TR 2019 Internal Combustion Engine

Chapter 3
Fuels and Working Fluid (Fuel-air)
of ICE and
Basic Combustion
 Petroleum Crude Oil
• Formed due to the fossilization of organic matter, under ground
(although evidence of earth mantel inorganic methane is rising).
• All formed of carbon and hydrogen, some with little oxygen, plus
sulfur, mercury and other minerals, and non combustibles.
• Most require some form of processing: sulfur removal, grinding and
washing, oil refining, gas desulfurization.
• Made up of many organic compounds + hydrogen + nitrogen +
sulfur. Sweet and sour refer to the amount of sulfur.
CHm, 1 < m < 2.
• “Light oil” is generally composed of three hydrocarbon families:
– Saturated hydrocarbons: paraffins (or normal alkanes), CnH2n+2,
with gas, n = 1-4, liquid, n = 5-15, and solids, n > 15.
– Unsaturated hydrocarbons, or aromatics, like benzene, C6H6,
toluene, C7H8 and nephthalene, C10H8.
– Resin and asphaltenes, heavier hydrocarbons rich in nitrogen,
oxygen, sulfur and vanadium.
• Refining: distillation (separation of lighter components), catalytic
cracking (heating) and reforming (with steam or hydrogen). Products
are typically refinery gas, LPG, gasoline (mostly octane C8H18),
aviation fuels (JPx) diesels, heating and lube oils ….
Refinery of crude oil
Refinery Processes
 Products made from crude oil

Gasoline distillation temperature is 35 – 200 C

Jet fuel 35 – 150 C
Diesel fuel 175 – 370 C
Heavy fuels, oil 370 – 550 C
 Fuel Types

• Gasoline and diesel fuel are both produced from

crude oil. Together, gasoline and diesel fuel power
approximately 99% of the motor vehicle fleet.
• However, alternative fuels are being used more and
more to reduce vehicle emissions.
• This section briefly explains various fuel types
 1 Fuel Types
1.Indolene - Indolene is used as the standard gasoline
emission test fuel for spark ignition engines.
Indolene is a well refined gasoline with low levels of
sulfur, phosphorus, and vapor pressure.
2.Diesel Fuel - The diesel fuel is commonly used in
relatively large displacement compression ignition
engines.
Diesel fuel is used in a broader range of engine sizes in
Europe and other areas of the world.
The average molecular weight and boiling point of diesel
fuel is greater than that for gasoline, which makes it
suitable for use in compression ignition engines,
characterized by higher in-cylinder temperatures and
pressures.
 1 Fuel Types
1.3 California Phase-2 Gasoline - California phase-2
(CF2) is a gasoline blend designed specifically for
mileage accumulation and emissions testing of vehicles
to be sold in California.
The blend contains 11.0% by volume MTBE (an
oxygenate), very low sulfur, and controlled levels of
benzene and aromatics.
CF2 volatility is adjusted for the summer and winter
seasons (6.8 psi in the summer vs. 11.0 psi in the winter).
 1 Fuel Types
4.Reformulated Gasoline - Reformulated gasoline is
similar to CF2 gasoline.
The reformulated blends usually contain an oxygenate
additive such as MTBE, EtOH, or ETBE.
5.Compressed Natural Gas - Compressed natural
gas (CNG) is comprised primarily of methane (CH4).
CNG vehicles generally produce lower emissions than
their gasoline counterparts.
However, there are tradeoffs in engine power and
efficiency.
 1 Fuel Types
1.6 Methanol (CH3OH) - Methanol is a promising
alternative fuel because it generally produces lower
tailpipe emissions than gasoline and can be manufactured
at prices comparable to gasoline.
A blend of 85% methanol and 15% unleaded gasoline
(M85) is typically used. However, M85 vehicles are
virtually phased out of new vehicle manufacture in Brazil.
Vehicles that operate on methanol consume more fuel
than if they were operating on 100% gasoline because its
energy content (calorific value) is less.
 1 Fuel Types
1.7 Ethanol (C2H5OH) - Ethanol is an important
component of automotive fuel used in Brazil.
A mixture of 22% ethanol with gasoline (E22) is
commonly used.
Ethanol is also used in the USA as an octane enhancer
for gasoline (up to 10%).
It is also used for flexible fuel vehicles as a blend of 85%
ethanol and 15% unleaded gasoline.
Ethanol is produced from corn, sugar cane or other crops
but is currently more expensive than gasoline.
 1 Fuel Types

Molecular mass LHV Fuel exergy Fuel exergy/

Fuel (kg/kmol) AF (stoich) (MJ/kgf) (MJ/kgf) LHV

Hydrogen, H2 2.016 34.15 120.0 113.5 0.946

Methane, CH4 16.04 17.17 50.0 49.9 0.998

Propane, C3H8 44.10 15.61 46.4 47.1 1.015
Hexane, C6H14 86.18 15.16 45.1 46.1 1.022
Isooctane, C8H18 114.2 15.07 44.4 45.5 1.025
Methanol, CH3OH 32.04 6.45 20.0 21.1 1.055
Ethanol, C2H5OH 46.07 8.97 26.9 28.4 1.056

Carbon monoxide 28.01 2.46 10.1 9.18 0.909

 2 Fuel Properties
• Fuel properties and compositions are regulated by most
governments.
• U.S. Federal requirements for test fuels are specified in
the Code of Federal Regulations (CFR).
• The following subsections briefly describe some
important fuel characteristics and their influence on
engine performance.
• Subsequent to these sections, Tables 1 and 2 provide
some fuel properties for liquid and gaseous fuels.
 2 Fuel Properties
2.1 Fuel Volatility - Volatility is loosely defined as the
tendency of a liquid to evaporate.
Fuel for engines must conform to strict specifications
regarding their volatility characteristics to ensure
satisfactory operation.
The fuel must contain a large enough proportion of highly
volatile components to ensure good cold starts, but the
volatility must not be so high as to impair operation
(vapor lock) and starting when the engine is hot.
 2 Fuel Properties
2.2 Distillation Curve - Three areas on the distillation or
boiling curve have a pronounced effect on an engine's
operating behavior. They can be defined according to the
percent of fuel evaporated at three temperatures during a
standard ASTM distillation test.
a.The volume of fuel that evaporates up to 70 C must be
adequate to ensure good cold starting, but not so large as
to cause vapor lock when the engine is hot.
b.The vaporized volume at 100 C should be high enough
to minimize dilution of the engine's lubricating oil.
c.The percentage of fuel which evaporates at 180 C
determines the engine's warm up qualities, as well as it's
acceleration and response characteristics once it has
reached normal operating temperature.
 2 Fuel Properties
2.2 Distillation Curve -

Figure The Fuel Distillation Curve

 2 Fuel Properties
2.2 Distillation Curve -
Figure below illustrates the effect of changing the shape
of the distillation curve.

