Combustion Theory

1
 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 )

where Po is 1 bar and so is corresponds to 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

The mixture specific internal energy u and enthalpy h is:

n mi n n mi n
u = ∑ ui = ∑ xi ui h = ∑ hi = ∑ xi hi
i =1 m i =1 i =1 m i =1
3
 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

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
 Ideal Gas Model

The mass specific mixture entropy (units: kJ/kg K) at P, T is :

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

n

i =1

The molar specific mixture entropy (units: kJ/mol K) is:

s = ∑ yi ( sio − Ri ln yi ) − R ln( P Po )
n

i =1

Note, if the mixture pressure is at 1 bar the second terms drops out.

6
 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 (mole fraction).
nN nN ntot y N 0.79
= 2
⋅ 2
= = 2
= 3.76
nO 2
ntot nO yO2
0.21
2

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

• The molecular weight of air is

n
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

7
 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:
mH O PH O
ω= 2
Φ= 2
0 < Φ <1
mair Psat (T )

• The two are related by:

M H O ⋅ nH O  18  PH O   PH O 
 = 0.62 Φ ⋅ Psat (T ) 
mH O
ω= 2
= 2 2
=   2
= 0 . 62 2

mair M air ⋅ nair  29  Pair  P−P 

 H O
2 
 P − Φ ⋅ P (T ) 
 sat 

• The number of moles of water can be calculated knowing ω or Φ :

mH 2O ω ⋅ mair ω ⋅ ( nair ⋅ M air ) ω ⋅ nair nH 2O

nH 2O = = = = → = 1.61 ⋅ ω
M H 2O M H 2O M H 2O 0.62 nair
8
 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)

CnH2n+2 n= 1 CH4 methane

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

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

H H H H H H H H H H H

methane ethane n-octane

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

9
which replace hydrogen atoms (eg. a side H is replaced with 3 CH3)
 Hydrocarbon Fuels (organic compounds)

Olefins (alkenes): open-chain containing one double-bond, unsaturated

(break bond more hydrogen can be added)
H H
H
CnH2n n=2 C2H4 ethene C C C H
n=3 C3H6 propene H
H
Note: n=1 yields CH2 is an unstable molecule propene

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

unsaturated

CnH2n-2 n=2 C2H2 acetylene H C C H

n=3 C3H4 propyne acetylene

For alcohols one hydroxyl (OH) group is substituted for one hydrogen
e.g. methane becomes methyl alcohol (CH3OH) also known as methanol
ethane becomes ethyl alcohol (C2H5OH) also known as ethanol
10
 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: b= 3
H balance: 2c= 8  c= 4
O balance: 2b + c = 2a  a= 5

Thus the above reaction is:

C3 H 8 + 5O2 → 3CO2 + 4 H 2O

11
 Combustion Stoichiometry

Air contains molecular nitrogen N2, when the products are low temperature
the nitrogen is not significantly affected by the reaction, it is considered inert.

The complete reaction of a general hydrocarbon Cα Hβ with air is:

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

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)
 β β  β
Cα H β +  α + (O2 + 3.76 N 2 ) → αCO2 + H 2O + 3.76 α +  N 2
 4 2  4
The above equation defines the stoichiometric proportions of fuel and air.

Example: For propane (C3H8) α = 3 and β = 8

C3 H 8 + ( 5) (O2 + 3.76 N 2 ) → 3CO2 + 4 H 2O + 3.76( 5) N 2 12

 Combustion Stoichiometry

The stoichiometric mass based air/fuel ratio for Cα Hβ fuel is:

 α + β  M + 3.76 α + β  M
( ∑ ni M i ) air   O   N
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

For methane (CH4), β /α = 4  (A/F)s = 17.2

13
For octane (C8H18 ), β /α = 2.25  (A/F)s = 15.1
 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:

β β
Cα H β + γ (α + )(O2 + 3.76 N 2 ) → αCO2 + H 2O + dN 2 + eO2
4 2

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

14
 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

where for fuel rich mixture have 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.

