Chapter - 1

Energy
Sources of Energy
- Primary energy sources (sources that are
naturally available on earth)
- Two types of energy resources
1. Renewable energy (a source of energy that
can never be exhausted) - sources of
renewable energy (are recurring or
continuous) (sun, wind, water, agricultural
waste, firewood and animal dung)
2. Non-renewable energy or conventional energy
(sources that can not be replenished during a
man’s life time) – sources (fossil fuels- coal,
oil, natural gas and U & Pu used in reactor)
Fuel
- a naturally occurring or artificially prepared
combustible carbonaceous material used mainly as a
source of heat and light and a few cases as a source
of raw material
- Classification of fuel
depending on origin – primary and secondary
fuels
depending on their physical state of existence –
solid, liquid and gaseous fuels.
 Fuels

Depending on origin

Primary fuels Secondary fuels

Depending on physical state

Solid fuel Liquid fuel Gaseous Solid Liquid Gas

eg.coal, eg. fuel eg. Coke, eg. Petrol, diesel, eg. LPG
peat,wood, petroleum charcoal kerocene
lignite
Characteristics of a good fuel
- It (fuel) should be easily available in natural or any other
form.
- Storage, transportation and handling of the fuel should
be easy.
- It should have a low ignition temperature and burn
efficiently. % H in fuel ↑ ignition temp ↓
- The combustion rate should be low which evidently
depends on the chemical composition of the fuel and
availability of oxygen.
- The level of emission of smoke should be less.
% C in fuel ↑ smoke ↑
- There should be minimum of residue after the combustion.
- The fuel should have a high calorific value.
- The fuel should have a low moisture content.
Hydrocarbon fuels
- chief H/C fuels – coal, petroleum, natural gas
- Coal – main source of aromatic compounds.
- Petroleum – organic compounds containing nitrogen,
sulphur, oxygen.
- C (1-4) – all gases, C (5-7) – all light liquids,
- C (16-20) – lubricating oils and semi-solid greases
- C (20 above) – solids, starting with paraffin wax, tar and
asphaltic bitumen
Calorific value (CV) of a fuel
- The quantity of heat evolved by the complete combustion of
unit quantity (mass or volume) of the fuel in air or oxygen.
- Unit – for solid and liquid ( cal/g (or) kcal/kg (or) J/g (or) kJ/kg )
- for gas ( J/cm3 (or) kJ/m3 )
- Two ways of calorific value of fuels
- Gross (higher) calorific value (GCV or HCV)
The quantity of heat evolved by the complete combustion of a unit
mass (a unit volume) of the fuel in air or oxygen and the products of
combustion are brought down to normal temperature.
- Net (lower) calorific value (NCV or LCV)
The quantity of heat evolved by the complete combustion of a unit
mass (or unit volume) of the fuel and the products of combustion are
let off into the atmosphere.
NCV = GCV − latent heat of condensation of steam
Determination of calorific value of a fuel
• Bomb calorimeter (instrument)
• Theory - A known mass of the solid or liquid fuel is completely burnt
in excess of oxygen in a bomb calorimeter. The heat liberated is
absorbed by the surrounding water and the brass calorimeter. The
increase in temperature of the calorimeter and water is noted using a
sensitive thermometer. The calorific value of the fuel is calculated
using the principle that the heat lost by the burning fuel is equal to the
heat gained by water and the calorimeter.
• Apparatus - A thick steel cylinder or bomb, which can be closed with
a needle valve (for oxygen)
- Two Pt wires (connect with graphite/Pt cup and ignition coil)
- Ignition coil connect the cup and Pt wire.
- A known quantity of water in another outlet brass calorimeter (kept
inside a non conducting jacket over ebonite blocks)
- A sensitive thermometer and stirrer dipped in water.
Bomb Calorimeter
Calculation of GCV
• Mass of solid or liquid = m kg
• Mass of water taken = w1 kg
• water equivalent mass of calorimeter and other accessories = w2 kg
• Total water equivalent mass = w1 + w2 kg
• Initial temperature = T1 °C
• Final temperature = T2 °C
• Increase in temperature = (T2 - T1 )°C
• Heat lost by m kg of a fuel = heat gained by calorimeter and water
= mass x specific heat x increase in temp.
= (w1 + w2 ) x 4.187 x (T2 - T1 ) kJ
(w + w2 ) x 4.187 x (T2 − T1 )
gross calorific value = 1 kJ/kg
𝑚
* Because the products of combustion remain inside the calorimeter and
brought down to ambient temperature.
Calculation for NCV
• If the % of hydrogen in the fuel is known, NCV of a fuel can be
calculated.
100 kg fuel contains x kg hydrogen (H)
𝑥
1 kg fuel kg (H)
100
H2 + ½ O2 → H2O
2 kg 18 kg
𝑥 18 𝑥
kg kg = 0.09 x kg
100 2 x 100
1 kg fuel produces = 0.09 x kg steam
latent heat of steam = 587 x 4.187 kJ/kg

