Applied Chemistry

Unit-2: Energy : Sources, Conversion and Storage

Dr Rangarajan B
 Syllabus :
• Chemical fuels – Introduction, Calorific value - definition, gross and net calorific values;
• Determination of calorific value of a solid / liquid fuel using Bomb calorimeter and numerical
on calorific value;
• Petroleum cracking - fluidized bed catalytic cracking;
• Octane number- Reformation of petrol.
• Sustainable energy sources:
• Hydrogen as a fuel - advantages, production and storage.
• Biofuels- Production of Biodiesel.
• Solar cells –
• Construction and working of Si based PV cell, advantages.
• Quantum Dot Sensitized Solar Cells (QDSSC’s)- Principle, Properties and Applications.
• Electrochemical Energy Systems: Introduction to batteries,
• Classification of batteries - primary and secondary batteries;
• Battery characteristics;
• Construction, working and applications of Lithium ion batteries.
Energy is a fundamental component to our daily lives, and everyday we use energy or power in
some form or another. Energy can be defined as the capacity to do work.
Energy source—a supply of energy available for use (sometimes referred to as resources).
Energy sources can be classified into :
• Renewable energy : Solar, Wind ,Hydro, Geothermal
• Nonrenewable energy : Fossil fuels, Nuclear
A fuel is a substance that produces useful energy
through combustion.

Fuel Maybe defined as a naturally occurring or

artificially prepared combustible carbonaceous
material used as source of heat/energy.

Fossil Fuels : Coal , Natural Gas, Crude Oil still

account for more than 60% energy generation
Fuels that produce heat energy by combustion are termed as chemical fuels.
During combustion, carbon and hydrogen that are present in the fuel combine
with oxygen and release energy.
Calorific Value : It is defined as the total amount of heat liberated when a unit mass or volume
of fuel is burnt completely. (units: kJ/kg)

Gross Calorific Value (GCV) : It is also called Higher calorific value (HCV) and is defined as the
total amount of heat produced when a unit quantity (mass/volume) of fuel is burnt completely,
and the products of combustion are cooled to room temperature (288K)

Low Calorific Value (LCV) : It is also termed as Net calorific value (NCV) and is defined as the
heat produced when a unit quantity (mass/volume) of a fuel is burnt completely and the hot
combustion products are allowed to escape.

LCV = GCV – (0.09 x % of Hydrogen in fuel x Latent heat of steam)

 Determination of
Calorific Value
Principle: A known amount of fuel
is burnt in excess of oxygen and the
heat liberated is absorbed in a known
amount of water. This heat liberated is
measured by noting the change in
temperature.

Calorific value of the fuel is then

calculated by applying the following
principle:

Heat liberated by fuel = Heat absorbed

by water and the calorimeter.
Construction :
• The bomb calorimeter consist of a stainless-steel vessel known as bomb with a capacity of
around 500ml. It has an airtight lid and inlet valve for supplying Oxygen.

• A known mass of fuel (0.5 –1 g) is taken in a clean crucible supported over the ring.

• A fine magnesium wire (fuse), touching the fuel sample, is then stretched across the
electrodes.

• The bomb is filled with oxygen at 25-30 atmospheric pressure and placed in the calorimeter
containing a known weight of water and an electrical stirrer.

• The stirrer is started, and the initial temperature of water is noted. The electrodes are then
connected to a power supply and powered up fire the fuse. The sample burns and heat is
liberated.