15
 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
Cα H β +  α + (O2 + 3.76 N 2 ) → Products
φ 4 16
 Off-Stoichiometric Conditions
Other terminology used to describe how much air is used in combustion:

150% stoichiometric air = 150% theoretical air = 50% excess air

β
C3 H 8 + γ (α + )(O2 + 3.76 N 2 ) γ = 1.5  mixture is fuel lean
4
Example: Consider a reaction of octane with 10% excess air, what is φ ?

The stoichiometric reaction is:

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

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

( A/ F )s 12.5(4.76) / 1
φ= = = 0.91
( A / F ) mixture 1.1(12.5)(4.76) / 1 17
 First Law Analysis for Reacting System

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

na moles of air to produce np moles of product:
n f F + na A → n p P

Reactants Products

Reactants
Q Products

State 1 State 2
Reaction

Applying First Law with state 1 being the reactants at P1, T1 and state 2
being products at P2, T2:
Q = ∆U + W

Q1→2 = (U 2 − U1 ) + P (V2 − V1 ) 18
First Law Analysis for Reacting System

Q = (U 2 − U1 ) + P (V2 − V1 )

= (U 2 + P2V2 ) − (U1 + P1V1 )

= H 2 − H1

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

H P < HR Q<0 exothermic reaction

H P > HR Q>0 endothermic reaction

19
 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).

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

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

reaction, ∆ HR ,

∆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

20
 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 referred to as the heat of combustion or the heating
value and it is typically given per mass of fuel
∆ HR(298K)

hydrocarbons

alcohols
21
 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

∆ HR = HP – HR < 0 (exothermic)

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

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

22
 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
o
h
and takes the symbol f so:
hf,oH 2O = −286,000 kJ / kmol
hf,oCO2 = −394,000 kJ / kmol

Values for standard heat of formation for different species are tabulated
23
Heat of Formation for Different Fuels

24
 Enthalpy Scale for a Reacting System

We need to take into account that for a reacting system the working fluid
changes molecularly from reactants to products while undergoing a process.

Consider the following identity:

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

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

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

h (1atm,298 K ) = h fo = 0 (note the notation convention)

at STP

25
 Enthalpy Scale for a Reacting System

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

recall @ STP Q = hH 2O ( l ) − 1 / 2hO2 ( g ) − hH 2 ( g ) ≡ h fo, H 2O ( l )

→ hH 2O ( l ) = h fo, H 2O ( l )

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 )]

T
chemical enthalpy sensible enthalpy = ∫298 K c p ,i dT

26
 -5000

Enthalpy (kJ/kg)
CO2

-9000
H2O

h of ,i

-14000
298 2800
Temperature K

The data is also found in the JANNAF tables provided at course web site
27
28
 Adiabatic Flame Temperature

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

Reaction
Q

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.

29
 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 (298K ) )
P
o

R
o
]

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

o o

P R P R 

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

∆H Ro

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

o o

P R P R  P

If reactants are at 298K, term =0 30

 Adiabatic Flame Temperature, example

Consider constant pressure complete combustion of stoichiometric liquid

butane-air initially at 298K and 1 atm

C4 H10 (l ) + 6.5(O2 + 3.76 N 2 ) → 4CO2 + 5 H 2O + 24.4 N 2

∑ 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: first term = 0 since T1 = 298K, also h fo,O2 = h fo, N 2 = 0

4{ hCO2 (Ta ) − hCO2 (298 K )} + 5{ hH 2O (Ta ) − hH 2O (298 K )} + 24.4{ hN 2 (Ta ) − hN 2 (298 K )}

[
= − 4h fo,CO2 + 5h fo, H 2O − h fo,C4 H10 ]
Look up enthalpy values, and iteration gives Ta = 2500K

31
Constant Pressure Adiabatic Flame Temperature
with products at equilibrium

Ta,

32
 Adiabatic Flame Temperature, example

Now consider butane air with 300% excess air

C4 H10 (l ) + 4(6.5)(O2 + 3.76 N 2 ) → 4CO2 + 5H 2O + 97.8 N 2 + 19.5O2

4{ hCO2 (Ta ) − hCO2 (298 K )} + 5{ hH 2O (Ta ) − hH 2O ( 298 K )} + 97.8{ hN 2 (Ta ) − hN 2 ( 298K )}

[
+ 19.5{ hO2 (Ta ) − hO2 (298 K )} = −4 h fo,CO2 + 5h fo, H 2O − h fo,C4 H10 ]

Look up values and iteration gives Ta = 1215K

Excess air adds 92.8 moles of diatomic molecules (O2 and N2) into the
products that does not contribute to heat release just soaks it up.

