Module 3: Energy Systems

Fuel is a carbonaceous combustible substance, which on combustion liberates a large amount of

energy in the form of heat.
Classification
1. On the basis of occurrence, fuels are classified as
a. Primary fuels - occur in nature and are used without processing.
Example: wood, peat, lignite, anthracite, crude petroleum, natural gas, etc.
b. Secondary fuels - are obtained by chemical processing of primary fuels.
Example: charcoal, coke, petrol, kerosene, diesel, biogas, coal gas.
2. On the basis of physical state, fuels are classified as
a. solid fuels
b. liquid fuels
c. gaseous fuels

Calorific Value
The quality of a fuel is determined by the amount of energy released per unit mass or volume
referred to as calorific value.
Thus Calorific value (CV) of a fuel can be defined as the amount of thermal energy liberated
when a unit mass or a unit volume of the fuel is burnt completely in air or oxygen.

Calorific value (CV) of a fuel can be expressed in two ways,

1. Gross or Higher calorific value (GCV/HCV) and
2. Net or lower calorific value (NCV/LCV)

1. Gross or Higher calorific value (GCV/HCV) can be defined as the amount of thermal
energy liberated when a unit quantity (unit mass or volume) of the fuel is burnt completely
in air or oxygen and the products of combustion are cooled to ambient temperature (room
temperature).
i.e., while determining the calorific value of the fuel if the products of combustion are cooled to
ambient temperature (room temperature), the latent heat of steam is also included. This is
referred to as gross calorific value (GCV) or higher calorific value.

Dr. M. N. K. Harish, Dept of Chemistry, AIT, Bangalore (2018-19) Page 1

 Module 3: Energy Systems

2. Net or lower calorific value (NCV/LCV) can be defined as the amount of thermal energy
liberated when a unit quantity (unit mass or volume) of the fuel is burnt completely in air
or oxygen and, the products of combustion are allowed to escape.
i.e., while determining the calorific value of the fuel if the products of combustion are not
cooled to room temperature and are allowed to escape from the system is referred as net calorific
value (NCV) or lower calorific value.
NCV = [GCV] - [latent heat of water vapor formed]
Here the amount of heat realized is lesser than the GCV (since the latent heat of vaporization is
not released).
Therefore GCV = NCV + latent heat of steam

Determination of Calorific Value of a Solid or liquid Fuel Using Bomb Calorimeter

Construction
The set up of bomb calorimeter is as shown in figure

Oxygen
inlet

Wires for
ignition
Thermometer
Lid

Cylindrical
steel vessel
(Bomb)
Calorimeter

Stirrer Pt crucible
Water
Ignition wire

The bomb consists of a cylindrical steel vessel with an airtight screw and an inlet for oxygen.
Inside the bomb a platinum crucible with a loop of ignition wire is placed. The ends of the
ignition wire are connected to a source of electric current. The bomb is immersed in a
rectangular vessel called calorimeter which is provided with Beckmann thermometer, a stirrer
and air tight lid.

Dr. M. N. K. Harish, Dept of Chemistry, AIT, Bangalore (2018-19) Page 2

 Module 3: Energy Systems

Working
A known mass (m) of the fuel is taken in the crucible.
Oxygen is passed into the bomb at 25-30 atmosphere pressure.
A known mass (W) of water is taken in the calorimeter and is closed with the lid.
The water is stirred and the initial temperature of water is noted (t1 C).
The fuel is now ignited by ignition wire connected to electric source.
The fuel burns and thermal energy is liberated.
The thermal energy released is absorbed by water and hence the temperature of water rises and
finally attains maximum. The final temperature is noted (t2).
Calculation:
If m g = mass of fuel
Wg = mass of water
wg = water equivalent of calorimeter
t1 C = initial temperature of water
t2 C = final temperature of water
s j/g C = specific heat of water = 4.187 kJ/kg C

Then, Gross calorific value can be given by the equation

( W  w ) x ( t 2  t 1 ) xs
GCV( solid / liq . fuel ) 
m
or
( W  w ) x ( t ) xs
GCV( solid / liq . fuel ) 
m

Now the Net calorific value can be expressed as

NCV = [GCV] - [latent heat of water vapor formed]
[Latent heat of water formed = mass of water produced from unit weight of fuel  latent heat of steam]

 NCV = [GCV] - [mass of H2 x 9 x latent heat of steam]

NCV = [GCV] - [H2 (%) x 0.09 x latent heat of steam]
Note: Bomb calorimeter can be used for determination of calorific value of a liquid or solid fuel but not of
gaseous fuel.

