FUEL, BATTERIES AND

LUBRICANTS
A fuel is defined as any substance used to produce heat or power by
combustion

Any chemical process accompanied by the evolution of light and heat

is called combustion

Fuel + Oxygen  Combustion product + Heat

The combustible substances

which on burning in air
produces large amount of heat
that can be used economically
for domestic and industrial
purposes are called fuels.

Eg. Wood, Coal, LPG, Gasoline

etc
The term combustion refers to the exothermal oxidation
of a fuel, by air or oxygen occurring at a sufficiently rapid
rate to produce a high temperature, usually with the
appearance of a flame.
As most of the fuels contain carbon or carbon and hydrogen,
the combustion involves the oxidation of
carbon to carbon dioxide
hydrogen to water
Sulphur, if present, is oxidised to sulphur dioxide

while the mineral matter forms the ash. Complex fuels like coal
undergo thermal decomposition during combustion to give
simpler products which are then oxidized to carbon dioxide,
water etc.

e.g.: Coke on combustion gives carbon dioxide

Coal  Coke + Coal gas

C (coke) + O2  CO2
 Based on Physical State
Solid Fuel: Characterized by its mass, composition, specific heat,
combustion residue and thermal properties. Eg: Coal etc.

Liquid Fuel: Characterized by its composition, density, viscosity,

specific heat, thermal properties. Eg: Petroleum etc.

Gaseous Fuel: Characterized by its composition, volume and

pressure and thermal properties. Eg: CNG etc.
 Based on occurrence
Fuels are classified as
Primary fuels – fuels which occur naturally such as coal, crude
petroleum and natural gas. Coal and crude petroleum, formed from
organic matter many millions of years ago, are referred to as fossil
fuels.

Secondary fuels – fuels which are derived from naturally

occurring ones by a treatment process such as coke, gasoline, coal
gas etc.
 FUEL

Primary Fuels Secondary fuels

Solid
Eg. Wood,peat Liquid Solid Liquid
Eg.crude oil EgCoke,charcoal Eg. Petrol ,LPG

Gas Gas 8
Eg.Natural gas Eg.coal gas ,water gas
Characteristics of a Good Fuel

 Should have high calorific value.

It should ignite easily.
The temperature of the fuel at which ignition starts and
continues to burn without further addition of heat is called ignition
temperature. It should be moderate for a good fuel. Very low
ignition temperature leads to fire hazard and very high ignition
temperature disfavors the starting of fi re.
It should give out a lot of heat, that is, its specific heat should
be high [is the amount of heat per unit mass required to raise
the temperature by one degree Celsius].
 It should have low smoke and combustible matter such as ash.
It should not give out harmful combustion products. This
property depends on the nature of elements present in the fuel.
 It should be inexpensive and readily available.
 It should be easy to store and transport.
 It should have low ash content.
Ash reduces the calorific value of the fuel, causes hindrance to
the flow of air and heat, reduces the specific heat and leads to
unwanted disposable problems.
 Calorific Value:

The amount of heat obtained from the fuel is called its calorific
value, it is expressed in :

British thermal units (BTU): It is 1/180 of the amount of heat

necessary to raise 1lb of water from 32°F to 212°F

Calorie (cal): it is 1/100 of the amount of heat necessary to raise

1g of water from 0°C to 100°C.

1 BTU=252 cal
With fuels containing hydrogen, two calorific values are
distinguished, the gross and the net calorific value.

GROSS CALORIFIC VALUE/ HIGH CALORIFIC

VALUE

The gross calorific value refers to the total heat evolved when 1
unit of fuel is burnt completely and combustion products are
cooled at room temperature.
Hydrogen is present in almost all the fuels and it is
converted to steam when fuel is combustioned. When
the product of combustion are heated at room
temperature, the. latent heat of condensation of steam
is also included in measured heat

NET CALORIFIC VALUE/ LOW CALORIFIC

VALUE
Actually the water vapors escapes along with hot
combustion gases and thus are not condensed. So less
amount of heat is obtained, called net calorific value
net calorific value= Gross calorific value – Latent heat of water
vapour

Since 1g of hydrogen gives 9g of water, so

net calorific value= Gross calorific value – (Weight of hydrogen

× 9 × Latent heat of water vapour)
Q. Calculate the LCV of a fuel which has 8% H and HCV
as 6500 cal/gm. Given latent heat of steam 587 cal/gm
Bomb calorimeter
•Used to measure enthalpy
changes of combustion
reactions at a constant
volume

•Occurs inside a tiny inner

metal chamber called a
bomb

•The bomb contains pure

oxygen, the reactants are
ignited using an electric
coil

•A known quantity of
water surrounds the bomb
and absorbs energy that is
released by the reaction
Experimentally Determination

Bomb calorimeter

1.For calorific values of solid and liquid

fuels
2.Known amount of fuel is burnt at
constant volume
3.Temperature of surrounding water
increases as heat is produced.
4.Quantity of heat and calorific values are
calculated.

