5.

Chemical Kinetics
5.1 Rate Laws and Reaction Orders
(f)

D + E + F + ... describes an empirical

The rate law of a chemical reaction A + B + C + ... k
formulation of the reaction rate e.g. of A in the form
d[ A ]
= k ( f ) [ A ]a [B]b [C]c .....
dt
a, b, c, ... are the reaction orders with respect to the species A, B, C, ... . The sum of all exponents is the
overall reaction order. Frequently some species are in excess. In this case their concentrations do not
change noticeable and therfore e.g., [B], [C], ... remain nearly constant during the reaction; using k = k
b
c
[B] [C] . . . one ontains

(f)

d[A]/dt = - k [A] .
Integration of this differential equation for the special cases a = 1, a = 2, a = 3 yields:

[A]t
= k (t - t0 )
[A]0

1st-order time behavior

first-order reactions, a = 1:

ln

second-order reactions, a = 2:

1
1

= k (t t0 )
[ A ]t [ A]0

2nd-order time behavior

third-order reactions, a = 3:

1
1

= 2 k (t t0 )
2
[ A ]t
[ A ]0 2

3rd-order time behavior

If the time behavior is measured and plotted in a suitable way, the reaction order can be determined (linear
dependences, see figure).
[ A] t
ln [ ]
A

1
[ A]

first order reaction

second order reaction

t

1
[ A]

19

5.2 Elementary Reactions, Reaction Molecularity

An elementary reaction is one that occurs on a molecular level exactly in the way which is described by
the reaction equation. Example: OH + H2 H2O + H
A hydroxyl radical collides with a hydrogen molecule and as a result of a reaction a water
molecule and a hydrogen atom bounce apart.
In net reactions (complex reaktions, overall reactions) many reactive intermediates are formed.
Example: 2 H2 + O2 2 H2O
A detailed examination shows that both intermediates (e.g., H, O and OH) and very small
amounts of other reactants than H2O are formed.
Usually net reactions have more complex rate laws than the ones above. The reaction orders a, b, c,... are
usually not integers, can be negative, depend on time and reaction conditions, and an extrapolation to
conditions where no experiments exist is not reliable or even completely wrong. In many cases, a
mechanistic interpretation of non-elementary rate laws is not possible.
The resolution of chemical kinetics into elementary reactions is a hard and time-consuming task. But the
concept of using elementary reactions has many advantages: The reaction order of elemtary reactions is
always constant (in particular, independent of time and of experimental conditions) and can be determined
easily. One only has to look at the molecularity of the reaction.
In fact, only three possible values of the reaction molecularity are observed:
Unimolecular reactions:
Dissociation or rearrangement of molecules A products. First-order rate law: if the initial concentration
is doubled, the reaction rate is also doubled.
Bimolecular reactions:
Reactions of two atoms or molecules A + B products or A + A products. They have always secondorder rate laws: doubling of the concentration of each reaction partner quadruples the reaction rate.
Bimolecular reactions are the reaction type found most.
Trimolecular reactions:
Usually recombination reactions A + B + C products or A + A + B products or A + A + A
products. They obey a third-order rate law.
In general the molecularity equals the order of elementary reactions. Thus, the rate laws are easily derived.
For a mechanism
S

rs ( r ) A s
s =1

( p)
rs

As

r = 1,..., R

s =1

with R reactions and S species the rate law for the formation of species i is given by the general expression:
ci

t chem
(r)

r =1

kr ( ri ( p ) ri ( r ) )

(p)

rs ( r )

i = 1,...,S

s =1

Here ri , rs denote stoichiometric coefficients of reactants and products and ci concentrations.

20

5.3 Relation of Forward and Reverse Reactions

For the forward and reverse reaction of the trimolecular reaction

H + H + M
H2 + M

one obtains the rate laws

d[ H ]
2
= 2 k ( f ) [H] [M]
dt foreward

d[ H ]
dt reverse

= 2 k ( r ) [H 2 ] [M]

At chemical equilibrium, no net reaction can be observed on a macroscopic level (on a microscopic level,
forward and backward reactions have the same rate). Therefore, in chemical equilibrium one has
2 k ( f ) [H] 2 [M] = 2 k ( r ) [H 2 ] [M]
k ( f ) [H 2 ]
=
= Kc
k ( r ) [H] 2
(f)

(r)

and so the law of mass action leads to the correlation Kc = k /k .

Naturally one obtains analogous relations for all other elementary reactions.