Dr. M. N. K. Harish, Dept of Chemistry, AIT, Bangalore (2018-19) Page 3

 Module 3: Energy Systems

Petrol or gasoline Knocking –

In an Internal Combustion (IC) engine the
petrol-air mixture is drawn into the
cylinder of the engine and undergoes
compression followed by ignition. The
hydrocarbons in petrol undergo
combustion and the flame propagates.
Thus the compression ration can be
expressed as
cylinder volume when piston is at the bottom of the cylinder
Compressio n ratio 
cylinder volume when air  fuel mixture is compressed
Under ideal conditions, the hydrocarbons in petrol undergo complete combustion and the flame
propagates smoothly (i.e., 20 - 25 m/s).
But when compression ratio reaches certain point the fuel undergoes autoignition. The
flame propagation reaches 2500 m/s. Due to insufficient supply of air, the hydrocarbons form
peroxides. This sends shock waves across the engine and piston as a result rattling sound is
produced this process is known as Petrol knocking.
Mechanism of Knocking in petrole: The reactions that take place in an IC engine are given
below (taking ethane as an example for the hydrocarbon present in petrol):
Under ideal conditions
C2H6 + 7/2 O2  2 CO2 + 3H2O (Normal combustion)
Under knocking conditions (Explosive combustion)
C2H6 + O2  CH3-O-O- CH3 (Dimethyl peroxide)
CH3-O-O- CH3  CH3CHO (acetaldehyde) + H2O
CH3CHO + 3/2 O2  HCHO (formaldehyde) + CO2 + H2O
HCHO + O2  H2O + CO2
Thus Knocking is due to the generation of peroxides and other byproducts.
Harmful effects of knocking
1. Decreases life of engine and damages Piston,
2. Consumption of fuel is more,
3. Decreases the power output and hence decreases the efficiency of the engine.

Dr. M. N. K. Harish, Dept of Chemistry, AIT, Bangalore (2018-19) Page 4

 Module 3: Energy Systems

Octane Number
The resistance offered to knocking by petrol is expressed in terms of an arbitrary scale called
octane number.
Thus octane number can be defined as the percentage by volume of isooctane present in a
standard mixture of isooctane and n-heptane, which has the same knocking characteristic
(the same compression ratio) as the petrol under test.
In order to measure the octane number of a fuel, mixture of isooctane and n-heptane is taken as
standard.
Here, isooctane has least tendency for autoignition and has least knocking property so its octane
number is arbitrarily taken as 100.
Whereas n-heptane has greater tendency for autoignition and has greater knocking property so
its octane number is arbitrarily taken as 0 (zero).
Different ratio of isooctane and n-heptane (90:10; 80:20, 75:25 etc) are prepared and there
compression ratio of each of these is determined under standard conditions. The compression
ratio of the fuel under test is determined under the same conditions and its values are compared
with that of standard isooctane and n-heptane mixture.
Suppose the compression ratio of the fuel is same as that of 80:20 mixture, the octane number of
the fuel is 80.

Antiknocking Agents / Prevention of Knocking: knocking can be prevented by using

antiknocking agents such as
1. Tetraethyl lead (TEL) and
2. Methyl tertiary butyl ether (MTBE)
Tetraethyl lead (TEL) to Petrol: (Leaded petrol)
Tetra ethyl lead, in the form of ethyl fluid, is added to petrol to prevent
knocking.
Ethyl fluid consists of TEL, dichloroethane and dibromoethane.
Tetraethyl Lead decomposes the peroxides formed during the fuel
combustion in the IC engine and thus prevents knocking.

