1

1
COMBUSTION THEORY
Lesson 5: Reaction Mechanism
and Calculation of Combustion
Downloaded and presented by Ly Ngoc Minh
Hochiminh City University of Industry
2
Contens
Fuel Types
Air composition
A/F ratio
Heat of combustion
Chemical equilibrium
Chemical kinetics
Reaction mechenism
Combustion Methods
3
Molecules and Covalent Bonds
Chemical bonds result from a mutual sharing of electrons between atoms,
the shared electrons are in the outermost shell, known as valence electrons
Lewis notation:
Hydrogen Atomic # 1 1 valence electron
Carbon Atomic # 6 4 valence electrons
Oxygen Atomic # 8 6 valence electrons
H
C
O
Atoms like to have electron configuration like noble gas, usually eight valence
electrons, an octet.
H H C H
H
H
H
H
2
CH
4

Atoms and molecules with unpaired valence electrons are called radicals
e.g. O, H, OH, N, C 4
Hydrocarbon Fuels (organic compounds)
Most common hydrocarbon fuels are Alkyl Compounds and are grouped as:
Paraffins (alkanes):
C
n
H
2n+2
n= 1 CH
4
methane
n= 2 C
2
H
6
ethane
n= 3 C
3
H
8
propane
n= 4 C
4
H
10
butane
n= 8 C
8
H
18
octane
C
H
H
H
H
C
H
H
methane ethane
H H
H
C
H
Olefins (alkenes):
C
n
H
2n
n=2 C
2
H
4
ethene
n=3 C
3
H
6
propene
propene
Acetylenes (alkynes):
C
n
H
2n-2
n=2 C
2
H
2
acetylene
n=3 C
3
H
4
propyne
H C C H
acetylene
Note: n=1 yields CH
2
is an unstable molecule
H
C
H
H C C
H
H
H
5
Alcohols
An alcohol molecule is simply a hydrocarbon molecule with one of the
hydrogen atoms replaced by a hydroxyl molecule (OH)
The main alcohols used as engine fuels are:
Ethanol ethyl alcohol (C
2
H
5
OH) consists of ethane molecule (C
2
H
6
) with
OH substitution
Methanol methyl alcohol (CH
3
OH) consists of methane molecule (CH
4
)
with OH substitution
Butanol (C
4
H
9
OH) consists of methane molecule (CH
4
) with OH substitution
C
H
H
H
H
C
H
OH
Ethyl alcohol
C
H
H
H
OH
Methyl alcohol
6
IC Engine Fuels
Crude oil contains a large number of hydrocarbon compounds (25,000).
The purpose of refining is to separate crude oil into various fractions via
a distillation process, and then chemically process the fractions into fuels
and other products.
A still is used to heat a sample, preferentially boiling off lighter
components which are then condensed and recovered.
The group of compounds that boil off between two temperatures are
referred to as fractions.
The order of the fractions as they leave the still are naptha, distillate,
gas oil, and residual oil. These are further subdivided using adjectives
light, middle, and heavy.
The adjectives virgin or straight run are often used to signify that no
chemical processing has been performed to a fraction.
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Distillation Process
Refining Process
8
Gasoline
Light virgin (or straight run) naptha can be used as gasoline.
Gasoline fuel is a blend of hydrocarbon distillates with a range of boiling
points between 25 and 225
o
C (for diesel fuel between 180 and 360
o
C)
Chemical processing is used to:
Produce gasoline from a fraction other than light virgin, or
Upgrade a given fraction (e.g., Alkylation increases the MW and octane
number of fuel: produce isooctane by reacting butylenes with isobutane in
the presence of an acid catalyst.
9
Octane
The octane molecule is often used to simulate the properties of gasoline
C
H
H
H
C
H
H
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
n-octane
There are 18 isomers of octane, depending on position of methyl (CH
3
)
branches which replace hydrogen atoms (eg. a side H is replaced with CH
3
)
C
CH
3
H
C
H
C
H
CH
3
CH
3
CH
3
CH
3
iso-octane
10
Reformulated Gasoline (RFG)
In order to reduce emissions such as carbon monoxide (CO) and unburned
hydrocarbons (HC) the oxygen content of gasoline is increased to about 3%
by weight (U.S. oxygenated fuels program, winter only).
The US Clean Air Act requires certain large US cities to use RFG year-round
in order to reduce ozone by requiring a minimum oxygen content of 2% by
weight and maximum benzene content of 1%.
The primary oxygenates are MTBE (CH
3
)OC(CH
3
)
3
and ethanol (C
2
H
5
OH)
As part of the reformulated gasoline program sulfur is restricted to 31 ppm
11
Currently most automotive IC engines use fossil fuels (gasoline or diesel)
Due to the ever increasing cost of oil, due to diminishing oil reserves and
accessibility to the oil reserves, and environmental concerns such as global
warming, alternative fuels have become very attractive. The 2007 US Energy
Bill set a 36 billion gal target for renewable fuels to be used in autos by 2020
Alcohols such as ethanol, methanol, and butanol are receiving a lot of
Attention because they can be synthesized biologically, i.e., bioalcohols or
biofuels.
Renewable Fuels
Since there is oxygen in the fuel, combustion of alcohols produces no CO
but more greenhouse gas carbon dioxide (CO
2
) than fossil fuel combustion.
However, since the fuel is derived from plant matter the CO
2
produced is
extracted from the atmosphere during the growth of the plant, i.e.CO
2
neutral
6CO
2
+ 6H
2
0 + solar energy C
6
H
12
O
6
+ 6O
2
sugar photosynthesis
12
Alcohol Fuels
Ethanol used for fuel is obtained by fermentation. Yeast metabolizes sugar
(C
6
H
12
O
6
) in the absence of oxygen to produce ethanol and carbon dioxide
C
6
H
12
O
6
2C
2
H
5
OH +CO
2
In Brazil ethanol is derived from sugar cane whereas in the US and Canada
corn is used as the feed stock (sugar cane has 30% more sugar than corn).
Sugars for ethanol fermentation can also be obtained from cellulose
(C
5
H
10
O
5
)
n
that makes up agricultural byproducts, such as corn cobs, corn
stalks, straw, switch grass, and wood, into renewable energy resources
Alcohol fuels have several drawbacks compared to fossil fuels:
- lower energy density (kJ/m
3
) than gasoline (10% less for butanol,
27% less for ethanol, 55% less for methanol),
- corrosive to fuel systems (methanol > ethanol > butanol)
- toxicity (methanol)
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Ethanol is quickly becoming the alternative fuel of choice for IC engines
An IC engine can run on gasoline with up to 10% ethanol (E10) without any
modifications, the use of higher blends requires changing certain components
in the fuel system, i.e, use stainless steel fuel lines and tank.
In Brazil half of the cars can run on 100% ethanol including flex fuel engines
that can run on all ethanol, all gasoline, or any combination of the two
Gasoline with up to 85% ethanol (E85) is now starting to enter the US and
Canadian markets. Flex fuel engines in this market can run on E85 or all
gasoline, 100% ethanol not yet permitted
Ethanol as a Fuel
14
Other Alternative Fuels
Natural gas and propane have been used for many years as a fuel for IC
engines, especially in Europe where the price of gasoline has been
historically high. Gaseous state at room temperature therefore have a low
energy density (kJ/m
3
). Same emissions as gasoline and diesel.
Hydrogen (H
2
) is the new natural gas with similar issues. The main benefit
is no CO, CO
2
and HC emissions. Biggest problem with hydrogen is that
there is no infrastructure to transport and store the fuel at fill stations. Also
hydrogen gas cannot be found in nature it must be manufactured
Biodiesel manufactured from vegetable oils, waste cooking oil, or animal
fats. It is produced by reacting the oil with an alcohol (usually methanol)
and a catalyst (such as sodium hydroxide). The resulting chemical reaction
produces glycerine and alkyl esters (biodiesel). It is a liquid at RTP and
has 9% lower energy content than regular diesel
Dimethyl ether (C
2
H
6
O) good diesel fuel because of good autoignition
quality. Is a gas at RTP, produced from syngas or methanol.
15
Other Alternative Fuels
Producer gas (syngas) engines run on the gaseous products from thermal
gasification of biomass such as wood. The carbon reacts with steam, or a
limited amount of air, at high temperature (>700C) to produce a mixture
consisting of roughly 25% CO, 15% H
2
, and 5% CO
2
, 50%N
2
.
Drawback is very low energy content, ten times lower than natural gas.
Benefit CO
2
neutral.
16
Ideal Gas Model
The ideal gas equation of state is:
T R n T
M
R
m mRT PV
,
_