Figure The Effects of Altering the Fuel Distillation Curve

 2 Fuel Properties

2.2 Distillation Curve - From Figure 1,

• Raising the left end, by reducing the amount of highly
volatile (low boiling point) compounds in the blend,
degrades cold starting.
• Lowering the left end can cause vapor lock, poor hot
starts, and high evaporative losses.
• Raising the right end, by adding compounds with higher
molecular weights, leads to increased oil dilution and
deposit formation.
• Lowering the right end increases fuel consumption during
warm engine operation.
• Raising the middle degrades warm-up driveability, causes
rough accelerations, and degrades fuel economy during
short trips.
 2 Fuel Properties
2.3 Vapor Pressure - Fuel vapor pressure curves are
strongly influenced by fuel composition.
The curves for fuels containing alcohol, for instance, are
much steeper than those for pure hydrocarbon mixtures.
The result is that fuels with alcohol display a greater
tendency to vaporize and form vapor lock, thus impairing
operation at higher temperatures.
Since 1992, federal emission laws have regulated
maximum RVP to reduce evaporative and exhaust
emissions, particularly in California.
 2 Fuel Properties
2.4 Vapor/Liquid Ratio - This specification provides an
index of a fuel's tendency to form vapor bubbles (vapor
locks).
It is based on the volume of vapor generated by a
specific quantity of fuel at a set temperature.
Assuming a constant temperature, a larger volume of
vapor will form at low pressures (i.e., at high altitudes)
than at higher pressures (i.e., at sea level).
This phenomenon can lead to vapor-lock problems when
driving in mountainous areas.
The addition of alcohols, methanol in particular, raises
the vapor/liquid ratio.
 2 Fuel Properties
2.5 Driveability Index - The driveability index (DI) is
used often by engineers to predict engine performance
based on three points from a fuel‟s distillation curve.
These points are referred to as the T10, T50 and T90
temperatures, and correspond to temperatures in F at
which 10%, 50%, and 90% of the volume of a fuel has
evaporated.
The index is calculated using Equation 1:
DI = 1.5 T10 + 3.0 T 50 + T 90. (1)
 2 Fuel Properties
2.5 Driveability Index –
• Note that more emphasis is placed on the T50
temperature since this is the approximate temperature
at which the fuel enters the combustion chamber.
• A larger DI results from a less volatile fuel and vice
versa.
• Typical DI‟s for gasoline range from 1,000 to 1,200.
• Fuels with a DI greater than 1200 may cause
hesitation, stumbles and misfires, contributing to
higher emissions.
 2 Fuel Properties
2.6 Octane/Cetane Rating –
The octane rating defines a gasoline's ignition quality
(engine "knock resistance") for gasoline engines.
The cetane number carries similar meaning but for
diesel engines.
However, the two numbers have inverse relationships
with respect to knock resistance; the resistance to
engine knock increases with increasing octane number
and decreasing cetane number.
 2 Fuel Properties
2.7 Knock Inhibitors - The most effective knock
inhibitors are organic lead compounds. These can raise
the octane number by several points.
Environmental concerns have lead to a steady reduction
in the amount of lead in fuels.
A compound developed to replace lead compounds
methylcyclopentadienyl manganese tricarbonyl (MMT) is
currently used in Canada and adversely affects
emissions.
In U.S. gasoline, refiners have not currently used MMT.
Data is being generated to effect a ban of MMT by the
U.S. EPA.
 2 Fuel Properties
2.8 Calorific Value - The specific values for the net
(lower) and gross (higher) calorific values, provide an
index for the energy content of fuels.
When fuels (such as methanol), with a lower calorific
value are used, greater quantities will be required to
achieve comparable engine output.
 3 Fuel Composition

Fuels vary widely in chemical composition, depending on

the source of crude and on the methods used in refining.
In every case, however, the fuel consists almost entirely
of a mixture of hydrocarbon compounds having different
molecular weights and different types of structure
 3 Fuel Composition
Most common hydrocarbon fuels are Alkyl Compounds
and are grouped as:
3.1 Paraffins - Paraffins are straight chained
hydrocarbons, also called alkanes. Some examples are
propane and butane. Isoparaffins have a branched chain
structure.

-All the carbon bonds are single bonds – they are “saturated” high number of H
atoms, high heat content and low density (620 – 770 kg/m3)

-The carbon atoms can be arranged as a straight chain or as branched chain

compounds.

-Straight chain group (normal paraffins)

-Saturated hydrocarbons which are arranged in a circle (Called as cycloparaffins

and represented as CnH2n) have stable structure and low tendancy to autoignite
compared to alkanes (normal paraffins)
 3 Fuel Composition
Paraffins (alkanes): single-bonded, open-chain, saturated (no more hydrogen
can be added)

CnH2n+2 n= 1 CH4 methane

n= 2 C2H6 ethane
n= 3 C3H8 propane
n= 4 C4H10 butane
n= 8 C8H18 n-octane and isooctane

H H H H H H H H H H H H

H C H H C C C H H C C C C C C C C H

H H H H H H H H H H H H

methane propane n-octane

There are several isooctanes, depending on position of methyl (CH3) branches

which replace hydrogen atoms (eg. 3 H are replaced with 3 CH3)
 3 Fuel Composition
3.2 Aromatics – They are based on a six-membered ring having
three conjugated double bonds. Examples are benzene, toluene,
xylene.
• Aromatic rings can be fused together to give polynuclear aromatics,
PAN, also called polycyclic aromatic hydrocarbons, PAH simplest
member is benzene (C6H6)
• Aromatics are high octane blending hydrocarbons that have a
benzene ring in their molecular structure.
 3 Fuel Composition
3.3 Olefins

Olefins are gasoline hydrocarbons resulting from several

refining processes. Examples are ethylene, propylene,
butylene. Olefins often contribute to the formation of gum
and deposits in engines and the induction system. Olefins
are also called alkenes.
 3 Fuel Composition
3.3 Olefins –
• Olefins or alkenes are represented as Mono olefins-CnH2n or
Dio-olefins CnH2n-2
• Olefins have the same C-to-H ratio and the same general formula
as naphthenes, their behavior and characteristics are entirely
different
• They are straight or branch chain compounds with one or more
double bond. The position of the double bond is indicated by the
number of first C atom to which it is attached
• Olefinic compounds are easily oxidized, have poor oxidation
stability
• Can be used in SI-engines, obtained by cracking of large
molecules low heat content and density in the range of 620 – 820
kg /m3
 3 Fuel Composition
Olefins (alkenes): open-chain containing one double-bond, unsaturated
(break bond more hydrogen can be added)
H H
H
CnH2n n=2 C2H4 ethene C C C H
n=3 C3H6 propene H
H
Note: n=1 yields CH2 is an unstable molecule propene

Acetylenes (alkynes): open-chain containing one C-C triple-bond

unsaturated

CnH2n-2 n=2 C2H2 acetylene

n=3 C3H4 propyne acetylene

For alcohols one hydroxyl (OH) group is substituted for one hydrogen
e.g. methane becomes methyl alcohol (CH3OH) also known as methanol
ethane becomes ethyl alcohol (C2H5OH) also known as ethanol
 3 Fuel Composition
3.4 Oxygenates - Oxygenates are an octane component
containing hydrogen, carbon, and oxygen in their
molecular structure.