W = Weight of water, w = water equivalent of calorimeter. S = specific heat of water, T 2

=final temp, T1 =initial temp, x = weight of fuel.
On burning 0.83 gm of coal, the temperature of 3500 gm
water increased from 25.5 0C to 29.2 0C. Water equivalent
is 385 gm. Latent heat = 587 cal/gm Calculate the gross
and net calorific value. [H % = 0.7%]

Ans= 17318.68 cal/ gm = 17318.68 kcal/ kg

Proximate Analyses of Coal
It includes the determination of moisture content, volatile matter, ash
and fixed carbon. In this analysis, the data varies with the procedure
adopted for study. The content of moisture, volatile matter and ash
are experimentally determined, while that of fixed carbon is
calculated.

1.Moisture content: About 1 gm of finely powdered , air dried coal

sample is weighted in a crucible which is placed inside electric hot
air oven (105 -1100C). After 1h, take it out and cooled in desiccator
and take the weight again.

Lesser moisture content better is the quality of coal.

2. Volatile matter: Lesser the volatile matter, better is the
rank of coal. [Non combustible volatile matter do not add
the heat value] After moisture analysis, it’s kept in 925 0C for
7 min with lid. Taken weight after cooling
3. Ash content: Lower the ash content, better is the quality of
coal. Ash causes the hindrance to the flow of air , lower the
temperature. Heat for 30 min at 700 0C without lid. Taken
weight after cooling down.

4. Fixed carbon: Higher fixed carbon content, better is the

quality of coal.
Ultimate Analysis:
For determination of content of carbon, hydrogen, nitrogen,
sulphur and ash present in a coal sample.

Except oxygen all other content are determined experimentally.

1. Carbon & Hydrogen: 1-2 g of coal sample is burnt in presence
of oxygen. C and H are converted to CO2 and H2O respectively.
Gaseous products are absorbed in KOH and CaCl2 tubes of
known weights. Inc in weight of these tubes determine to
calculate to H and C percentage.
2. Nitrogen: 1 g of coal sample is heated with H2SO4 along with
K2SO4 in a long-necked flask called Kjeldahl’s flask.

After the solution become clear, it is treated with excess of

KOH and then liberated ammonia is distilled over and
absorbed in a known solution of acid solution.

Unused acid is then determined by back titration with

standard NaOH solution. From the volume of acid used by
ammonia liberated, the %age of N in a coal sample is
calculated.
3. Sulphur: determined by washing obtained from the known
mass of coal used in bomb calorimeter for the determination
of calorific value.

During this S is converted to sulphate. The washing are

treated with BaCl2, when the BaSO4 is precipitated. This
precipitate is filtered, washed and heated to constant weight.
4. Ash: determined is as in proximate analysis

5. Oxygen: calculated theoretically by following method

Significance:

High %age of C, H: better coal quality

N% should be low

S% should be low

O content decrease the calorific value of coal

Semi-Solid Fuels – Some Recent Advances

The term semi-solid fuel (wax, fats, resins) in modern

context refers to non-volatile substances that are
environmentally safe and produce no hazardous
waste on burning. These have long shelf-life and their
ignition can be easily started and stopped.

The conventional solid and liquid fuels are now being

used as formulations in semi-solid form to circumvent
the problems associated with their use in the regular
form.
Liquid fuels – Petroleum

1.Petroleum is made from the remains of plants

and animals buried millions of years ago.
2.It is a non-renewable resource.
3.It contains straight or cycloparaffins.
4.Olefins
5.Aromatics
6.Other organic compounds containing N, O, S.
Production from Refining of Crude Oil

The petroleum obtained by mining is viscous and dark

colored liquid. Due to the presence of sulphur, it has an
unpleasant smell. It also contains impurities of sand, brine
or sea water. Hence it is called crude oil. High sulphur
content is called sour crude oil while low sulphur content
is called sweet crude oil.

The important steps involved are:

1.Fractional distillation to give various fractions.

