Module -1 Chemical Fuels

Chemical Fuels: Introduction, classification,

 definitions of calorific value
determination of calorific value
of solid/liquid fuel using bomb calorimeter
Knocking of petrol engine – Definition, mechanism, ill effects and prevention.
Power alcohol, unleaded petrol and biodiesel.
Cracking: Introduction fluidized catalytic cracking, gasoline
Reformation of petrol, octane number and cetane number, anti- knocking agents
and unleaded petrol.
Hydrogen Energy: Introduction, methods of hydrogen generation
Photovoltaic Cells: Construction and working, advantages and disadvantages of
PV cells.
Production of solar grade silicon. Purification of silicon by zone refining.
Introduction
Classification of chemical fuel
Classification
LCV = [HCV - 0.09 H x 587] kcal/kg
Determination of calorific value of solid/liquid fuel using
bomb calorimeter
Knocking of petrol engine – Definition, mechanism,
ill effects and prevention.
“Knocking is defined as the production of shock wave in an IC engine due to
explosive combustion of mixture of petrol and air which increases compression ratio
beyond a certain value leading to rattle sound.”
Step 1

C2H6 + O2 2CO2 + 3H2O (Normal combustion)

Step 2
C2H6 + O2 CH3-O-O-CH3 (Explosive conditions)

CH3-O-O-CH3 CH3CHO

CH3CHO + O2 HCHO + CO2 + H2O

HCHO + O2 CO2 + H2O
Reformation of petrol:
 OCTANE NUMBER

 The percentage of isooctane present in the standard mixture of isooctane and n-heptane which

produces knocking at the same compression ratio as that of the petrol being tested.

n-heptane (OC No-0)
Iso-octane (OC No-100)
Let us consider two standards iso-octane and n-heptane.
The iso-octane produces minimum knocking when used as
the fuel, Thus it has good anti-knocking quality, it has been
assigned an octane number of 100.
Types of gasoline
Third grade gasoline- O.C.no<74
Regular grade gasoline-O.C.no-74.
Premium gasoline-O.C.no-81 and above
Aviation gasoline-O.C.no-100
The octane number changes with the change in the
structure of the hydrocarbons as follows
Straight chain alkanes< branched chain
alkanes<alkenes<cycloalkanes<aromatics.

The n-heptane produces maximum knocking in IC engine,

however, so it has poor ant-knocking quality, it has been
assigned an octane number of zero. The octane number of fuels can be improved by two ways
1. Cracking and 2. Reforming process.
 CETANE NUMBER

The percentage of cetane present in the standard mixture of cetane and α-methyl naphthalene which
produces knocking as that of the diesel sample being tested.

1.CH3-(CH2)14-CH3 The knocking characteristics of Diesel are described by the

Cetane Number
Cetane (C.NO=100)
2.
α-methyl naphthalene (C.NO= 0)
Cetane (n-hexadecane) ignites rapidly
and is given a cetane number of 100.
The α-methyl naphthalene ignites slowly
and is given a cetane number of zero.
When diesel oil has cetane number 40, it means that this behaves
like a mixture of 40% cetane and 60% α-methyl naphthalene.
Types of cetane numbers
High speed-C.no-45
medium speed-C.no-35
low speed diesel -C.no-25
The cetane number of oil can be improved by adding (about 2%)
substances like acetylene, ethyl nitrate, ethyl nitrite, acetone,
diethyl ether etc.
In petrol engine, knocking is due to the sudden spontaneous combustion
whereas; knocking in a diesel engine is due to the delay in the spontaneous
combustion. The crude oil which gives petrol of high octane number gives a
diesel of low cetane number.

An oil of high octane number has a low cetane number and

vice versa.
 ANTI - KNOCKING AGENTS
The knocking tendency of fuel can be reduced by adding small amount of chemical
substance called as anti knocking agents.

These substances improve the octane number of petrol.

Examples :
1. Tetra ethyl lead [TEL-Pb(C2H5)4]
2. Tetra methyl lead [TML-Pb(CH3)4]
3. Diethyl telluride - Te(C2H5)2
TEL: it is added in the form of ethyl fluid containing 68% TEL, 26% dibromoethane and 9%dichloro
ethane. .
Pb(C2H5)4 + 1/2O2 → PbO + 4 C2H5

TEL and 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, dibromide, Pb and PbO are converted to
volatile PbCl2 or PbBr2 that escape as gases into atmosphere
Pb + C2H4Cl2 → PbCl2+ C2H4

NOTE: Leaded petrol cannot be used in automobile exhaust pipes fitted with catalytic
converter, since the released lead compounds poisons the catalyst itself, thereby
destroying its catalytic activity.
 UNLEADED PETROL

The petrol, which contains antiknocking agent other than lead, is known as unleaded petrol.

Knocking tendency can be reduced without the addition of lead compounds is called unleaded
petrol.

These compounds are having oxygen in

Examples: 1. Methyl tertiary butyl ether (MTBE) its structure itself, which is supplied to
2. Ethyl tertiary butyl ether (ETBE) combustion process to reduce the
3. Methanol formation of peroxides. There by
4. Ethanol knocking is reduced in IC engine.