33
Constant Pressure Adiabatic Flame Temperature
with products at equilibrium

nitromethane

hydrogen
octane
ethanol

34
 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

35
 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 ) = ∑ ni ( hi (T1 ) − hi (298 K ) )  − ∑ ni h f ,i − ∑ ni h f ,i  + ∑ ni hi (298K )

o o

P R  P R  P 
+ ∑ 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

36
 Constant Volume Combustion Pressure

Assuming ideal gas behavior:

VR = VP
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 the mole ratio term is close to one

37
 Engine Fuel Comparison

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

C8 H 18 + 12.5(O2 + 3.76 N 2 ) → 8CO2 + 9 H 2 O + 47 N 2 A/F = 15.1

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):

H 2 + 0.5(O2 + 3.76 N 2 ) → 1H 2 O + 1.88 N 2 A/F = 34.3

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):

C 2 H 6 O + 3.5(O2 + 3.76 N 2 ) → 2CO2 + 3H 2 O + 13.2 N 2 A/F = 16.7
PCV  n p  Ta   18.2  2197 
=    =    = 1.02 ⋅ 7.37 = 7.5
Pi  R  i  
n T 17 . 7  298  38
 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
39
 Chemical Equilibrium

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

• For the general equilibrium reaction

n A A + nB B ↔ ncC + nD D

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

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

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

temperature for different equilibrium reactions, Pref is 1 atm and P is in
units of atmospheres.
nA
Note XA =
n A + nB + nC + nD
40
 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 and described
by the water-gas reaction:
CO2 + H 2 ↔ CO + H 2O

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

Note K is tabulated as a function of T

41
 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

42
 Chemical Equilibrium, example

From the equilibrium constant expression

X CO ⋅ X O1 / 2
K1 = 0.3273 = 2

X CO 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
X CO = X O2 = X CO2 =
(4 + a) / 2 (4 + a) / 2 (4 + a) / 2

Substituting yields:

X CO ⋅ X O1 / 2 a 1 + a − b 
1/ 2
K1 = 0.3273 = 2
=   (1 )
X CO 2
1− a  4 + a 

43
 Chemical Equilibrium, example

Similarly for the second equilibrium reaction

X NO 2b
K 2 = 0.1222 = = (2)
X O1 / 2 ⋅ X 1N/ 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 + 0.03NO + 0.29CO2 + 0.30O2 + 0.21N 2
44
 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

45
Equilibrium Composition for Combustion Products of Octane-air

(lean) (stoich) (rich)

Mole fraction, Xi

Nitric Oxide (NO)

is an air pollutant

46
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

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

• Again computer programs are used for these calculations:

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

and STANJAN
47
 Chemical Kinetics

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

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

H 2 + 1 / 2O2 → H 2O
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:
d[F ]
ω''' = −
dt
where [ F ] refers to the fuel concentration (kmol/m3 or kg/m3), negative sign
due to the fact that the fuel is consumed. 48
 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:
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

49
( M is any species present that acts as a collision partner)
 Radicals

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

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

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

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

the overall reaction to proceed extremely fast  explosively

• The reaction comes to completion through chain termination reactions

where the radicals recombine to form the final products.

