Module II: Fuels

Course Title: Engineering Chemistry

Course Code: CHEM136
Definition of fuel:
A fuel is any substance used to produce heat or power (energy) by combustion. Combustion
is a chemical process in which a substance reacts rapidly with oxygen and gives off heat. The
original substance is called the fuel, and the source of oxygen is called the oxidizer.
Fuel + Oxygen → Combustion products + Heat
Energy should be released in a controlled manner and can be harnessed economically for
domestic and industrial purposes. Fuels that produce heat energy by combustion are called
as chemical fuels. Fuels constitute our most important source of energy for industrial use. the
production of power is more economical in a large majority of industries. Examples: wood,
oil, natural gases, producer gas etc.
Nowadays wood is generally not the main source of fuel in many parts of the world. Natural
gas or oil is used as a part of domestic fuel. Oil and coal are mainly used to heat the water to
produce steam for rotating the turbines for huge power generation. The fuels namely coal,
oil and natural gas are commonly referred to as fossil fuels.
Classification of fuels:
The fuels are classified on the basis of their occurrence and on their physical state.
Classification on the basis of their physical state:

Classification of the fuels can also be done on the basis of their physical states.
Dr. Anuradha Mahanty
Assistant Professor
Amity Institute of Applied Sciences
 • Solid fuels: It is characterized by its mass, composition, specific heat, combustion
residue and other thermal properties. (Specific heat is the quantity of heat required
to raise the temperature of one gram of a substance by one Celsius degree. The units
of specific heat are usually calories or joules per gram per Celsius degree).
• Liquid fuels: It is characterized by its composition, density, viscosity (most important
characteristics in the storage and use of fuel oil), specific heat and other thermal
properties.
• Gaseous fuels: Characterized by composition, volume and pressure and thermal
properties.
Classification of fuels on the basis of their occurrence:

Types of fuels (Occurence)

Primary or natural fuels Secondary or Synthetic

fuels

On the basis of occurrence, fuels are of two types:

o Primary or natural fuels: These are found in nature and are used as such, generally
without processing. These are also known as fossil fuels. Examples include wood, peat,
lignite, petroleum, natural gas etc.
o Secondary or synthetic fuels: These are derived from the natural fuels by further
chemical processing. Examples of this type are coke, charcoal, kerosene, producer gas,
water gas etc.

Primary fuels → Solid Fuels

Wood
Peat (The precursor to coal is peat. Peat is a soft, organic material consisting of partly
decayed plant and mineral matter. When peat is placed under high pressure and heat,
it undergoes physical and chemical changes (coalification) to become coal).

Dr. Anuradha Mahanty

Assistant Professor
Amity Institute of Applied Sciences
 Lignite (the lowest grade coal with the least concentration of carbon. Lignite has a low
heating value and a high moisture content and is mainly used in electricity generation.
Coal
Secondary Fuels → Solid Fuels
Charcoal (Charcoal, impure form of graphitic carbon, obtained as a residue when
carbonaceous material is partially burned, or heated with limited access of air).
Coke
Petroleum Coke (Petroleum coke, or Petcoke, is a solid, carbon-rich material similar to
coal but with different properties. It is derived from oil refining, and it's a by-product
produced during the cracking process).

Primary fuels → Liquid

Crude Petroleum
Natural gasoline
Secondary fuels → Liquid
Tar
Petroleum distillates
• Gasoline: gasoline, mixture of volatile, flammable liquid hydrocarbons derived
from petroleum and used as fuel for internal-combustion engines,
• Kerosene
• Gas Oil
• Petroleum residues
• Fuel Oil
• Alcohol
Characteristic of good fuel:

✓ High calorific value: The amount of heat energy released when a unity quantity of
fuel is burnt completely is known as calorific value. Higher is the calorific value, the
greater is the heat liberated per unit mass or volume of the fuel and the better is
the fuel quality.
✓ Ignition temperature: It is the lowest temperature to which the fuel must be
preheated so that it starts burning smoothly. An ideal fuel should have moderate
ignition temperature. Fuels with low ignition temperature can burn spontaneously
and cause explosion. High ignition temperature makes the fuel difficult to ignite.
✓ Moisture content: It should be low because the presence of moisture lowers the
calorific value of the fuel.
✓ Non-combustible matter (Ash): Non-combustible matter reduces the calorific
value of the fuel. It also needs additional investment for its storage, handling and
disposal.