• This heat is absorbed by water. Maximum temperature shown by the thermometer is

recorded. The gross calorific value of the fuel is calculated as follows
 Determination of Calorific Value

Mass of fuel sample taken = m kg

Weight of water in the calorimeter = W kg
Water equivalent* of calorimeter = w kg (* Water equivalent of a calorimeter is the product
of mass of calorimeter and its specific heat. It is constant for a particular instrument )

Initial temperature of water in the calorimeter = t1 °C

Final temperature of water in the calorimeter = t2 °C

Heat liberated on combustion (GCV) = Heat absorbed by water + calorimeter

Heal liberated on combustion of mass ‘m’ kg of fuel = m x GCV

Heat required to raise temperature of 1kg of water by 1°C = s = 4.187 kJ/kg/°C (Specific heat
of water)
Latent heat of steam = L = 2454 kJ/kg/°C
Heat absorbed by water + calorimeter (W+w) to raise its temperature
from t1 to t2 °C = ( W + w ) x (t2 – t1) x s

𝑚 × 𝐺𝐶𝑉 = 𝑊 + 𝑤 × 𝑡2 − 𝑡1 × 𝑠

Or

𝑊+𝑤 × 𝑡2 −𝑡1 ×𝑠
𝐺𝐶𝑉 = kJ/kg
𝑚

and

𝑊+𝑤 × 𝑡2 −𝑡1 ×𝑠
𝑁𝐶𝑉 = − 0.09 × %𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛 𝑖𝑛 𝑓𝑢𝑒𝑙 × 𝐿 kJ/kg
𝑚

𝑁𝐶𝑉 = 𝐺𝐶𝑉 − 0.09 × %𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛 𝑖𝑛 𝑓𝑢𝑒𝑙 × 𝐿 kJ/kg

1. When 0.935g of fuel undergoes combustion in excess oxygen the increase in
temperature of water in calorimeter containing 1365g of water was 2.4°C, Calculate GCV/HCV
of the fuel if water equivalent of caloriemeter is 135g. Given specific heat of water is 4.187
kJ/kg
𝑊+𝑤 × 𝑡2 −𝑡1 ×𝑠
Answer : 𝐺𝐶𝑉 = kJ/kg
𝑚

Given : W = 1365g , w = 135g , (W+w) = (1365+135)x10-3 kg

(t2 – t1) = 2.4°C , m = 0.935g = 0.935 x 10-3 kg , s = 4.187 kJ/kg

1365+135 × 2.4 ×4.187×10−3

𝐺𝐶𝑉 = −3 kJ/kg
0.935×10

GCV = 16121.07 kJ/kg

2. 0.8g of coal with 92% Carbon, 5% hydrogen and 3%ash on combustion in excess oxygen
raises the temperature of 4000g water in calorimeter by 6.2°C, Calculate GCV and NCV of the
coal if water equivalent of caloriemeter is 400g. Given specific heat of water is 4.187 kJ/kg ,
Latent heat of steam = 587cal/g
𝑊+𝑤 × 𝑡2 −𝑡1 ×𝑠
Answer : 𝐺𝐶𝑉 = kJ/kg
𝑚
Given : (Weight of water) W = 4000g ,
(water equivalent) w = 400g ,
(W+w) = (4000+400)x10-3 kg

(t2 – t1) = 6.2°C , m = 0.8g = 0.8 x 10-3 kg , s = 4.187 kJ/kg

L = 587 cal/g (1cal = 4.18kJ) , 587cal = 2454 kJ/kg , %H = 5

4000+400 × 6.2 × 4.187×10−3

𝐺𝐶𝑉 = kJ/kg
0.8×10−3

GCV = 142776.7 kJ/kg

𝑁𝐶𝑉 = 𝐺𝐶𝑉 − 0.09 × %𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛 𝑖𝑛 𝑓𝑢𝑒𝑙 × 𝐿 kJ/kg
𝑁𝐶𝑉 = 142776.7 − 0.09 × 5 × 2454 kJ/kg
NCV = 141672 kJ/kg
 Processing of Fuels :
Petroleum (the term petroleum means rock oil. Latin-Petra means rock; oleum means
oil) is a dark, greenish-brown viscous oil found deep inside the earth’s crust.

It is a mixture of hydrocarbons such as straight chain paraffins, cycloparaffins or naphthalene,

olefins and aromatics along with small amount oxygen, nitrogen and sulphur containing
compounds. Crude oil is difficult to use as a direct source of fuel due to its poor efficiency and
the impurities present in crude oil tends to leave a lot of solid residue after combustion making
it difficult to use in engines.