Includes ethers such as MTBE and alcohols such as

ethanol and methanol.

Adding an oxygenate to gasoline results in enleanment

thereby improving combustion and reducing tailpipe
emissions.
 3 Fuel Composition
Table 1 Typical Properties of Liquid Fuels and Hydrocarbons
 3 Fuel Composition
Table 2 Typical Properties of Gaseous Fuels and Hydrocarbons
 3 Fuel Composition
3.5 Additives - Chemicals are added to gasoline in very
small quantities to improve and maintain gasoline
quality.

Examples include: detergents which prevent or clean up

carburetor and fuel injector deposits, corrosion inhibitors,
antioxidants to reduce gum formation in storage, acetone
or similar water absorbents, and ethers such as methyl
tertiary butyl ether (MTBE) for increased octane levels.
 3 Fuel Composition
3.5.1 Effects of fuel additives
Fuel additive serve two distinct purposes.
 to improve combustion and pollutant emissions,
 to ensure reduced wear and limit deposit formation during the
engine life cycle of several hundreds of thousands of miles
 3 Fuel Composition
3.5.1 Effects of fuel additives
Figure 2 shows some important fuel-relevant problem
areas in a spark-ignition engine

Figure 2 Problem areas related to fuel in a spark ignition engine.

 3 Fuel Composition
3.5.2 Additive for gasoline engine
Most important additives that have a direct effect on
combustion are “anti-knock products”. Additives
containing metals are designed to improve combustion
(combustion enhancers).
Deposits will accumulate on the valve heads that act
like a sponge during cold starting and cause the air-fuel
mixture to become leaner.
At full throttle, the deposits reduce the cylinder charge
and thus cause power losses.
 3 Fuel Composition
Figure 3 shows how exhaust emission are affectd
adversely by deposit formation and residues inside the
combustion chamber and on the inlet valves. Additive
will help avoid these problems.

Figure 3 Effect of deposit formation on pollutant emissions

 3 Fuel Composition
3.5.3 Additive for diesel engines
Additives, for diesel engine, concentrates on improving
combustion, reducing deposit formation during
combustion of the fuel and keeping the injectors clean.
Three group of additives are used for diesel engines:\
Cetane number enhancers: Increasing the cetane
number by using cetane number enhancers means that
ignition lag is reduced, i.e. ignition is advanced.
Extensive research has proven that increased additive
concentration help to reduce HC, CO and particulate
emission by a significant degree without causing NOx
emission to increase.
When the cetane number was increased by ten units,
HC emissions dropped by up to 80%, CO emissions
were up to 50% lower and particulate emissions were
reduced by up to 30%. Combustion noise is also
reduced considerably.
 3 Fuel Composition
Combustion enhancers: Combustion enhancers act
directly on the combustion process.
This effect is achieved both in clean and in coked
engines, Unburned hydrocarbons and particulates are
reduced by a significant degree whereas CO and NOx
emissions remain unchanged.
Multifunctional diesel additive: This additive pack
includes components for corrosion protection,
demulsification and reducing the foaming tendency.
Oxidation inhibitors and detergents are used to keep the
injectors clean.
After run with the additive pack, HC emissions had
dropped and CO and particulates were more lower
without causing any significant increase of NOx
emissions.
 4 Basic Combustion

Basic definitions
• „combustion‟ reactions are one form of chemical reaction
1. combustion is defined as the oxidation of a „fuel‟, with
large amounts of released energy
2. the oxidiser is in most cases air (or more specifically,
O2 in air) because of its abundance.
3.a „fuel‟ is any material (mostly Hydrocarbons that
store energy in their chemical bonds. Highest energy
storage per unit mass or unit volume (in liquid form))
that can be burned to release energy. Hydrocarbon
fuels of the form CxHy are the most common.
 4 Basic Combustion
Basic definitions
• many hydrocarbon fuels are mixtures of many different
hydrocarbons although they mainly consist of the
following:
– gasoline ~ octane, C8H18
– diesel ~ dodecane, C12H26
– methanol = methyl alcohol, CH3OH
– LNG (liquefied natural gas) ~ methane, CH4
– LPG (liquefied petroleum gas) ~ propane, C3H8
 4 Basic Combustion
Composition of air

• on a molar (or volume) basis, dry air is composed of:

– 20.9% oxygen O2
– 78.1% nitrogen N2
– 0.9% CO2, Ar, He, Ne, H2, and others

• a good approximation of this by molar or volume is: 21%

oxygen, 79% nitrogen

• thus, each mole of oxygen is accompanied 0.79/0.21 =

3.76 moles of nitrogen.
 4 Basic Combustion

Composition of air
• at ordinary combustion temperatures, N2 is inert, but
nonetheless greatly affects the combustion process
because its abundance, and hence its enthalpy change,
plays a large part in determining the reaction
temperatures.
1. this, in turn, affects the combustion chemistry, as we shall see
later.
2. also, at higher temperatures, N2 does react, forming species
such as oxides of nitrogen (NOx), which are a significant
pollutant.
 4 Basic Combustion

Stoichiometry and air/fuel ratios

• the amounts of fuel and air taking part in a combustion
process are often expressed as the „air to fuel‟ ratio:
mair
AFR  m
fuel
where:
• mfuel, mair = mass of fuel or air (kg),
 equivalent, and widely used, terms to the AFR are the
fuel/air ratio FAR, the equivalence ratio, , and the
„lambda‟ ratio :
1 FAR
   FAR
 stoich
 4 Basic Combustion

• It is important to define what measure is being used in

describing the relationship between A/F and other
parameters.
• Keys for remembering the trends in each measure of A/F
is:

Measure Leaner Richer

Combustion Combustion
A/F Bigger Smaller
F/A Smaller Bigger
 Bigger Smaller
 Smaller Bigger
 4 Basic Combustion
Thermodynamics of Combustion
• When molecules undergo chemical reaction, the reactant
atoms are rearranged to form new combinations
(oxidized). The chemical reaction can be presented by
reaction equations. However, reaction equations
represent initial and final results and do not indicate the
actual path of the reaction, which may involve many
intermediate steps and intermediate species. This
approach is similar to thermodynamics system analysis,
where only end states and not path mechanism are
used.
• The dissociation of the products into species with a
higher enthalpy of formation occurs in many combustion
reactions of practical importance. In such cases, the
temperature of the products is lower than the
undissociated temperature, because some of the energy
released by the original combustion reaction is absorbed
by endothermic, dissociative reactions.
Hydrocarbon oxidation mechanism
 COMBUSTION STOICHIOMETRY

