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Combustion

Ideal Gas Model


The ideal gas equation of state is:
R
M

PV mRT m

T nR T

where R is the Universal Gas Constant (8.314 kJ/kmol K), M is the molecular
weight (29 kg/kmol for air) and n is the number of moles.
In combustion one deals with mixtures of gases such as fuel vapour and air.
The mass m of a mixture is equal to the sum of the mass of all n components
n

m mi
i 1

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


m
xi i
m

and

xi 1

i 1

Ideal Gas Model


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

U mu mi ui

H mh mi hi

i 1

i 1

The specific internal energy u and enthalpy h of the mixture (units: kJ/kg) is:
n

u xi ui

h xi hi

i 1

i 1

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
yi i
n

and

yi 1

i 1

The mixture molecular weight, M, is given by:


n

M yi M i
i 1

Ideal Gas Model


The internal energy U and enthalpy H of the mixture (units: kJ) is:
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 of the mixture
(units kJ/ kmol) is:
n

u yi ui

h yi hi

i 1

i 1

The partial pressure of a component, Pi, in the mixture (units: kPa) is:
Pi yi P

or

yi

ni Pi

n P

Ideal Gas Model


The entropy of a component (units: kJ/kg K) at Pi and T is:
si sio Ri ln(Pi Po )
where Po is 1 bar and so is tabulated as a function of T.
The mass specific mixture entropy (units: kJ/kg K) at P, T is :

s R ln P Po xi sio Ri ln(Pi / P )
i 1

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


n

s R ln P Po yi sio Ri ln yi
i 1

Note, if the mixture pressure is at 1 bar then the first terms drops out.
5

Composition of Standard Dry Air


Dry air is a mixture of gases that we will assume is composed of 21%
oxygen (O2) and 79% nitrogen (N2) by volume.
nN 2
nO2

n N 2 ntot
1

0.79
3.76
ntot nO2
0.21

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


Actual air also contains about 0.93% argon (Ar) and trace amounts of
carbon dioxide (CO2).
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


6

Composition of Standard Moist Air


In general atmospheric air always contains some amount of water vapour.

The amount of water in moist air at T is specified by the specific humidity, ,


or the relative humidity, defined as follows:

mH 2O
mair

PH 2O
Psat (T )

The two are related by:

mH 2O
mair

M H 2O nH 2O
M air nair

PH 2O
PH 2O
0.62 Psat (T )
0.62
0.62
P P (T )
P PH O

sat
Pair

The number of moles of water can be calculated knowing or :


nH 2O

mH 2O
M H 2O

nH 2O
mair nair M air nair

1.61
M H 2O
M H 2O
0.62
nair
7

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)
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

methane

propane

n-octane

There are several isooctanes, depending on position of methyl (CH 3) branches


8
which replace hydrogen atoms (eg. 3 H are replaced with 3 CH 3)

Hydrocarbon Fuels (organic compounds)


Olefins (alkenes): open-chain containing one double-bond, unsaturated
(break bond more hydrogen can be added)
CnH2n

n=2 C2H4 ethene


n=3 C3H6 propene

H
C

Note: n=1 yields CH2 is an unstable molecule

propene

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


unsaturated
CnH2n-2

n=2 C2H2 acetylene


n=3 C3H4 propyne

acetylene

For alcohols one hydroxyl (OH) group is substituted for one hydrogen
e.g. methane becomes methyl alcohol (CH3OH) also known as methanol
ethane becomes ethyl alcohol (C2H5OH) also known as ethanol
9

Combustion Stoichiometry
If sufficient oxygen is available, a hydrocarbon fuel can be completely
oxidized, the carbon is converted to carbon dioxide (CO2) and the hydrogen is
converted to water (H2O).
The overall chemical equation for the complete combustion of one mole of
propane (C3H8) is:
C3 H 8 aO2 bCO2 cH 2O
# of moles

species

Elements can not be created or destroyed so


carbon balance gives b= 3
hydrogen balance gives 2c= 8 c= 4
oxygen balance gives 2b + c = 2a a= 5
Thus the above reaction is:
C3 H 8 5O2 3CO2 4 H 2O
10

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 CH with air is:

C H (O2 3.76 N 2 ) CO2 H 2O 3.76 N 2


4
2
4

The above equation defines the stoichiometric proportions of fuel and air.

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


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

11

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

A/ F s

( F / A) s

3
.
76

O2

M N2
4
4

M C M H

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.

