1

Combustion Theory
2
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 − ·
where P
o
is 1 bar and s
o
is corresponds to P
o
3
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 h
m
m
h u x u
m
m
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
4
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
5
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
6
Ideal Gas Model
The mass specific mixture entropy (units: kJ/kg K) at P, T is :
( ) ( )
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


− ·
·
The molar specific mixture entropy (units: kJ/mol K) is:
Note, if the mixture pressure is at 1 bar the second terms drops out.
7
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
.
• The 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
8
Composition of Standard Moist Air
• Atmospheric air always contains some amount of water vapour.
• The amount of water in moist air at T is specified by the specific humidity,
ω , or the relative humidity, Φ , defined as follows:
1 0
) (

2 2
< Φ < · Φ ·
T P
P
m
m
sat
O H
air
O H
ω
( )
ω
ω ω ω
⋅ · →

·
⋅ ⋅
·

· · 61 . 1
62 . 0
2
2 2 2
2
2
air
O H
air
O H
air air
O H
air
O H
O H
O H
n
n
n
M
M n
M
m
M
m
n

,
`

.
|
⋅ Φ −
⋅ Φ
·

,
`

.
|

·

,
`

.
|

,
`

.
|
·


· ·
) (
) (
62 . 0 62 . 0
29
18
2
2 2 2 2 2
T P P
T P
P P
P
P
P
n M
n M
m
m
sat
sat
O H
O H
air
O H
air air
O H O H
air
O H
ω
• The two are related by:
• The number of moles of water can be calculated knowing ω or Φ :
9
Hydrocarbon Fuels (organic compounds)
Most common hydrocarbon fuels are Alkyl Compounds and are grouped as:
Paraffins (alkanes): single-bonded, open-chain, saturated (no more hydrogen
can be added by breaking a bond)
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
n-octane and isooctane
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
C
H
H
H
H
C
H
H
methane ethane
n-octane
H H
H
C
H
There are several isooctanes, depending on position of methyl (CH
3
) branches
which replace hydrogen atoms (eg. a side H is replaced with 3 CH
3
)
10
Olefins (alkenes): open-chain containing one double-bond, unsaturated
(break bond more hydrogen can be added)
C
n
H
2n
n=2 C
2
H
4
ethene
n=3 C
3
H
6
propene
propene
Acetylenes (alkynes): open-chain containing one C-C triple-bond
unsaturated
C
n
H
2n-2
n=2 C
2
H
2
acetylene
n=3 C
3
H
4
propyne
H C C H
acetylene
Hydrocarbon Fuels (organic compounds)
For alcohols one hydroxyl (OH) group is substituted for one hydrogen
e.g. methane becomes methyl alcohol (CH
3
OH) also known as methanol
ethane becomes ethyl alcohol (C
2
H
5
OH) also known as ethanol
Note: n=1 yields CH
2
is an unstable molecule
H
C
H
H C C
H
H
H
11
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: b= 3
H balance: 2c= 8  c= 4
O balance: 2b + c = 2a  a= 5
Thus the above reaction is:
O H CO O H C
2 2 2 8 3
4 3 5 + → +
# of moles species
12
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
α
H
β
with air is:
2 2 2 2 2
) 76 . 3 ( dN O cH bCO N O a H C + + → + +
β α
The above equation defines the stoichiometric proportions of fuel and air.
Example: For propane (C
3
H
8
) α = 3 and β = 8
( ) ( )
2 2 2 2 2 8 3
5 76 . 3 4 3 ) 76 . 3 ( 5 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

,
`

.
|
+ + + → +

,
`

.
|
+ +
β
α
β
α
β
α
β α
C balance: α = b
H balance: β = 2c  c = β /2
O balance: 2a = 2b + c  a = b + c/2  a = α + β /4
N balance: 2(3.76)a = 2d  d = 3.76a/2  d = 3.76(α +
β /4)
13
( )
( )
( ) 1 12
) 28 76 . 3 32 (
4
1
) / (
1
/
⋅ +
⋅ +

,
`

.
|
+
· ·
α β
α β
s
s
A F
F A
Combustion Stoichiometry
Substituting the respective molecular weights and dividing top and bottom
by α one gets the following expression that only depends on the ratio of the
number of hydrogen atoms to hydrogen atoms (β /α ) in the fuel.
Note above equation only applies to stoichiometric mixture
For methane (CH
4
), β /α = 4  (A/F)
s
= 17.2
For octane (C
8
H
18
), β /α = 2.25  (A/F)
s
= 15.1
The stoichiometric mass based air/fuel ratio for C
α
H
β
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
β α
β
α
β
α
+