It is a condition when sufficient oxygen is available, thus, a

hydrocarbon fuel can be completely oxidized.
 The Carbon in the fuel is then converted to carbon
dioxide, CO2, and
 the Hydrogen to water, H2O.
4.1 Combustion Reaction of Hydrocarbon in O2

• Oxyfuel combustion, that is burning in pure oxygen, is

also used to further raise the products temperature, in
gasifiers (reformers), or to avoid the formation of nitric
oxides.
 4.1 Combustion Reaction of Hydrocarbon in O2
Combustion Stoichiometry
If sufficient oxygen is available, a hydrocarbon fuel can be completely
oxidized, the carbon is converted to carbon dioxide (CO2) and the hydrogen is
converted to water (H2O).
The overall chemical equation for the complete combustion of one mole of
propane (C3H8) is:
C3 H8  aO2  bCO2  cH2O
# of moles species

Elements can not be created or destroyed so

carbon balance gives b= 3
hydrogen balance gives 2c= 8  c= 4
oxygen balance gives 2b + c = 2a  a= 5

Thus the above reaction is:

C3 H8  5O2  3CO2  4H 2O
Stoichiometric air/fuel ratio for air-hydrocarbon fuel
mixtures as a function of fuel molar H/C ratio.
4.2 Combustion Reaction of Hydrocarbon in Air

• Air contains molecular nitrogen N2, when the products are

low temperature
• the nitrogen is not significantly affected by the reaction, it is
considered inert.
• The complete reaction of a general hydrocarbon CnHm with
air is:

• The above equation defines the stoichiometric proportions

of fuel and air.
4.2 Combustion Reaction of Hydrocarbon in Air

• In complete, stoichiometric combustion of hydrocarbons,

the products are water and carbon dioxide.
• Even with stoichiometric combustion, carbon monoxide
and nitric oxides form, as well very small amounts of
hydrocarbons and their fragments (PAH).
• The amount of CO, NOx and “CH” in the products depend
on the fuel, combustion conditions, nature of the
combustion process, and how fast the products are
cooled.
4.2 Combustion Reaction of Hydrocarbon in Air
There is no complete combustion !
The amount of CO, NOx and “CH” in the products depend
on the fuel, combustion conditions, nature of the
combustion process, and dissociation of the products.

dissociation products
4.2 Combustion Reaction of Hydrocarbon in Air
Combustion Stoichiometry
Example: For propane (C3H8) n= 3 and m= 8

C3 H 8  5(O2  3.76N 2 )  3CO2  4H 2O  3.765N 2

The stoichiometric mass based air/fuel and fuel/air ratio is:

Substituting the respective molecular weights and dividing top and bottom
By n = one gets the following expression that only depends on the ratio of the
number of hydrogen atoms to carbon atoms (mn) in the fuel.
4.2 Combustion Reaction of Hydrocarbon in Air
4.2.1 Combustion Stoichiometry

Note above equation only applies to stoichiometric mixture

For methane (CH4), m/n = 4  (A/F)s = 17.2

For octane (C8H18), m/n = 2.25  (A/F)s = 15.1

4.2 Combustion Reaction of Hydrocarbon in Air
4.2.2 Fuel Lean Mixture

• Fuel-air mixtures with more than stoichiometric air, excess air, can burn.

•With excess air you get fuel lean combustion, the extra air appears in the
products in unchanged form.
m m
Cn H m   (n  )(O2  3.76N2)  nCO2  H 2 O  dN 2  eO2
4 2
where for fuel lean mixture have excess air so  > 1

•Above reaction equation has two unknowns (d, e) and we have two
atom balance equations (O, N) so can solve for the unknowns
4.2 Combustion Reaction of Hydrocarbon in Air
3. Fuel Rich Mixture

• Fuel-air mixtures with less than stoichiometric air can also burn.
•With less than stoichiometric air you get fuel rich combustion, there is
insufficient oxygen to oxidize all the C and H in the fuel to CO2 and H2O.
•Get incomplete combustion where carbon monoxide (CO) and molecular
hydrogen (H2) also appear in the products.

m
Cn H m   (n  )(O2  3.76N 2 )  aCO2  bH2O  dN 2  eCO  fH 2
4
where for fuel rich mixture have insufficient air   < 1

•Above reaction equation has three unknowns (a, b, d, e, f) and we only have
two atom balance equations (C, H, O, N) so cannot solve for the unknowns
unless additional information about the products is given.
4.2 Combustion Reaction of Hydrocarbon in Air
4.2.4 Off-Stoichiometric Mixtures
The equivalence ratio, , is commonly used to indicate if a mixture is
stoichiometric, fuel lean, or fuel rich.


A / F s  F / Amixture
A / F mixture F / As
stoichiometric  = 1
fuel lean <1
fuel rich >1
Stoichiometric mixture:

Cn H m  
m
n  (O 2  3.76N 2 )  Products
 4
Off-stoichiometric mixture:
1  m
Cn H m  n  (O 2  3.76N 2 )  Products
 4
4.2 Combustion Reaction of Hydrocarbon in Air
Off-Stoichiometric Conditions
Other terminology used to describe how much air is used in combustion:
150% stoichiometric air = 150% theoretical air = 50% excess air
m
C3 H 8   (n 
)(O2  3.76N 2 )   1.5  mixture is fuel lean
4
Example: Consider a reaction of octane with 10% excess air, what is ?
The stoichiometric reaction is:
C8 H18 12.5(O2  3.76N2 )  8CO2  9H 2O  47N 2
10% excess air is:

C8 H18 1.1(12.5)(O2  3.76N2 )  8CO2  9H 2O  aO2  bN2

16 + 9 + 2a = 1.1(12.5)(2)  a = 1.25, b = 1.1(12.5)(3.76) = 51.7

A / F s 12.5(2)(4.76) /1
   0.91
A / F mixture 1.1(12.5)(2)(4.76) /1
4.2 Combustion Reaction of Hydrocarbon in Air

• Consider the combustion of octane, C8H18. Under ideal

conditions, all of the hydrocarbon fuel consumed by the
engine would be converted to CO2, H2O, and N2. Since
ambient air contains approximately 21% oxygen and
78% nitrogen by volume, each mole of oxygen
consumed involves (78/21) = 3.7 moles of N2.
• With this information, the ideal combustion equation for a
fuel such as octane can be written by balancing the
number of moles of each constituent on either side of the
combustion equation:
• C8H18 + (12.5)O2 + (12.5)(3.7)N2 --> (8.0)CO2 +
(9.0)H2O + (47.0)N2
4.2 Combustion Reaction of Hydrocarbon in Air
• Hence, ideal combustion of octane produces
approximately 13% carbon dioxide, 14 % water vapor,
and 73 % nitrogen. However, actual vehicle exhaust gas
also contains unburned hydrocarbons (HC), carbon
monoxide (CO), oxides of nitrogen (NOx), aldehydes,
and various other constituents. The emissions in exhaust
as it leaves the engine are called engine-out or feedgas
emissions; they are carried through a catalytic converter,
and the net output to the air is called tailpipe emissions.
• The ratio of air mass to fuel mass is called air fuel ratio
(A/F). The stoichiometric or theoretical A/F is defined as
the minimum amount of air that supplies sufficient
oxygen for the complete combustion of all the carbon,
hydrogen and any other elements in the fuel that may
oxidize. For example, the stoichiometric A/F for the ideal
combustion of octane can be calculated as follows:
4.2 Combustion Reaction of Hydrocarbon in Air