A/ F s

( F / A) s

(32 3.76 28)

4
12 1

Note above equation only applies to stoichiometric mixture


For methane (CH4), = 4 (A/F)s = 17.2
For octane (C8H18), = 2.25 (A/F)s = 15.1

12

Fuel Lean Mixture


Fuel-air mixtures with more than stoichiometric air, excess air, can burn.
With excess air you get fuel lean combustion, the extra air appears in the
products in unchanged form.

C H ( )(O2 3.76 N 2 ) CO2 H 2O dN 2 eO2


4
2
where for fuel lean mixture have excess air so > 1
Above reaction equation has two unknowns (d, e) and we have two
atom balance equations (O, N) so can solve for the unknowns

13

Fuel Rich Mixture


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

C H ( )(O2 3.76 N 2 ) aCO2 bH 2O dN 2 eCO fH 2


4
where for fuel rich mixture have insufficient air < 1
Above reaction equation has three unknowns (a, b, d, e, f) and we only have
two atom balance equations (C, H, O, N) so cannot solve for the unknowns
unless additional information about the products is given.

14

Off-Stoichiometric Mixtures
The equivalence ratio, , is commonly used to indicate if a mixture is
stoichiometric, fuel lean, or fuel rich.

A/ F s
F / A mixture

A / F mixture
F / A s

stoichiometric = 1
fuel lean
<1
fuel rich
> 1
Stoichiometric mixture:

C H (O2 3.76 N 2 ) Products


4

Off-stoichiometric mixture:
1

C H (O2 3.76 N 2 ) Products

4
15

Off-Stoichiometric Conditions
Other terminology used to describe how much air is used in combustion:
150% stoichiometric air = 150% theoretical air = 50% excess air

C3 H 8 ( )(O2 3.76 N 2 )
1.5 mixture is fuel lean
4
Example: Consider a reaction of octane with 10% excess air, what is ?
The stoichiometric reaction is:
C8 H18 12.5(O2 3.76 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(2)(4.76) / 1

0.91
A / F mixture 1.1(12.5)(2)(4.76) / 1
16

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

W
Q

Reactants
State 1

Products
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
Q12 (U 2 U1 ) P (V2 V1 )

17

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

HP < H R

Q<0

exothermic reaction

HP > H R

Q>0

endothermic reaction

18

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
To

Reaction

P1=P2=Po
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

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


P

19

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

C H (O2 3.76 N 2 ) CO2 H 2O 3.76 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)

20

Heat of Combustion
There are two possible values for the heat of combustion that can be calculated
depending on whether the water in the products is taken to be in a liquid or
vapour state.
T
hf

From steam tables:


hfg = hg hf > 0

hg

Tp

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
The term lower heat of combustion is used when the water in the products
is taken to be in the vapour state
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 )
C ( s ) O2 ( g ) CO2 ( g )

Q 286,000 kJ / kmol H 2O
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
22

Enthalpy Scale for a Reacting System


We need to take into account that for a reacting system the working fluid
changes molecularly from reactants to products while undergoing a process.
Consider the following identity:
h ( P, T ) h (1atm,298K ) [h ( P, T ) h (1atm,298K )]
By international convention, the enthalpy of every element in its natural state
(e.g., O2(g), N2(g), H2(g), C(s)) at STP has been set to zero
h (1atm,298K ) h o 0

(note the notation convention)

at STP

23

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 f , H 2O (l )
hH 2O (l ) h f , H 2O (l )

Therefore, the enthalpy of the ith component in a mixture is:


hi ( P, T ) h fo,i [ hi ( P, T ) hi (1atm,298K )]
chemical enthalpy

sensible enthalpy

T
298
K c p ,i dT

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


temperature (JANNAF Tables).
24

Ideal Properties of N2 and N, Heat of Formation and Enthalpy vs T

25

Adiabatic Flame Temperature


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

Reaction

P2=Pa
T2=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

ni hi (Ta ) ni hi (T1 )
P

For a given reaction where the nis are known for both the reactants and the
products, Ta can be calculated explicitly.
26

Adiabatic Flame Temperature


ni hi (Ta ) ni hi (T1 )
P

o
o
ni h f ,i hi (Ta ) hi (298K ) ni h f ,i hi (T1 ) hi (298K )
P

ni hi (Ta ) hi (298K ) ni hi (T1 ) hi (298K ) ni h f ,i ni h f ,i


P

P
R
R
o

OR

Ta
Ti
c p ,i dT ni 298
c p ,i dT ni h fo,i ni h fo,i
ni 298

P
P
R
R

H Ro
o
o
ni hi (Ta ) ni hi (T1 ) hi (298K ) ni h f ,i ni h f ,i ni hi (298K )
P
P
P
R
R

