CONTENTS

Knocking in engines
Prevention of knocking in engines
Octane number
Cetane number
 KNOCKING
Pre- ignition of the engine causes the piston
to knock the cylinder . This is called knocking
of the engine.
The air or fuel mixture in the cylinder ignites
before the spark plug fires. This results in
knocking of the engine.
When the rate of oxidation becomes so great
that the last portion of the fuel-air mixture
gets ignited instantaneously producing an
explosive violence known as knocking.
 4-stroke engine cycling through the intake, compression, power and
exhaust strokes.
INTERNAL COMBUSTION ENGINES are mechanical devices that use
controlled explosions (combustions) of petrol (gasoline) and air
mixtures to rotate wheels.
The reciprocating (back and forth) engine explodes the mixture (of
fuel + air) in a cylinder that forces the contained piston to move.
This movement of the piston is transmitted (via the connecting rod)
to a rotating device (crankshaft shown as a simple red disc) which is
ultimately connected to the wheels (via gears, usually). This is how
cars run on petrol.
The four stroke engine is so called because the piston repeats a
sequence of four strokes for every explosion.
In reality, the components often have highly complex and irregular
shapes. Since a realistic rendering might obscure the underlying
process -reduced the components to their simplest form.
Car engines have multiple cylinders contained together in an engine
block.
 PETROL FOUR STROKES IN SUMMARY:
1st Stroke INTAKE: piston moves down, air + fuel
mixture drawn in
2nd Stroke COMPRESSION: piston moves up, air +
fuel mixture compressed then ignited by sparking
plug
3rd Stroke POWER: piston pushed down by
exploding air + fuel mixture
4th Stroke EXHAUST: piston moves up, spent
gases pushed out through exhaust
 4-Stroke Engine: Operating Cycle
In a 4-stroke engine, air-fuel mixture is drawn into the cylinder and
ignited with the help of a spark plug. Gases produced by combustion
exert a back-pressure on the piston and force it downward. Repetition of
this sets up a circular motion of the wheel. There are four steps involved
in this process:
1. Suction Stroke (or Induction Part): Vaporised Fuel-air mixture is drawn
into the cylinder from carburettor.
2. Compression Stroke: The mixture is compressed by the upward
movement of the piston.
3. Power Stroke: Compressed fuel-air mixture is ignited by an electric
spark. Due to pressure exerted by the hot gases produced in the
combustion, the piston moves downward and provides output power.
4. Exhaust Stroke: The piston moves upward and expels the exhaust
gases from the cylinder. Then a second suction stroke commences.
4-Stroke Engine: Operating Cycle
 For petrol IC engine:
Alkane compound having more knocking
property.
Alkene compound having less knocking
property.
Branched hydro carbon having less knocking
property.
Aromatic compound having less knocking
property.
 In alkane series octane number decreases as
the carbon chain is lengthened and increases
with branching of chains.
Alkenes have higher octane ratings than the
corresponding alkanes and the octane number
increases as the double bond is shifted to the
centre of the molecule.
Octane number of n-heptane is 0 since it
causes very high knocking.
 Knocking
Compression Ratio (CR):

Definition: The ratio of the volume of the gas mix in the cylinder
at the end of the suction stroke (V1) to the volume at the end of
the compression stroke (V2).

The power output and efficiency of an IC engine increases with

increase in compression ratio.

An increase in CR from 5:1 to 10:1 results in 25-30% increase in

efficiency.
 Knocking
Knocking:
The fuel-air mixture can sometimes be heated above its ignition
temperature due to compression resulting in spontaneous ignition
before sparking. This is called pre-ignition.
The last portion of the fuel-air mixture can ignite spontaneously after
sparking due to high temperatures and the spreading flame front. This
is called self-ignition.
Pre-ignition and self-ignition lead to an explosive combustion
producing a shock wave within the cylinder.
The shock wave dissipates the energy by hitting the cylinder wall. This
produces a rattling sound called knocking.
Knocking results in a decreased power output and causes mechanical
damage to the engine due to overheating.

Knocking increases with increase in Compression Ratio.