Advantages Of Unleaded Petrol :

1. Eliminates the pollution level of lead in atmosphere.

2. This permits the attachment of catalytic converters to the exhaust pipe in automobiles .
 POWER ALCOHOL (Gasohol)

-Power alcohol is cheaper than petrol.

When ethyl alcohol is used as fuel in internal combustion engine, it is called as
"power alcohol".
Generally power alcohol is blend of absolute alcohol with petrol. Containing 10-85%
of ethanol and 90-15% of petrol by volume.

Advantages of power alcohol:

Ethyl alcohol has good antiknocking property than MTBE. Therefore, addition of
ehtyl alcohol increases the octane number of petrol.
Reduces the emission of CO, NOx and volatile organic compounds.
It is biodegradable.
Ethanol is renewable material; extracted from molasses.
 Biodiesel

A fuel derived from organic oils, such as vegetable oil, rather than petroleum.
Biodiesel's use and production are increasing. It's typically used for aircraft,
vehicles and as heating oil.

Transesterification
Animal and plant fats and oils are composed of triglycerides, which are esters
containing three free fatty acids and the trihydric alcohol, glycerol. In the
transesterification process, the alcohol is deprotonated with a base to make it a
stronger nucleophile. Commonly, ethanol or methanol are used. Under normal
conditions, this reaction will proceed either exceedingly slowly or not at all, so
heat, as well as catalysts (acid and/or base) are used to speed the reaction. It is
important to note that the acid or base are not consumed by the transesterification
reaction, thus they are not reactants, but catalysts. Common catalysts for
transesterification include sodium hydroxide, potassium hydroxide, and sodium
methoxide.
 DISADVANTAGES OF NON RENEWABLE ENERGY

 Once a non renewable energy source is used up it

cannot be replaced again.
 Non renewable energy source are highly
polluting sources and increase the greenhouse
gasses.
 The non renewable energy source are responsible
for all kinds of non-biodegradable material
accumulation.
 The exposure to non renewable energy sources
has increased the level of pollution.
 The rise in temperature due to greenhouse gas
accumulation.
 Solar cells or photovoltaic cell
The device which is used to convert heat energy of the sun into electricity is called
solar cells or photo voltaic cells.

Introduction
Photovoltaic cell provides enormous amount of energy from sun which is unlimited,
inexhaustible and renewable.
•Semiconductors like silicon has the capacity to absorb light and deliver a portion
of
the energy of the absorbed photons to carry charge carriers (electrons and hole).

•Thus solar cell is a semiconductor diode that has been designed carefully so that it
can absorb the light energy efficiently and convert light energy from the sun into
electrical energy.
Physical properties of silicon relative to photovoltaics:

•Silicon is a semiconductor with band gap of 1.2eV at 25oC.

•Silicon contracts when melted and expand when solidify.
•High refractive index limits the optical applications of silicon

Chemical properties relevant to photovoltaics:

•Silicon is stable in the tetravalent and has a strong affinity for oxygen, forming stable
oxides and silicates.
•Silicon and carbon form a strong Si-C bond and stable products.
• Silicon forms hydrides, and monosilane (SiH4) is key chemical compound for the
production.
Construction and Working of Photo-Voltaic cells:
 Advantages Disadvantages

 It is a clean and non-polluting energy source.  Cost. The initial cost of purchasing

 It is renewable energy. a solar system is fairly high.
 Solar cells do not produce noise for electricity  Weather Dependent. Although solar energy can
generation. still be collected during cloudy and rainy days,
 It requires very little maintenance. the efficiency of the solar system drops.
 Long lifetime.  Solar Energy Storage Is Expensive.
 There are no fuel costs or fuel supply problems  Uses a Lot of Space.
in this electrical energy production.  Air pollution and whether can affect the
 They need no recharging production of electricity.
 They do not corrode
 They do not suffer wear and tear as they have no
movable parts
Production of solar grade silicon: (Union carbide process)
•Silicon is obtained by reducing silicon dioxide (SiO2) with coke in an electrode arc furnace at
about 1500-2000 ° C.
SiO2 + C Si+ CO2
The silicon obtained by this process is called metallurgical grade silicon. It is 98 % pure silicon.
4Al + 3SiO2 → 3Si + 2Al2O3
2Ca + SiO2 → Si + 2CaO
2Mg + SiO2 → Si + 2MgO
•This metallurgical grade silicon is not suitable for semiconductor devices. It demands greater
purity than the metallurgical grade silicon.
To get high purity silicon, metallurgical grade silicon is refined by treating it with anhydrous HCl
at 300 ° C in a fluidized bed reactor to form trichlorosilanes (SiHCl 3).
Si(s) + 3HCl SiHCl3 + H2
Si(s) + 4HCl SiCl4 + H2
•Finally, pure SiHCl3 is treated with hydrogen at 1000° C for 200-300 hrs to produce a very pure
form of silicon. This process is often referred to as UNION CARBIDE process.
SiHCl3+H2 Si+3HCl
2HSiCl3 → H2SiCl2 + SiCl4
3H2SiCl2 → SiH4 + 2HSiCl3
Pyrolysis
 Purification of Silicon (Zone refining)
Principle
Zone refining technique is based on the principle that “impurities gets concentrated in
the molten zone than in solid phase”.

