1

COMBUSTION THEORY
 Ideal Gas Model

The ideal gas equation of state is:

R 
PV = mRT = m T = nR T
M 

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

Specific internal energy (units: kJ/kg) u (T ) = ∫ cv (T )dT

Specific enthalpy (units: kJ/kg) h(T ) = ∫ c p (T )dT

Specific entropy (units: kJ/kg K) s ( P, T ) = s o (T ) − R ln( P Po )

(Po = 1 bar, so entropy at Po)

2
 Ideal Gas Model for Mixtures

The mass m of a mixture is equal to the sum of the mass of n components

n
m = ∑ mi
i =1

The mass fraction, xi, of any given species is defined as:

mi n
xi = and ∑ xi = 1
m i =1

The mixture internal energy U and enthalpy H (units: kJ) is:

n n
U = mu = ∑ mi ui H = mh = ∑ mi hi
i =1 i =1

where ui and hi are mass specific values (units: kJ/kg)

The mixture specific internal energy u and enthalpy h is:

U n mi ui n H n mi hi n
u= =∑ = ∑ xi u i h= =∑ = ∑ xi hi
3 m i =1 m i =1 m i =1 m i =1
 Ideal Gas Model for Mixtures

The total number of moles in the mixture is:

n
n = ∑ ni
i =1

The mole fraction, yi, of any given species is defined as:

n n
yi = i and ∑ yi = 1
n i =1

The mixture internal energy U and enthalpy H (units: kJ) is:

n n
U = ∑ ni ui H = ∑ ni hi
i =1 i =1

where ui and hi are molar specific values (units: kJ/kmol)

The mixture molar specific internal energy and enthalpy (units kJ/ kmol) is:
n n
u = ∑ yi ui h = ∑ yi hi
i =1 i =1
4
 Ideal Gas Model for Mixtures

Mass specific entropy (kJ/kg K) molar specific mixture entropy (kJ/mol K) :

s = ∑ xi (s − Ri ln( Pi / P ) ) − R ln( P Po ) s = ∑ yi (sio − Ri ln yi ) − R ln ( P Po )

n n
o
i
i =1 i =1

The mixture molecular weight, M, is given by:

n

m i∑
mi n
ni M i n
M = = =1
=∑ = ∑ yi M i
n n i =1 n i =1

The partial pressure of a component, Pi, in the mixture (units: kPa) is:
PiV
n RT = Pi
yi = i = or Pi = yi P
n PV P
RT

5
 Composition of Standard Dry Air

Air is a mixture of gases including oxygen (O2), nitrogen(N2), argon (Ar),

carbon dioxide (CO2), water vapour (H20)….

For combustion dry air is taken to be composed of 21% O2 and 79% N2

by volume (yO2=0.21, yN2=0.79).
nN nN ntot y N 0.79
2
= ⋅ 2
= = 2
= 3.76
nO 2
ntot nO 2
yO 0.212

For every mole of O2 there are 3.76 moles of N2.

n
Molecular weight of air is M air = ∑ yi M i = yO2 ⋅ M O2 + y N 2 ⋅ M N 2
i =1

= 0.21(32) + 0.79(28) = 28.84 kg/kmol

The amount of water in moist air at temperature T is specified by the

specific humidity (ω) or the relative humidity (Φ) defined as follows:
mH O PH O
ω= 2
Φ= 2
0 < Φ <1
6 mair Psat (T )
 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) with oxygen is:
C3 H 8 + aO2 → bCO2 + cH 2O
# of moles species

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 stoichiometric reaction is:

C3 H 8 + 5O2 → 3CO2 + 4 H 2O
7
 Combustion Stoichiometry

Air contains molecular nitrogen N2, if products are at a “low” temperature

the nitrogen is not significantly affected by the reaction, it is considered inert.

The complete reaction of a general hydrocarbon CαHβ with air is:

Cα H β + a (O2 + 3.76 N 2 ) → bCO2 + cH 2O + dN 2

C balance: α=b →b=α

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)

 β β  β
Cα H β +  α + (O2 + 3.76 N 2 ) → αCO2 + H 2O + 3.76 α +  N 2
 4 2  4

Example: The stoichiometric reaction of octane (C8H18) α= 8 and β= 18

C8 H 18 + (12.5)(O2 + 3.76 N 2 ) → 8CO2 + 9 H 2O + 47 N 2

8
 Combustion Stoichiometry

The stoichiometric mass based air/fuel ratio for CαHβ fuel is:

 β  β
 α +  O +  α + M N
(∑ ni M i )air M 3 . 76
=
mair 4  4
( A / F )s
2 2

= =
m fuel (∑ ni M i ) fuel αM C + β M H

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.