Dr. M. N. K. Harish, Dept of Chemistry, AIT, Bangalore (2018-19) Page 5

 Module 3: Energy Systems

In the process, lead gets deposited on the inner walls of the engines and at spark plugs. Hence
dichloroethane and dibromoethane are added along with tetraethyl lead. These convert the lead
into lead halides, which are volatile and escape with exhaust gases.
Limitations of TEL: The release of lead compounds pollutes the atmosphere.
Catalytic converters (rhodium catalyst) are used in IC engines to convert CO in the exhaust to
CO2. Tetraethyl Lead used as anti knocking agent poisons the catalyst and hence leaded petrol is
not advisable in such IC engines.
Addition of Methyl tertiary butyl ether (MTBE) to Petrol: (Unleaded petrol)
Methyl tertiary butyl ether (MTBE) is added to petrol to to prevent
knocking.
The oxygen present in ether group of MTBE brings about complete
combustion of petrol. This prevents the formation of peroxide and
thus prevents knocking.
Advantages of unleaded petrol:
MTBE can be used as antiknocking agent in IC engines with catalytic converter.
MTBE does not cause lead pollution unlike TEL

Power alcohole: Blend of gasoline (petrol) and absolute ethanol is called power alcohole. A
blend of 10-85% absolute ethanol and 90-15 % gasoline called gasohol is used as fuel.
Alcohol contains higher percentage of oxygen than MTBE and hence brings about complete
oxidation of petrol more effectively. Therefore power alcohol has better antiknocking
characteristics than unleaded petrol.
Advantages of power alcohol
1. Reduced fuel consumption
2. Ethanol has better antiknocking property
3. Power output is high
4. Ethanol helps in complete combustion of HC and it does not release CO, hence causes
less pollution.
5. It has the same lubricating property as that of petrol
6. Alcohol is obtained from molasses, an agricultural product and hence renewable.

Dr. M. N. K. Harish, Dept of Chemistry, AIT, Bangalore (2018-19) Page 6

 Module 3: Energy Systems

Biodiesel: is a mixture of monoalkyl esters of long chain fatty acids.

Biodiesel is a renewable energy source derived from plant source that can be obtained from
vegetable oils such as soybean, sunflower, rapeseed, cotton seed oil.
The oils are triglyceride esters of fatty acids and their direct use in diesel engines require
extensive engine modifications.
These triglycerides are subjected to transesterification in the presence of NaOH and methanol.
During transesterification, along with glycerol a mixture of monoalkyl esters of fatty acids is
obtained and this mixture is called biodiesel.
CH2OCOR1 CH3OCOR1 CH2OH
NaOH
CHOCOR2 + 3CH3OH CH3OCOR2 + CHOH
CH2OCOR3 CH3OCOR3 CH2OH
(Triglyceride oil) (Biodiesel) (Glycerol)
Where R = long chain fatty acids in the oil. Glycerol is soluble in water and can be separated
from the reaction mixture.
Advantages of Biodiesel
1. It is produced using renewable sources.
2. It has a higher flash point than diesel but lower ignition point
3. Biodiesel has a higher cetane number compared to diesel.
4. Fewer harmful emissions compared to diesel
5. It is non-toxic

Dr. M. N. K. Harish, Dept of Chemistry, AIT, Bangalore (2018-19) Page 7

 Module 3: Energy Systems

FUEL CELLS
Definition: Fuel cell is an energy conversion device which can be defined as “a galvanic cell in
which the electrical energy is directly derived by the combustion of chemical fuels supplied
continuously by means of electrochemical processes in which the fuel oxidized at anode.
Generally representation  Fuel | electrode | electrolyte | electrode | oxidant

The reactions are as follows

At anode, fuel undergoes oxidation: Fuel  oxidation products + ne-
At cathode, the oxidant gets reduced: Oxidant + ne-  reduced products

Classification of fuel cells based on temperature

a. Low temperature fuel cells – which operates below  100 C.
b. Medium temperature fuel cells – operate at  600 C.
C. High temperature fuel cells – operate at 1000 C.