On a molar basis:
(A/F)mole = (12.5 moles O2 + 47.0 moles N2)
(1 mole of fuel)
(A/F)mole = 59.5 mole air/mole fuel

On a mass basis:
(A/F)mass = (59.5 mole air/mole fuel)*(28.97 kg/mole air)
(114.2 kg/mole fuel)
(A/F)mass = 15.0 kg air/kg fuel
THE FIRST LAW OF THERMODYNAMICS AND COMBUSTION

n f F  na A np P

Reactants Products
 4.3 First Law Analysis for Reacting System

Consider a constant pressure process in which nf moles of fuel react with

na moles of air to produce np moles of product:
n f F  na A  n p P

Reactants Products

Reactants
Q Products

State 1 State 2
Reaction

Applying First Law with state 1 being the reactants at P1, T1 and state 2
being products at P2, T2:
Q  U  W

Q12  (U 2 U 1 )  P(V2 V1)

4.3 First Law Analysis for Reacting System

Q  (U 2 U 1 )  P(V2 V1)

 (U 2  P2V2 )  (U1  P1V1)

 H 2  H1

 H P  H R   ni hi (Tp )   ni hi (TR )
P R

HP < HR Q<0 exothermic reaction

HP > HR Q>0 endothermic reaction

 5 Heat of Combustion
Consider the case where the final temperature of the products is the same as
the initial temperature of the reactants (e.g., calorimeter is used to measure Q).

W
P1=P2=Po
To Q
Reaction T1=T2=To

The heat released under this situation is referred to as the enthalpy of

reaction, HR ,

H R   ni hi (Tp )   ni hi (TR )
P R
  ni hi (To )   ni hi (To ) units : kJ per kg or kmol of fuel
P R
 5 Heat of Combustion
The maximum amount of energy is released from a fuel when reacted with a
stoichiometric amount of air and all the hydrogen and carbon contained in the
fuel is converted to CO2 and H2O

This maximum energy is referred to as the heat of combustion or the heating

value and it is typically given per mass of fuel

HR(298K)
 5 Heat of Combustion

• The amount of heat transferred out this reaction, when

burning at constant pressure is also known as the
enthalpy of reaction.

• For most hydrocarbon the maximum enthalpy of reaction

per unit mass of fuel, or heating value, is 45 -50 MJ/kg,
for hydrogen it is 123 MJ/kg.
 5 Heat of Combustion
There are two possible values for the heat of combustion that can be calculated
depending on whether the water in the products is taken to be in a liquid or
vapor state.
T
hf hg
From steam tables:
Tp hfg = hg – h f > 0

S
(exothermic)

The term higher heat of combustion is used when the water in the products
is taken to be in the liquid state

The term lower heat of combustion is used when the water in the products
is taken to be in the vapor state
 5 Heat of Combustion
HHV vs. LHV

• This is also the Higher Heating Value (HHV), if water in

the products is in the liquid phase, or the Lower Heating
Value (LHV), if it is in the gaseous phase (getting either
depends on T and p of the process).
Schematic plots of internal energy of reactants and products as a function of
temperature: (a) Effect of water in products as either vapor or liquid;
(b) effect of fuel in reactants as either vapor or liquid.
 6 Heat of Formation
Consider the following reactions taking place at atmospheric pressure and
with TP = TR = 298K

1/ 2O2 (g)  H 2 (g)  H2O(l ) Q  286,000 kJ / kmol H 2O

C(s)  O2 (g)  CO2 (g ) Q  394,000 kJ / kmol CO2

In these reactions H2O and CO2 are formed from their elements in their
natural state at standard temperature and pressure (STP) 1 atm and 298K.

Reactions of this type are called formation reactions and the corresponding
measured heat release Q is referred to as the standard heat of formation
and takes the symbol h of so:
hf,oH2O  286,000 kJ / kmol
hf,oCO2  394,000 kJ / kmol

Values for standard heat of formation for different species are tabulated
 6.1 Enthalpy Scale for a Reacting System
We need to take into account that for a reacting system the working fluid
changes molecularly from reactants to products while undergoing a process.

Consider the following identity:

h (P,T )  h (1atm,298K ) [h (P,T )  h (1atm,298K )]

By international convention, the enthalpy of every element in its natural state

(e.g., O2(g), N2(g), H2(g), C(s)) at STP has been set to zero

h (1atm,298K )  h o  0 (note the notation convention)

at STP
 6.1 Enthalpy Scale for a Reacting System

The enthalpy of all other substances at STP is simply the heat of formation
of the substance, since it is formed from its elements, for example:
1/ 2O2 (g)  H 2 (g)  H 2O(l )

recall @ STP Q  hH O(l ) 1/ 2hO ( g )  hH ( g )  h f ,H O(l )

2 2 2 2

 hH O(l )  h f ,H O(l )
2 2

Therefore, the enthalpy of the i‟th component in a mixture is:

h (P,T )  h o  [h (P,T )  h (1atm,298K )]

i f ,i i i

chemical enthalpy sensible enthalpy  298K

T
cp,idT

The sensible enthalpy for different species is tabulated as a function of

temperature (JANNAF Tables).
 6.1 Enthalpy Scale for a Reacting System
Enthalphy of Reaction

• Under adiabatic conditions, the products‟ temperature is

high ~ 2000 C (depending on the initial temperature and
the process). It is called the Adiabatic Flame Temperature.
 6.1 Enthalpy Scale for a Reacting System
Ideal Properties of N2 and N, Heat of Formation and Enthalpy vs T
 7 Adiabatic Flame Temperature
7.1 Adiabatic Flame Temperature at constant pressure
Consider the case where the cylinder is perfectly insulated so the process is
adiabatic (Q = 0)

W
P2=Pa
Q
Reaction T2=Ta

For a constant pressure process, the final products temperature, Ta, is known
as the adiabatic flame temperature (AFT).