NCV = GCV – heat of condensation of steam formed from 1 kg fuel

NCV = [GCV – 0.09 x x 587 x 4.187 ] kJ/kg
Eg 1.1
Mass of fuel = 0.6 g = 0.6 x 10-3 kg
Water equivalent mass of calorimeter = 2200 g = 2.2 kg
Specific heat of water = 4.187 kJ/kg/C
Increase in temperature = 6.52°C

total water equivalence x specific heat of water x Rise in temp.

GCV =
mass of fuel
2.2 x 4.187 x 6.52
=
0.6 x 10 −3

= 1000097.2 kJ/kg
Fractional distillation of petroleum (non-renewable source of
chemical energy)
- Crude oil - a complex mixture that is between 50 and 95% aliphatic
H/C (by weight) with a dark color and an unpleasant odor.
- Impure petroleum is first freed from dirt and water.
- The expulsion of dissolved gases is done by heating the crude.
- Separation of the mixture of hydrocarbons – fractional distillation of
the crude using a fractionating column.
Fractionating column – a tall steel cylinder filled with trays at various
heights. Each tray contains a number of holes closed with bubble caps
with tooth edges.
- Purified crude oil is vapourized and sent up the fractionating column.
- At the bottom of the column, the temperature – around 500°C
- The height increases the temperature becomes less (decreases)
- The vapor rises up the column, the heavier and less volatile
components condense and return to the lower tray.
• The heat released during the condensation vaporizes the more volatile
components, which rise up the tower. the vapors pass through the
bubble cap, they blow through the already condensed liquid leading to
further vaporization of the liquid and condensation of heavier
fractions.
• Repeated condensation and vaporization is achieved in the column.
• Crude oil gets separated into various fractions and collects at the trays
at different heights in the column. any excess liquid in a tray
overflows through the downspout into the lower tray.
• Each fraction (a mixture of H/C with a range of boiling points) is
drained off through the respective outlet .
• Each fraction may be further fractionated to get products of the
desired properties.
Chemical Processing of Petroleum
• Primary distillation of crude oil yields about 20% of straight run
petrol only. (not enough demand of petrol)
• Three main conversion process in the refinery
- (1)Cracking [ the process of breaking down
hydrocarbons of higher molar mass (high
boiling point)into lighter hydrocarbons
(low boiling)]
- (2)Combining [one needs to combine smaller
hydrocarbons to make larger ones]
- (3)Reforming [ a process involving modification of the
structure of molecules which uses heat,
pressure and a catalyst to produce high
octane petrol and petrolchemical feedstock.]
(1) Cracking
heat+pressure
C12H26 C6H14 + C6H12
absence of air
(dodecane) (hexane) (1-hexene)
- Three types of cracking (a) thermal cracking
(b) catalytic cracking
(c) hydrocracking
(a) Thermal Cracking
- Heavy oil feed stock is subjected to high pressure and
temperature (700°C) in the absence of air and a catalyst.
- The cracked products are cooled and fractionated to
get gasoline and other products of low molecular mass.
- Disadvantages – it is old and seldom used now since
there is no control over the products of cracking.
The efficiency is low.
(b) Catalytic Cracking ( Fixed bed catalytic cracking and
Fluidized bed catalytic cracking)

- Cracking takes place at low temperature and pressure and can

control the nature of the end products by controlling the conditions.
- It has largely superseded thermal cracking because it produces
gasoline richer in branched paraffins, cycloparaffins and aromatics.