 Knocking
Chemical Reactions Involved in Knocking:
Knocking is principally due to straight chain aliphatic compounds of
gasoline, e.g., n-heptane CH3(CH2)5CH3.
Under the conditions prevailing in the cylinder like high temperature
and polished surface of the inner wall of the cylinder, such compounds
undergo chain fission producing free radicals.
CH3(CH2)5CH3 CH3(CH2)2CH2 + CH3CH2
Free Radicals

These free radicals are highly reactive and can react with other
hydrocarbons present in petrol with explosion.
Free radicals can also react with oxygen to form organic peroxides
which can also explode violently.
O2
CH3(CH2)2CH2 + CH3CH2 CH3(CH2)2CH2 O O CH2CH3

Peroxide
 Knocking
Knocking Tendency of Gasoline Constituents:
Branched chain hydrocarbons (iso-paraffins) such as iso-octane have
less tendency to form free radicals and hence have less tendency to
knock.
The knocking tendency of constituent hydrocarbons of gasoline has
been related to their structure. Knocking Tendency decreases in the
order:

n-alkanes>branched chain alkanes>cycloalkanes>alkenes>aromatics

This implies that olefins (alkenes) of the same carbon chain length will
have better anti-knock properties than the corresponding alkanes and
so on.
 Octane Rating or Octane Number:
An arbitrary scale used to express the knocking characteristics of gasoline.
n-heptane knocks very badly and hence its anti-knock value is arbitrarily
assigned as 0 (zero).
Iso-octane (2,2,4-trimethylpentane) gives very little knocking under
normal conditions and so an anti-knock value of 100 is fixed for it.
CH3 CH3

H3C (CH2)5 CH3 H3C CH2 CH CH3

CH3
n-heptane Iso-Octane

The octane number (or octane rating) is the percentage of iso-octane

present in a mixture of iso-octane and n-haptane which matches the
knocking characteristics of the fuel under test under the same set of
conditions.
An 80-octane fuel will have the same combustion characteristics as a
mixture of 80% iso-octane and 20% n-heptane.
Greater the octane rating of gasoline, greater is its resistance to knocking.
 Knocking
Determination of Octane Number:

Octane rating is determined using a variable compression ratio engine.

The critical CR at which knocking of the given fuel occurs is determined

under a standard set of conditions.

It is matched with the % of iso-octane in the iso-octane - n-heptane

mixture that gives knocking at the same CR.

Octane number determined in the laboratory is quoted as research

octane number (RON).

Octane number determined under the actual conditions of high speed

and temperatures is reported as motor octane number (MON).
RON is widely used even though their values are greater than those of
MON.
 Prevention of Knocking:
1. Use of anti-knocking agents:
Knocking can be prevented by adding a small amount of anti-knocking agents
such as tetraethyl lead (TEL Pb(C2H5)4), tetramethyl lead (TML Pb(CH3)4) and
diethyl telluride (DET - Te(C2H5)2) They increase the octane rating.
For motor fuels 0.05% and for aviation fuels 0.1-0.15% of TEL is commonly added.
When TEL is injected into the engine it is converted into finely divided lead or
lead oxide which readily reacts with any free radical formed and thus prevents
knocking.
But lead oxide or lead formed is deposited in the cylinder and reduce the
diameter of the cylinder. This leads to cessation of the engine.
Ethylene dibromide (BrCH2-CH2Br) is also added to help simultaneous elimination
of lead or lead oxide. Ethylene dibromide converts lead or lead oxide into volatile
lead bromide (PbBr2) which is expelled along with exhaust gases.
Br CH2 CH2 Br + Pb CH2 CH2 + PbBr2
Methyl cyclo penta dienyl manganese tricarbonyl (MMT) can also be used in
place of TEL or TML.
2. Using lower air to fuel ratio by increasing the amount of fuel injection
3. By Using Unleaded Petrol.
 Unleaded Petrol:
Use of TEL or TML to increase the octane rating releases volatile lead halides
into the atmosphere.
They lead to high lead pollution of the atmosphere.
Lead is extremely toxic. It affects brain cells and causes severe loss of memory.
To avoid lead pollution, alternative anti-knock agents free of lead are used.
Some of the anti-knocking agents are: high anti-knock compounds such as
isopentane, isooctane, ethyl benzene, isopropyl benzene and methyl tert-
butyl ether (MTBE).
MTBE is preferred because it contains oxygen in the form of ether group and
supplies oxygen for combustion of petrol and reduces the extent of peroxide
formation.
Such a petrol in which octane rating is enhanced without addition of lead
compounds is called unleaded petrol.
Advantages:
1. No lead pollution to the atmosphere.
2. Lead deposited from leaded petrol poisons the rhodium catalyst of
catalytic converter which converts harmful gases into harmless gases (e.g. CO and
NO are converted to CO2 and NO2, un-burnt hydrocarbons into CO2 and H2O).
Use of unleaded petrol permits the use of catalytic converters.
 Knocking-Diesel Knock:
In diesel engine (Compression ignition engine), air is drawn into the
cylinder and compressed to a pressure of 35-40kg/cm2. Air is heated to
500C due to compression.
Fuel is drawn at the end of the compression stroke and sprayed into the
heated air and ignites spontaneously.
Pressure of the combustion gases moves the piston which constitutes
the power stroke.
Fuel injection stops at the exhaust stroke.
There is time lag between the injection of fuel and its ignition: ignition
delay.
It is desirable to have a short ignition delay but the delay should be long
enough to complete the compression stroke.