,
`

.
|
+ +

,
`

.
|
+
·


· ·
2 2
4
76 . 3
4
/
14
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 γ > 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 + + + → + + +
β
α
β
α γ
β α
15
• 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 + + + + → + + +
β
α
β
α γ
β α
where for fuel rich mixture have insufficient air  γ < 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.
16
The equivalence ratio, φ , 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
/
/
/
/
· · φ
Off-Stoichiometric Mixtures
stoichiometric φ = 1
fuel lean φ < 1
fuel rich φ > 1
Products ) 76 . 3 (
4
2 2
→ +

,
`

.
|
+ + N O H C
β
α
β α
Stoichiometric mixture:
Off-stoichiometric mixture:
Products ) 76 . 3 (
4
1
2 2
→ +

,
`

.
|
+ + N O H C
β
α
φ
β α
17
Example: Consider a reaction of octane with 10% excess air, what is φ ?
The stoichiometric reaction is:
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
φ
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:
150% stoichiometric air = 150% theoretical air = 50% excess air
5 . 1 ) 76 . 3 )(
4
(
2 2 8 3
· + + + γ
β
α γ N O H C
 mixture is fuel lean
18
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
− + − ·
+ ∆ ·

19



· − ·
− ·
+ − + ·
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
20
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
21
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

,
`

.
|
+ + + → +

,
`

.
|
+ +
β
α
β
α
β
α
β α
∆ H
R
(298K)
hydrocarbons
alcohols
22
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
)
23
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 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 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
24
Heat of Formation for Different Fuels
25
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
26
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 i’th 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
· →
≡ − − ·
→ +
27
-14000
-5000
-9000
298
2800
H
2
O
CO
2
Temperature K
Enthalpy (kJ/kg)
The data is also found in the JANNAF tables provided at course web site

,
o
i f
h
28
29
Adiabatic Flame Temperature
Reaction
Q
W
Consider the case where 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 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.
30
Adiabatic Flame Temperature
( ) [ ] ( ) [ ]
( ) ( )
]
]
]

∑ ∑
− −

− ·



− + ·

− +

·

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 ( ) (
) ( ) (
( ) ) 298 ( ) 298 ( ) ( ) (
, , 1
K h n h n h n K h T h n T h n
i
P
i
P R
o
i f i
o
i f i
R
i i i
P
a i i


]
]
]

∑ ∑
− −

− ·

o
R
H ∆
]
]
]

∑ ∑
− −




·
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
If reactants are at 298K, term =0
31
{ ¦ { ¦ { ¦
[ ]
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
10 4 2 2
2 2 2 2 2 2
, , ,
5 4
) 298 ( ) ( 4 24 ) 298 ( ) ( 5 ) 298 ( ) ( 4
− + − ·
− + − + −
2 2 2 2 2 10 4
4 . 24 5 4 ) 76 . 3 ( 5 . 6 ) ( 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
( )
]
]
]

∑ ∑
− −
]
]
]


− · −

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
= 2500K
Adiabatic Flame Temperature, example
32
T
a,
Constant Pressure Adiabatic Flame Temperature
with products at equilibrium
33
Now consider butane air with 300% excess air
2 2 2 2 2 2 10 4
5 . 19 8 . 97 5 4 ) 76 . 3 )( 5 . 6 ( 4 ) ( O N O H CO N O l H C + + + → + +
Look up values and iteration gives T
a
= 1215K
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
10 4 2 2 2 2
2 2 2 2 2 2
, , ,
5 4 ) 298 ( ) ( 9.5 1
) 298 ( ) ( 8 . 97 ) 298 ( ) ( 5 ) 298 ( ) ( 4
− + − · − +
− + − + −
34
Constant Pressure Adiabatic Flame Temperature
with products at equilibrium
nitromethane
octane
ethanol
hydrogen
35
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
) ) ( (
36
( )
∑ ∑
− +
]
]
]


+
]
]
]

∑ ∑
− −
]
]
]


− ·

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 , ,
37

,
`

.
|

,
`

.
|
· →

,
`

.
|

,
`

.
|
·
·
·
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 behavior:
For large hydrocarbons the mole ratio term is close to one
38
Stoichiometric octane-air (∆ H
R
= 47.9 MJ/kg):
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):
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):
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
39
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 + → + → → →
40
Chemical Equilibrium