If reactants are at 298K, term =0

27

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 5H 2O 24.4 N 2
o
o
ni hi (Ta ) ni hi (T1 ) hi (298K ) ni h f ,i ni h f ,i ni hi ( 298K )
R
P
P

P
R

Note: first term = 0 since T1 = 298K,

h fo,O2 h fo, N 2 0

4 hCO2 (Ta ) hCO2 ( 298K ) 5 hH 2O (Ta ) hH 2O (298K ) 24.4 hN 2 (Ta ) hN 2 (298K )

4h fo,CO2 5h fo, H 2O h fo,C4 H10


Look up enthalpy values, and substituting gives Ta = 2500K
28

Constant Pressure Adiabatic Flame Temperature


with products at equilibrium

Ta,

29

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 ( 298K ) 5 hH 2O (Ta ) hH 2O (298K ) 97.8 hN 2 (Ta ) hN 2 (298K )

19.5 hO2 (Ta ) hO2 (298K ) 4 h fo,CO2 5h fo, H 2O h fo,C4 H10

Look up values and substituting gives Ta = 1215K


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

30

Constant Pressure Adiabatic Flame Temperature


with products at equilibrium

31

Constant Volume AFT


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

Reaction

P2=PCV
T2=Ta

Q ni ui (T p ) ni ui (TR ) 0
P

ni ui (Ta ) ni ui (T1 )
P

Note h = u + pv = u + RT, so
ni (hi (Ta ) R T ) ni(hi(T1 ) R T)
P

32

Constant Volume AFT

o
o
ni h f ,i hi (Ta ) hi (298K ) R Ti ni h f ,i hi (T1 ) hi ( 298K ) R Ti
P

o
o
ni hi (Ta ) ni hi (T1 ) hi ( 298K ) ni h f ,i ni h f ,i ni hi (298K )
R
P
P

P
R
ni R Ta ni R T1
p

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

33

Constant Volume Combustion Pressure


Assuming ideal gas behavior:
VR VP
nR R TR n p R T p

PR
Pp
np


PR nR
Pp

Tp

TR

PCV n p


Pi nR

Ta

Ti

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


Pi
nR

Ta 64 Ta
T



1.06 a
Ti 60.5 Ti
Ti

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


34

Chemical Equilibrium
In general the combustion products consist of more than just CO 2, H2O
O2, and N2
For rich mixtures CO also exists in the products and at high temperatures
the molecules dissociate to form H, O, OH, NO via the following reactions:
H 2 2H

O2 2O

H 2 O2 2OH

O2 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
35

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 CD is given by:
X
K (T )
X

nC
C
nA
A

X
X

nD
D
nB
B

P
ref

nC nD n A 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 X A
n A nB nC nD
36

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)

C H ( )(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 :
K (T )

X CO X H O
2

X CO X H
2

eb
a f

P 1 atm

Note K is tabulated as a function of T


37

Chemical Equilibrium, example


1 kmol of CO2, kmol of O2 and 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
O
N

1 = a+c
3 = a+b+2c+2d
1 = b+2e

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

Have 2 unknowns a, b so need 2 equilibrium equations


1.

CO2 CO 1 / 2O2

K1( 3000K) 0.3273

2.

1 / 2O2 1 / 2 N 2 NO

K 2( 3000K) 0.1222
38

Chemical Equilibrium, example


From the equilibrium constant expression
K1 0.3273

X CO X O1 / 2
2

X CO

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


X CO

a
(4 a) / 2

X O2

1 / 2(1 a b)
(4 a) / 2

X CO2

1 a
(4 a) / 2

Substituting yields:
K1 0.3273

X CO X O1 / 2
2

X CO

a 1 a b

1 a 4 a

1/ 2

(1)
39

Chemical Equilibrium, example


Similarly for the second equilibrium reaction
K 2 0.1222

X NO
2b

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

40

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 CO 2, H2O, N2 and O2.

C H ( )(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 considered, one
uses a computer program to calculate the product equilibrium composition.
http://www.wiley.com/college/mechs/ferguson356174/wave_s.html
Equilibrium Combustion Solver Applet
A popular program used for equilibrium calculations is STANJAN

41

Composition of Octane-air Mixtures at Equilibrium

(stoich)

(rich)

Mole fraction, Xi

(lean)

Nitric Oxide (NO)


is an air pollutant

Temperature (K)

42

Adiabatic Flame Temperature for Products at Equilibrium

C H ( )(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.