2.Conversion of less desirable fractions to valuable
products by processes like cracking.
3.Treatment of fractions to remove undesirable substances.
 Fractionating Column: The fractionating column is a tall steel tower
attached to an electrically heated furnace. Throughout the length of the
tower, there are trays with raised holes covered with loose fitting caps
called the bubble caps. These caps allow the vapours to rise up and not
descend down. The tower has outlet pipes at various levels along it's length.
Fractional Distillation
PROCESS OF FRACTIONAL
DISTILLATION
 Crude petroleum is pumped into the furnace where it is
heated to a temperature of about 400oC. Petroleum is
converted to vapours in the furnace.
 The vapours of petroleum are fed into the fractionating
column from the bottom.
 As the vapours enter the column, they rise up and
gradually get cooled.
 At the bottom of the furnace, the temperature is about
400oC. Here, the component that has a boiling point close
to 400oC condenses (liquifies) first and is collected on the
tray. From the tray it is let off through the outlet pipe.
The remaining vapours rise up through the bubble caps.

When the vapours reach a particular height in the tower,

the fraction that has a boiling point close to the
temperature at that height condenses on the tray. The
remaining vapours continue to rise upwards.

Like this, at different levels in the tower, different fractions

get condensed, collect on the trays and flow out of the
outlet pipes.
 Products of Fractional distillation:
 Residual oil is that component of petroleum, which is collected first at the
bottom of the tower. It has a boiling range of over 400 oC. It can be further
distilled separately to obtain lubricating oil, paraffin wax, asphalt etc.

 Most fractions of petroleum are fuels.

 lubricating oil and petroleum jelly are not used as fuels.

 Uncondensed gas is liquefied to give LPG which consist of mixture of

methane, ethane, propane and butane.
Distillation of crude oil with the respected temperature
Fractions of petroleum
CRACKING
 Industrial cracking is used to crack larger chains into more
valuable shorter chains.
 Cracking is decomposition of high molecular weight
compounds (with high boiling points) to low molecular weigh
compounds with low boiling points).
 An additional benefit of cracking is that some alkenes are
produced, alkenes are more reactive than alkanes and
therefore have some desirable uses.
 There are two sub-categories of industrial cracking.
 Thermal cracking and Catalytic cracking
Petrol engine vs Diesel engine
The petrol engine requires a spark plug to ignite the fuel-air mixture in the
cylinder. But, the diesel engine doesn't require a spark plug. The air is first
compressed in the cylinder, then the fuel is injected into hot compressed air and
it’s ignited without spark.

The compression ratio of an internal-combustion engine or external combustion

engine is a value that represents the ratio of the volume of its combustion
chamber from its largest capacity to its smallest capacity. Higher the
compression ratio better is the efficiency of the engine.

Straight chain hydrocarbon gives Ignition without spark.

Petrol fuel should contain more of branched chain hydrocarbon and diesel fuel
should contain more of straight chain hydrocarbon.
Knocking

Knocking in Spark Ignition Engines and Octane Number (Petrol)

The air-petrol mixture is compressed to 1/6 or1/10th of it’s volume and then
spark is introduced to burn the fuel. Petrol is used in spark ignition
engines.
If the rapid compression of the fuel-air mixture heats the engine, and it
detonates without the spark being passed. This causes a violent jerk to
the piston giving a metallic sound called knocking. Straight chains have
more knocking tendency. Knocking reduce engine efficiency.

Anti knocking expressed in Octane number. It’s the percentage volume of

isooctane in the isooctane-heptane mixture that matches the knocking
characteristics of the fuel being tested

Molecular structure affects the octane number.

Unleaded petrol: petrol having low octane no.,
not of good quality,
produces lot of noise
fuel is wasted, energy is lost
TEL (Tetra ethyl lead ) is added as an anti-knocking agent. The petrol is
called leaded Petrol.
Effect: Harm engine
Presence of Sulphur effects the effeciency of TEL
Now a days ethyl fluid / anti knocking fluid is used instead of only TEL to
reduce Knocking .
Anti knocking fluid is the mixture of- TEL (60%) + Ethyl bromide (26%) +
ethyl chloride (9%)+ red dye (2%)
Knocking in Compression Ignition Engines and Cetane Number (Diesel)

Diesel is used in compression ignition engines. Air is compressed to 1/12 th

or 1/20 th of it’s volume so the temperature is raised to 300 0C. Then diesel
is introduced and it ignites without spark is introduced. So diesel engine
fuels contains more straight chain hydrocarbons.
In contrast to petrol, the desirable characteristic of diesel is low
spontaneous ignition temperature. Higher cetane number easier is the
ignition.

The ignition delay in a diesel engine is defined as the time interval

between the start of injection and the start of combustion. The ignition
delay should be as low as possible.