Dr. Anuradha Mahanty

Assistant Professor
Amity Institute of Applied Sciences
 ✓ Velocity of combustion: Fuel must burn with a moderate rate. If the velocity is
low, then a part of heat may get radiated instead of raising the temperature. If it
is very high, then combustion may be uncontrollable.
✓ Combustion products should be harmless and non-polluting.
✓ Cost of the fuel: A good fuel should be readily available at low cost.
✓ Storage & transportation: A good fuel should be easy to handle, store & transport
at low cost

Calorific Value:
The most important characteristics of a fuel is the amount of heat generated from it. Calorific
values or heating values of a fuel express the heat obtained from one unit of the fuel. The
estimation of amount of heat generated from the particular fuel is expressed in terms of
British Thermal units and in the metric system, it is expressed in Calories.

Calorie (cal): It is 1/100 of the amount of heat necessary to raise 1g of water from 0°C to
100°C.

A larger unit i.e. kilocalorie (Kcal) is also used to express the amount of heat generated
1Kcal = 1000 cal
Combustion:
Combustion is a chemical reaction that occurs when a substance (typically a fuel) reacts
rapidly with oxygen, releasing energy in the form of heat and light. This process is commonly
known as burning.
The terminology associated with combustion:
Fuel: This is the substance that undergoes combustion, like wood, gasoline, or natural
gas.
Oxygen: Combustion requires oxygen, usually from the air.
Heat: A certain amount of heat is necessary to start the combustion process. Once it
starts, the reaction itself releases more heat.
Products: Combustion produces by-products such as carbon dioxide (CO₂), water
vapor (H₂O), and sometimes other gases, depending on the fuel.
There are two main types of combustion:
Complete Combustion: When there is enough oxygen, the fuel burns completely, producing
carbon dioxide and water.

CH4 + 2O2→CO2 + 2H2O + heat

(methane + oxygen → carbon dioxide + water + heat)
Incomplete Combustion: When there is insufficient oxygen, the fuel doesn’t burn
completely, resulting in products like carbon monoxide (CO) and soot.
Dr. Anuradha Mahanty
Assistant Professor
Amity Institute of Applied Sciences
Gross and Net Calorific value:
The calorific value of substances is categorized as gross (higher) calorific value or net (lower)
calorific value.
Higher Calorific Value or Gross Calorific Value (HCV):

When 1 kg of a fuel is burnt, the heat obtained by the complete combustion after the products
of the combustion are cooled down to room temperature (usually 15°C) is called higher
calorific value of that fuel.

GCV = LCV + Latent Heat of condensation

Lower Calorific Value or Net Calorific Value (LCV):
When 1 kg of a fuel is completely burned and the products of combustions are not cooled
down or the heat carried away the products of combustion is not recovered and the steam
produced in this process is not condensed then the heat obtained is known as the Lower
Calorific Value.
LCV = GCV ‒ Latent Heat of condensation
Relationship between LCV and GCV:
Usually, all fuels contain hydrogen. During the combustion, the hydrogen in the fuel is
converted into steam. When the combustion products are cooled to room temperature, the
steam gets condensed and heat equals to the latent heat of steam is evolved. This heat gets
added in the measured heat and so GCV value is higher than NCV.
What is latent heat:
o A phase change is the change of a substance's physical state from solid to liquid, liquid
to gas, gas to solid, and so on.
o Latent heat is the heat needed to cause a phase change to a specific amount of matter
at a fixed temperature. It is the amount of heat that is absorbed or released divided
by the amount of substance that is undergoing a phase change.
Latent heat of condensation:
Latent heat of condensation refers to the heat that is released when a specific amount of
vapor condenses and returns to the liquid phase at a fixed temperature. An example of such
is the formation of morning dew.
Latent heat of evaporation:
Latent heat of vaporization is defined as the heat required to change specific amount of liquid
at its boiling point. When a material in liquid state is given energy, it changes its phase from
liquid to vapor; the energy absorbed in this process is called heat of vaporization.