Crude oil coming out from the oil well is a mixture of solid, liquid and gaseous hydrocarbons
containing sand and water in suspension. After removal of dirt, water, sulphur and other
impurities, this oil is subjected to fractional distillation.
Refining of Petroleum/Crude oil : Fractional distillation

The process of removing unwanted impurities and separating petroleum into useful fractions
with different boiling ranges is called refining of petroleum.

Fractional distillation :
The crude oil is heated to 400 °C in an iron retort whereby all the volatile constituents, except
asphalt or coke are evaporated.

The vapours are then passed into a fractionating column, which is a tall cylindrical tower. The
tower is hot towards the lower end and comparatively cooler at the upper end. It consists of a
number of horizontal stainless steel trays at short distances.

These trays are provided with individual chimneys which are covered with a loose cap. As the
vapours go up, fractional condensation occurs at different heights of the column. Higher boiling
fractions condense first, while lower boiling fractions condense late
• Light oil is one of the more important fractions, and its products have boiling points around
70-150°C. Useful hydrocarbons in this range include gasoline, naphta (a chemical feedstock),
kerosene, jet fuel, and paraffin. These products are highly volatile, have small molecules, have
low boiling points, flow easily, and ignite easily.

• Medium Oil are products that have boiling points of 150-350°C. Products in this range
include Kerosene, diesel and light gas oil - used in the manufacturing of town gas/Coal
gas and for commercial heating.

• Heavy oil are the products with the lowest volatility and have boiling points above 350°C.
These fractions can be solid or semi-solid and may need to be heated in order to flow (Like
tar). These products have large molecules, a low volatility, flow poorly, and do not ignite easily
Ex : Asphalt, wax, lubricating oils
The crude oil obtained on fractionation yields approximately 20–30% gasoline, 30–35% middle
oils and 20–25% heavy oils. Among all these fractions, gasoline (also called straight run petrol) is
in maximum demand because of its use as fuel in the automobile industry. Hence there is a need
to convert the middle oil and heavy oil fractions into a more useful fraction gasoline
 Cracking of petroleum
Cracking is defined as the process of converting high-molecular-weight, high boiling
hydrocarbons (Petroleum fractions) into low-molecular-weight, low boiling hydrocarbons by
the application of heat, with or without a catalyst.

Heavy oil fraction of petroleum on cracking yield low boiling range products like petrol,
naptha, diesel which have high value and high market demand . Cracking involves
breaking of C-C bonds. These reactions are endothermic and hence favoured by high
temperature.

Cracking can be carried out by two ways

1) Thermal cracking.
2) Catalytic cracking.
Thermal Cracking :

❑ Thermal cracking process was developed in the early 1900s When the heavy oils are
subjected to high temperature and pressure in the absence of catalyst. The bigger
hydrocarbons breakdown to give smaller molecules

❑ It involves breaking of heavy oil fractions by thermal decomposition at 450 - 540°C and
pressures of 100-1000 psi.

❑ C - C bond is broken by free radical mechanism in which reactions are not selective.

❑ In this process, the gasoline was obtained with lower yield and lower quality with octane
number of 70. More amounts of mono-olefins and diolefins were formed, which undergo
further polymerization producing coke. Therefore, this process was replaced by more
efficient catalytic cracking process.
Catalytic Cracking :

❑ By catalytic cracking method, gasoline can be obtained in better yield which contains
more of iso-alkanes and aromatics having higher octane numbers.

❑ Breaking of C-C bond is catalyzed by acidic catalysts and proceeds through

carbocation formation. Carbocation is more stable intermediate than free radical
intermediate of thermal cracking. Therefore, reactions are more selective

❑ Catalyst used : Zeolites ( Microporous crystalline aluminosilicates).

❑ The two main types of Catalytic cracking :

1. Fixed bed catalytic cracking
2. Fluidized catalytic cracking
Fluidized catalytic cracking ➢ In the fluidized catalytic cracking process, heavy oil
is preheated to about 300°C and introduced into the
reactor through a riser column.