Long ignition delays cause fuel accumulation in the cylinder leading to

explosive combustion upon ignition called diesel knock.
 Cetane Rating (or Cetane Number
or Cetane Value):
The suitability of a diesel fuel is determined by Cetane Number.
Cetane (n-hexadecane) has a very short ignition delay compared to any diesel
and is assigned an arbitrary value of 100.
a-Methyl Naphthalene has a long ignition delay compared to other diesel oils
and is assigned a value of 0 (zero).
Cetane number is the percentage of cetane in a mixture of cetane and a-
methylnaphthalene that has the same ignition delay as the diesel fuel under
test.
Ignition quality of Hydrocarbons decreases in the order:
n-alkanes>cycloalkanes>alkenes>Isoalkanes>Aromatics
Greater the cetane number, shorter is the ignition lag.
CH3

H3C (CH2)14 CH3

Cetane a-Methyl Naphthalene

Cetane Rating (or Cetane Number or Cetane Value):

Low speed engines: 100-500 rpm. Used in Ships. Requires heavy oils of
high viscosity and cetane number about 25.
Medium speed engines: 500-1500 rpm. Tractors, Locomotives and
Electricity Generators. Require diesel oil of moderate viscosity and
cetane number 25-35.
High speed diesel engines: 1500-20,00rpm. Buses and trucks. Require
low viscosity diesel with cetane number 45-60.

Cetane number can be increased by adding pre-ignition dopes like

isoamyl nitrate,
Isopropyl-N-methyl-N-Nitro-carbamate,
and di tert-butyl peroxide.
 EFFECTS
Higher octane rating correlate to higher
activation energies. This being the amount of
applied energy required to initiate combustion.
During the compression stroke of an internal
combustion engine , as the air/fuels mix is
compressed its temperature rises (PV=nRT)
Many high performance engine are designed to
operate with a high maximum compression , and
thus demand fuels of higher octane.
 Octane are a family of hydrocarbon that are
typical components of gasoline. They are
colourless liquids that boil around 1250 C.
The octane rating of gasoline is measured in a
test engine and is defined by comparison with
the mixture of 2,2,4-trimethylpentane (isooctane)
and heptane that would have the same anti-
knocking capacity as the fuel under test.
 Improvement of anti-knock characteristics of a
fuel can be done by increasing the octane
number by the addition of extremely poisonous
additives such as TEL(tetra ethyl lead) or TML
(tetra methyl lead) or diethyl telluride.