 (β α ) 
1 + (32 + 3.76 ⋅ 28)
=
1 4 
( A / F )s =
( F / A) s 12 + (β α ) ⋅1

Note above equation only applies to stoichiometric mixture

Example: For octane (C8H18), β/α = 2.25 → (A/F)s = 15.1

9 (gasoline (A/F)s≈ 14.6

 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 as

O2 and N2:
β β
Cα H β + γ (α + )(O2 + 3.76 N 2 ) → αCO2 + H 2O + dN 2 + eO2
4 2
a fuel lean mixture has 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

10
 Fuel Rich Mixture
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 CO2 and H2O.

Get incomplete combustion where carbon monoxide (CO) and molecular

hydrogen (H2) also appear in the products.

β β
Cα H β + γ (α + )(O2 + 3.76 N 2 ) → αCO2 + H 2O + dN 2 + eCO + fH 2
4 2

a fuel rich mixture has insufficient air → γ < 1

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.

11
 Off-Stoichiometric Mixtures

The equivalence ratio, φ, is commonly used to indicate if a mixture is

stoichiometric, fuel lean, or fuel rich.

( A / F )s (F / A)mixture
φ= =
( A / F )mixture (F / A)s

stoichiometric φ = 1
fuel lean φ<1
fuel rich φ>1

Stoichiometric mixture:
 β
Cα H β +  α + (O2 + 3.76 N 2 ) → Products
 4
Off-stoichiometric mixture:

1 β 1
Cα H β +  α + (O2 + 3.76 N 2 ) → Products γ=
φ 4 φ
12
 Off-stoichiometric Conditions
Other terminology used to describe how much air is used in combustion:

110% stoichiometric air = 110% theoretical air = 10% excess air

β
C3 H 8 + γ (α + )(O2 + 3.76 N 2 ) γ = 1.1 → mixture is fuel lean
4
Example: Consider a reaction of octane with 10% excess air, what is φ?

Stoichiometric : C8 H18 + 12.5(O2 + 3.76 N 2 ) → 8CO2 + 9 H 2O + 47 N 2

10% excess air is: C8 H18 + 1.1(12.5)(O2 + 3.76 N 2 ) → 8CO2 + 9 H 2O + aO2 + bN 2

O balance: 1.1(12.5)(2) = 16 + 9 + 2a → a = 1.25,

N balance: 1.1(12.5)(3.76)(2) = 2b → b = 51.7

( A / F )s 12.5( 4.76) / 1 1 1
φ= = = 0.91 = = 1.1
( A / F )mixture 1.1(12.5)( 4.76) / 1 φ .91
13
 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
14 being products at P2, T2:
 First Law Analysis for Reacting System

Q = ∆U + W

Q1→2 = (U 2 − U1 ) + P (V2 − V1 )

= (U 2 + P2V2 ) − (U1 + P1V1 )

= H 2 − H1

= HP − HR

Q = ∑ ni hi (T p ) − ∑ ni hi (TR )
P R

15
 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).

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

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

reaction, ∆HR ,

Q = ∆H R
= ∑ ni hi (T p ) − ∑ ni hi (TR )
P R

= ∑ ni hi (To ) − ∑ ni hi (To ) units : kJ per kg or kmol of fuel

P R

16
 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

 β β  β
Cα H β +  α + (O2 + 3.76 N 2 ) → αCO2 + H 2O + 3.76 α +  N 2
 4 2  4

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

the heating value, given per unit mass of fuel or air

∆HR = HP – HR < 0 (exothermic)

∆HR = HP – HR > 0 (endothermic)

17
 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
hf hg
From steam tables:
Tp hfg = hg – hf > 0

The term higher heat of combustion and heating value (HHV) is used
when the water in the products is taken to be in the liquid state (hH20 = hf )

