Fuels and Combustion

Combustion
𝐹𝑢𝑒𝑙 + 𝐴𝑖𝑟 → 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠 + 𝐻𝑒𝑎𝑡
𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
If fuel composition is known, some questions are considered:
1. What is the minimum quantity of air (theoretical or stoichiometric) required for
complete combustion and what are the species of the product?
2. If excess air is used what will occur to the combustion product?
3. If dry (flue gas) analysis of the product is known what is the quantity of air used?
4. What is the heat of reaction?
5. What are the higher heating (Calorific) value (HHV) and the lower heating value
(LHV) of this fuel?
6. What is the maximum (adiabatic flame) temperature of this reaction?
7. At high temperature, if dissociation occurs what will the composition of the product?
8. What is the rate of this reaction?
9. What are the pollutants of this reaction? etc…………,
 Fuels

Gasoline and diesel fuels are composed of blends of hydrocarbons, grouped into families of hydrocarbon molecules
termed paraffins, olefins, naphthenes, and aromatics. The hydro- carbon families each have characteristic carbon-
hydrogen bond structures and chemical formulae.
The number of carbon atoms is specified by a prefix:

1-meth 2-eth 3-prop 4-but 5-pent 6-hex

7-hept 8-oct 9-non 10-dec 11-undec 12-dodec
 Gases
 
Meth Eth Pr op But Pent
Liquid

Hex Non Dodec Pentadec
Hept Dec Tridec
Oct Undec Tetradec
Paste
 
Hexadec Octadec Ei cos
Heptadec Nonadec
 Structure of Hydrocarbons

Hydrocarbon

Chain Structure Cyclic Structure

Saturated Unsaturated Saturated Unsaturated

"Paraffins" Napthene or Cycloparaffins Aromatic
(CnH2n+2) CnH2n
Cyclo- ane

Olefins Diolifins Benzen Naphtalene

"one double bond or tripple bond" Two Double or Tripple bond" CnH2n-6 CnH2n-12
CnH2n CnH2n-2
 Fuels (Continue)
1- Paraffins (alkanes)

• They are called saturated hydrocarbons because there are

no double or triple bonds. ( i.e., impossible to add any
more H atom into HC) and chemically represented as
Propane C3H8
Methane CH4
CnH2n+2.

• They are denoted by a prefix “n” (e.g., n-Octane).

Examples of alkanes include methane (CH4), ethane
(C2H6), propane C3H8), and butane (C4H10). Butane C4H10
• Paraffins names all end in “ane”
➢ The carbon atoms can be arranged as a straight chain or as
branched chain compounds.
-Straight chain group (normal paraffins)
shorter the chain, stronger the bond
not suitable for SI engines – high tendency for autoignition.
• Typically, increasing the number of hydrogen and carbon atoms, produce heavier gases, increase the bond
energy, and increase molar heating value because of increase in C and H atoms. For example, CH4 has heat
content of 37000 kJ/ m3, propane 92500 kJ/m3, and butane 118000 kJ/ m3.

• Low density (620 – 770 kg/ m3)

• Further, the ignition temperature (at which the fuel ignites) decreases with increase in the number of C atoms
in the paraffins.

• Paraffins have maximum H/C ratio and clean combustion.

• The greater the C in paraffins, the greater the number of isomers.

• A few paraffinic components in natural gas are
CH4 and C2H6 ; in liquid petroleum gas, C3H8
and C4H10 ; and in gasoline, C8H18.
2, methyl propane
• Sometimes the chains in the molecule are
branched, and other molecular structures
obtained with the same number of carbon and
hydrogen atoms. It is called Isomers.

• One such isomer Is Isobutane, which has the

same chemical formula as butane (C4 H10 ) but
has a different structure:

• Iso-octane can also be called 2,2,4-

trimethylpentane, pentane because it has five
car bon atoms in the main chain, trimethyl
because it has three methyl radicals (CH3 ), and
2,2,4 because the three radicals are on the
second, second, and fourth carbon atoms in the
chain.
2- Olefins CnH2n)
Olefins or alkenes are HCs having open
unsaturated (i.e., H atom <2n + 2 in
CnH2n) chain structures and are
represented by the chemical formula
CnH2n as shown. They contain both
single and double bonds. The names of
alkenes generally end in “ene.”
• They can also be either straight or
branched chain . They are clean
burning . Mono-olefins have an open-
chain structure.
• Olefins are unstable (i.e., more prone
to oxidation during storage) and can
form residues.
➢ Can be used in SI-engines, obtained by
cracking of large molecules low heat
content and density in the range 620 –
820 kg /m3
3- Diolefins CnH2n–2