Cetane number represents the spontaneous ignition temperature of a

particular diesel fuel. It is the percentage of cetane present in a mixture of
cetane and alpha-methylnaphthalene which matches the fuel under test in
ignition property.
Cetane no.: the percentage of cetane present ina mixture of cetane and α-
methylnapthalene which matches the fuel under test in ignition property

Cetane no. of any fuel can be increase by adding some additive (1-5%) such as,
ethyl nitrate, isoamyl nitrate, acetone, nitronapthalene, etc.
Secondary Cell
Nickel–Cadmium Cell

This cell, also known as alkaline storage battery

Nickel oxy-hydroxide
Nickel Cadmium (Ni-Cd) Cells and Batteries

 The electrolyte is potassium hydroxide (KOH) its function

is to act as a conductor for the transfer of the hydroxyl
(OH) ions.
 It gives 1.4 V potential.

The products of the reaction are solid hydroxides and they are sticky, cling to
the innards of the battery, and remain in place.
If current is applied, the reaction can be driven backwards!
 Nickel Cadmium (Ni-Cd) Cells and Batteries

o Also called alkaline storage battery

o This type of cell delivers high current.
o It can be recharged many times.
o It can be stored for long periods of time.
o Applications include
o Portable power tools and pocket calculators.
o Alarm systems.
o Portable radio and TV equipment.
 BATTERIES: THE NICKEL-CADMIUM
BATTERY

In a nickel-cadmium battery, we can recharge the battery by

applying an electrical current from another source

Cd(s) + 2NiO(OH)(s) + 2H2O(l) Cd(OH)2(s) + 2Ni(OH)2(s)

 Nickel–Metal Hydride Batteries

 Anode of cell composed of metal hydride MH and MH 2

 Active hydrogen storage alloy like LaNi5 are pasted on thin,
highly porous nickel sheet.
 Cathode NiO(OH)
 aq. KOH as electrolyte
 Separator contains a thin layer of polypropylene.
 Component are housed in a glass container.

Anode is the Metal- hydride (usually alloy of lanthanum) and cathode is

Nickel oxy hydroxide, aqueous KOH is electrolyte. Separator contains
The cell is represented as:
polypropylene,all components are housed in a glass container.
The characteristics of nickel–metal hydride batteries are as follows:
1.They have long shelf life and cycle life.
2.They have high capacity and rapid recharge capability.
3. EMF is 1.3 V.
4.Laptop computers, cellular phones ets
4. Lithium-ion battery (Li-ion Battery)
Li-ion batteries are secondary batteries.

• The battery consists of a anode of Lithium-ions, into a carbon.

(Graphite)
• The cathode material is made up from Lithium liberating
compounds, typically the three electro-active oxide materials.

• Lithium Cobalt-oxide (LiCoO2 )

• Lithium Manganese-oxide (LiMn2 O4 )
• Lithium Nickel-oxide (LiNiO2)

•Electrolyte: solid lithium-salt electrolytes

(LiPF6, LiBF4, or LiClO4)
and organic solvents (ether)
Principle

• During the charge and discharge processes, there is no so-called

oxidation reduction reaction, rather lithium ions are transported from
one electrode to other through electrolyte (Li salt in organic solvent)

• Simply, the Li-ion is transfers from anode (Graphite) to cathode

(LiCoO2 ) through Electrolyte during discharging as a result the electron
flows through the external circuit to balance the positive charge of Li+ .
• During charging Li-ion moves to opposite direction so the electron also
moves to opposite direction.

52
 Li- ion Electrolyte

cathode Graphite anode

Li-Ion battery Principle

Lithium Ion Cells

anode cathode
anode cathode
Applications

• The Li-ion batteries are used in cameras, calculators

• They are used in cardiac pacemakers and other

implantable device

• They are used in telecommunication equipment,

instruments, portable radios and TVs, pagers

• They are used to operate laptop computers and mobile

phones and aerospace application
• EMF 3 V.
Fuel Cells

The conversion of fuel into electrical energy involves a number of steps and
there is loss of energy at every step. The efficiency of the process is around
40%. There is also a viable way of converting the chemical energy of fuel
directly into electrical energy through catalytically activated redox reactions.
Such devices are called fuel cells. Fuel cell is a galvanic cell in which the
electrical energy is directly obtained from redox reaction of the fuel.
 Principle: The basic principle of the fuel cell is same as that of
electrochemical cell.

The only difference is that the fuel & oxidant are stored outside the cell.
Fuel and Oxidant are supplied continuously and separately to the
electrodes at which they undergo redox reactions.

Fuel + Oxidant  Oxidation Products + electricity

Cell Fuel/ Electrode/ Electrolyte/ Electrode/ Oxidant.

Examples of fuel cell- : 1)H2 -O2 fuel cell

2) Propane -O2 fuel cell
3) CH3OH-O2 fuel cell
Electrolyte is polymer
membrane which allows
the H+ to pass through but
not electron to pass through
 Advantage of using H2 as fuel.

1. It emits only water only harmful chemicals.

2. Efficiency is 75%.

3. It’s a light element and provides a lot of energy

4. Cause less noise pollution.