The term lower heat of combustion and heating value (LHV) is used
when the water in the products is taken to be in the vapour state (hH20 = hg )

18
 Heat of Combustion, graphical

Reactants
h(kJ/kg fuel)
0

Products with H2O (g)

∆hlow Products with H2O (l)

∆hhigh

hfg,H2O per kg fuel

298K T

19
20 Source: Pulkrabek
 Fuel A/F Energy Specific
density energy
(MJ/L fuel) (MJ/kg air)

Gasoline* 14.6 32 2.9

Butanol 11.2 29.2 3.2

Ethanol 9.0 19.6 3.0
Methanol 6.5 16 3.1

Hydrogen 34.3 ** 4.1

* Diesel about 10% more energy per volume than gasoline

** liquefied hydrogen has roughly ¼ the energy density of gasoline

21
 Heat of Formation

Consider the following reactions taking place at atmospheric pressure and

with TP = TR = 298K

1 / 2O2 ( g ) + H 2 ( g ) → H 2O(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
( h fo ) so:
h f,o H O = Q = −286,000 kJ / kmol
2

h f,o CO = Q = −394,000 kJ / kmol

2

Values for standard heat of formation for different species are tabulated
22
 Heat of Formation for Different Fuels

23
 Enthalpy Scale for a Reacting System

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

i.e, h (1atm,298 K ) = h f = 0
o

Consider the following identity:

h ( P, T ) = h (1atm,298 K ) + [h ( P, T ) − h (1atm,298 K )]

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

hi ( P, T ) = h fo,i + [hi ( P, T ) − hi (1atm,298 K )]

chemical enthalpy 298K sensible enthalpy = ∫298

T
K c p ,i dT

24
 -5000

Enthalpy (kJ/kg)
CO2

-9000
H2O

h of ,i

-14000
298 2800
Temperature K

The data is also found in the JANNAF tables

25
26
 Adiabatic Flame Temperature
Consider the following adiabatic constant pressure process:

Fuel
Reactants Products
(T1) Air (Ta )

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

Q = ∑ ni hi (T p ) − ∑ 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.

27
 Adiabatic Flame Temperature

∑ ni hi (Ta ) = ∑ ni hi (T1 )
P R

[ ] [
∑ ni h f ,i + (hi (Ta ) − hi ( 298 K ) ) = ∑ ni h f ,i + (hi (T1 ) − hi ( 298 K ) )
P
o
R
o
]

∑ ni (hi (Ta ) − hi ( 298 K ) ) = ∑ ni (hi (T1 ) − hi ( 298 K ) ) −  ∑ ni h f ,i − ∑ ni h f ,i 

o o
P R  P R 

Sensible heat of products Sensible heat of reactants ∆H Ro

(equal to 0 if T1 = 298K)

OR ∑ ni ∫298
Ta
c p ,i dT = ∑ ni ∫298
Ti
c p ,i dT − ∑ ni h fo,i − ∑ ni h fo,i 
P R  P R 

28
 Adiabatic Flame Temperature, example

C8 H18 (l ) + 12.5(O2 + 3.76 N 2 ) → 8CO2 + 9 H 2O + 47 N 2

Consider constant pressure complete combustion of stoichiometric liquid

butane-air initially at 298K and 1 atm

∑ ni {hi (Ta ) − hi (298 K )} = ∑ ni (hi (T1 ) − hi (298 K ) ) − ∑ ni h f ,i − ∑ ni h f ,i 

o o

P R  P R 

Note: h fo,O2 = h fo, N 2 = 0

8{hCO (Ta ) − hCO ( 298K )}+ 9{hH O (Ta ) − hH O ( 298K )}+ 47{hN (Ta ) − hN ( 298K )}
= −[8h fo,CO + 9h fo,H O − h fo,C H ]
2 2 2 2 2 2

2 2 8 18

Look up enthalpy of formation values and iterate Ta → 2410K

29
 Adiabatic Flame Temperature
with products at equilibrium

Ta,

30
 Adiabatic Flame Temperature, example

Now consider octane air with 10% excess air

C8 H18 + 1.1(12.5)(O2 + 3.76 N 2 ) → 8CO2 + 9 H 2O + 1.25O2 + 51.7 N 2

8{hCO2 (Ta ) − hCO2 ( 298K )}+ 9{hH 2O (Ta ) − hH 2O ( 298K )}+ 1.25{hO2 (Ta ) − hO2 ( 298K )}
+ 51.7{hN 2 (Ta ) − hN 2 ( 298 K )}= −[8h fo,CO2 + 9h fo, H 2O − h fo,C8 H18 ]

∆HR same as for φ =1

Look up values and iteration gives Ta = 2262K

Excess air adds 6 moles of diatomic molecules (O2 and N2) into the
products that does not contribute to heat release just soaks it up.