Diolefins CnH2n–2 have two double

bonds, and their names end in “diene,”

4- Acetylene series CnH2n–2

Acetylenes have one triple carbon

atom bond. The general formula for
this series CnH2n–2 , and some typical
compounds are acetylene C2H2 and Ethyleacetylene C4H6
ethylacetylene C4H6
5- Alcohols

• Alcohols are partially oxidized

HCs having saturated structure.
In the case of alcohols, an H
atom of a paraffin is replaced
by an OH radical (CnH2n+1 OH).
6- Naphthenes or Cycloparaffin CnH2n
The naphthenes or cycloparaffin family is denoted by
the formula CnH2n. These fuels are like paraffins except
for their ring saturated (instead of straight chain)
structure.

• Stable structure and low tendency to autoignite

compared to alkanes (normal paraffins)
• Can be used both in SI-engines and CI-engines
• Low heat content and high density (740–790 kg/m3)
7- Aromatics (CnH2n–6)

• Double-bonded HCs can also be arranged in

cyclic forms. Aromatics are represented by
CnH2n–6 and include benzene C6H6, toluene
C7H8, ethyl benzene C8H10 (which is
identical to benzene but with a H atom
replaced by an ethyl radical C2H5). The
double bonds can alternate in aromatic rings.
• Rings can be connected in polycyclic form.
For example, when two rings are united it
forms naphthalene C10H8 when 3 rings are
united it forms anthracene C14H10, and
benzopyrene has 5 rings united.
• Aromatics chemically more stable and
make good gasoline fuel components,
with some exceptions due to exhaust
pollution.
Note: If OH group is attached to benzene, it forms phenol.
• Can be used in SI-engines, to increase the
resistance to knock not suitable for CI-
engines due to low cetene number
 Common Liquid Fuels

Gasoline (C8H16): Gasoline is a mixture that results from the fractionation of crude oil. It consists mostly of C5–C10
hydrocarbon groups; it can be represented as CnH1.97n and has a molecular weight of 110, HHV = 47300 kJ/kg,
LHV = 44000 kJ/kg, True Boiling Point (TBP) = 30 to 200°C, LHV per unit stoichiometric mixture = 2830 kJ/kg of
mix, A:F = 14.6 and density of 0.72–0.78 g/cm3.
• An octane number of N implies that for every 100 m3 of a surrogate mixture of octane and n-heptane, N m3 is
occupied by isooctane C8H18 and (100–N) m3 by n-heptane C7H16. If gasoline is rated with an octane number of 93,
then its knock characteristics are similar to an isooctane and n-heptane surrogate mixture that contains 93%
isooctane by volume. They are determined using ASTM-D2699 for RON (research octane number) and D2700 for
MON (motor octane number).

Diesel fuel (C11.6H23.2): This is a mixture boiling in the range of 240 to 370°C; A:F ≈ 14.7 a typical surrogate fuel is
n-heptane. Sometimes diesel fuel is treated as dodecane C12H26.

Kerosene: These are crude oil derivatives (12 to 16 carbon atoms per molecule) boiling in the range of 140 to 250°C.
Surrogate fuels are tridecane C13H28, C12H26, etc. JP5 is a kerosene distillate fuel. Aircraft fuels are essentially kerosene
fuels in the C10 to C18 hydrocarbon groups. A higher C/H ratio in a fuel results in enhanced soot formation.

Fuel oil (12 to 16 carbon atoms per molecule): Typically, they are used in burners for heating and power generation.
They boil in the range of 340 to 420°C.
Data on Fuel Properties
 Alternative Fuels for Internal Combustion Engines
• Researchers have studied on alternative fuels that can be used with gasoline and diesel fuels. Alternative fuels
such as hydrogen, acetylene, natural gas, ethanol and biofuels also uses in internal combustion engines.
• Natural gas is generally consisting of methane (85–96%) and it can be used in both petrol and diesel engines.
 Hydrogen
Hydrogen in the gas phase is about 14 times lighter than the air. Moreover, it is the cleanest fuel in the world. On the
other hand because of its high ignition limit (4–75%), low ignition energy, needs special design to use as pure
hydrogen in internal combustion engines. It is proved that hydrogen improves the combustion, emissions and
performance, when is added as 20% to fuels.
Disadvantages of using Hydrogen fueled engine
Advantages of using Hydrogen fueled engine
• Due to high heat release the combustion temperature
• It provides high efficiency because it utilizes a higher may be high and also a level of nitrogen oxide is high. It
proportion of the energy in the fuel. can be reduced by reducing the combustion
temperature by injecting water vapor into the cylinder
• The amount of carbon monoxide and hydrocarbons from the exhaust.
in the exhaust is very small since they are originating
only from the cylinder lubricating oil. • It requires heavy, bulky fuel storage both in vehicle and
at the service station.
• It can be easily available because it is produced by
electrolysis of water. • Fuel cost would be high at present day technology.