Dr. Anuradha Mahanty

Assistant Professor
Amity Institute of Applied Sciences
Normality in Chemistry is one of the expressions used to measure the concentration of a
solution. It is abbreviated as ‘N’ and is sometimes referred to as the equivalent concentration
of a solution. involving acid-base chemistry. As per the standard definition, Normality is
described as the number of gram or mole equivalents of solute present in one litre of a
solution. The number of equivalents is the valency of the solute or the number of electrons
involved in the chemical reaction.

i. Solid Fuel: Coal

Coal is a complex organic compound derived from the dead plants buried under the ground
for several years.
The degraded matter was converted into various types of coal:
✓ Peat
✓ lignite
✓ Bituminous coal and
✓ Anthracite coal
This classification is made based on the carbon content. The highest ranking of coal, which
has largest carbon content, is anthracite. The lowest rank of the coal is peat, which is formed
at the first stage of the coalification. The next rank is lignite (also called as brown coal) and
then bituminous coal.

Thus, the order of ranking of coals is:

Anthracite > Bituminous > Sub-bituminous > Lignite > Peat
In order to know the calorific values of the varieties of coal with varying composition of
carbon, moisture, volatile matters, analysis of coal is very much important. There are two
types of analysis for determination of the quality of the coal.
✓ Proximate Analysis
✓ Ultimate Analysis

Proximate Analysis:
It includes the determination of moisture content, volatile matter, ash and fixed carbon
content. In this analysis, the data varies with the procedure adopted for study.
ii. Moisture content: About 1g of finely divided powder of air-dried coal sample is
weighed in a crucible and placed inside an electric hot air oven, maintained at 105 –
110°C. The crucible is allowed to remain in the oven for an hour and then taken out,
cooled in desiccators and weighed. The loss of weight is reported as moisture
percentage.
𝐿𝑜𝑠𝑠 𝑖𝑛 𝑤𝑒𝑖𝑔ℎ𝑡
𝑀𝑜𝑖𝑠𝑡𝑢𝑟𝑒 % = × 100
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑐𝑜𝑎𝑙 𝑡𝑎𝑘𝑒𝑛

Dr. Anuradha Mahanty

Assistant Professor
Amity Institute of Applied Sciences
 iii. Volatile matter: The dried sample of coal left in the crucible after analysis of moisture
content is then covered with a lid and placed in an electric furnace maintained at
925°C. The crucible taken out after 7 min of heating and then cooled in air and then in
desiccators. After taking weight, the loss in weight is reported as volatile matter in
percentage terms.
𝑉𝑜𝑙𝑎𝑡𝑖𝑙𝑒 𝑀𝑎𝑡𝑡𝑒𝑟 (%)
𝐿𝑜𝑠𝑠 𝑖𝑛 𝑤𝑒𝑖𝑔ℎ𝑡 𝑑𝑢𝑒 𝑡𝑜 𝑟𝑒𝑚𝑜𝑣𝑎𝑙 𝑜𝑓 𝑣𝑜𝑙𝑎𝑡𝑖𝑙𝑒 𝑚𝑎𝑡𝑡𝑒𝑟
= × 100
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑐𝑜𝑎𝑙 𝑠𝑎𝑚𝑝𝑙𝑒 𝑡𝑎𝑘𝑒𝑛

iv. Ash content: The residual coal in the crucible after analysis of volatile matter is then
heated without lid in muffle furnace at 700±5°C. After 0.5h, the crucible is taken out,
cooled first in air, then in a desiccator and weighed. Heating, cooling, weighed is
repeated till a constant weight is obtained. The residue is reported as ash in
percentage term.
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑎𝑠ℎ 𝑙𝑒𝑓𝑡
𝐴𝑠ℎ (%) = × 100
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑐𝑜𝑎𝑙 𝑡𝑎𝑘𝑒𝑛

v. Fixed carbon: This refers to the amount of carbon present in the coal sample. This is
calculated by deducting the percentage amount of moisture, volatile matter and ash
from 100.