where is the Universal Gas Constant (8.314 kJ/kmol K), is the molecular
weight and n is the number of moles.
Specific internal energy (units: kJ/kg)
R M

dT T c T h
p
) ( ) (
dT T c T u
v
) ( ) (
Specific enthalpy (units: kJ/kg)
Specific entropy (units: kJ/kg K) ) ln( ) ( ) , (
o
o
P P R T s T P s
(P
o
= 1 bar, s
o
entropy at P
o
)
17
Ideal Gas Model for Mixtures
The mixture internal energy U and enthalpy H (units: kJ) is:


n
i
i i
n
i
i i
h m mh H u m mu U
1 1

The mixture specific internal energy u and enthalpy h is:


n
i
i i
n
i
i i
n
i
i i
n
i
i i
h x
m
h m
m
H
h u x
m
u m
m
U
u
1 1 1 1

n
i
i
m m
1
The mass fraction, x
i
, of any given species is defined as:

n
i
i
i
i
x
m
m
x
1
1 and
The mass m of a mixture is equal to the sum of the mass of n components
18
The mole fraction, y
i
, of any given species is defined as:

n
i
i
i
i
y
n
n
y
1
1 and
The mixture internal energy U and enthalpy H (units: kJ) is:


n
i
i i
n
i
i i
h n H u n U
1 1

where are molar specific values (units: kJ/kmol)
The mixture molar specific internal energy and enthalpy (units kJ/ kmol) is:


n
i
i i
n
i
i i
h y h u y u
1 1

i i
h u and

n
i
i
n n
1
The total number of moles in the mixture is:
Ideal Gas Model for Mixtures
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Ideal Gas Model for Mixtures
The partial pressure of a component, P
i
, in the mixture (units: kPa) is:
P y P
P
P
RT
PV
RT
V P
n
n
y
i i
i
i
i
i
or
The mixture molecular weight, M, is given by:
i
n
i
i
n
i
i i
n
i
i
M y
n
M n
n
m
n
m
M