• Fuel leakage to environment is not pollutant.

 Acetylene
Acetylene was used as fuel in internal combustion engines in the early 1900s. Gustave Whitehead used a 15 kW engine
powered by acetylene on his flying machine in 1901. Towards the year 1940s, acetylene began to be used in automobiles.

Acetylene has higher flame speed and energy density than gasoline and diesel hence acetylene engines could more
approach thermodynamically ideal engine cycle efficiency. But the octane number of acetylene is lower than other
fuels which use in internal combustion engines. Therefore the maximum amount of acetylene consumption is limited to the
onset of knock.

In SI engines, acetylene and gasoline are either

injected into the intake manifold or directly into
the cylinder and the mixture is ignited by spark
plug at the end of the compression stroke.

In diesel engines, acetylene is either inducted

along with intake air or injected directly into the
cylinder.
 Ethanol

• Ethanol fuel is the most common biofuel worldwide, particularly in Brazil. Alcohol fuels
are produced by fermentation of sugars derived from wheat, corn, sugar beets and
molasses.

• Ethanol can be used as pure fuel or mixed with different fuels in internal combustion
engines.

• Ethanol can be used in petrol engines as a replacement for gasoline; it can be mixed with
gasoline to any percentage. Most existing car petrol engines can run on blends of up to
15% bioethanol with petroleum/gasoline.

• An advantage of ethanol (CH3CH2OH) is that it has a high-octane rating, which allows

an increase of an engine's compression ratio for increased thermal efficiency.
 SELF-IGNITION AND OCTANE NUMBER

• If the temperature of an air–fuel mixture is raised high enough, the mixture

will self ignite without the need of a spark plug or another external igniter.
The temperature above which this occurs is called the self-ignition
temperature (SIT).

• This is the basic principle of ignition in a compression ignition engine. The

compression ratio is high enough that the temperature rises above SIT during
the compression stroke. Self ignition then occurs when fuel is injected into the
combustion chamber.

• On the other hand, self-ignition (or preignition, or autoignition) is not

desirable in an SI engine, where a spark plug is used to ignite the air–fuel at
the proper time in the cycle. The compression ratios of gasoline-fueled SI
engines are limited to about 11:1 to avoid self-ignition.

• When self-ignition does occur in an SI engine, higher than desirable pressure

pulses are generated. These high-pressure pulses can cause damage to the
engine and quite often are in the audible frequency range. This phenomenon is
often called knock or ping.
 Fig. Cylinder pressure as a function of time in a typical SI engine combustion chamber showing
(a) normal combustion, (b) combustion with light knock, and (c) combustion with heavy knock.

(a) Mass of air–fuel is equally distributed as spark plug is fired to start combustion.
(b) As flame front moves across chamber, unburned mixture in front of flame is compressed into smaller volume.
(c) Flame front continues to compress unburned mixture into smaller volume, which increases its temperature and
pressure. If compression raises temperature of end gas above SIT, self-ignition and knock can occur.
 Knocking and Octane Number

But sometime, due to high compression the gasoline air mixture get heated to a temp., so
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 & delayed ignition causes Knocking (i.e. a sharp metallic sound)
Knocking causes loss of energy & decrease the efficiency

** Greater CR ,more efficiency.

**Knocking tendency depends on the structure of constituents presents:

Paraffins > Branched chain paraffins > Olefins > Cycloparaffins > aromatic
 OCTANE NUMBER

• The most commonly used of gasoline efficiency, to burn without knocking is its
octane number.

n-Heptane whereas iso-octane

(Knocks very badly) (resistant to Knocking)
Antiknock value=0 Antiknock value =100
The Octane number of a fuel under standard conditions is the % of volume of
iso octane in a mixture of iso octane & n-heptane having the same Knocking
characteristics as the fuel .
eg. , gasoline that contain 75% of iso-octane &25%of n-heptane are given an
octane number 75.
 CETANE NUMBER

• The diesel fuel should easily get ignited below compression temp. The interval between
fuel injection & ignition is termed as induction lag. Induction lag shorted for efficient
functioning of Diesel engine. So, diesel engine fuels requires low ignition temperature to
minimize the induction lag.

• Induction lag occur: n-paraffins < Olefins < Naphthalenes < iso paraffin < Aromatic