The octane number in leaded petrol can be

increased by adding TEL or tetra methyl lead .
However combustion of lead petrol leads to
formation of litharge (PbO) .Therefore unleaded
petrol is better than leaded petrol.
 TEL is converted into a cloud of finely divided
lead oxide particles in the cylinder and these
particles react with any hydrocarbon peroxide
molecules formed
This slows down the chain oxidation reaction
and thus decreases the chances of an early
detonation.
Formation of lead is removed by adding
ethylene di-bromide CHBr=CHBr volatile
PbBr2
 OCTANE NUMBER
The efficiency of a fuel is rated by giving its
octane numbers.
Octane number is inversely proportional to the
knocking of the fuel . i.e higher the octane
number higher is the anti knocking property.
The octane number of a given fuel is defined as
the percentage of isoctane in a mixture of iso-
octane and n-heptane that has the same
knocking characteristics of the fuel under test.
 Detonation can be prevented by any or all of the
following techniques:
the use of a fuel with high octane rating, which
increases the combustion temperature of the
fuel and reduces the proclivity to detonate;
enriching the air-fuel ratio which alters the
chemical reactions during combustion, reduces
the combustion temperature and increases the
margin above detonation.
 reducing peak cylinder pressure by decreasing
the engine revolutions (e.g., shifting to a higher
gear, there is also evidence that knock occurs
more easily at high rpm than low regardless of
other factors);
decreasing the manifold pressure by reducing the
throttle opening, boost pressure or reducing the
load on the engine.
 OCTANE NUMBER
Octane number is a value used to indicate the
Resistance of a motor fuel to knock .
Octane Number are based on which isooctane is
100 (minimal knock) and heptane is 0(bad knock).

Ethyl alcohol -80% iso octane + 20% n-heptane

Non-Aviation petrol -40% isooctane+60%n-
heptane
Aviation petrol -100% isooctane+0%n-heptane
 CETANE NUMBER
Cetane number or CN is a measure of a fuels
ignition delay , the time period between the
start of injection and the first identifiable
pressure increase during combustion of fuel .
In a particular diesel engine ,higher centane
fuels will have shorter ignition delay periods
than lower cetane fuels.
Cetane numbers are only used for the
relatively light distillate diesel oils.
 CETANE NUMBER
Cetane number or CN is a measurement of
the combustion quality of diesel fuel during
compression ignition.
Cetane number or CN is a measure of a fuel's
ignition delay, the time period between the
start of injection and the first identifiable
pressure increase during combustion of the
fuel.
 KNOCKING IN DIESEL ENGINE:
Diesel knock is the clanking, rattling
sound emitted from a running diesel engine.

This noise is caused by the compression of air in

the cylinder and the ignition of the fuel as it is
injected into the cylinder.

This is much the same as a gasoline engine

suffering from pre ignition or spark knocking
 The tendency of fuel constituents to knock in
diesel fuel is in the following order :
Straight-chain paraffins < branched-chain
paraffins < olefins < cyclo-paraffins <aromatics.
ALTERNATIVE FUELS;
1)Biodiesel from vegetable oil sources have been
recorded as having a cetane number of 46 to 52
2) animal fat based biodiesels cetane numbers
range from 56 to 60.

3)Dimethyl ether is a potential diesel fuel as it has a

high cetane rating (55-60) and can be produced as
a biofuel.
 The suitability of a diesel fuel is determined by
its cetane number which is

the percentage of hexadecane in a mixture of

hexadecane and 2-methyl naphthalene which
has the same ignition characteristics as the
diesel fuel under test.
To reduce anti knocking in diesel engine -The
cetane number can be raised by the addition
of small quantity of certain pre-ignition dopes
like

1-5% ethyl nitrate

Iso-amyl nitrate
Acetone peroxide
Nitro naphthalene
 Aviation Gasoline
Gasoline to be used as fuel in aeroplanes and combat planes is called
aviation gasoline or high octane fuel.
Generally aviation gasoline contains high percentage of isoparaffins
and smaller percentage of naphthenes and aromatics.
Polymerisation, alkylation, isomerisation and aromatisation are used
to produce aviation gasoline.
Isoparaffins are superior to other HCs in CV, anti-knock value, stability
and volatility; They have higher octane number too.
Prepared by blending alkylated branched paraffins with cracked
gasoline containing unsaturated open chain paraffins, which also have
higher octane number.
Anti-knock values can be increased further by adding tetra ethyl lead
(0.1-0.15% for aviation gasoline).
Gasoline grades are colour coded:
Grade 73-80: Colourless; Grade 91/96: blue; Grade 100/130: green;
Grade 115-145: Purple.