1 1
1
Mass specific entropy (kJ/kg K) molar specific mixture entropy (kJ/mol K) :
( ) ( )
o
n
i
i i
o
i i
P P R P P R s x s ln ) / ln(
1

( ) ( )
o
n
i
i i
o
i i
P P R y R s y s ln ln
1

20
Composition of Standard Dry Air
Air is a mixture of gases including oxygen (O
2
), nitrogen(N
2
), argon (Ar),
carbon dioxide (CO
2
), water vapour (H
2
0).
For combustion dry air is taken to be composed of 21% O
2
and 79% N
2
by volume (mole fraction).
76 . 3
21 . 0
79 . 0
2
2
2
2
2
2

O
N
O
tot
tot
N
O
N
y
y
n
n
n
n
n
n
For every mole of O
2
there are 3.76 moles of N
2
.
Molecular weight of air is
kg/kmol 84 . 28 ) 28 ( 79 . 0 ) 32 ( 21 . 0
2 2 2 2
1
+
+

N N O O i
n
i
i air
M y M y M y M
The amount of water in moist air at T is specified by the specific humidity,
, or the relative humidity, , defined as follows:
1 0
) (

2 2
< <
T P
P
m
m
sat
O H
air
O H

21
Combustion Stoichiometry
If sufficient oxygen is available, a hydrocarbon fuel can be completely
oxidized, the carbon is converted to carbon dioxide (CO
2
) and the hydrogen
is converted to water (H
2
O).
The overall chemical equation for the complete combustion of one mole of
propane (C
3
H
8
) with oxygen is:
O cH bCO aO H C
2 2 2 8 3
+ +
Elements cannot be created or destroyed, so
C balance: 3 = b b= 3
H balance: 8 = 2c c= 4
O balance: 2a = 2b + c a= 5
Thus the above reaction is:
O H CO O H C
2 2 2 8 3
4 3 5 + +
# of moles species
22
Combustion Stoichiometry
Air contains molecular nitrogen N
2
, 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 C

with air is:

2 2 2 2 2
) 76 . 3 ( dN O cH bCO N O a H C + + + +

The above equation defines the stoichiometric proportions of fuel and air.
Example: For octane (C
8
H
18
) = 8 and = 18
( )
2 2 2 2 2 18 8
47 9 8 ) 76 . 3 ( 5 . 12 N O H CO N O H C + + + +
2 2 2 2 2
4
76 . 3
2
) 76 . 3 (
4
N O H CO N O H C
,
_

+ + + +
,
_

+ +

C balance: = b b =
H balance: = 2c c = /2
O balance: 2a = 2b + c a = b + c/2 a = + /4
N balance: 2(3.76)a = 2d d = 3.76a/2 d = 3.76( + /4)
23
( )
( )
( ) 1 12
) 28 76 . 3 32 (
4
1
) / (
1
/
+
+
,
_

+



s
s
A F
F A
Combustion Stoichiometry
Substituting the respective molecular weights and dividing top and bottom
by one gets the following expression that only depends on the ratio of the
number of hydrogen atoms to hydrogen atoms (/) in the fuel.
Note above equation only applies to stoichiometric mixture
Example: For octane (C
8
H
18
), / = 2.25 (A/F)
s
= 15.1
The stoichiometric mass based air/fuel ratio for C

fuel is:
( )
( )
( )
H C
N O
fuel i i
air i i
fuel
air
s
M M
M M
M n
M n
m
m
F A

,
_

+ +
,
_

2 2
4
76 . 3
4
/
24
Fuel Lean Mixture
Fuel-air mixtures with more than stoichiometric air (excess air) can burn
With excess air you have fuel lean combustion
At low combustion temperatures, the extra air appears in the products in
unchanged form:
for a 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
2 2 2 2 2 2
2
) 76 . 3 )(
4
( eO dN O H CO N O H C + + + + + +

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25
Fuel-air mixtures with less than stoichiometric air (excess fuel) can burn.
With less than stoichiometric air you have fuel rich combustion, there is
insufficient oxygen to oxidize all the C and H in the fuel to CO
2
and H
2
O.
Get incomplete combustion where carbon monoxide (CO) and molecular
hydrogen (H
2
) also appear in the products.
2 2 2 2 2 2
2
) 76 . 3 )(
4
( fH eCO dN O H CO N O H C + + + + + + +

where for fuel rich mixture have insufficient air < 1
Fuel Rich Mixture
Above reaction equation has three unknowns (d, e, f) and we only have
two atom balance equations (O, N) so cannot solve for the unknowns
unless additional information about the products is given.
26
The equivalence ratio, , is commonly used to indicate if a mixture is
stoichiometric, fuel lean, or fuel rich.
( )
( )
( )
( )
s
mixture
mixture
s
A F
A F
F A
F A
/
/
/
/