Classification of fuel cells based on electrolyte

a. Proton exchange membrane fuel cells or Polymer electrolyte membrane fuel cells uses
perfluoro sulfonic acid as electrolyte
b. Phosphoric acid fuel cells use phosphoric acid as electrolyte
c. Alkaline fuel cells use aqueous solution of KOH or NaOH as electrolyte
d. Molten carbonate fuel cells use alkali carbonates (Li, Na or K) as electrolyte
d. Solid-oxide fuel cells use ceramic as electrolyte

Differences between a battery and a fuel cell

Conventional cell (Battery) Fuel cell
1. Energy storage device 1. Energy conversion device
2. Reactants are within the cell 2. Reactants are supplied continuously.
3. Products remain in the cell 3. Products are continuously removed from the cell.

Dr. M. N. K. Harish, Dept of Chemistry, AIT, Bangalore (2018-19) Page 8

 Module 3: Energy Systems

Methanol–Oxygen fuel cell e- L

e-
Construction: It consists of Anode Cathode
anode and cathode made of CH3OH + O2
3.7M H2SO4 H+
→
platinum. Sulphuric acid acts as
the electrolyte. A membrane is Platinum
electrode Ion exchange
inserted adjacent to the cathode H2SO4
membrane

on the electrolyte side to

minimize the diffusion of CH3OH + H2O
3.7M H2SO4
methanol into the cathode. CO 2 trap
Methanol–H2SO4 mixture is
circulated through the anode chamber. Pure oxygen is passed through the cathode chamber.
Working: At anode methanol undergoes oxidation to produce CO2 and electrons and at cathode
O2 undergoes reduction to produce water. The cell produces a potential of 1.21 V.
Cell reactions:

At anode : CH3OH + H2O CO2 + 6H+ + 6e-

At cathode : 11/2 O2 + 6H+ + 6e- 3H2O
Over all reaction: CH3OH + 11/2 O2 CO2 + 2H2O
Uses: It is used in large-scale power production.
Advantages: Methanol is an efficient electro active organic fuel at low temperatures.
1. It has low carbon content.
2. It has a readily oxidisable OH group.
3. It has a high solubility in aqueous electrolytes.

Advantages of fuel cells:

 Theoretically, the efficiency can be 100%. In practice, the efficiency is 50-80 % which
is high compared to conventional methods.
 Harmful products are absent. Hence fuel cells are environment friendly.
 No need of charging.
 Silent operation.
 No moving parts. Hence wear and tear is eliminated.

Dr. M. N. K. Harish, Dept of Chemistry, AIT, Bangalore (2018-19) Page 9

 Module 3: Energy Systems

Solid Oxide Fuel cell [SOFC] is an energy conversion device which provides electrical energy
by electrochemical combustion of chemical fuels supplied continuously.
Construction and working
Solid-oxide fuel cell is high temperature fuel cells which operate at 1000 C and use ceramic
active components.
It consists of following ceramic components
Anode - Nickel and Yttria stabilized Zirconia (Ni Y2O3 ZrO2)
Cathode - Lanthanum Strontium Manganite (La Sr MnO3)
Electrolyte - Yttria stabilized Zirconia (Y2O3 ZrO2)
These active components are assembled in interconnect made of chromia forming ferritic
stainless steel.
The ceramics used in SOFCs do not become electrically and ionically active until they reach
very high temperature 1000 °C. Hydrogen fuel is fed continuously at the anode and oxygen as
oxidant at the cathode at 1000 °C. At anode hydrogen undergoes oxidation to provide H+ ions
and two electrons. The electrons from the anodic compartment move through the external load
and combine with oxygen to form oxygen anion (O2-) at the cathode. These O2- ions then diffuse
through the solid oxide electrolyte to the anode where they combine with H+ ions to produce
water. e- L
e-
Anode Cathode
At anode
H2 H+ + 2e H2 O2
H+ + O2- H2O 2-
O
At cathode
2-
O2 + 2e 2O-2 O Electrolyte
Yttria
stabilized
Over all reaction Zirconia
H2 + O2 H2O
H2O O2

Anode Cathode
Ni & Yttria La Sr MnO3
stabilized
Advantages of SOFC Zirconia
High efficiency, Long-term stability, Fuel flexibility, Low emissions,
Disadvantage of SOFC is the high operating temperature which results in longer start-up times
and mechanical and chemical compatibility issues

Dr. M. N. K. Harish, Dept of Chemistry, AIT, Bangalore (2018-19) Page 10

 Module 3: Energy Systems

Solar Energy
Photovoltaic cells or Solar cells: are semiconductor energy conversion devices which convert
sun light to electrical energy. Example is Silicon Solar cells.
The sun radiates in all regions of the spectrum, from radio waves to gamma rays. Our eyes are
sensitive to less than one octave of this, from 750 to 400 nm, a region known, for obvious
reasons, as visible. Although narrow, it contains about 45% of all radiated energy.