5.4 Experimental Investigation of Elementary Reactions

Reactors:
Usually static reactors or flow reactors are used.
Generation of the Reactive Species:
Usually reactive atoms (e.g., H, O, N, ... ) or radicals (e.g., OH, CH, CH2, CH3, C2H5, ...) have to be
produced as reactants. This is either done by a microwave discharge, flash photolysis, laser photolysis, or
thermally using high temperatures .
Analysis:
The concentration measurement has to be very fast and sensitive (if, e.g., the reaction rate of bi- or
trimolecular reactions is slowed down by dilution). Methods used are mass spectroscopy, electron spin
resonance, all kinds of optical spectroscopy and gas chromatography.

5.5 Temperature Dependence of Rate Coefficients

According to Arrhenius, this temperature dependence can be described by
k = A exp(-Ea/RT).
The activation energy Ea corresponds to an energy barrier which has to be overcome during the reaction.
For T the exponential term tends to 1 and the reaction rate coefficient is only governed by the
preexponential factor.

21

Ea forward

reaction

reactants

Ea

reverse reaction

reaction coordinate
b

Accurate measurements show a temperature dependence of the preexponential factor A = A' T , which,
however, is usually small in comparison to the exponential dependence .
For unimolecular reactions, the reciprocal value of A corresponds to a mean lifetime of an activated
molecule. In dissociation reactions, this lifetime is determined by the frequency of the vibration of the bond
which is broken. Typically, the preexponential factor is given by twice the frequency of the bond vibration
14
17 -1
(A = 10 -10 s ).
For bimolecular reactions the preexponential factor A corresponds to a product of collision rate and
13
14
3
.
probability of reaction. The kinetic theory of gases yields values of 10 -10 cm /mol s for A.
In trimolecular reactions, a third collision partner has to hit the bimolecular reaction complex in order to
remove the energy of the bimolecular reaction. The simultaneity of the collision of three reacting
molecules is hard to define. Therefore a useful rule of thumb does not exist.

22

6. Reaction Mechanisms
Reaction mechanisms of elementary reactions can be very large (thousands of reactions, hundreds of
substances, if high hydrocarbons like i.e. octan are burned).
Principle:
formation of reactive species (atoms and radicals), e.g.: O, H, OH, CH3
reactive species attack the hydrocarbon
principle questions:

1. How are the reactive species formed?

2. How are the hydrocarbons oxidized?

6.1 Radical Chain Reactions (example: hydrogen/oxygen-system)

(0)

H2

O2

chain initiation (reaction rate I)

2 OH

(1)
OH + H2 =
H2O +
H
(2)
H
+ O2 =
OH +
O
(3)
O + H2 =
OH +
H
___________________________________________________
(1+2+3)
2H2 + O2 =
H + OH + H2O

chain propagation
chain branching
chain branching

(4)
(5)

chain termination on the wall

chain termination (homogeneous)

H
H + O2 + M

=
=

1/2 H2
HO2 +

For the speed of formation of the free valences (H-, -OH, -O-) we obtain (O atoms counted twice)

d ([H] + [OH] + 2[O]) / dt = J + 2 k2 [O 2 ] k4 k5 [O 2 ][M])[H]

If, as a very crude approximation, the concentraction of the hydrogen atoms [H] is replaced by the
concentraction [n] of the free valences, one abtains (with f = 2k2[O2] and g = k4 + k5 [O2][M]):
d[n] / dt = J + ( f g) [n]
Given he initial conditions [n]0 = 0 at t = 0 the result is:
for g = f

[ n] = J t

for g f

[ n] =

J
1 exp [( f g) t ]
g f

23

[n]

g<f

g=f

g>f
t

Three cases:
g > f: For t results [n] = J/(g-f), that means, a stationary solution is obtained for the chain carriers,
and an explosion does not take place.
g = f: For this limiting case a linear increase of the chain barriers [n] with time t is obtained.
g < f : For t the "1" can be neglected in comparison to an exponential term after a short time,
and the result is an exponential growth of the radical concentration and thus an explosion:

[ n]

J
exp [( f g) t ]
f g

6.2 Combustion of Hydrocarbons

Combustion process: several hundred species react in more than several thousand reactions
In flammes: Radicals (H, O, or OH) attack the hydrocarbon R-H (like octan, C8H18) forming a radical
R.
H, O, OH + RH H2, OH, H2O + R (H-atom abstaction).
which then decomposes to an alkene and a smaller radical R'. This is called -decomposition.

R' CH2 C H R"

R' + CH2=CH R"

(-decomposition),

Finally, after successive decomposition, the radicals methyl (CH3) and ethyl (C2H5) are formed.