Off-Stoichiometric Mixtures
stoichiometric = 1
fuel lean < 1
fuel rich > 1
Products ) 76 . 3 (
4
2 2
+
,
_

+ + N O H C

Stoichiometric mixture:
Off-stoichiometric mixture:
Products ) 76 . 3 (
4
1
2 2
+
,
_

+ + N O H C

27
Example: Consider a reaction of octane with 10% excess air, what is ?
Stoichiometric :
Off-Stoichiometric Conditions
2 2 2 2 2 18 8
47 9 8 ) 76 . 3 ( 5 . 12 N O H CO N O H C + + + +
10% excess air is:
2 2 2 2 2 2 18 8
9 8 ) 76 . 3 )( 5 . 12 ( 1 . 1 bN aO O H CO N O H C + + + + +
( )
( )
91 . 0
1 / ) 76 . 4 )( 5 . 12 ( 1 . 1
1 / ) 76 . 4 ( 5 . 12
/
/

mixture
s
F A
F A

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

Other terminology used to describe how much air is used in combustion:
110% stoichiometric air = 110% theoretical air = 10% excess air
1 . 1 ) 76 . 3 )(
4
(
2 2 8 3
+ + +

N O H C mixture is fuel lean

28
First Law Analysis for Reacting System
Consider a constant pressure process in which n
f
moles of fuel react with
n
a
moles of air to produce n
p
moles of product:
P n A n F n
p a f
+
Applying First Law with state 1 being the reactants at P
1
, T
1
and state 2
being products at P
2
, T
2
:
Reactants Products
Reactants
Products
Reaction
State 1 State 2
Q
W
) ( ) (
1 2 1 2 2 1
V V P U U Q
W U Q
+
+

29


+ +
R
R i i
P
p i i R P
T h n T h n H H
H H
V P U V P U
) ( ) (
) ( ) (
1 2
1 1 1 2 2 2
H
P
< H
R
Q < 0 exothermic reaction
H
P
> H
R
Q > 0 endothermic reaction
) ( ) (
1 2 1 2
V V P U U Q +
First Law Analysis for Reacting System
30
Enthalpy of Reaction
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).
Reaction
Q
W
P
1
=P
2
=P
o
T
1
=T
2
=T
o
The heat released under this situation is referred to as the enthalpy of
reaction, H
R
,
fuel of kmol or kg per kJ : units ) ( ) (
) ( ) (


R
o i i
P
o i i
R
R i i
P
p i i R
T h n T h n
T h n T h n H
T
o
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31
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 CO
2
and H
2
O
This maximum energy is referred to as the heat of combustion or the heating
value and it is typically given per mass of fuel
Heat of Combustion
2 2 2 2 2
4
76 . 3
2
) 76 . 3 (
4
N O H CO N O H C
,
_

+ + + +
,
_

+ +

H
R
(298K)
alcohols
32
1.2 MJ/kg 3.1 6.5 16 Methanol
0.92 MJ/kg 3.0 9.0 19.6 Ethanol fuel
0.43 MJ/kg 3.2 11.2 29.2 Butanol fuel
0.36 MJ/kg 2.9 14.6 32 Gasoline and
biogasoline
Heat of
vaporizatio
n
Specific
energy
(MJ/kg air)
Air-
fuel
ratio
Energy
density
(MJ/L)
Fuel
33
Heat of Combustion
There are two possible values for the heat of combustion depending on
whether the water in the products is taken to be saturated liquid or vapour.
T
p
T
S
h
g
h
f
From steam tables:
h
fg
= h
g
h
f
> 0
H
R
= H
P
H
R
< 0 (exothermic)
The term higher heat of combustion is used when the water in the products
is taken to be in the liquid state (h
H20
= h
f
)
The term lower heat of combustion is used when the water in the products
is taken to be in the vapour state (h
H20
= h
g
)
34
0
h(kJ/kg fuel)
T
Products with H2O (g)
Products with H2O (l)
Reactants
h
fg,H2O
per kg fuel
h
low
h
high
Heat of Combustion, graphical
298K
35
Heat of Formation
Consider the following reactions taking place at atmospheric pressure and
with T
P
= T
R
= 298K
2 2 2
2 2 2 2
/ 000 , 394 ) ( ) ( ) (
/ 000 , 286 ) ( ) ( ) ( 2 / 1
CO kmol kJ Q g CO g O s C
O H kmol kJ Q l O H g H g O
+
+
In these reactions H
2
O and CO
2
are formed from their elements in their
natural state at standard temperature and pressure (STP) 1 atmand 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 so:
o
f
h
kmol kJ h
kmol kJ h
C
O
/ 000 , 394
/ 000 , 286
o
O f,
o
H f,
2
2