50
 Chemical Reaction Equations

Consider the following general reaction involving n species

ν 1' A1 + ν 2' A2 + ν 3' A3 + ν n' An → ν 1" A1 + ν 2" A2 + ν 3" A3 + ν n" An

Ai = species
ν ’ = stoichiometric coefficient for reactants
ν ” = stoichiometric coefficients for products

As an example, consider the following elementary reaction

H + H + H → H2 + H

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

A 1 = H  ν 1’ = 3 , ν 1” = 1

A 2 = H2  ν 2’ = 0 , ν 2” = 1

reactants products
51
 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.
'
νj
d [ Ai ] n
= (ν i −ν i )k ∏ [ A j ]
" '

dt j =1

n ν 'j
ν 1' ν 2' ν 3' ν n'
where ∏ [ A j ] = [ A1 ] ⋅ [ A2 ] ⋅ [ A3 ] [ An ]
j =1
n
the overall order of the reaction is given by ∑ν 'j
j =1

For m simultaneous equations:

ν '
d [ Ai ] m " n j .l

= ∑ (ν i ,l −ν i ,l )kl ∏ [ A j ]
'

dt l =1 j =1
52
 Law of mass Action

k
Applying the law of mass action to the reaction H + H + H → H2 + H

d [ A1 ]
= (ν 1" −ν 1' )k[ A1 ]ν ⋅ [ A2 ]ν
' '
1 2
Recall n = 2
dt
d[H ]
A1 = H = (1 − 3) k[ H ]3 ⋅ [ H 2 ]0 = −2k[ H ]3
dt

d [ A2 ]
= (ν 2" −ν 2' ) k[ A2 ]ν ⋅ [ A2 ]ν
' '
1 2

dt
A 2 = H2 d[H 2 ]
= (1 − 0)k[ H ]3 ⋅ [ H 2 ]0 = k[ H ]3
dt

1 d[ H ] d[ H 2 ]
note k[H] 3 = − =
2 dt dt

53
 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

 E 
k = AT b exp − a 
 RT 
where A and b are the rate coefficients, Ea is the activation energy
and R is the universal gas constant.
k
Therefore, for the reaction H + H + H → H 2 + H the reaction rate is
d[H 2 ]  E 
= k[ H ]3 = AT b exp − a  ⋅ [ H ]3
dt  RT 
The values of a, b and Ea are tabulated for different reactions.

This expression indicates that molecular hydrogen is produced faster at

higher temperature and at higher atomic hydrogen concentrations.

54
 Rate Coefficients for H2-O2 Reactions

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

* n is the reaction order 55

 Ozone (O3) Decomposition

Global reaction: 2O3 → 3O2

Important elementary O3 + M k→
1
O + O2 + M
k2
reactions include:
O + O3 k→
3
O2 + O2
k4

O + O + M k→
5
O2 + M
k6
Here m = 6 (3 forward and 3 backward reactions)
n =3 (O, O2, O3)
ν 'j . l
d [ Ai ] m n
= ∑ (ν i",l −ν i',l )kl ∏ [ A j ]
dt l =1 j =1

The O3 reaction rate is:

d [O3 ]
ωO''' = = − k1[O3 ][ M ] + k 2 [O][O2 ][ M ] − k3 [O ][O3 ] + k 4 [O2 ]2
3
dt
56
 Relationship Between Rate Constant and Equilibrium Constant
kf
ν A A +ν B B → ν C C +ν D D
kb

d [ A]
= − k f [ A]ν ⋅ [ B ]ν + kb [C ]ν ⋅ [ D ]ν
A B C D

dt
d [ A]
At equilibrium: = − k f [ A]ν ⋅ [ B ]ν + kb [C ]ν ⋅ [ D]ν = 0
A B C D

dt
k f [ A]ν ⋅ [ B ]ν = kb [C ]ν ⋅ [ D]ν
A B C D

kf [C ]ν ⋅ [ D ]νC D

=
kb [ A]ν ⋅ [ B ]ν A B

vC +vD −v A −vB vC +vD −v A −vB

X CvC ⋅ X DvD  P  [C ] ⋅ [ D ]  R T
vC vD 
Recall: K=   = 
X AvA ⋅ X BvB P  [ A]v ⋅ [ B ]v  Pref 
 ref  
A B

nC nC / V RT
Note: XC = = = [C ]
ntotal ntotal / V P 57
 Relationship Between Rate Constant and Equilibrium Constant

vC +vD −v A −vB
k f  RT 
K= ⋅  
kb  Pref 
−( vC +vD −v A −vB )
kf  RT 
= K ⋅  
kb 
 Pref 