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
43

Chemical Kinetics
First and Second Laws of thermodynamics are used to predict the final
equilibrium state of the products after the reaction is complete.
Chemical kinetics deals with how fast the reaction proceeds.

F F A A C C D D
How fast the fuel is consumed is of interest, the reaction rate is defined
as:
d[F ]
'''
dt
where [ F ] refers to the fuel concentration (kmol/m3 or kg/m3), negative sign
due to the fact that the fuel is consumed.
Global (or overall) reactions describe the initial and final states:
C8 H18 12.5(O2 3.76 N 2 ) 8CO2 9 H 2O 47 N 2
H 2 1 / 2O2 H 2O

44

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
H 2 O OH H

Chain branching

H OH M H 2 O M
H H M H2 M

Chain termination

O O M O2 M
( M is any species present th at acts as a collision partner)

45

Radicals
Species such as H, O, OH and HO2 are called radicals.
Radicals have unpaired valence electrons which make them very reactive
and short lived, they try to partner with other radicals to form covalent bonds
In chain branching reactions there is a net production of radicals
Chain branching reactions lead to rapid production of radicals which causes
the overall reaction to proceed extremely fast explosively
The reaction comes to completion through chain termination reactions
where the radicals recombine to form final products.

46

Chemical Reaction Equations


Consider the following general reaction involving n species

1' A1 2' A2 3' A3 n' An 1" A1 2" A2 3" A3 n" An


Ai = species
= stoichiometric coefficient for reactants
= 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)
A1 = H 1 = 3 , 1 = 1
A2 = H2 2 = 0 , 2 = 1
reactants

products
47

Law of mass Action


The law of mass action states that for an elementary reaction the reaction
rate is proportional to the product of the concentrations of the reactants
present raised to a power equal to the corresponding stoichiometric
coefficient. The constant of proportionality is called the reaction rate
constant k.
'

j
n
d [ Ai ]
"
'
( i i )k [ A j ]
dt
j 1

'j

1'

2'

3'

n'

where [ A j ] [ A1 ] [ A2 ] [ A3 ] [ An ]
j 1

the overall order of the reaction is given by 'j


j 1

For m simultaneous equations:

n
d [ Ai ] m "
'
( i ,l i ,l )kl [ A j ]
l 1
dt
j 1

'
j .l

48

Law of mass Action


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

d [ A1 ]
( 1" 1' )k[ A1 ] [ A2 ]
dt
d[H ]
(1 3)k[ H ]3 [ H 2 ]0 2k[ H ]3
dt
'
1

A1 = H

'
2

d [ A2 ]
( 2" 2' )k[ A2 ] [ A2 ]
dt
d[H 2 ]
(1 0)k[ H ]3 [ H 2 ]0 k [ H ]3
dt
'
1

A2 = H2

Recall n = 2

note k[H]3

'
2

1 d[H ] d[ H 2 ]

2 dt
dt
49

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 a higher atomic hydrogen concentration.
50

Rate Coefficients for H2-O2 Reactions


A
Reactions

* n is the reaction order

Ea

((cm /gmol) /s)*


3

n-1

Temperature range
(kJ/gmol)
(K)

51

Ozone (O3) Decomposition


Global reaction:

2O3 3O2
k

1
O3 M
O O2 M

Important elementary
reactions include:

k2

3
O O3 k
O2 O2

k4

5
OOM
O2 M

k6

Here m = 6 (3 forward and 3 backward reactions)


n =3 (O, O2, O3)
'j . l

d [ Ai ]
( i",l i',l )kl [ A j ]
l 1
dt
j 1
m

The O3 reaction rate is:

O'''
3

d [O3 ]
k1[O3 ][ M ] k 2 [O][O2 ][ M ] k3 [O][O3 ] k 4 [O2 ]2
dt
52

Relationship Between Rate Constant and Equilibrium Constant


kf

A A B B C C D D
kb

d [ A]
k f [ A] [ B ] kb [C ] [ D]
dt
A

d [ A]
k f [ A] [ B ] kb [C ] [ D ] 0
dt

At equilibrium:

[C ] [ D]

kb [ A] [ B ]

kf

Note:

X CvC
X AvA

X DvD
X BvB

P
P
ref

k f [ A] [ B ] kb [C ] [ D]