Values for standard heat of formation for different species are tabulated
36
Heat of Formation for Different Fuels
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37
Enthalpy Scale for a Reacting System
By international convention, the enthalpy of every element in its natural state
(e.g., O
2
(g), N
2
(g), H
2
(g), C(s)) at STP has been set to zero
0 ) 298 , 1 (
o
f
h K atm h
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:
)] 298 , 1 ( ) , ( [ ) 298 , 1 ( ) , ( K atm h T P h K atm h T P h +
(note the notation convention)
at STP
i.e,
38
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:
)] 298 , 1 ( ) , ( [ ) , (
,
K atm h T P h h T P h
i i
o
i f i
+
sensible enthalpy chemical enthalpy

T
K i p
dT c
298 ,
Therefore, the enthalpy of the ith component in a mixture is:
Enthalpy Scale for a Reacting System
o
l O H f l O H
o
l O H f g H g O l O H
h h
h h h h Q STP recall
l O H g H g O
) ( , ) (
) ( , ) ( ) ( ) (
2 2 2
2 2
2 2 2 2

2 / 1 @
) ( ) ( ) ( 2 / 1


+
39
-14000
-5000
-9000
298 2800
H2O
CO2
Temperature K
Enthalpy (kJ/kg)
The data is also found in the JANNAF tables provided at course web site

,
o
i f
h
40
41
Adiabatic Flame Temperature
Consider the following adiabatic constant pressure process:
) ( ) (
0 ) ( ) (
1


R
i i
P
a i i
R
R i i
P
p i i
T h n T h n
T h n T h n Q
For a constant pressure process, the final products temperature, T
a
, is known
as the adiabatic flame temperature (AFT).
For a given reaction where the n
i
s are known for both the reactants and the
products, T
a
can be calculated explicitly.
Fuel
Air
Products Reactants
42
Adiabatic Flame Temperature
( ) [ ] ( ) [ ]
( ) ( )
1]
1

+ +

P R
o
i f i
o
i f i
R
i i i
P
i a i i
R
i i
o
i f i
P
i a i
o
i f i
R
i i
P
a i i
h n h n K h T h n K h T h n
K h T h h n K h T h h n
T h n T h n
, , 1
1 , ,
1
) 298 ( ) ( ) 298 ( ) (
) 298 ( ) ( ) 298 ( ) (
) ( ) (
o
R
H Sensible heat of reactants
(equal to 0 if T
1
= 298K)
Sensible heat of products
1]
1

P R
o
i f i
o
i f i
R
T
i p i
P
T
i p i
h n h n dT c n dT c n
i a
, , 298 , 298 , OR
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8
43
{ } { } { }
[ ]
o
H C f
o
O H f
o
CO f
N a N O H a O H CO a CO
h h h
K h T h K h T h K h T h
18 8 2 2
2 2 2 2 2 2
, , ,
9 8
) 298 ( ) ( 47 ) 298 ( ) ( 9 ) 298 ( ) ( 8
+
+ +
2 2 2 2 2 18 8
47 9 8 ) 76 . 3 ( 5 . 12 ) ( N O H CO N O l H C + + + +
Consider constant pressure complete combustion of stoichiometric liquid
butane-air initially at 298K and 1 atm
( )
1]
1

1]
1

P R
o
i f i
o
i f i
R
i i i i
P
a i i
h n h n K h T h n K h T h n
, , 1
) 298 ( ) ( )} 298 ( ) ( {
Note: first term = 0 since T
1
= 298K, also 0
2 2 , ,

o
N f
o
O f
h h
Look up enthalpy values, and iteration gives T
a
= ????K
Adiabatic Flame Temperature, example
44
T
a,
Constant Pressure Adiabatic Flame Temperature
with products at equilibrium
45
Now consider octane air with 10% excess air
Look up values and iteration gives T
a
= ????K
Excess air adds 92.8 moles of diatomic molecules (O
2
and N
2
) into the
products that does not contribute to heat release just soaks it up.
Adiabatic Flame Temperature, example
{ } { } { }
{ } [ ]
o
H C f
o
O H f
o
CO f O a O
N a N O H a O H CO a CO
h h h K h T h
K h T h K h T h K h T h
18 8 2 2 2 2
2 2 2 2 2 2
, , ,
9 8 ) 298 ( ) ( 3.8 1
) 298 ( ) ( 7 . 51 ) 298 ( ) ( 9 ) 298 ( ) ( 8
+ +
+ +
2 2 2 2 2 2 18 8
7 . 51 25 . 1 9 8 ) 76 . 3 )( 5 . 12 ( 1 . 1 N O O H CO N O H C + + + + +
46
Constant Pressure Adiabatic Flame Temperature
with products at equilibrium
nitromethane
octane
ethanol
hydrogen
47
Constant Volume AFT
Reaction
Q
W
Consider the case where the piston is fixed and the cylinder is perfectly
insulated so the process is adiabatic (Q = 0)
) ( ) (
0 ) ( ) (
1