Clamp

Pure solidified
Si-rod(99.9999%)

RF coil slowly
Molten Zone moving downwards
(10000 C)
Reduced
atmosphere
N2
 Hydrogen Energy
• Hydrogen is the simplest and most abundant element on earth. Hydrogen combines readily
with other chemical elements, and it is always found as part of another substance, such as
water, hydrocarbon, or alcohol. 
• Hydrogen fuel is a zero carbon fuel burned with oxygen; provided it is created in a zero
carbon way. It can be used in fuel cells or internal combustion engines.
• Regarding hydrogen vehicles, hydrogen has begun to be used in commercial 
fuel cell vehicles, such as passenger cars, and has been used in fuel cell buses for many years.
It is also used as a fuel for spacecraft propulsion.
• In the early 2020s, most hydrogen is produced by steam methane reforming of fossil gas.
Only a small quantity is made by alternative routes such as biomass gasification or 
electrolysis of water or solar thermochemistry.

Methods of hydrogen generation,

• Hydrogen from Fossil Fuels: Steam reforming method (thermal process)

• Hydrogen from Renewable Sources: Biomass Gasification
• Electrolysis: A promising method for the production of hydrogen in the future
could be water electrolysis. Currently, approximately only 4% of hydrogen
worldwide is produced by this process.
• Solar driven process.
 ELECTROLYTIC PROCESSES

Electrolysis is a process in which a direct current passing

through two electrodes in a water solution results in the
breaking of the chemical bonds present in water molecule
into hydrogen and oxygen:
Hydrogen gas released in this way can be used as 
hydrogen fuel.

Cathode: 2H2O (l) + 2e- → H2 (g) + 2OH- (aq)

Anode: 4OH- (aq) → O2 (g) + 2 H2O (l) + 4e-
Overall : 2 H2O(l) → 2 H2(g) + O2(g)

Advantage
Disadvantage
1. Renewable and Readily Available
2. Hydrogen fuel cells do not produce any CO2 emissions 1. It is expensive
3. The refuelling process for hydrogen fuel cells is easy and 2. Highly Flammable
takes about three minutes 3. Storage and transportation of
4. the energy density of hydrogen fuel cells is very high hydrogen is more complex
4. This hydrogen production process
is costly and emits carbon dioxide
1. Define chemical fuels. Classify the fuels based on occurrence and physical state with
examples.
2. Define calorific, gross and net calorific values.
3. Illustrate with a neat diagram the determination of calorific value of a fuel by bomb
calorimeter method.
4. Solve for the net and gross calorific values of a sample of coke from the following
data:
mass of coke = 0.795 x 10 -3 kg; mass of water = 2.5 kg; water equivalent of
calorimeter = 1.3 kg; specific heat of water = 4.187 kJ/kg/K; rise in temperature =
1.8K; % of hydrogen in coke = 2.5; latent heat of steam = 587 cal/g.
5. Solve for gross and net calorific values: On burning 1.15 g of a fuel in a bomb
calorimeter, the temperature of 3.5 kg of water increased from 26.5 °C to 28.5 °C.
Water
equivalent of calorimeter is 325 g, specific heat of water is 4.187 J/g/K, latent heat of
steam is 2458 J/g and the fuel contains 4 % hydrogen.
6. Solve for the gross and net calorific values of a sample of coal from the following
data:
mass of coal = 0.98 g; mass of water = 2600 g; water equivalent of calorimeter = 368 g;
specific heat of water = 4.187 J/g/K; rise in temperature = 2.8 K; % of hydrogen in coal
= 5.8; latent heat of steam = 2454 J/g.
7. On burning 0.96 x 10-3 kg of a fuel in a bomb calorimeter, the temperature of 2.75
kg ofwa ter was increased by 2.7 °C. Water equivalent of calorimeter, specific heat of
waterand and latent heat of steam are 0.385 kg, 4.187 kJ/kg/K and 2455 kJ/kg
respectively. If the fuel contains 5% hydrogen, solve for its gross and net calorific
values.
8. Examine the role of fluidized bed catalyst in cracking process with a diagram.
9. Summarize the disadvantages of non-renewable energy sources.
10. Illustrate the following: (a) octane number (b) cetane number.
11. Analyze the mechanism of knocking of gasoline in internal combustion engine.
12. Define anti-knocking agents and elaborate their role in minimizing knocking.
13. Define unleaded petrol and appraise how anti-knocking properties are achieved in
unleaded petrol.
14. Justify the use of anti-knocking agent in gasoline.
15. Define: (a) petroleum cracking (b) reformation of gasoline (c) knocking of petrol
16. Define power alcohol. Explain its production and give its advantages and
disadvantages.
17. Define bio-diesel. Explain the production of bio-diesel by trans-esterification of
triglycerides. List its advantages.
18. Define photovoltaic cell. Describe the construction and working of a photovoltaic
cell.
19. Record the advantages and disadvantages of a photo-voltaic cell.
20. Outline the Union Carbide process of production of solar grade silicon.