Construction and working of Silicon Solar Cells

Antireflective
layer

Metallic
grid
n-type
h+ h+ h+ h+ h+ h+ h+
e- e- e- e- e- e- e- Load

p-type
Silver

Silicon solar cells consist of a p-n junction. This p-n junction has two electrical contacts one
bottom layer coated with nobel metal silver and metallic grids of aluminum at the top. The load
is connected between the two electrical contacts as shown in the figure.
Electromagnetic radiations consisting of photons (h), these photons carry certain amount of

energy given by Planck’s quantum equation =


Where E is energy, h is Planck’s constant, c is velocity of light and  is wavelength of light.
When electromagnetic radiations from sun having the energy greater than barrier potential falls
on the photovoltaic cell electron-hole pair produced away from the junction. Electron will
migrate to the n-region and holes will migrate to p-region and the circuit gets completed. This
energy can be used for various domestic and industrial purposes.

Production of solar cell grade silicon by union carbide process: It involves following steps
1. Reduction of silica with carbon
2. Refining
3. Zone refining

Dr. M. N. K. Harish, Dept of Chemistry, AIT, Bangalore (2018-19) Page 11

 Module 3: Energy Systems

1. Reduction of silica with carbon

( )+ ( ) > +
− 

Silica in the form of quartz and carbon in the form of coke are placed in electric arc furnace. Two
carbon electrodes are placed in the crucible and an electric arc is struck. Temperature of around
1500-2000 C is produced and silica undergoes reduction to form elemental silicon and carbon
undergoes oxidation to form oxides of carbon. So obtained elemental silicon will be in molten
state which contain trace amount of metallic impurities such as Al, Mg, Ca.

2. Refining
Oxygen is passed through molten Silicon mixed with silica. The impurities (Al, Mg, Ca) are
oxidized to corresponding oxides (Al 2O3, MgO, CaO). The oxides forms slag which floats at the
surface of the reactor. The slag is removed and refined Silicon melt is poured in to moulds to
form solid silicon. So obtained silicon is called as metallurgical grade silicon.
The following reactions take place during the above process
+ → +
+ → +
+ → +
The metallurgical grade silicon is then treated with dry HCl gas at 300 C to form mixture of
trichloro silane (SiHCl3) in major quantity and tetrachloro silane (SiCl4) in minor quantity.
+ → + +
Trichloro silane (SiHCl3) which has boiling point of 31.8 C is purified by distillation.
Trichloro silane (SiHCl3) is then hydrogenated at 1100 C for 200-300 h to get semiconductor
grade silicon

+ → +
−

Dr. M. N. K. Harish, Dept of Chemistry, AIT, Bangalore (2018-19) Page 12

 Module 3: Energy Systems

3. Zone refining:
In zone refiner the semiconductor grade silicon rod is heated with radio frequency induction wire
in argon atmosphere as shown in the figure. As the radio frequency induction coil is moved from
top to bottom, the impurities move down gradually in the molten region and pure part gets
solidified. The bottom portion containing impurities is removed. This process is repeated many
times and finally ultra pure Solar cell grade silicon is obtained.

Argon
gas

Radio frequency
induction coil
Molten zone
Impurity

Semiconductor
grade Si
Argon Clamp
gas

Advantages of Solar cells

Renewable energy resource
Environmentally friendly energy resource
Infinite and long term energy resource
It does not require fuels or water to produce electricity
Emissions or radiations free

Disadvantages of Solar cells

It cannot be used in absence of the light
Very high initial cost for installation.
Very large geographical area is needed in order to deploy solar panels or cells.
Off grid applications require energy storage systems.
Solar cells generate direct current (DC). It requires DC appliances or inverters (to convert DC to
AC).

Dr. M. N. K. Harish, Dept of Chemistry, AIT, Bangalore (2018-19) Page 13