R
i i
P
a i i
R
R i i
P
p i i
T u n T u n
T u n T u n Q
Note h = u + pv = u + RT, so
T) R ) (T h ( n T R T h n
R
i i
P
a i i

1
) ) ( (
48
( )
+
1]
1

+
1]
1

1]
1

p R
i a i
i
P
i
P R
o
i f i
o
i f i
R
i i i
P
a i i
T R n T R n
K h n h n h n K h T h n T h n
1
, , 1

) 298 ( ) 298 ( ) ( ) (
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
Constant Volume AFT
( ) [ ] ( ) [ ] + +
R
i i i
o
i f i
P
i i a i
o
i f i
T R K h T h h n T R K h T h h n ) 298 ( ) ( ) 298 ( ) (
1 , ,
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49

,
_

,
_

,
_

,
_

i
a
R
p
i
CV
R
p
R
p
R
p
p
p p
R
R R
P R
T
T
n
n
P
P
T
T
n
n
P
P
P
T R n
P
T R n
V V

Constant Volume Combustion Pressure
Assuming ideal gas behaviour:
For large hydrocarbons like octane the mole ratio term is close to one
2 2 2 2 2 18 8
47 9 8 ) 76 . 3 ( 5 . 12 ) ( N O H CO N O l H C + + + +
06 . 1
5 . 60
64
) 76 . 4 ( 5 . 12 1
47 9 8

+
+ +

R
p
n
n
50
Stoichiometric octane-air (H
R
= 47.9 MJ/kg-fuel):
1 . 15 A 47 9 8 ) 76 . 3 ( 5 . 12
2 2 2 2 2 18 8
+ + + + /F N O H CO N O H C
1 . 8 604 . 7 06 . 1
298
2266
5 . 60
64

,
_

,
_

,
_

,
_

i
a
R
p
i
CV
T
T
n
n
P
P
Stoichiometric hydrogen-air (H
R
= 141.6 MJ/kg-fuel):
3 . 34 88 . 1 1 ) 76 . 3 ( 5 . 0
2 2 2 2 2
A/F N O H N O H + + +
8 . 6 0 . 8 85 . 0
298
2383
38 . 3
88 . 2

,
_

,
_

,
_

,
_

i
a
R
p
i
CV
T
T
n
n
P
P
Engine Fuel Comparison
Stoichiometric ethanol-air (H
R
= 29.7 MJ/kg-fuel):
7 . 16 2 . 13 3 2 ) 76 . 3 ( 5 . 3
2 2 2 2 2 6 2
A/F N O H CO N O O H C + + + +
5 . 7 37 . 7 02 . 1
298
2197
7 . 17
2 . 18

,
_

,
_

,
_

,
_

i
a
R
p
i
CV
T
T
n
n
P
P
51
Chemical Equilibrium
In general the combustion products consist of more than just CO
2
, H
2
O
O
2
and N
2
For rich mixtures CO also exists in the products. At high temperatures
the molecules dissociate to form H, O, OH, NO via the following reactions:
NO N O OH O H O O H H 2 2 2 2
2 2 2 2 2 2
+ +
At equilibrium the rate of the forward reaction equals the rate of the
backward reaction.
NO N O OH O H O O H H 2 2 2 2
2 2 2 2 2 2
+ +
The opposite direction reactions are also possible
2 2 2 2 2 2
2 2 2O 2 N O NO O H OH O H H + +
52
Chemical Equilibrium
At equilibrium the relative proportion of the species mole fraction is fixed
For the general equilibrium reaction
The equilibrium composition for species , , C, D is given by:
D n C n B n A n
D c B A
+ +
B A D C
B A
D C
n n n n
ref
n
B
n
A
n
D
n
C
P
P
X X
X X
T K
+

,
_

) (
where K is the equilibrium constant which is tabulated as a function of
temperature for different equilibrium reactions, P
ref
is 1 atmand P is in
units of atmospheres.
D C B A
A
A
n n n n
n
X Note
+ + +

53
2 2 2 2 2 2
) 76 . 3 )(
4
( fH eCO dN O bH aCO N O H C + + + + + + +



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)
If the product species CO
2
, H
2
O, CO and H
2
are at equilibrium, an additional
equation can be obtained from the water-gas reaction:
O H CO H CO
2 2 2
+ +
The equilibrium constant for this reaction provides the fifth equation :
atm 1 ) (
2 2
2

P
f a
b e
X X
X X
T K
H CO
O H CO
Note K is tabulated as a function of T
54
Chemical Equilibrium, example
1 kmol of CO
2
, kmol of O
2
and kmol of N
2
reacts to form a mixture
consisting of CO
2
, CO, O
2
, N
2
and NO at 3000K and 1 atm. Determine the
equilibrium composition of the product mixture.
2 2 2 2 2 2
2 / 1 2 / 1 eN dO cCO bNO aCO N O CO + + + + + +
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
1222 0 3000 2 / 1 2 / 1 . 2
3273 0 3000 2 / 1 . 1
2 2 2
1 2 2
. K) ( K NO N O
. K) ( K O CO CO
+
+
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55
n
tot
= a+b+c+d+e = a+b+(1-a)+1/2(1+a-b)+1/2(1-b) = (4+a)/2
) (
a
b a
a
a
X
X X
K
CO
O CO
1
4
1
1
3273 . 0
2 / 1 2 / 1
1
2
2