Recall:

vC vD v A vB

nC
nC / V
RT
XC

[C ]
ntotal ntotal / V
P

[C ] [ D] R T

[ A]v [ B ]v Pref
vC

vD

53

vC vD v A vB

Relationship Between Rate Constant and Equilibrium Constant


k f RT

K

kb Pref
RT

kb
Pref

kf

vC vD v A vB

vC vD v A vB

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


reaction can get kf from kb
For a bimolecular reaction A B C D
kf
kb

54

Reaction Rate for Global Reaction


Even for the simplest hydrocarbon fuels the chemistry is very complicated.
GRI mechanism has 49 species and 227 elementary reactions.
For engineering purposes better to use global description:

f Fuel O O2 i Inert 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 dont have to be integers, typically l= 0
55

Example: Nitric Oxide (NO) Formation


Global NO formation reaction:
d [ NO]
kG [ N 2 ]m [O2 ]n
dt

G
N 2 O2 k
2 NO

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:
KPref
d [ NO]
2k f 1
[ N 2 ][O2 ]1/ 2
dt
RT
kG

56

Explosion Limits

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


spherical vessel and monitor the vessel pressure.
P

H2-O2
P
Vacuum
T

time

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


you vary the temperature of vessel you will find that there is a critical
temperature below which an explosion occurs and above which an
explosion does not occur (note there is no spark ignition).
An explosion is characterized by a rapid rise in vessel pressure faster than
the normal pressure rise due to gas filling.
This critical temperature is referred to as the autoignition57or explosion limit
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.
The shape of this limit curve can be explained by the temperature and pressure
dependencies of the H2-O2 elementary reactions.

1 atm

NO Explosion

Explosion Limits of
Stoichiometric H2-O2
Explosion

58

Laminar Premixed Flames


A flame represents an interface separating the unburned gas from the
combustion products.
A flame can propagate as in an engine application or be stationary as in a
burner application.
For a given P, T, and laminar conditions a flame has two basic properties:
a) adiabatic flame temperature,Tad
b) laminar burning velocity, Sl

burned

Vb
b

Vu = Sl

unburned

Stationary flame

Vb-Sl

Sl

Vu = 0
u

Moving flame

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


59
Pressure is roughly constant across the flame so ~ 1/T

Laminar Burning velocity


Maillard-LeChatelier theory gives:
Sl2 Tu P n1 exp( E / R Tad )
Higher flame velocity corresponds to:
1) higher unburned gas temperature
2) lower pressure
3) higher adiabatic flame temperature (chemical reaction)
4) higher thermal diffusivity (= kcond/cp)

60

Laminar Burning Velocity Correlation


The following is a correlation developed by Metghalchi and keck
Sl Sl ,ref

Tu P

298K 1atm

(1 2.1Ydil )

where Ydil is the mass fraction of diluent, e.g., residual gas, and
Sl ,ref BM B2 ( M )

2.18 0.8( 1)
0.16 0.22( 1)
Fuel

Methanol
Propane
Isooctane

1.11
1.08
1.13

BM (cm/s)
36.92
34.22
26.32

B2 (cm/s)
-140.51
-138.65
-84.72
61

Structure of Flame
Vu = SL
u

Vb
b

[Fuel]
[O2]

d[F ]
Ea
[ F ]n [O2 ]m exp

dt
RT

Products
zone

Visible part of the flame

[radicals]

Reaction
Zone
Flame
thickness

Pre-heat
Zone

Diffusion of heat
and radicals
62

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
b

Vf

Vu

Vf

Vb=Vf
b

Moving flame

V f - V u= S l
u
Stationary flame

Applying the conservation of mass across the flame:



u Sl b V f V f u Sl
b

63

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

The IC engine in-cylinder flow is always turbulent and the smallest eddies
(Kolmogorov scale) are typically larger than the laminar flame thickness (1 mm).
Under these conditions the flame is said to display a structure known as
wrinkled laminar flame.
A wrinkled laminar flame is characterized by a continuous flame sheet that is
distorted by the eddies passing through the flame.
The turbulent burning velocity depends on the turbulent intensity ut and can
be up to 30 times the laminar burning velocity
Sl
Laminar flame

St
Turbulent flame

S t / S l 1 a ut / S l
64

Flame Thickness and Quenching Distance


A rough estimate of the laminar flame thickness can be obtained by:
2 2 kcond

1 mm

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

Local quenching

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
65

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

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


within a range of mixture compositions known as the flammability limits.
The fuel-lean limit is known as the lower (or lean) flammability limit and the
fuel-rich limit is known as the upper (or rich) flammability limit.
The flammability limit is affected by both the mixture initial pressure and
temperature.
66

67