At equilibrium the relative proportion of the species mole fraction is fixed
• For the general equilibrium reaction
• The equilibrium composition for species Α , Β , 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 atm and P is in
units of atmospheres.
D C B A
A
A
n n n n
n
X Note
+ + +
·
41
2 2 2 2 2 2
) 76 . 3 )(
4
( fH eCO dN O bH aCO N O H C + + + + → + + +
β
α γ
β α
Chemical Equilibrium
Recall that for a rich mixture (γ <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 and described
by 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
42
Chemical Equilibrium, example
1 kmol of CO
2
, ½ kmol of O
2
and ½ 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
· ↔ +
· + ↔
43
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:
44
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 + + + +
45
 + + + + + +
+ + + + + → + + +
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
β
α
β α
• 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
46
M
o
l
e

f
r
a
c
t
i
o
n
,

X
i
Temperature (K)
Equilibrium Composition for Combustion Products of Octane-air
(lean) (rich)
Nitric Oxide (NO)
is an air pollutant
(stoich)
47

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
β
α
β α

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
48
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 ω ’’’ 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 ] [
' ' ' − · ω
D C A F
D C A F
ν ν ν ν + → +
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:
49
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
50
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 the final products.
51
Chemical Reaction Equations
Consider the following general reaction involving n species
n n n n
A A A A A A A A
"
3
"
3 2
"
2 1
"
1
'
3
'
3 2
'
2 1
'
1
ν ν ν ν ν ν ν ν   + + + → + + +
A
i
= species
ν ’ = stoichiometric coefficient for reactants
ν ” = stoichiometric coefficients for products
As an example, consider the following elementary reaction
H H H H H + → + +
2
For this reaction n = 2 (species are H and H
2
)
A
1
= H  ν
1
’ = 3 , ν
1
” = 1

A
2
= H
2
 ν
2
’ = 0 , ν
2
” = 1
reactants
products
52
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.

⋅ ⋅ ·


− ·
·
·
·
n
j
j
n
n
j
j
n
j
j i i
i
n
j
j
A A A A A
A k
dt
A d
1
'
3 2 1
1
1
' "
by given is reaction the of order overall the
] [ ] [ ] [ ] [ ] [ where
] [ ) (
] [

' '
3
'
2
'
1
'
'
ν
ν ν
ν ν ν ν
ν
ν

For m simultaneous equations:
∑ ∏
− ·
· ·
m
l
n
j
j l l i l i
i
l j
A k
dt
A d
1 1
'
,
"
,
'
.
] [ ) (
] [
ν
ν ν
53
Law of mass Action
Applying the law of mass action to the reaction H H H H H + → + +
2
dt
H d
dt
H d
k[H]
H k H H k
dt
H d
A A k
dt
A d
H k H H k
dt
H d
A A k
dt
A d
] [ ] [
2
1
note
] [ ] [ ] [ ) 0 1 (
] [
] [ ] [ ) (
] [
] [ 2 ] [ ] [ ) 3 1 (
] [
] [ ] [ ) (
] [
2
3
3 0
2
3
2
2 2
'
2
"
2
2
3 0
2
3
2 1
'
1
"
1
1
'
2
'
1
'
2
'
1
· − ·
· ⋅ − ·
⋅ − ·
− · ⋅ − ·
⋅ − ·
ν ν
ν ν
ν ν
ν ν
A
1
= H
A
2
= H
2
k
Recall n = 2
54
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

,
`

.
|
− ·
T R
E
AT k
a
b
exp
where A and b are the rate coefficients, E
a
is the activation energy
and R is the universal gas constant.
Therefore, for the reaction the reaction rate is
H H H H H + → + +
2
3 3
2
] [ exp ] [ H
T R
E
AT H k
dt
] d[H
a
b

,
`

.
|
− · ·
The values of a, b and E
a
are tabulated for different reactions.
This expression indicates that molecular hydrogen is produced faster at
higher temperature and at higher atomic hydrogen concentrations.
k
55
Rate Coefficients for H2-O2 Reactions
* n is the reaction order
A b E
a
Temperature range
Reactions ((cm
3
/gmol)
n-1
/s)* (kJ/gmol) (K)
56
Ozone (O
3
) Decomposition
Global reaction:
2 3
3 2 O O →
Important elementary
reactions include:
M O M O O
O O O O
M O O M O
+ → + +
+ → +
+ + → +
2
2 2 3
2 3
k
1
k
2
k
3
k
6
k
4
k
5
Here m = 6 (3 forward and 3 backward reactions)
n =3 (O, O
2
, O
3
)
∑ ∏
− ·
· ·
m
l
n
j
j l l i l i
i
l j
A k
dt
A d
1 1
'
,
"
,
'
.
] [ ) (
] [
ν
ν ν
The O
3
reaction rate is:
2
2 4 3 3 2 2 3 1
3
' ' '
] [ ] ][ [ ] ][ ][ [ ] ][ [
] [
3
O k O O k M O O k M O k
dt
O d
O
+ − + − · · ω
57
Relationship Between Rate Constant and Equilibrium Constant
D C B A
D C B A
ν ν ν ν + → +
k
f
k
b
D C B A
D C k B A k
dt
A d
b f
ν ν ν ν
] [ ] [ ] [ ] [
] [
⋅ + ⋅ − ·
At equilibrium:
B A
D C
D C B A
D C B A
B A
D C
k
k
D C k B A k
D C k B A k
dt
A d
b
f
b f
b f
ν ν
ν ν
ν ν ν ν
ν ν ν ν
] [ ] [
] [ ] [
] [ ] [ ] [ ] [
0 ] [ ] [ ] [ ] [
] [