,
_

+
+

2 / ) 4 (
1

2 / ) 4 (
) 1 ( 2 / 1

2 / ) 4 (
2 2
a
a
X
a
b a
X
a
a
X
CO O CO
+

+
+

Chemical Equilibrium, example

2
2
2 / 1
1
3273 . 0
CO
O CO
X
X X
K


From the equilibrium constant expression
Substituting yields:
56
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
Substituting and dividing through by the total number of moles gives:
[ ]
) (
b b a
b
X X
X
K
N O
NO
2
) 1 )( 1 (
2
1222 . 0
2 / 1 2 / 1 2 / 1 2
2 2
+

Chemical Equilibrium, example
Similarly for the second equilibrium reaction
2 2 2
21 . 0 30 . 0 29 . 0 03 . 0 17 . 0 N O CO NO CO + + + +
57
+ + + + + +
+ + + + + + + +
kN jNO iOH hO gH
fH eCO dO cN O bH aCO N O H C

) 76 . 3 )(
4
(
2 2 2 2 2 2 2

If the products are at high temperature (>2000K) minor species will be
present due to the dissociation of the major species CO
2
, H
2
O, N
2
and O
2
.
Hand calculations are not practical when many species are involved, 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 chemical equilibrium calculations is STANJAN
Computer Programs Equilibrium Solvers
58
M
o
le

f
r
a
c
t
io
n
,
X
i
Temperature (K)
Equilibrium Composition for Combustion Products of Octane-air
(lean) (rich)
Nitric Oxide (NO)
is an air pollutant
(stoich)
59
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.
Adiabatic Flame Temperature for Products at Equilibrium
+ + + + + +
+ + + + + + + +
kN jNO iOH hO gH
fH eCO dO cN O bH aCO N O H C

) 76 . 3 )(
4
(
2 2 2 2 2 2 2

Again computer programs are used for these calculations:
http://www.wiley.com/college/mechs/ferguson356174/wave_s.html
Adiabatic Flame Temperature Applet
and STANJAN
) ( ) (
1

R
i i
P
a i i
T h n T h n
60
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.
How fast the fuel is consumed is of interest, the reaction rate is defined
as:
where [ F ] refers to the fuel concentration (kmol/m
3
or kg/m
3
), negative sign
due to the fact that the fuel is consumed.
dt
F d ] [
' ' '
D C A F
D C A F
+ +
O H O H
N O H CO N O H C
2 2 2
2 2 2 2 2 18 8
2 / 1
47 9 8 ) 76 . 3 ( 5 . 12
+
+ + + +
Global (or overall) reactions describe the initial and final states:
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61
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:
partner) collision a as acts at present th species any is (
M O M O O
M H M H H
M O H M OH H
H OH O H
O OH O H
H O H H OH
OH O H H HO
M HO M O H
2
2
2
2
2
2 2
2 2 2
2 2
2
M
M H H M H
+ + +
+ + +
+ + +
+ +
+ +
+ +
+ +
+ + +
+ + + Chain initiation
Chain propagation
Chain branching
Chain termination
62
Chain Branching
In chain initiation reactions radicals are formed
In chain branching reactions there is no net production or destruction of
free radicals
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 the final products.
63
Global Reaction Rate
Even for the simplest hydrocarbon fuels the chemistry is very complicated.
The GRI HC mechanism has 49 species and 227 elementary reactions.
For engineering purposes easier to use global description of reaction:
( ) ( ) ( ) oduct Inert O Fuel
P i O f
Pr
2
2
+ +
Empirical correlations have been developed for the fuel reaction rate:
l m n
Inert O Fuel
T R
E
A
dt
Fuel d
] [ ] [ ] [ exp
] [
2

,
_

where [ ] in units of gmol/cm
3
R = 1.987 cal/gmolK
E typically 20 - 40 kcal/gmol
Note this is a correlation so n, m and l dont have to be integers, typically l= 0
64
Explosion Limits
Perform an experiment where a fuel-oxygen mixture is injected into a
preheated evacuated vessel and monitor the vessel pressure.
Fuel-air
Vacuum
P
T
For a given fuel-oxygen mixture, e.g. stoichiometric, and fill pressure, if
you vary the temperature of vessel you will find that there is a critical
temperature above which an explosion occurs and below 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
P
time
P
fill
65
If you repeat the experiment for different fill pressures and plot all the results on a
pressure-temperature graph one can define an explosion limit curve.
For H
2
-O
2
the shape of this limit curve can be explained by the temperature and
pressure dependencies of the elementary reactions.
Explosion Limits
NO Explosion
Explosion
Explosion Limits of
Stoichiometric H
2
-O
2
1 atm
66
Explosion Limits for HC Fuels
Autoignition for hydrocarbon fuels is more complicated than that for
hydrogen, different types of behaviour are possible including single- and
two-stage ignition.
At 300-400
o
C one or more combustion waves often appear, accompanied
by a faint blue emission, only a small fraction of the reactants react and the
temperature rise is only tens of degrees. These are called cool flames.
A rapid compression machine (RCM) consisting of a piston-cylinder
assembly is used to raise the pressure and temperature of a fuel-air
mixture very quickly to a predetermined value P
2
, T
2
.
1
1
2
1
1
1
2
1
2

