Vehicular Fuels

Motor Fuels
Fuels consists primarily of hydrocarbon
compounds, Paraffin, Olefin, Naphthene &
Aromatics and contains additives that are
determined by the specific use of the fuel. Non
hydrocarbon compounds such as sulfur & sulfur
compounds are also found.

Crude Petroleum Oil

Crude oil is a mixture of an almost infinite
number of HC compounds, ranging from light
gases of simple chemical structure to heavy tar
like liquids and waxes of complex chemical
structure.
The oil as it comes from the ground also contains
various amounts of Sulfur, oxygen, Nitrogen,
Sand & Water
The percentage of Carbon varying generally from
83% to 87% & that of Hydrogen from 11% to
14%.

Refining Crude
Separation process exploits the fact that various components in
crude oil have different boiling points. When crude oil is heated,
following are produced.
1- gases evolved (methane, ethane, propane & butane)
2- Vapors are released that condensed to form light distillate
3- Gasoline
4- Kerosene
5- Middle distillate
6- Residue (lub.oil, wax, bitumen)

Refining Processes
Some of the refining processes are:
Distillation

(Separation process)

Cracking

(Conversion Process)

Polymerization (Conversion Process)

Alkylation

(Conversion Process)

Isomerization

(Conversion Process)

Refining Processes
Cracking: Cracking is the process of breaking large
molecular components into more useful components of
smaller molecular weight
Distillation: Distillation is used to separate the mixtures
into single components or smaller ranges of components.
Generally, the larger the molecular weight of a
component, the higher is its boiling temperature. Low
boiling temperature components (smaller molecular
weights) are used for solvents and fuels (gasoline), while
high boiling temperature components with their large
molecular weights are used for tar and asphalt or
returned to the refining process for further cracking.

Fuel (Gasoline) requirement for SI Engine

A small percentage of components that vaporize (boil) at low temperature is
needed to assure the starting of a cold engine; fuel must vaporize before it
can burn. How ever, too much of this front-end volatility can cause problems
when the fuel vaporizes too quickly. Volumetric efficiency of the engine will
be reduced if fuel vapor replaces air too early in the intake system. Another
serious problem this can cause is vapor lock, which occurs when fuel
vaporizes in the fuel supply lines or in the carburetor in the hot engine
compartment. When this happens, the supply of fuel is cut off and the engine
stops. A large percent of fuel should be vaporized at the normal intake
system temperature during the short time of the intake process. To maximize
volumetric efficiency, some of the fuel should not vaporize until late into the
compression stroke and even into the start of combustion. This is why some
high-molecular-weight components are included in gasoline mixtures. If too
much of this high-end volatility is included in the gasoline, however, some of
the fuel never gets vaporized and ends up as exhaust pollution or
condenses on the cylinder walls and dilutes the lubricating oil.

Average Distillation Ranges

(Combustion-Engine Fuels)

Gasoline-Description
One way that is sometimes used to describe a gasoline is to use
three temperatures: the temperature at which 10% is vaporized, at
which 50% is vaporized, and at which 90% is vaporized. The
gasoline in Fig. could therefore be classified as 57-81-103C.

Chemical Structure
The Carbon & Hydrogen combine in different proportions
to form a variety of hydrocarbons
The Carbon to Hydrogen ratio and their ratio of bonding
determine the energy characteristics of hydrocarbon fuel
and affect the combustion processes
Depending upon the number of Carbon & Hydrogen the
products are classified in to different groups.
A saturated hydrocarbon molecule will have no double or
triple carbon-to carbon bonds and will have a maximum
number of hydrogen atoms.
An unsaturated molecule will have double or triple
carbon-to-carbon bonds.

Basic Families of Hydrocarbons

Family

General
Formula

Molecular Saturated/
Stability
Structure Unsaturated

Paraffin

CnH2n+2

Chain

Saturated

Stable

Olefin

CnH2n

Chain

Unsaturated

Unstable

Naphthene

CnH2n

Ring

Saturated

Stable

Aromatic

CnH2n-6

Ring

Un Saturated

More
Stable,
than other
unsaturate
d
compounds

(Alkanes)

HYDROCARBON FUELS
The paraffin family (alkane) in turn can be subdivided into
normal parrafin hydrocarbons, which have a straight or
open-chain structure with one bond between each atom
such as heptane and isomers, which have the same
number of C and H atoms and the same molecular mass
but a different structure, such as the three isomers of
normal heptane.
More complicated paraffin hydrocarbons may have a
greater number of isomers. The difference in the structure
of the molecules results in different physical properties
and reaction characteristics.