Fixed bed catalytic cracking –

- to convert heavy hydrocarbon fractions obtained by vacuum distillation
into a mixture of more useful products such as petrol and light fuel.
- Controlled heat(450-500°C) and pressure, small pellets of silica-
alumina or silica magnesia
- petrol, LPG, unsaturated olefin compounds, cracked gas oils, liquid
residue(cycle oil), light gases and a solid coke residue.(Products)
- Cycle oil is recycled to cause further breakdown.
- Coke, which forms a layer on the catalyst, is removed by burning.
Fluidized bed catalytic cracking
Principle: in fluidized bed catalytic cracking, the finely powdered
catalyst is kept agitated by a gas stream of the vaporized heavy oil
feed stock. Catalyst can be handled like a fluid system and can be
pumped like a liquid. This brings about a close contact between the
catalyst and the reactant and results in a more efficient cracking.
- Cracked products are with-drawn from the top of the catalyst chamber
and fed directly into a fractionating column for further separation.
- The un-cracked oil is sent for a second stage of cracking.
- Spent catalyst is continuously pumped from the catalyst chamber into
a regeneration chamber. Hot air is blown through it to burn the carbon
deposit on the catalyst surface. The regenerated catalyst is sent back to
the catalyst chamber.
- Advantages – more efficient cracking, made continuous.
(c) Hydrocracking
- similar to fluid catalytic cracking but uses a different
catalyst, lower temperature, higher pressure and hydrogen
gas.
- Heavy oil → gasoline and kerosene (jet fuel)
- Advantages –
(i) it can increase yield of petrol components.
(ii) it produces no residues, only light oils, because of
cracking in the presence of hydrogen.
(iii) it is a also treating process, because the hydrogen
combines with contaminants such as sulphur and nitrogen,
allowing them to be removed.
- Gas oil feed mixed with H2, heated and sent to a reactor
vessel with fixed bed catalyst, where cracking and
hydrogenation take place.
• Products are sent to a fractionator to be separated.
• Hydrogen is recycled.
• Residue is mixed again with hydrogen, reheated and sent to
a second for further cracking under higher temperature and
pressure.
• In addition to cracked naphtha for making petrol, it yields
light gases useful for refinery fuel or alkylation as well as
components for high quality fuel oils, lube oils and
petrochemical feedstock.
(2) Combinig
- Three units –
- the alkylation unit (a process in which the structures of
molecules in one fraction are rearranged to produce another)
- Acid catalyst (sulphuric acid or AlCl3) eg. Benzene reacts
with propene to yield isopropylbenzene.
- the dimersol unit eg. Isobutane reacts with butene(butylene)
to form isooctane. (catalyst – HF or H2SO4)
- the polymerization unit (LPG → larger gasoline molecule)
(3) Reforming
- A change in molecular structure but without much in molar
mass.
- Convert straight chain hydrocarbon with low octane number to
branched chain or cyclic compounds with high octane number
- (a) isomerization – chemical rearrangement of straight-chain
hydrocarbons(paraffins), so that they contain branches attached
to the main chain(isoparaffins) (create extra isobutane feed for
alkylation, improve the octane of straight run pentane and
hexane and make into better petrol blending components)
eg. n-hexane → 2-methyl pentane (or) 2,2-dimethyl butane
- (b) dehydrogenation – cyclic alkanes → cyclic alkenes and
aromatic compounds. eg. Cyclohexane → benzene + 3H2
- (c) cyclization and dehydrogenation –
n-alkanes → cycloalkane and H2 → aromatic compound
eg. n-hexane → cyclohexane + H2 → benzene + 3 H2
Petrol knocking
- Compression detonation of fuel in the power stroke of the
engine.
- Knocking occurs when the air-fuel mixture auto-ignites all
at once before the flame front from the spark plug ignition
can reach it. The explosive reaction causes combustion to
stop before the optimum timing causing a decrease in
performance.
- A fuel with a high auto-ignition temperature that burns
reasonably fast, does not need early ignition timing, will
have high practical value knock resistance.
• Petrol composition – a mixture of at least 100 different
hydrocarbons compounds. Most of these are branched-chain
alkanes and some are aromatic compounds.
- A number of things happen to the petrol in an internal
combustion engine, including the following:
- the petrol is vaporised.
- the vapor is mixed with air.
- the petrol-air mixture is compressed.
- the mixture is ignited by a spark from the spark plug
and burned.
- the gases produced by the combustion reaction expand
- expansion causes the piston to move, i.e. kinetic
energy is produced.
- Octane number of a fuel - a measure of its ability to resist
knocking.
- A fuel with a high octane number has a greater resistance to
spontaneous combustion.
- Octane rating – a measure of the tendency of a fuel to
auto- ignite.
- Heptane (a high tendency to auto-ignite) octane no. 0
(C7H16)
- 2,2,4-trimethyl pentane (low tendency to auto-ignite)
octane no. 100
- A mixture of these two compounds containing 95% of 2,2,4-
trimethyl pentane(isooctane) octane no. = 95
- A mixture of compounds with an identical to auto-ignite, under
the same conditions of compression, octane no = 95
octane no. ↑ octane rating ↑ knocking ↓
Methods of obtaining high octane compounds (in petrol
manufacture)
- To have high-octane rating in compounds ( a high degree of
branching, short chain length, the existence of rings )
- High-octane compounds can be obtained from low-octane by the
following three processes, each involving the use of catalysts:
isomerization, dehydrocyclization, catalytic cracking
- Isomerization -
n-pentane (octane no.= 62) → 2-methylbutane (octane no.=93)
- Dehydrocyclization –
Hexane (octane no.=25) → cyclohexane (octane no =83)
C6H14 (CH2)6 + H2
cyclohexane (octane no =83) → benzene (octane no.>100)
(CH2)6 C6H6 + 3H2
- Catalytic cracking – dodecane → isooctane & 3-methyl butane
- Unsaturated products (feedstock for the polymer industry)
- Saturated products (high octane branched alkane suitable for making
petrol)
• Good fuel (octane no. ≥ 97)
• Petrol with octane no. 98 = a mixture of 98% iso-octane and
2% heptane
- A high tendency to auto-ignite (or) low octane rating, is
undesirable to a gasoline engine but desirable for diesel
engine.