Q   ni hi (Tp )   ni hi (TR )  0
P R
 ni hi (Ta )   ni hi (T1)
P R

For a given reaction where the ni‟s are known for both the reactants and the
products, Ta can be calculated explicitly.
 7 Adiabatic Flame Temperature
7.1 Adiabatic Flame Temperature at constant pressure
7.1 Adiabatic Flame Temperature at constant pressure
Example
Consider constant pressure complete combustion of stoichiometric liquid
butane-air initially at 298K and 1 atm

C4 H10 (l)  6.5(O2  3.76N2 )  4CO2  5H 2O  24.4N2

Note: first term = 0 since T 1 = 298K, h fo,O2  h fo,N2  0

4hCO2 (Ta )  hCO2 (298K ) 5hH 2O (Ta)  h H 2O (298K ) 24.4hN2 (Ta )  hN2 (298K )

  4h fo,CO2  5h fo,H2O  h fo,C4H10 
Look up enthalpy values, and substituting gives Ta = 2500K
7.1 Adiabatic Flame Temperature at constant pressure
Constant Pressure Adiabatic Flame Temperature
with products at equilibrium

Ta,
7.1 Adiabatic Flame Temperature at constant pressure
Example
Now consider butane air with 300% excess air

C4 H10 (l)  4(6.5)(O2  3.76N2 )  4CO2  5H 2O  97.8N2 19.5O2

4hCO2 (Ta )  hCO2 (298K ) 5hH 2O (Ta)  h H 2O (298K ) 97.8hN2 (Ta )  hN2 (298K )

 19.5hO2 (Ta )  hO2 (298K )  4 h fo,CO2  5h fo,H 2O  h fo,C4 H10 

Look up values and substituting gives Ta = 1215K

Excess air adds 92.8 moles of diatomic molecules (O2 and N2) into the
products that does not contribute to heat release just soaks it up.
7.1 Adiabatic Flame Temperature at constant pressure
Effects of Fuel-air mixture on Constant Pressure
Adiabatic Flame Temperature with products at equilibrium
7.2 Adiabatic Flame Temperature at constant volume
Consider the case where the piston is fixed and the cylinder is perfectly
insulated so the process is adiabatic (Q = 0)

W
P2=PCV
Q
Reaction T2=Ta

Q   niui (Tp )   niui (TR )  0

P R

 niui (Ta )   niui (T1)

P R

Note h = u + pv = u + RT, so

 ni (hi (Ta )  RT )   ni(hi(T1 )  RT)

P R
7.2 Adiabatic Flame Temperature at constant volume

  
 ni hfo,i  hi (Ta )  hi (298K ) RT i   ni hfo,i  hi (T1)  hi (298K ) RT i
P R


Extra term compared to constant pressure AFT ( term > 0)

The AFT for a constant volume process is larger than for a constant pressure
process.

The AFT is lower for constant pressure process since there is Pdv work done
7.2 Adiabatic Flame Temperature at constant volume
Assuming ideal gas behavior:

VR  VP
nR RTR n p RT p

PR Pp

For large HCs the mole ratio term is small, e.g., for stoichiometric octane
air
C8 H18 12.5(O2  3.76N2 )  8CO2  9H 2O  47N 2

For stoichiometric octane-air Ta is 2266K so PCV/Pi = 8.1

 8 Chemical Equilibrium

•In general the combustion products consist of more than just CO2, H2O
O2, and N2

•For rich mixtures CO also exists in the products and at high temperatures
the molecules dissociate to form H, O, OH, NO via the following reactions:

H 2  2H O2  2O H 2  O2  2OH O2  N2  2NO

• The opposite direction reactions are also possible

2H  H 2 2O  O2 2OH  H 2  O2 2NO  O2  N 2

•At equilibrium the rate of the forward reaction equals the rate of the
backward reaction.

H 2  2H O2  2O H 2  O2  2OH O2  N2  2NO
 8 Chemical Equilibrium
• At equilibrium the relative proportion of the species mole fraction is fixed

• For the general equilibrium reaction

n A A  n B B  n cC  n D D

• The equilibrium composition for species   C D is given by:

where K is the equilibrium constant which is tabulated as a function of

temperature for different equilibrium reactions, Pref is 1 atm and P is in
units of atmospheres.

nA
Note XA 
nA  nB  nC  n D
 8 Chemical Equilibrium
Recall that for a rich mixture (<1) the reaction equation could not be
balanced (5 unknowns a, b, d, e, f and only 4 atom balance equations for
C,H,O,N ) even if we neglect dissociation (i.e., low product temperature)
m
C n H m   (n  )(O2  3.76N2)  aCO2  bH2O  dN 2  eCO  fH 2
4

If the product species CO2, H2O, CO and H2 are at equilibrium and described
by the water-gas reaction:
CO2  H 2  CO  H 2O

The equilibrium constant for this reaction provides the fifth equation :
X CO X H O e b
K (T )  2
 P  1 atm
X CO X H
2 2
a f

Note K is tabulated as a function of T

 8 Chemical Equilibrium
Example
1 kmol of CO2, ½ kmol of O2 and ½ kmol of N2 reacts to form a mixture
consisting of CO2, CO, O2, N2 and NO at 3000K and 1 atm. Determine the
equilibrium composition of the product mixture.

CO2 1/ 2O2 1/ 2N 2  aCO  bNO  cCO2  dO2  eN2

3000K and 1 atm

C 1 = a+c c=1-a
O 3 = a+b+2c+2d d = 1/2(1 + a - b)
N 1 = b+2e e = 1/2(1 - b)

Have 2 unknowns a, b so need 2 equilibrium equations

1. CO2  CO 1/ 2O2 K1( 3000K)  0.3273

2. 1/ 2O2 1/ 2N 2  NO K2( 3000K)  0.1222

 8 Chemical Equilibrium
Example
From the equilibrium constant expression

ntot= a+b+c+d+e = a+b+(1-a)+1/2(1+a-b)+1/2(1-b) = (4+a)/2

a 1/ 2(1 a  b) 1 a
X CO  X O2  X CO2 
(4  a) / 2 (4  a) / 2 (4  a) / 2

Substituting yields:
 8 Chemical Equilibrium
Example
Similarly for the second equilibrium reaction

X NO 2b
K 2  0.1222   (2)
X O1/ 2  X 1/N 2 (1 a  b)(1 b)1/ 2
2 2

Solving equations 1 and 2 yields:

a= 0.3745 b= 0.0675

From the atom balance equations get:

c= 0.6255 d= 0.6535 e= 0.4663

 8.1 Computer Programs Equilibrium Solvers

•If the products are at high temperature (>2000K) minor species will be
present due to the dissociation of the major species CO2, H2O, N2 and O2.

m
Cn H m  (n  )(O2  3.76N2 )  aCO2  bH2O  cN 2  dO2  eCO  fH 2
4
 gH  hO  iOH  jNO  kN  L

•Hand calculations are not practical when many species are considered, one
uses a computer program to calculate the product equilibrium composition.

http://www.wiley.com/college/mechs/ferguson356174/wave_s.html
Equilibrium Combustion Solver Applet

A popular program used for equilibrium calculations is STANJAN

Composition of Octane-air Mixtures at Equilibrium

(lean) (stoich) (rich)

Mole fraction, Xi

Nitric Oxide (NO)

is an air pollutant

Temperature (K)
 8.2 Adiabatic Flame Temperature for Products at Equilibrium

m
Cn H m  (n  )(O2  3.76N2 )  aCO2  bH2O  cN 2  dO2  eCO  fH 2
4
 gH  hO  iOH  jNO  kN  L

•One can calculate the AFT for the above stoichiometric reaction where the
products are at equilibrium.