Paraffins

CnH2n+2

Paraffins
Heptane, C7H16
H H H H H H H
|
| | | | | |
HCCCCCCCH
| | |
| | | |
H H H H H H H

Paraffins
Isomer of normal heptane
H H H
H C H H H H
|
| |
| | |
2-Methyl Hexane, HCCCCCCH
|
| |
| | |
H H H H H H
The number indicates the position of the carbon
atom to which the methyl group is attached.

Paraffins
Isomer of normal heptane
H H H
H C H H H
| |
| | |
2,2 Dimethyl Pentane, HCCCCCH
| |
| | |
H C H H H
H H H

Paraffins

Olefins (CnH2n ) suffix-ene

The olefins (alkenes), CnH2n, are also straight or openchain hydrocarbons but have two atoms of hydrogen
fewer per molecule with one carbon-carbon double bond.

C8H16

H H H H H H H H
|
| | | | | |
|
HCCCC=CCCCH
| |
|
| | |
H H H
H H H

The open-chain hydrocarbons, paraffins and olefins, are

classed jointly as aliphatics.

Olefins (CnH2n ) suffix-ene

Diolefins (CnH2n-2 ) suffix-diene

The diolefins, CnH2n-2, are unsaturated hydrocarbons with
two double-bonded molecules.

1,5-Hexadien, C6H10

H
H H
H
|
| |
|
C=CCCC=C
| | | | | |
H H H H H H

The olefins and diolefins are unsaturated compounds and

therefore unstable; the carbon atoms with a double bond can
attach themselves to and absorb additional atoms of hydrogen,
oxygen, or sulphur if such are present.

Diolefins (CnH2n-2 ) suffix-diene

Cycloparaffins (CnH2n )
The naphthenes (Cycloparaffins/cycloalkanes), have the
same chemical formula, CnH2n, but are closed-chain
hydrocarbons and there are no double bonds.
H HHHHH
|
|
HCCCCH
|
|
HCCCCH
|
|
H HHHHH
Cyclo-Octane, C8H16

Cycloparaffins (CnH2n )

Alkynes (CnH2n-2 )
The
alkynes,
CnH2n-2,
are
unsaturated
hydrocarbons with a triple carbon-carbon bond.
The best known member of the family is
acetylene (C2H2).
H C

C H

Aromatics (CnH2n-6 )
The aromatics, CnH2n-6, are hydrocarbons with carbon-carbon doublebonds internal to a ring structure. The most common aromatic is
benzene.

The double bonds alternate in position between the carbon atoms.

This makes the molecule hard to break and, as a result, aromatics
are desirable in gasoline since they increase the octane number.
Aromatics are undesirable components of diesel fuels.

Aromatics (CnH2n-6 )

Aromatics generally make good gasoline fuel components,

with some exceptions due to exhaust pollution. They have
high densities in the liquid state and thus have high energy
content per unit volume. Aromatics have high solvency
characteristics, and care must be used in material selection
for the fuel delivery system (e.g., they will dissolve or swell
some gasket materials). Aromatics will dissolve a greater
amount of water than other hydrocarbons and thus can
create fuel line freezing problems when the temperature is
lowered and some of the water comes out of solution.
Aromatic make poor CI engine fuel.

HYDROCARBON FUELS:
General Remarks
At atmospheric conditions, hydrocarbon molecules with a
low number of carbon atoms, 1 to 4, are gases.
Hydrocarbons with 5 to 15 carbon atoms are more or less
volatile light oils, and those with 16 to 26 carbon atoms
are referred to as heavy oils.
Commercial fuels and lubricating oils are mixtures of
many kinds of hydrocarbons in various proportions.
Another group of hydrocarbons consists of methyl, CH4O,
ethyl, C2H6O, and butyl, C4H9OH, alcohols. These are not
true hydrocarbons, since each contains oxygen in the
molecule.

Alcohols
Alcohols are similar to paraffins with one of the hydrogen atoms replaced
With hydroxyl radical OH. The most common alcohols are:

Nitromethane (CH3NO2)
Nitromethane (CH3NO2) is formed from a paraffinic hydrocarbon by
replacing a hydrogen atom with a NO2 group. It has twice the bound
oxygen and can combust without air. At ambient temperature, it is a
liquid, and is widely used as a drag racing fuel.