𝐹𝑖𝑥𝑒𝑑 𝑐𝑎𝑟𝑏𝑜𝑛 (%) = 100 − (𝑀𝑜𝑖𝑠𝑡𝑢𝑟𝑒 + 𝑉𝑜𝑙𝑎𝑡𝑖𝑙𝑒 𝑚𝑎𝑡𝑡𝑒𝑟 + 𝐴𝑠ℎ)

Significance of Proximate Analysis:

i. Moisture lowers the calorific value of coal and it quenches the fire in the furnace. So,
lesser is the moisture content, better is the quality of coal as fuel.
ii. High volatile matter content means that a large proportion of the matter escapes
unburnt. This matter may be combustible gasses or non-combustible matter. The
presence of non-combustible matters does not add calorific value, but it increases the
volume of the furnace required. Hence, higher volatile content in coal is undesirable.
iii. Ash is a useless non-combustible matter, which reduces the calorific value of coal. Ash
causes the hindrance of flow of air and heat, thereby, lowering the temperature. It
also causes wear of furnace walls, burning of apparatus and feeding mechanism.
Hence, lower is the ash content; better is the quality of coal. The presence of ash also
increases the transport, handling, storage and disposal cost.
iv. Higher is the fixed carbon content, better is the quality of coal. It is useful for designing
the furnace and firebox.

Ultimate Analysis:

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Assistant Professor
Amity Institute of Applied Sciences
  This analysis involves the determination of content of carbon, hydrogen, nitrogen,
sulphur, oxygen and ash present in a coal sample.
 The content of carbon, hydrogen, nitrogen, sulphur and ash are determined
experimentally, whereas that of oxygen is determined theoretically.
 Greater is the percentage of carbon and hydrogen, better is the quality of the coal
and calorific value.
 Nitrogen has no calorific value; hence its presence is undesirable.
 Sulphur is present to the extent of 0.5- 3.0 % and its burning has harmful effects in
terms of corrosion of equipment and the atmospheric pollution. So, presence of
sulphur is undesirable even though it contributes to the heating value of coal on
combustion.
 Oxygen content decreases the calorific value of coal. High oxygen content coals are
characterized by high inherent moisture content, low calorific value and low cooking
power. Thus, a good quality coal should have low percentage of oxygen.

Carbon and Hydrogen:

About 1 to 2 grams of accurately weighed coal sample is bunt in a current of oxygen in a
combustion apparatus. C and H of the coal are converted into CO2 and H2O respectively. The
gaseous products of combustion are absorbed respectively in KOH and CaCI2 tubes of known
weights. The increase in weights of these tubes is then determined.