•Note dissociation in the products will result in a lower AFT since dissociation
reactions are endothermic.

• Again computer programs are used for these calculations:

http://www.wiley.com/college/mechs/ferguson356174/wave_s.html
Adiabatic Flame Temperature Applet

and STANJAN
 9 Chemical Kinetics

First and Second Laws of thermodynamics are used to predict the final
equilibrium state of the products after the reaction is complete.

Chemical kinetics deals with how fast the reaction proceeds.

 F F  A A   C C  D D

How fast the fuel is consumed is of interest, the reaction rate ‟‟‟ is defined
as:
 '''  d[F ]
dt
where [ F ] refers to the fuel concentration (kmol/m3 or kg/m3), negative sign
due to the fact that the fuel is consumed.

Global (or overall) reactions describe the initial and final states:
C8 H18 12.5(O2  3.76N2 )  8CO2  9H 2O  47N 2
H 2 1/ 2O2  H 2O
 9.1 Reaction Mechanism
In reality the reaction proceeds through elementary reactions in a chain
process known as chain reactions

The global hydrogen-oxygen reaction proceeds via the following elementary

reactions, collectively known as a reaction mechanism:
H 2 M  H  H M Chain initiation

H  O2  M  HO2  M
HO2  H2  H2O  OH Chain propagation
OH  H2  H2O  H

H  O2  OH  O
Chain branching
H 2  O  OH  H

H  OH  M  H 2O  M
H  H  M  H2  M Chain termination
O  O  M  O2  M

(M is any species present that acts as a collision partner)

 Radicals

• Species such as H, O, OH and HO2 are called radicals.

•Radicals have unpaired valence electrons which make them very reactive
and short lived, they try to partner with other radicals to form covalent bonds

• In chain branching reactions there is a net production of radicals

•Chain branching reactions lead to rapid production of radicals which causes

the overall reaction to proceed extremely fast  explosively

•The reaction comes to completion through chain termination reactions

where the radicals recombine to form final products.
 9.2 Chemical Reaction Equations

Consider the following general reaction involving n species

 1' A1  2' A2  3' A3  L  n' An  1" A1  2" A2  3" A3  L  n" An

Ai = species
‟ = stoichiometric coefficient for reactants
” = stoichiometric coefficients for products

As an example, consider the following elementary reaction

H  H  H  H 2H

For this reaction n = 2 (species are H and H2)

A1 = H  1‟ = 3 , 1” = 1

A2 = H2  2‟ = 0 , 2” = 1

reactants products
 9.3 Law of mass Action

The law of mass action states that for an elementary reaction the reaction
rate is proportional to the product of the concentrations of the reactants
present raised to a power equal to the corresponding stoichiometric
coefficient. The constant of proportionality is called the reaction rate
constant k.
j
'
d[ Ai ] n
 ( i  i )k  [ Aj ]
" '

dt j1

n  'j
where  [ A j ]  [ A1]1 [ A2]  2 [ A 3]  3 L [ An ] n
' ' ' '

j1
n
the overall order of the reaction is given by  'j
j1

For m simultaneous equations:

 '
d[ Ai ] m " n j .l
  ( i,  i,l )k l  [ Aj ]
'
dt l 1 l j1
 9.3 Law of mass Action

Applying the law of mass action to the reaction H  H  H k H 2  H

d[ A1]
 (1"  1')k[ A1] [ A2] 
' '
1 2
Recall n = 2
dt
d[H ]
A1 = H  (1 3)k[H ]3 [H 2 ]0  2k[H ]3
dt

d[ A2 ]
 ( 2"  2' )k[ A2 ] [ A2] 
' '
1 2

dt
d[H 2 ]
A2 = H2  (1 0)k[H ]3 [H 2 ]0  k[H ]3
dt

1 d[H ] d[H 2 ]
note k[H]3   
2 dt dt
 9.4 Reaction Rate Theory

Kinetic theory of gases is used to come up with the following expression

for the elementary reaction rate constant, first proposed by Arrhenius

where A and b are the rate coefficients, Ea is the activation energy

and R is the universal gas constant.

Therefore, for the reaction H  H  H k H  H the reaction rate is

2

The values of a, b and Ea are tabulated for different reactions.

This expression indicates that molecular hydrogen is produced faster at

higher temperature and at a higher atomic hydrogen concentration.
 Rate Coefficients for H2-O2 Reactions

A b Ea Temperature range
Reactions ((cm3/gmol)n-1/s)* (kJ/gmol) (K)

* n is the reaction order

 Ozone (O3) Decomposition

Global reaction: 2O3  3O2

Important elementary O3  M k
1
O  O2  M
k2
reactions include:
O  O3 k
3
O2  O2
k4

O  O  M k
5
O2  M
k6
Here m = 6 (3 forward and 3 backward reactions)
n =3 (O, O2, O3)
 '
d[ Ai ] m " n j .l
  ( i,  i,l' )kl  [ Aj ]
dt l 1 l j1

The O3 reaction rate is:

O'''  d[O3 ]  k1[O3][M ]  k2 [O][O2][M ]  k3 [O][O3 ]  k4 [O2] 2

3
dt
 9.5 Relationship Between Rate Constant and Equilibrium Constant

 A A  B B 
kf
 C C  D D
kb

d[ A]
 k f [ A] [B]   kb[C]  [D] 
A B C D

dt
d[ A]
At equilibrium:  k f [ A] [B]   kb[C]  [D]  0
A B C D

dt
k f [ A] [B]  kb[C] [D]
A B C D

kf [C] [D]
C D

kb [ A] [B]
A B

Recall:

nC n /V RT
Note: XC   C  [C]
ntotal ntotal /V P
9.5 Relationship Between Rate Constant and Equilibrium Constant

Therefore, if the equilibrium constant K is available for the elementary

reaction can get kf from kb

For a bimolecular reaction A  B  C  D

kf
K
kb
 9.6 Reaction Rate for Global Reaction

To consider chemical reaction of fuel and air, it is better use

global description:

 f Fuel  O O2  iInert   P Pr oduct 

2

Empirical correlations have been developed for the fuel reaction rate:

where [ ] in units of gmol/cm3

R = 1.987 cal/gmolK
E typically 20 - 40 kcal/gmol

Note this is a correlation so n, m and l don‟t have to be integers, typically l= 0

 Example: Nitric Oxide (NO) Formation

Global NO formation reaction:

N 2  O2 k d[NO]
G
2NO  kG [N 2] m[O ]2 n

dt
Thermal (Zeldovich) Mechanism:
(1) O  N2  NO  N Ea  315 kJ/mol
(2) N  O2  NO  O Ea  26 kJ/mol

Forward reaction (1) is endothermic and due to the high Ea requires high
temperature (>1800K) to proceed and is very slow.