➢ The reactor contains finely powdered catalyst

maintained at about 700°C. When the preheated oil
and catalyst are mixed up in the reactor,
temperature falls to about 530°C.

➢ Cracking occurs on the surface of the catalyst in a

contact time of 3 seconds. The products obtained
are passed into fractionating column.

➢ Unreacted reactants and products left out on the

catalyst surface are stripped off by introducing
steam in stripper chamber

➢ Then catalyst is regenerated by introducing hot air

into the regenerator at 550°C. Hot air burns the
carbon deposited on the catalyst surface and the
waste gases released are allowed to escape out. Hot
regenerated catalyst is again fed into the reactor.
Knocking :
• Automobiles use internal combustion engines where the fuel
(petrol)-air mixture is sucked in (suction stroke) and
compressed using a piston (compression stroke) .

𝒄𝒐𝒎𝒑𝒓𝒆𝒔𝒔𝒊𝒐𝒏 𝒓𝒂𝒕𝒊𝒐
• The compressed mixture is then ignited using an electric
spark to burn smoothly and release energy. 𝑉𝑜𝑙𝑢𝑚𝑒 𝑎𝑡 𝑡ℎ𝑒 𝑒𝑛𝑑 𝑜𝑓 𝑠𝑢𝑐𝑡𝑖𝑜𝑛 𝑠𝑡𝑟𝑜𝑘𝑒
=
𝑉𝑜𝑙𝑢𝑚𝑒 𝑎𝑡 𝑡ℎ𝑒 𝑒𝑛𝑑 𝑜𝑓 𝐶𝑜𝑚𝑝𝑟𝑒𝑠𝑠𝑖𝑜𝑛 𝑠𝑡𝑟𝑜𝑘𝑒
• Some hydrocarbons/petrol cannot withstand high pressure
and combine with oxygen and pre-ignite.

• These pre-ignitions are sudden bursts that propagate at

speeds of 2500m/s and generate shockwaves in the engine
and produces a rattling noise

• Knocking is the rattling sound produced because of the

shockwave arising in the engine due to explosive
combustion of fuel-air mixture at higher compression ratio
Structure of fuel and knocking tendency :
1. Knocking decreases with increase in compactness of the molecule.
2. Decreases with the increase in the number of double bonds and rings (cyclic structure)
3. Decreases as the branching in carbon chain increases
4. Increases with increase in length of the hydrocarbon chain

The tendency of fuel constituents (hydrocarbons) to knock is in the following order :

Straight chain > branched chain (i.e., iso) olefins > cycloparaffins (i.e., naphthalenes) > aromatics

Most Knocking Least knocking

In order to classify the fuels according to their knocking property, an arbitrary scale was provided
known as octane number/octane rating

It is observed that n-heptane knocks very badly; hence, it was arbitrarily assigned an antiknock
value of zero. On the other hand, isooctane (2,2,4-trimethylpentane) has a high resistance to
knocking and hence was arbitrarily assigned an antiknock value of 100

Octane number of a fuel sample is “the percentage of iso-octane present in a standard

mixture of isooctane and n-heptane which produces knocking at the same compression ratio
as that of the fuel sample being tested”.

Higher the quality of petrol/fuel - Higher is its octane rating

Reformation of petrol :
Fuels(Petrol) which are obtained after cracking / distillation might produce high knocking due to
their structure hence they need to be modified into a less knocking structure through a process
called reformation.

Reforming is the process of improving the anti-knocking characteristics of gasoline by bringing

about certain structural modifications in it. The modifications are due to the rearrangement of
molecules without disturbing their average molecular weight

Thermal Reforming : In this process, the straight run gasolines are heated to a temperature of
500–600 °C at a pressure of about 85 kg/cm2.

Catalytic Reforming : Catalytic reforming is carried out in the presence of a catalyst (platinum
supported on alumina). It is carried out at 460 –530°C and a pressure of 35 –51 kg/cm2. It can
be either fixed bed or fluidized bed
The main reactions involved in reforming process are :