31
 Adiabatic Flame Temperature
with products at equilibrium

nitromethane

hydrogen
octane
ethanol

32
 Constant Volume AFT

Consider the case where the piston is fixed and the cylinder is perfectly
insulated so the process is adiabatic (Q = 0)

Reaction
Q

Q = ∑ ni ui (T p ) − ∑ ni ui (TR ) = 0
P R

∑ ni ui (Ta ) = ∑ ni ui (T1 )
P R

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

∑ ni (hi (Ta ) − R T ) = ∑ ni(hi(T1 ) − R T)

P R

33
 Constant Volume AFT

[ ] [
∑ ni h f ,i + (hi (Ta ) − hi (298 K ) ) − R Ti = ∑ ni h f ,i + (hi (T1 ) − hi (298 K ) ) − R Ti
P
o

R
o
]

∑ ni (hi (Ta ) − hi ( 298K ) ) =  ∑ ni (hi (T1 ) − hi ( 298 K ) ) −  ∑ ni h f ,i − ∑ ni h f ,i 

o o
P  R   P R 
+ ∑ ni R Ta − ∑ ni R T1
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

34
 Constant Volume Combustion Pressure

Assuming ideal gas behaviour:

VR = V P
nR R TR n p R T p
=
PR Pp
Pp  n p  T p  PCV  n p  Ta 
=    → =   
PR  nR  TR  Pi  nR  Ti 

For large hydrocarbons like octane the mole ratio term is close to one

C8 H18 (l ) + 12.5(O2 + 3.76 N 2 ) → 8CO2 + 9 H 2O + 47 N 2

np 8 + 9 + 47 64
= = = 1.06
nR 1 + 12.5(4.76) 60.5

35
 Engine Fuel Comparison

Stoichiometric octane-air (∆HR= 47.9 MJ/kg-fuel):

C8 H 18 + 12.5(O2 + 3.76 N 2 ) → 8CO2 + 9 H 2O + 47 N 2
PCV  n p  Ta   64  2266 
=    =    = 1.06 ⋅ 7.604 = 8.1
Pi  n R  Ti   60.5  298 

Stoichiometric hydrogen-air (∆HR= 141.6 MJ/kg-fuel):

H 2 + 0.5(O2 + 3.76 N 2 ) → 1H 2O + 1.88 N 2

PCV  n p  Ta   2.88  2383 
=    =    = 0.85 ⋅ 8.0 = 6.8
Pi  n R  Ti   3.38  298 

Stoichiometric ethanol-air (∆HR= 29.7 MJ/kg-fuel):

C2 H 6O + 3.5(O2 + 3.76 N 2 ) → 2CO2 + 3H 2O + 13.2 N 2
PCV  n p  Ta   18.2  2197 
=    =    = 1.02 ⋅ 7.37 = 7.5
36 Pi  R  i  
n T 17 . 7  298 
 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. 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 + N 2 → 2 NO

The opposite direction reactions are also possible

2H → H 2 2O → O2 2OH → H 2 + O2 2 NO → 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 + N 2 ↔ 2 NO

37
 Chemical Equilibrium

At equilibrium the relative proportion of the species mole fraction is fixed

For the general equilibrium reaction

n A A + nB B ↔ nc C + nD D

The equilibrium composition for species Α, Β, C, D is given by:

nC + nD − n A − nB
Y ⋅ Y  P
nC nD


K (T ) = C D
Y ⋅ Y  Pref
A
nA
B
nB 


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 YA =
n A + nB + nC + nD
38
 Equilibrium Constants

water gas reaction

Log10(k)

