a process of bringing about structural modifications, such
as conversion of straight chain hydrocarbons into branched, cyclic and
aromatic in order to increase the octane number. Reforming process is done
by thermal reforming or by catalytic reforming.

Catalytic reforming: Catalytic reforming is a process of upgrading gasoline

(increasing an octane number) in presence of a catalyst
Reforming conditions:
 Feed: straight run gasoline
Catalyst: pt supported on Al2O3-SiO2 base
Temperature: 470 – 525 °C
Pressure: 15 – 50 atmospheres
The main reforming reactions are
a) Dehydrogenation
b) Dehydro cyclisation
c) Isomerization
d) Hydro cracking

a) Dehydrogenation: Ex: Cycloalkanes undergo dehydrogenation reactions

+ 3H2

Cycloalkanes C6H12 C6H6 (ON > 100)

b)Dehydrocyclisation: Ex: a straight chain hydrocarbon undergoes

cyclisation by dehydrogenation to produce aromatic hydrocarbons.

H3C –CH2-CH2-CH2-CH2-CH3 + H2
Hexane cyclo hexane

+ 3H2

Isomerization: (same mol. formula but different structural formula)

The straight chain hydrocarbons are converted into branched
hydrocarbons
H3C- CH2-CH2-CH2-CH2-CH2-CH2-CH3 H3C-CH-CH2-CH2-CH2-
CH3
N –heptane |
CH3
2 –methyl hexane

n-hexane 2, 2, dimethyl butane

Hydro cracking :( cracking in presence of hydrogen as a catalyst)

n-heptane + H2 propane + n-butane

Knocking of IC engines:-

In IC engine, mixture of gasoline and air is used as a fuel. This mixture

of petrol vapours and air is compressed and ignited by a spark in the cylinder
which causes the oxidation of hydrocarbon molecules. The ratio of original
volume of the fuel air mixture (V1) to that volume at the end of compression
(V2) is called compression ration.
Compression ratio = V1/ V2

The efficiency of IC engine depends upon the compression ratio. Higher

the compression ratio higher is the efficiency. The high compression ratio
depends on the quality of the fuel. Beyond certain compression ratio fuel is
converted into unstable hydrocarbon peroxide and decomposes rapidly to
give a number of gaseous products. This gives rise to high pressure waves
which knock engine walls producing sound. This is called knocking of IC
engines.

The following are the disadvantages of knocking:

a) It produces undesirable sound
b) It increases the fuel consumption
c) It causes mechanical damage to engine by overheating the engine
parts.
d) It results in decreases power output and driving becomes unpleasant.

Octane number: The quality of the petrol is determined by an arbitrary scale

called octane number. This was proposed by the Edger in 1972.
Octane number of gasoline is defined with reference to n- heptane and
isooctane. The straight chain hydrocarbon n-heptane which has poor
burning characteristics and knocks the engine badly is arbitrarily given an
octane number zero. But the branch chain hydrocarbon iso-octane which has
excellent burning characteristics and very little tendency to knock the engine
is given an octane number 100.
CH3
CH3 – (CH2)5 –CH3 CH3 – C –CH2 –CH2 – CH3
n -heptane CH3
(iso octane)
octane no. = zero octane no. 100 [ 2,2,4, - tri methyl petane)

The octane number of petrol is the percentage by volume of iso octane in

the mixture of isooctane and n-heptane blend which has the same knocking
characteristics of the gasoline sample under investigation.
Ex: 80 octane number fuel is one which has the same combustion
characteristics as 80: 20 (Mixture of isooctane and n- heptane)
The different gasoline samples rated by this octane number. Higher the
octane number least is the tendency of knocking and better is the quality of
fuel. Automobiles petrol has octane number ranging from 75 to 95.

It has been found that knocking tendency is largely related to chemical

structure of the fuels. The decreasing tendency of fuels to knocking is as
follows:
Alkane > [Branched chain] > cycloalkanes Alkenes> Aromatics

Aviation fuels (Aircraft fuels)

Aviation petrols have greater knock resistance than isooctane. Generally
aviation fuel has an octane number greater than 100. in such cases, octane
number and computed by using the following relation.
Octane Number=(power number-100)/3 + 100
Where power number=power extracted by the engine.
Cetane number: The knocking characteristics of diesel oil are expressed in
terms of centane number. The suitability of diesel fuel is determined by its
cetane number.

Hexadecane is a saturated hydrocarbon which has the least tendency of

knocking the diesel engine as given arbitrarily cetane number 100.
α-methyl naphthalene which knocks the diesel engine badly has given
cetane number zero
α-methyl naphthalene n-hexadecane
cetane No.=zero cetane No.=100

The cetane number of diesel oil is determined by comparing the burning

characteristics of the blend of specific composition of hexadecane and α-
methyl naphthalene.

The ignition quality among hydrocarbons is as follows:

Alkanes>Napthenes>Alkenes>Branched chain alkanes>Aromatics.

Prevention of Knocking: Knocking can be prevented or reduced by using

Ant knocking agents and Unleaded petrol.

Anti knocking Agents: Knocking can be reduced by adding some specific

compounds to the fuels which are called ant knocking agents.

Tetraethyl lead is commonly used as ant knocking agent. During the

combustion TEL is converted into cloud of finely divided lead dioxide
particles in the cylinder. These particles react with hydrocarbon peroxide
molecules thereby controls the chain reaction. Thus knocking is prevented.
The deposit of lead dioxide is harmful to the engine. In order to
eliminate this, a small amount of ethylene dibromide is added to the petrol.
In presence of this lead is removed from the cylinder as volatile lead-
bromide which escapes out through the exhaust pipe. The petrol containing
lead in the from TEL is called leaded petrol

Unleaded petrol: Knocking can also be prevented by mixing strain chain

hydrocarbons such as isopentane, ethyl benzene. Tertiary butyl methyl ether
etc. These compounds reduce the formation of peroxy compounds and
hence knocking will be reduced. Petrol where knocking tendency can be
reduced without the addition of TEL is called unleaded petrol. One of the
major advantages of using unleaded petrol is that it allows the use of
catalytic converted attached to the exhaust pipe in automobiles. The
catalytic converted is attached to the exhaust containing Rhodium catalyst
which converts the toxic gases like carbon monoxide into carbon dioxide
and oxides of nitrogen into nitrogen which are harmless. It also oxidizes
unburnt hydrocarbon into carbon dioxide and water.