,
_

,
_

k
k
k
k
r
V
V
P
P
T
T
P
2
T
2
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12
67
Two-stage ignition: first a cool flame propagates
through the mixture (D) followed by a hot flame
or high-temperature explosion (E).
Single-stage ignition: after a certain induction time
a hot flame or high-temperature explosion (E).
Ignition Process in Isooctane-air Mixtures
After compression the subsequent pressure transient is measured to
detect ignition.
Isooctane ignition can either be single or two-stage depending on the
post-compression pressure and temperature
68
Isooctane displays different types of ignition, including cool flames and two-
stage ignition, whereas methane only displays single-stage ignition.
Explosion Limits for HC Fuels
Two-stage ignition
Single-stage ignition
No ignition
Pressure, atm
I
g
n
i
t
i
o
n

t
e
m
p
e
r
a
t
u
r
e
,

o
C
No ignition
Isooctane
Methane
Single-stage ignition
69
Laminar Premixed Flames
A flame is a thin region in space where chemical reactions convert the
fuel-air mixture into combustion products.
A flame can propagate (engine application) or remain stationary (burner
application).
For a given P, T, a flame has two basic properties:
a) adiabatic flame temperature,T
ad
b) laminar burning velocity, S
l
V
u
= S
l
V
b

b ,
T
a
burnt
unburnt
Note, S
l
is defined in terms of the approaching unburnt gas velocity
Pressure is roughly constant across the flame so ~ 1/T
Stationary flame
V
u
= 0

u
V
b
-S
l

b
S
l
Moving flame

u
70
Structure of Flame
V
u
= S
L

u
V
b

b
[Fuel]
[O
2
]
T

,
_

T R
E
O F
dt
F d
a m n
exp ] [ ] [
] [
2
Pre-heat
Zone
Reaction
Zone
Products
zone
[radicals]
Diffusion of heat
and mass
Flame
thickness
Visible part of the flame
71
Laminar Burning velocity
Maillard-LeChatelier theory gives:
) / exp(
2 2
ad a
n
l
T R E P RR S


Higher flame velocity corresponds to:
1) higher unburned gas temperature
2) lower pressure (most hydrocarbons)
3) higher adiabatic flame temperature (chemical reaction)
4) higher thermal diffusivity (= k
cond
/c
p
)
1 < n < 2
72
Laminar Burning Velocity Correlation
The following is a correlation developed by Metghalchi and Keck
) 1 . 2 1 (
1 298
, dil
u
ref l l
Y
atm
P
K
T
S S
,
_

,
_

where Y
dil
is the mass fraction of diluent, e.g., residual gas, and
) 1 ( 22 . 0 16 . 0
) 1 ( 8 . 0 18 . 2
) (
2 ,
+

+



M M ref l
B B S
Fuel
M
B
M
(cm/s) B
2
(cm/s)
Methanol 1.11 36.92 -140.51
Propane 1.08 34.22 -138.65
Isooctane 1.13 26.32 -84.72
is equivalence ratio
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73
Flame Velocity
The laminar burning velocity is measured relative to the unburned gas ahead
and the flame velocity V
f
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
V
u
V
b
=0

b
V
f
Moving flame

u
- V
u
= S
l
V
b
=V
f

b
V
f
Stationary flame

u
V
f
l
b
u
f f b l u
S V V A S

,
_

A
Applying conservation of mass across the flame:
74
Turbulent Flames
Unlike the laminar burning velocity, the turbulent flame velocity is not a
property of the gas but instead depends on the details of the flow.
The IC engine in-cylinder flow is always turbulent and the Kolmogorov
eddies 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 u
t
and can
be up to 30 times the laminar burning velocity
Laminar flame Turbulent flame
S
l
S
t
( )
b
l t l t
S u a S S / 1 / +
75
Flame Thickness and Quenching Distance
A rough estimate of the laminar flame thickness can be obtained by:
mm 1
2 2

,
_

p
cond
l l
c
k
S S

As a flame propagates through a duct heat is lost from the flame to the wall
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 d
min
and is close
in magnitude to the flame thickness.

min
d
Local quenching
76
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 E
ign
It is found experimentally that the ignition energy is inversely proportional to
the square of the mixture pressure.
A flame will only propagate in a fuel-air mixture within a composition range
known as the flammability limits.
The fuel-lean limit is known as the lower flammability limit and the
fuel-rich limit is known as the upper flammability limit.
The flammability limit is affected by both the mixture initial pressure and
temperature.
2
/ 1 P E
ign

77
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