If the equilibrium constant K is available for the elementary

Reaction, then you can get kf knowing kb , or get kb knowing kf

For a bimolecular reaction A + B → C + D

kf
=K
kb

58
 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:

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

Note this is a correlation so n, m and l don’t have to be integers, typically l= 0

59
 Example: Nitric Oxide (NO) Formation
Global NO formation reaction:
N 2 + O2 k→ 2 NO d [ NO ]
G
= kG [ N 2 ]m [O2 ]n
dt
Thermal (Zeldovich) Mechanism:
(1) O + N 2 → NO + N Ea = 315 kJ/mol
(2) N + O2 → NO + O Ea = 26 kJ/mol

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

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

d [ NO ] KPref
= 2k f 1 [ N 2 ][O2 ]1/ 2
dt RT
kG 60
 Explosion Limits

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

spherical vessel and monitor the vessel pressure.

P
Fuel-air
P
Vacuum
time
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

61
temperature
 Explosion Limits
If you repeat the experiment for different fill pressures and plot all the results on a
pressure-temperature curve one can define an explosion limit curve.

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

1 atm

NO Explosion

Explosion Limits of
Stoichiometric H2-O2
Explosion

62
 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 300-400oC 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 P2, T2.

P2 T2
k −1
k −1
T2  P2  k V 
=   =  1  = r k −1
T1  P1   V2 

63
 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

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).

64
 Explosion Limits for HC Fuels

Isooctane displays different types of ignition, including cool flames and two-
stage ignition, whereas methane only displays single-stage ignition.

Isooctane
Methane
Ignition temperature, oC

Single-stage ignition

Single-stage ignition No ignition

Two-stage ignition

No ignition

Pressure, atm
65
 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,Tad
b) laminar burning velocity, Sl

Vu = Sl Vb-Sl Sl Vu = 0
V
burnt b
Ρ b, Ta ρ u
unburnt
ρ b
ρ u

Stationary flame Moving flame

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

Pressure is roughly constant across the flame so ρ ~ 1/T 66

 Structure of Flame

Vb Vu = SL
ρ b ρ u

[Fuel]
T
[O2]
d[F ]  − Ea 
∝ −[ F ]n [O2 ]m exp 
dt  RT  [radicals]

Products Reaction Pre-heat

zone Zone Zone

Flame
Visible part of the flame thickness δ
Diffusion of heat
and mass 67
 Laminar Burning velocity

Maillard-LeChatelier theory gives:

S l2 ∝ α ⋅ RR = α ⋅ P n − 2 exp(− E a / R Tad ) 1<n<2

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 (= kcond /ρ cp)

68
 Laminar Burning Velocity Correlation

The following is a correlation developed by Metghalchi and Keck

γ β
 T   P 
Sl = Sl ,ref  u    (1 − 2.1Ydil )
 298 K   1atm 

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

Sl ,ref = BM + B2 (φ − φM ) φ is equivalence ratio

γ = 2.18 − 0.8(φ − 1)
β = −0.16 + 0.22(φ − 1)

Fuel φ M BM (cm/s) B2 (cm/s)

Methanol 1.11 36.92 -140.51

Propane 1.08 34.22 -138.65
Isooctane 1.13 26.32 -84.72

69
 Flame Velocity

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

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

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

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

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

ρ b ρ ρ b ρ u
u

Moving flame Stationary flame

Applying conservation of mass across the flame:

ρ 
ρ u ⋅ S l ⋅ A = ρ b ⋅ V f ⋅ A → V f =  u  ⋅ S l
 ρb 
70
 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 ut and can
be up to 30 times the laminar burning velocity

S t / S l = 1 + a ( ut / S l )
b
Sl St

Laminar flame Turbulent flame 71

 Flame Thickness and Quenching Distance

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

2α 2  kcond 
δ= =
 
≈ 1 mm
Sl Sl  ρ ⋅ c p 

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

Local quenching d

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

critical value then the flame will extinguish

This critical value is referred to as the quenching distance dmin and is close
in magnitude to the flame thickness.
d min ∝ δ
72
 Minimum Ignition Energy and Flammability Limits

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

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

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

the square of the mixture pressure.
Eign ∝ 1 / P 2

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.
73
74