From above two reaction using basic arguments one can derive the following
expression for the “initial” NO reaction rate for the global reaction:

d[NO] KPref
 2k f 1 [N 2 ][O2 ]1/ 2
dt RT
kG
 10 Explosion Limits

Perform an experiment where a fuel-oxygen mixture is injected into a

preheated spherical vessel and monitor the vessel pressure.

P
H2-O2
P
Vacuum
time
T

For a given hydrogen-oxygen mixture, e.g. stoichiometric, and fill pressure if

you vary the temperature of vessel you will find that there is a critical
temperature below which an explosion occurs and above which an
explosion does not occur (note there is no spark ignition).

An explosion is characterized by a rapid rise in vessel pressure faster than

the normal pressure rise due to gas filling.

This critical temperature is referred to as the autoignition or explosion limit

temperature
 10 Explosion Limits
If you repeat the experiment for different fill pressures and plot all the results on a
pressure-temperature curve one can define an explosion limit curve.

The shape of this limit curve can be explained by the temperature and pressure
dependencies of the H2-O2 elementary reactions.

1 atm

NO Explosion

Explosion Limits of
Stoichiometric H2-O2
Explosion
 11 Finite Heat Release Model

•In the Otto cycle it is assumed that the heat is release instantaneously.
A finite heat release model specifies heat release as a function of crank
angle.

•This model can be used determine the effect of spark timing or heat transfer
on engine work and efficiency.

• The cumulative heat release or “burn fraction” for SI engines is given by:

where  = crank angle

s = start of heat release
d = duration of heat release
n = form factor
Used to fit experimental data
a = efficiency factor
 11 Finite Heat Release Model

A typical heat release curve consists of an initial spark ignition phase,

followed by a rapid burning phase and ends with burning completion phase

The curve asymptotically approaches 1 so the end of combustion is defined

by an arbitrary limit, such as 90% or 99% complete combustion where
xb = 0.90 or 0.99 corresponding values for efficiency factor a are 2.3 and 4.6

The rate of heat release as a function of crank angle is:

 11 Finite Heat Release Model

Applying First Law to the closed system containing the gas in the cylinder
for a small crank angle change, d ,

dU  Q  W
assuming ideal gas PV  mRT and dU  mcvdT

Q  PdV  cv PdV  VdP

R
per unit crank angle
 11 Finite Heat Release Model

The cylinder volume in terms of crank angle, V(), is

V ( ) 
Vd Vd

r 1 2

R1 cos  (R 2  sin2  )1 2 
Differentiating wrt 

dV Vd
d

 sin 1 cos (R 2  sin 2  )1 2
2

Vd 
 B 2 S  displacement volume
where
4
r  compression ratio
2l
R
s
For the portion of the compression and expansion strokes with no heat
Release, where  < s and  > s + d  dQ/d = 0 and
 Finite Heat Release Model Results

Start of heat release:

Engine 1 - 20o bTC
Engine 2 - TC

Duration 40o
Finite Heat Release Model Results
 12 Structure of Flame

Vb Vu = SL
b u

[Fuel]
T
[O2]
d[F ]  E 
 [F ]n [O2 ]m exp a 
dt RT  [radicals]

Products Reaction Pre-heat

zone Zone Zone

Flame
Visible part of the flame
thickness  Diffusion of heat
and radicals
 12.1 Minimum Ignition Energy and Flammability Limits

A flame is spark-ignited in a flammable mixture only if the spark energy is

larger than some critical value known as the minimum ignition energy Eign

It is found experimentally that the ignition energy is inversely proportional to

the square of the mixture pressure.

Experiments show that a flame will only propagate in a fuel-air mixture

within a range of mixture compositions known as the flammability limits.

The fuel-lean limit is known as the lower (or lean) flammability limit and the
fuel-rich limit is known as the upper (or rich) flammability limit.

The flammability limit is affected by both the mixture initial pressure and
temperature.
 12.2 Flame Velocity

The laminar burning velocity is measured relative to the unburned gas ahead
and the flame velocity Vf is measured relative to a fixed observer.

If the flame is propagating in a closed-ended tube the velocity measured is the

flame velocity and can be up to 8 times the burning velocity.

This is because the density of the products is lower than the fresh gas so a
flow is generated ahead of the flame

Vb=0 Vf Vu Vf Vb=Vf Vf - Vu= Sl

b u b u
Moving flame Stationary flame

Applying the conservation of mass across the flame:

 12.2.1 Laminar Premixed Flames

A flame represents an interface separating the unburned gas from the

combustion products.

A flame can propagate as in an engine application or be stationary as in a

burner application.

For a given P, T,  and laminar conditions a flame has two basic properties:
a) adiabatic flame temperature,Tad
b) laminar burning velocity, Sl

Vb Vu = Sl Vb-Sl Sl Vu = 0
b
burned
u unburned
b u

Stationary flame Moving flame

Note, Sl is defined in terms of the approaching unburned gas velocity

Pressure is roughly constant across the flame so  ~ 1/T

 12.2.1 Laminar Burning velocity

Maillard-LeChatelier theory gives:

Sl 2   T u Pn1 exp(E / RT ad )

Higher flame velocity corresponds to:

1) higher unburned gas temperature
2) lower pressure
3) higher adiabatic flame temperature (chemical reaction)
4) higher thermal diffusivity  (= kcond/cp)
 12.2.1 Laminar Burning Velocity Correlation

The following is a correlation developed by Metghalchi and keck

where Ydil is the mass fraction of diluent, e.g., residual gas, and

Sl ,ref  BM  B2 (  M )
  2.18  0.8( 1)
  0.16  0.22( 1)

Fuel M BM (cm/s) B2 (cm/s)

Methanol 1.11 36.92 -140.51

Propane 1.08 34.22 -138.65
Isooctane 1.13 26.32 -84.72
 12.2.2 Turbulent Flames

Unlike the laminar burning velocity, the turbulent flame velocity is not a
property of the gas but instead it depends on the details of the flow.

The IC engine in-cylinder flow is always turbulent and the smallest eddies
(Kolmogorov scale) are typically larger than the laminar flame thickness (1 mm)

Under these conditions the flame is said to display a structure known as

wrinkled laminar flame.

A wrinkled laminar flame is characterized by a continuous flame sheet that is

distorted by the eddies passing through the flame.

The turbulent burning velocity depends on the turbulent intensity ut and can
be up to 30 times the laminar burning velocity

St / Sl  1 aut / Sl b
Sl St

Laminar flame Turbulent flame

 12.3 Flame Thickness and Quenching Distance

A rough estimate of the laminar flame thickness  can be obtained by:

As a flame propagates through a duct heat is lost from the flame to the wall

Local quenching d

It is found experimentally that if the duct diameter is smaller than some

critical value then the flame will extinguish

This critical value is referred to as the quenching distance dmin and is close in
magnitude to the flame thickness.
dmin  