39 Source: Pulkrabek
 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)

β
Cα H β + γ (α + )(O2 + 3.76 N 2 ) → aCO2 + bH 2O + dN 2 + eCO + fH 2
4

If the product species CO2, H2O, CO and H2 are at equilibrium, an additional

equation can be obtained from the water-gas reaction:
CO2 + H 2 ↔ CO + H 2O

The equilibrium constant for this reaction provides the fifth equation:
YCO ⋅ YH O e⋅b
K (T ) = 2
= P = 1 atm
YCO ⋅ YH
2 2
a⋅ f

Note K is tabulated as a function of T

40
 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 / 2 N 2 → aCO + bNO + cCO2 + dO2 + eN 2

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( 3000 K) = 0.3273

2. 1 / 2O2 + 1 / 2 N 2 ↔ NO K 2( 3000 K) = 0.1222

41
 Chemical Equilibrium, example

CO2 ↔ CO + 1 / 2O2
From the equilibrium constant expression
YCO ⋅ YO1 / 2
K1 = 0.3273 = 2

YCO 2

CO2 + 1 / 2O2 + 1 / 2 N 2 → aCO + bNO + cCO2 + dO2 + eN 2

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
YCO = YO = YCO =
(4 + a) / 2 2
(4 + a) / 2 2
(4 + a) / 2

Substituting yields:

YCO ⋅ YO1 / 2 a 1 + a − b 
1/ 2
K1 = 0.3273 = 2
=   (1 )
YCO 1− a  4 + a 
42 2
 Chemical Equilibrium, example

Similarly for the second equilibrium reaction

YNO 2b
K 2 = 0.1222 = = (2)
YO1 / 2 ⋅ YN1 / 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

Substituting and dividing through by the total number of moles gives:

0.17CO + 0.03 NO + 0.29CO2 + 0.30O2 + 0.21N 2

43
 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.

β
Cα H β + (α + )(O2 + 3.76 N 2 ) → aCO2 + bH 2O + cN 2 + dO2 + eCO + fH 2
4
+ gH + hO + iOH + jNO + kN + 

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

44
 Equilibrium Composition for Combustion Products of Octane(C8H18)-air

N2, H2O and CO2

(lean) (stoich) (rich)
dissociate at high T

Mole fraction, Yi

CH4, NO and CO
are air pollutants

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

β
Cα H β + (α + )(O2 + 3.76 N 2 ) → aCO2 + bH 2O + cN 2 + dO2 + eCO + fH 2
4
+ gH + hO + iOH + jNO + kN + 

One can calculate the AFT for the above stoichiometric reaction where the
products are at equilibrium: ∑ ni hi (Ta ) = ∑ ni hi (T1 )
P R

Dissociation of 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
46
 Chemical Kinetics

Global (or overall) reactions describe the initial and final states:

C8 H 18 + 12.5(O2 + 3.76 N 2 ) → 8CO2 + 9 H 2O + 47 N 2

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.

ν F F +ν A A → ν C C +ν D D

How fast the fuel is consumed is of interest, the reaction rate ω’’’ is defined
as:
n Pi
ω'''= −
d[F ] [F ] = =
dt V ℜT

where [ F ] refers to the fuel concentration (kmol/m3 or kg/m3), negative sign

due to the fact that the fuel is consumed.
47
 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 subset

of elementary reactions, collectively known as a reaction mechanism:

H2 + M → H + H + M Chain initiation

H + O 2 + M → HO 2 + M
HO 2 + H 2 → H 2 O + OH Chain propagation
OH + H 2 → H 2 O + H

H + O 2 → OH + O
Chain branching
H 2 + O → OH + H

H + OH + M → H 2 O + M
H + H + M → H2 + M Chain termination
O + O + M → O2 + M

48
( M is any species present that acts as a collision partner)
 Chain Branching

In chain initiation reactions radicals are formed

In chain propagation 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.

49
 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 approximate global reaction:

ν f ( Fuel ) + ν O O2 + ν i ( Inert ) → ν P (Pr oduct )

2

Empirical correlations have been developed for the fuel reaction rate:

d [ Fuel ]  E 
= A exp −
−  ⋅ [ Fuel ] [O2 ] [ Inert ]
n m l
dt  RT 
where [ ] in units of gmol/cm3
R = 1.987 cal/gmolK
E typically 20 - 40 kcal/gmol

Note typically l= 0
50