Techniques to prevent knocking

(1) isomerization
(2) Reforming
(3) Catalytic cracking
(4) Adding oxygenates to petrol
(5) Adding anti-knocking agents (TEL or TML)
• Adding oxygenate (Addition of oxygenate)
- An oxygenate – any fuel that contains oxygen.
- Methanol (CH3OH), ethanol (C2H5OH), methyl tertiary
butyl ether (MTBE), ethyl tertiary butyl ether (ETBE)
- Advantages (3 points)
- The compounds work by raising the octane number of
the fuel.
- They cause less pollution because apart from not
containing lead.
- They produce lower level of carbon monoxide when
they burn.
Prevention of knocking ( minimize the knocking in
IC engine)
- a suitable change in engine design may be made to have
optimum combustion ratio (CR).
- High octane number fuel may be used.
- Anti-knocking agents may be used.
Adverse effect of knocking
- Knocking produces an undesirable rattling sound.
- It results in decrease in efficiency
- Deriving and travelling become unpleasant.
- It increases fuel consumption.
- It causes mechanical damage to the engine parts and spark
plug.
 Antiknocking Agents – TEL & TML
- The substance added to control knocking
- tetra ethyl lead (TEL), tetra methyl lead (TML) and a mixture of TEL
and TML (used along with ethylene dichloride or dibromide)
How may knocking be minimized by using antiknocking agents?
- TEL & TML produce ethyl and methyl free radical by dissociation.
- These radicals combine with free radicals formed by chain reaction
during the combustion of gasoline and form stable hydrocarbon.
- The population of chain carriers are kept under check. Thus knocking
is reduced greatly by the use of small quantities of TEL and TML.
Ill effects of TEL & TML
- TEL & TML get converted to Pb or PbO and get deposited on the
engine parts or the exhaust pipe causing damages.
- But if they are used along with ethylene dichloride or dibromide, Pb +
PbO are converted to volatile PbCl2 or PbBr2 which escape as gases
into atmosphere. These halides are poisonous to human beings and
animals.
 Synthetic Petrol
1. Burgius Process
- An intimate paste of finely powdered bituminous coal and heavy
oil is fed into the converter along with the catalyst Sn or nickel
oleate .
- The temperature of the reactor is maintained at 450°C and the
conversion is carried out at a pressure 250-300 atms for about 2
hours.
- Under these conditions, hydrogen combines with coal to form
saturated hydrocarbons, which decompose at the maintained
conditions to yield low boiling liquid hydrocarbons.
- When the issuing gases from the reacting vessel is condensed, a
liquid resembling crude oil is obtained and is subjected to
fractional distillation. The fractions are gasoline, middle oil and heavy
oil.
-The middle oil & heavy oil are further recycled to get more gasoline
and the yield of gasoline may be above 60%.
2. Fischer-Tropsch Process
- Water gas (CO+H2), obtained from passing steam over coke
mixed with H2, is passed through Fe2O3 (and /Na2CO3) to
remove any sulphide contents in mixture.
- The mixture of gases are compressed to 20 atms and then led
through a converter containing catalysts( cobalt, thoria, magnesia
and mostly keiselgular earth) at 250°C.
- The products are mainly saturated and unsaturated
hydrocarbons.
n CO + 2n H2 → CnH2n + n H2O
n CO + (2n+1) H2 → CnH2n+2 + n H2O
- The hot gaseous products are cooled by passing through a
condenser.
- The condensate is a crude oil which on fractionation yields
gasoline and high heavy oil. The heavy oil is again recycled to
get more gasoline.
Diesel Knocking
- Diesel engine – compression ignition engine (fuel = straight
chain hydrocarbons, b.pt. – around 100-360°C)
How is fuel burnt in diesel engine?
- In the suction stroke only air is drawn into the cylinder.