𝐶 + 𝑂2 → 𝐶𝑂2
𝐾𝑂𝐻 + 𝐶𝑂2 → 𝐾2 𝐶𝑂3 + 𝐻2 𝑂

𝐻2 + 1⁄2 𝑂2 → 𝐻2 𝑂

𝐶𝑎𝐶𝑙2 + 7𝐻2 𝑂 → 𝐶𝑎𝐶𝑙2 . 𝐻2 𝑂

𝐼𝑛𝑐𝑟𝑒𝑎𝑠𝑒 𝑖𝑛 𝑡ℎ𝑒 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝐾𝑂𝐻 𝑡𝑢𝑏𝑒 × 12 × 100
𝑃𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑜𝑓 𝐶 =
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑐𝑜𝑎𝑙 𝑠𝑎𝑚𝑝𝑙𝑒 × 44
𝐼𝑛𝑐𝑟𝑒𝑎𝑠𝑒 𝑖𝑛 𝑡ℎ𝑒 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝐶𝑎𝐶𝑙2 𝑡𝑢𝑏𝑒𝑠 × 2 × 100
𝑃𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑜𝑓 𝐻 =
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑜𝑎𝑙 𝑠𝑎𝑚𝑝𝑙𝑒 × 18
Nitrogen:
About 1 gram of accurately weighed powdered coal is heated with concentrated H2SO4 along
with K2SO4 (as the catalyst) in a long necked Kjeldahl’s flask. (Digestion)
𝑁 + 𝐻2 𝑆𝑂4 → (𝑁𝐻4 )2 𝑆𝑂4
After the solution becomes clear, it is treated with excess of KOH solution and the liberated
ammonia is distilled over and absorbed in a known volume of standard acid solution.
(distillation)

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Assistant Professor
Amity Institute of Applied Sciences
The unused acid is then treated with back titration with excess of standard NaOH solution.
From the volume of acid used by ammonia liberated, the percentage of nitrogen in coal is
determined
(𝑁𝐻4 )2 𝑆𝑂4 + 2𝑁𝑎𝑂𝐻 → 𝑁𝑎2 𝑆𝑂4 + 2𝑁𝐻3 + 2𝐻2 𝑂
𝑁𝐻3 + 𝐻2 𝑆𝑂4 → (𝑁𝐻4 )2 𝑆𝑂4

𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑐𝑖𝑑 × 𝑁𝑜𝑟𝑚𝑎𝑙𝑖𝑡𝑦 𝑜𝑓 𝑎𝑐𝑖𝑑 × 1.4

𝑃𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑜𝑓 𝑁 =
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑐𝑜𝑎𝑙 𝑡𝑎𝑘𝑒𝑛

Sulphur:
Sulphur is determined from the washings obtained from the known mass of the coal, used in
bomb calorimeter for determination of a calorific value. During this determination, S is
converted in to sulphate. The washings are treated with Barium chloride solution when
barium sulphate is precipitated. This precipitate is filtered, washed and heated to constant
weight.
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝐵𝑎𝑆𝑂4 𝑜𝑏𝑡𝑎𝑖𝑛𝑒𝑑 × 32 × 100
𝑃𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑜𝑓 𝑆 =
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑐𝑜𝑎𝑙 𝑠𝑎𝑚𝑝𝑙𝑒 𝑖𝑛 𝑡ℎ𝑒 𝑏𝑜𝑚𝑏 × 233

Ash:
The residual coal in the crucible after analysis of volatile matter is then heated without lid in
muffle furnace at 700±5°C. After 0.5h, the crucible is taken out, cooled first in air, then in a
desiccator and weighed. Heating, cooling, weighed is repeated till a constant weight is
obtained. The residue is reported as ash in percentage term.
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑎𝑠ℎ 𝑙𝑒𝑓𝑡
𝐴𝑠ℎ (%) = × 100
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑐𝑜𝑎𝑙 𝑡𝑎𝑘𝑒𝑛
Oxygen:
It is determined theoretically by deducting the combined percentage of carbon, hydrogen,
nitrogen and sulphur from 100.

𝑃𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑜𝑓 𝑂 = 100 − (𝐶 + 𝐻 + 𝑆 + 𝑁 + 𝐴𝑠ℎ)

Significance of Ultimate Analysis:

 Greater the content of carbon and hydrogen, better is the quality of the coal and
higher is the calorific value.
 Presence of nitrogen in coal is undesirable.

Dr. Anuradha Mahanty

Assistant Professor
Amity Institute of Applied Sciences
  Presence of sulphur in coal is undesirable because SO 2 and SO3 are harmful and
corrodes the equipment.
 Presence of oxygen in coal is undesirable because it increases the moisture holding
capacity.
Mixture of gasoline and air is used as fuel in internal combustion engine. It is highly
compressed and then ignited.
The process involves four strokes:
i. The fuel air mixture is drawn into cylinder (Suction stroke).
ii. The fuel air mixture is compressed (Compression stroke).
iii. The fuel air mixture is ignited by an electric spark. The gases produced due to
combustion increases the pressure and push the piston down (Power stroke).
iv. The piston moves up and expels the exhaust gases from the cylinder (Exhaust stroke).