·
⋅ · ⋅
· ⋅ + ⋅ − ·
B A D C
B A
D C
B A D C
B A
D C
v v v v
ref
v v
v v
v v v v
ref
v
B
v
A
v
D
v
C
P
T R
B A
D C
P
P
X X
X X
K
− − + − − +

,
`

.
|


·

,
`

.
|


·
] [ ] [
] [ ] [
Recall:
Note:
P
T R
C
V n
V n
n
n
X
total
C
total
C
C
] [
/
/
· · ·
58
Relationship Between Rate Constant and Equilibrium Constant
( )
B A D C
B A D C
v v v v
ref b
f
v v v v
ref b
f
P
T R
K
k
k
P
T R
k
k
K
− − + −
− − +

,
`

.
|
⋅ ·

,
`

.
|
⋅ ·
If the equilibrium constant K is available for the elementary
Reaction, then you can get k
f
knowing k
b
, or get k
b
knowing k
f

For a bimolecular reaction
D C B A + → +
K
k
k
b
f
·
59
Reaction Rate for Global Reaction
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
ν ν ν ν → + +
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 don’t have to be integers, typically l= 0
60
Example: Nitric Oxide (NO) Formation
Thermal (Zeldovich) Mechanism:
kJ/mol 6 2 (2)
kJ/mol 315 (1)
2
2
· + → +
· + → +
a
a
E O NO O N
E N NO N O
Forward reaction (1) is endothermic and due to the high E
a
requires high
temperature (>1800K) to proceed and is very slow.
2 / 1
2 2 1
] ][ [ 2
] [
O N
T R
KP
k
dt
NO d
ref
f
·
From above two reaction using basic arguments one can derive the following
expression for the “initial” NO reaction rate for the global reaction:
NO O N 2
2 2
→ +
k
G
k
G
Global NO formation reaction:
n m
G
O N k
dt
NO d
] [ ] [
] [
2 2
·
61
Explosion Limits
Perform an experiment where a fuel-oxygen mixture is injected into a preheated
spherical 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
62
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.
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
63
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
64
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
65
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
66
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, φ a flame has two basic properties:
a) adiabatic flame temperature,T
ad
b) laminar burning velocity, S
l
V
u
= S
l
V
b
Ρ
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 ρ ~ 1/T
Stationary flame
V
u
= 0
ρ
u
V
b
-S
l
ρ
b
S
l
Moving flame
ρ
u
67
Structure of Flame
V
u
= S
L
ρ
u
V
b
ρ
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 δ
Visible part of the flame
68
Laminar Burning velocity
Maillard-LeChatelier theory gives:
) / exp(
2 2
ad a
n
l
T R E P RR S − ⋅ · ⋅ ∝

α α
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 α (= k
cond
/ρ c
p
)
1 < n < 2
69
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 −

,
`

.
|

,
`

.
|
·
β γ
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 ,
− + − ·
− − ·
− + ·
φ β
φ γ
φ φ
M M ref l
B B S
Fuel φ
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
φ is equivalence ratio
70
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
ρ
b
V
f
Moving flame
ρ
u
- V
u
= S
l
V
b
=V
f
ρ
b
V
f
Stationary flame
ρ
u
V
f
l
b
u
f f b l u
S V V A S ⋅

,
`

.
|
· → ⋅ ⋅ · ⋅ ⋅
ρ
ρ
ρ ρ A
Applying conservation of mass across the flame:
71
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 / + ·
72
Flame Thickness and Quenching Distance
A rough estimate of the laminar flame thickness δ can be obtained by:
mm 1
2 2

,
`

.
|

· ·
p
cond
l l
c
k
S S ρ
α
δ
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.
δ ∝
min
d
Local quenching
73
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

74

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