- In the compression stroke air is highly compressed till its
temperature reaches to 500°C .
- Now the fuel is injected as a spray into the engine.
- The diesel vapourises, attains self-ignition temperature and
burns.
- If vapourisation and combustion are instantaneous, fuel
burns smoothly and efficiently.
- But there is a time lag between vapourisation and
combustion called diesel lag (ignition delay). This causes the
accumulation of diesel in the vapour state and the whole
mixture of diesel vapour and air gets ignited with explosion.
This is called diesel knocking.
Cetane Number (CN)
- an indicator of the readiness with which a given diesel
undergoes compression ignition. (OR)
- the percentage by volume of n-cetane in a mixture of
n- cetane and 1-methyl naphthalene that gives the same
knocking as the diesel under consideration.
- CH3(CH2)14CH3 (n-cetane) CN = 100
- 1-methyl naphthalene CN = 0
Prevention of diesel knocking (to minimize diesel knocking)
- by using diesel with high cetane number – containing more
straight chain hydrocarbons.
- certain organic additives such as ethyl nitrate(C2H5-O-NO2)
amyl nitrate, increase the cetane number of desel.
Power Alcohol
- Alcohol – an excellent alternative motor fuel for gasoline
engines.
- Only two alcohols are technically and economically suitable
as fuels for IC engines - methanol and ethanol
- Power alcohol for IC engine = petrol blended with about 20-
25% ethanol
- Gasohol = a mixture of 90% unleaded gasoline and 10%
ethanol (its performance is comparable to that of
100% unleaded gasoline, with added benefit of
superior antiknock properties, no engine
modifications are needed)
Combustion characteristics of alcohols as a fuel
- Alcohols have higher flame speeds and extended
flammability limits. Also they produce a great number of
product moles per mole of fuel burnt, higher pressure are
achieved.
- Alcohols burn with no luminous flame and produce no soot.
- The onset ignition leads to the formation of a flame front
which propagates at high speed throughout the whole
mixture (increased volumetric efficiency and reduced
compression temperatures). These effects improve the
thermal efficiency by 10%.
- The higher the flame speed, giving earlier energy release in the
power stroke, results in a power increase of 11% at normal
conditions and up to 20% at higher levels of compression
ratio (14:1)
- The oxygen content of alcohols depresses the heating value
of the fuel in comparison with hydrocarbon fuels.
- The heat of combustion per unit volume of alcohol is
approximately half of that of isooctane. However,
stoichiometric fuel-air mass ratios are so big that the
quantity of energy content based on unit mass of
stoichiometric mixture is comparable with that of
hydrocarbons.
Production of alcohol
Methanol – distillation of wood, distillation of coal, natural
gas and petroleum gas.
Ethanol – biomass transformation or bioconversion, synthesis
from petroleum or mineral coal.
 Advantages of power alcohol
- It has a high octane rating, which prevents engine
detonation under load.
- It burns clean, in fact, not only are noxious emissions
drastically reduced, but the internal parts of the engine are
purged of carbon and gum deposits which do not build up as
long as alcohol is used as a fuel.
- An alcohol burning engine tends to run cooler than its
gasoline-powered counterpart, thus extending engine life
and reducing the chance of overheating.
- It has less starting problems.
- Alcohol removes all traces of moisture in the petrol.
 Disadvantages of blended alcohol
- It lowers the calorific value of petrol.
- Due to considerable surface tension, alcohol does not
atomize at low temperature.
- Due to oxidation of alcohol during burning, corrosion can
occur.