What is Engine Knocking? What are its causes?

The flame on ignition should spread rapidly and smoothly through the gaseous mixture for
maximum efficiency of the engine. But sometimes, due to high compression, the gasoline air
mixture gets heated to a temperature. so that there is spontaneous combustion before regular
sparking. This is called premature ignition. There may be self-ignition of last portion of the
fuel-air mixture after sparking, resulting in an explosive violence. The pre-mature ignition
and delayed ignition causes knocking (that is a sharp metallic sound or an explosive violence).

✓ It is defined as metallic sound similar to rattling of hammer produced in internal

combustion (IC) engine
✓ Knocking, also known as engine knock, is the undesirable fuel combustion inside an
engine.
✓ Caused due to immature ignition of fuel oil-air mixture.
✓ Also due to low-quality fuel
✓ Frequent knocking can lead to engine damage and reduced performance.
✓ It decreases the efficiency of the engine and causes loss of energy.
Internal Combustion Engine:
o The ignition is brought about by means of an electric spark (in petrol engines) or by
compressing the air (in diesel engine).
o An IC engine uses either gasoline or diesel as fuel and a mixture of fuel-air is ignited
inside the IC.

Knocking in Spark Ignition engine and Octane Number

The order of knocking tendency is
straight chain alkanes > branched chain alkanes > olefins > cycloalkanes > aromatics.
Knocking also depends on nature of fuel, design of the engines and running conditions etc.

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Assistant Professor
Amity Institute of Applied Sciences
  The most commonly used measure of a gasoline's efficiency, to burn without knocking
is its octane number.
 It is found that n-heptane knocks very badly whereas iso-octane (2, 2, 4-trimethyl
pentane) is resistant to knocking. So, the octane number of iso-octane is taken as 100,
and that of n-heptane is zero.
 The octane number of a fuel under standard conditions, is the percentage of volume
of iso-octane in a mixture of iso-octane and n-heptane having the same knocking
characteristics as the fuel. For example, gasoline that contain 75% of isooctane and
25% of n-heptane are given an octane number of 75.
 Certain anti-knock quality is required for knock free operation of a gasoline engine.

Anti-Knocking Agents:
The knocking tendency can be minimized by adding some compounds known as anti-knocking
agents. Tetraethyllead [Pb(C2H5)4] and iron carbonyl [Fe(CO)5] are used as anti-knocking
agent.

 The knocking agents retard the rapid combustion of gasoline vapour in the cylinder.
Anyways these are poisonous compounds.
 Tetraethyllead is converted into lead oxide and reacts with any hydrogen peroxide
molecules formed, slowing down the chain oxidation reactions.
 The deposits of lead oxide are harmful to engine life.
𝑃𝑏 + 𝐶𝐻2 𝐵𝑟 − 𝐶𝐻2 𝐵𝑟 → 𝑃𝑏𝐵𝑟2 + 𝐶𝐻2 = 𝐶𝐻2
Ethylene bromide lead bromide

Cetane Number:
The suitability of diesel fuel is defined by its cetane number. The cetane number of a diesel
oil is defined as the percentage of n-hexadecane in a mixture of n-hexadecane and α-methyl
naphthalene which will have the same ignition characteristics as the fuel under test, under
same set of conditions.

The straight chain hydrocarbons ignite quite readily while aromatics do not ignite easily.
Ignition quality order among the constituents of diesel engine fuels in order of decreasing
cetane no, is as follows:

n-alkanes> naphthalene > alkenes > branched alkanes > aromatics

Dr. Anuradha Mahanty

Assistant Professor
Amity Institute of Applied Sciences
 Dr. Anuradha Mahanty
Assistant Professor
Amity Institute of Applied Sciences