H
|
HCNO2
|
H

Summary
Family

PROPERTIES

Paraffin
(Alkanes)

The alkanes are stable in storage, clean burning & don't attack the usual
gaskets or metals. Since they have the maximum possible amount of
hydrogen, so they have the highest heating values per unit mass of hydrogen
& due to lowest densities having lowest heating values per unit volume. The
paraffins are practically insoluble in water but are soluble in other
hydrocarbons. (High H---- high SE) & Storage Stability

Olefin
(Alkenes)

Because of the free bond, the olefins are chemically active. They may unite
with oxygen to form an undesirable residue, gum
Specification limit the olefin contents in jet fuel. Actual olefin concentration are
about 1 to 3 %--- Storage Instability

Naphthene
(Cyclanes)

In general, paraffins & Naphthenes comprise from 75% to 95% of most jet
fuel.--- Storage Stability

Aromatics

Aromatics have the highest densities of the hydrocarbons and therefore have
the highest heating value per unit volume. And the lowest per unit mass.
Aromatics are stable in storage, smoky in burning. Jet specification limit the
aromatic contents. The aromatics may dissolve as much as 6 gal water per
100,000 gal fuel, and when the fuel temp. decreases, the water comes out of
solution leading to troubles such as freezing. Concentration of aromatics is
limited to 25%.- Attack seals & diaphragms--- (High C---- Low SE)

Fuel Additives
Compounds are added to the fuel in very small amount to provide special or
improved quantities. These are
1 Anti-knock additives
2 Anti-oxidants (to prevent the formation of gums, caused by oxidation of fuel)
3 Static dissipater: (reduce the hazardous effects of static electricity generated
by movement of fuel through modern high flow rate fuel transfer system.
4 Corrosion Inhibitors:
5Anti-Icing additives: ( To reduce the freezing point of water precipitated from
fuels due to cooling at high altitudes and prevent the formation of ice
crystals which restrict the flow of fuel to the engine.
6 Metal de-activators To suppress the catalytic effect which some metals,
particularly copper , have on fuel oxidation.
7 Biocide additives: ( to combat microbiological growths in fuel)
8 Thermal Stability Improvers: ( to Inhibit deposit formation in the high
temperature areas of the aircraft fuel system.

Fuel Properties
Relative density (defines the energy contents in fuel tank)
Vapor pressure
Flashpoint ( lowest temp at which liquid gives off enough to form a
flammable mixture)

Volatility point (can be assessed by, flash point, dist. range &vap. pres)
Viscosity
Surface Tension
Freezing point
Specific heat
Calorific value
SIT
Flammability limit

Properties of Fuels

Properties of Fuels
Properties/Fuel

Propane

Nat. Gas

Hydrogen

Methanol

Ethanol

Gasoline

Molecular wt.

44.10

18.10

2.015

32.04
32

46.07
17

~110
62~90

-160

-253

65

78

30~225

1215

850

310

19.9

26.8

44.5

15.7

21.1

32.9

Vapor pressure (KPa) at

38C
Boiling Point (C) at 1bar
Enthalpy of vaporization
hfg (KJ/kg)at 298K

Lower heating Value, mass

(MJ/Kgfuel)

46.4

Lower heating Value,

volume (MJ/Lfuel)

50.0

120

8.1
at 15C, 22MPa

Lower heating Value,

Stoichiometric (MJ/Kgfuel)

2.98

2.92

3.52

3.09

3.00

2.96

O.N (research)

112
97
15.58

120
120
17.12
5.3~15

106
34.13
5~75

112
91
6.43
5.5~26

111
92
8.94
3.5~26

90~98
80~90
15.04
0.6~8

2268

2227

2383

2151

2197

2266

O.N (motor)
St. A/F ratio (mass)
Vapor Flammability Limit
(% Vol.)
Adiabatic Flame Temp.
(K)

Routine Fuel Tests (lab)

API-Gravity & Specific Gravity
Vapor Pressure (D323)
Flash & Fire point
ASTM Distillations (D86)
Color- Jet fuel grades vary from water white to light yellow
Viscosity
Cloud & Pour Point
Sulfur Test (D90)
Gum Test (D381, D525)
Smoke point (D1322)
Freezing Point (D2386
Doctors test

Thanks