H2
Oxidation

CO
Oxidation

CH 3 OH
Oxidation

CH 4 /C 2H 6
Oxidation

Cn H 2n+2 (n>2)
Oxidation

24

alkane
+HO 2, H, O, OH

-H2O 2, H2, OH, H2O

alkyl

+O2

alkene

CH4

C2H6

CH3

C2H5

CH2O

C2H4

CHO

C2H3

CO

C2H2

CO2

CH2

-HO 2
+M

-alkene

smaller alkyl

+O2

alkene

-HO 2

etc.

CH

CH3 , C2 H5

1.
H2-O2 Mechanism
1.1 H2-O2 Chain reactions
O2
+H
=OH
+O
H2
+O
=OH
+H
H2
+OH
=H2O
+H
OH
+OH
=H2O
+O
1.2 Recombination reactions
H
+H
+M*
=H2
H
+OH
+M*
=H2O
O
+O
+M*
=O2
1.3 HO2 Formation/Consumption
H
+O2
+M*
=HO2
HO2
+H
=OH
+OH
HO2
+H
=H2
+O2
HO2
+H
=H2O
+O
HO2
+O
=OH
+O2
HO2
+OH
=H2O
+O2
1.4 H2O2 Formation/Consumption
HO2
+HO2
>H2O2
+O2
OH
+OH
+M*
=H2O2
H2O2
+H
=H2
+HO2
H2O2
+H
=H2O
+OH
H2O2
+O
=OH
+HO2
H2O2
+OH
=H2O
+HO2
2. CO-CO2 Mechanism
2.1 CO-CO2 Reactions
CO
+OH
=CO2
CO
+HO2
=CO2
CO
+O
+M*
CO
+O2
=CO2
3. C1 Mechanism
3.1 Consumption of
CH
+O
CH
+O2
CH
+CO2
3.2 Consumption of
CHO
+H
CHO
+O
CHO
+O
CHO
+OH
CHO
+O2
CHO
+M*

CH
=CO
=CHO
>CHO
CHO
=CO
=CO
=CO2
=CO
=CO
=CO

+H
+OH
=CO2
+O

A(cm,mol,s)
2.20E+14
5.06E+04
1.00E+08
1.50E+09

E(kJ/mol)

0.00
2.67
1.60
1.14

70.3
26.3
13.8
0.4

+M*
+M*
+M*

1.80E+18 -1.00
2.20E+22 -2.00
2.90E+17 -1.00

0.0
0.0
0.0

+M*

2.30E+18 -0.80
1.50E+14 0.00
2.50E+13 0.00
3.00E+13 0.00
1.80E+13 0.00
6.00E+13 0.00

0.0
4.2
2.9
7.2
-1.7
0.0

(
(
(
(
(
(

15,
17,
19,
21,
23,
25,

16)
18)
20)
22)
24)
26)

2.50E+11 0.00
3.25E+22 -2.00
1.70E+12 0.00
1.00E+13 0.00
2.80E+13 0.00
5.40E+12 0.00

-5.2
0.0
15.7
15.0
26.8
4.2

(
(
(
(
(
(

27
28,
30,
32,
34,
36,

)
29)
31)
33)
35)
37)

(
(
(
(

38,
40,
42,
44,

39)
41)
43)
45)

+M*

4.40E+06
1.50E+14
7.10E+13
2.50E+12

1.50
0.00
0.00
0.00

-3.1
98.7
-19.0
200.0

+H
+O
+CO

4.00E+13
3.00E+13
3.40E+12

0.00
0.00
0.00

0.0
0.0
2.9

+H2
+OH
+H
+H2O
+HO2
+H

2.00E+14
3.00E+13
3.00E+13
1.00E+14
3.00E+12
7.10E+14

0.00
0.00
0.00
0.00
0.00
0.00

0.0
0.0
0.0
0.0
0.0
70.3

+M*

+M*

25

(
(
(
(

No.
1,
3,
5,
7,

2)
4)
6)
8)

( 9, 10)
( 11, 12)
( 13, 14)

( 46, 47)
( 48, 49)
( 50
)
(
(
(
(
(
(

51,
53,
55,
57,
59,
61,

52)
54)
56)
58)
60)
62)

3.3 Consumption
CH2
+H
CH2
+O
CH2
+O2
CH2
+O2
3.4 Consumption
CH2O
+H
CH2O
+O
CH2O
+OH
CH2O
+HO2
CH2O
+CH3
CH2O
+M*
3.5 Consumption
CH3
+H
CH3
+O
CH3
+OH
CH3
+OH
CH3
+O2
CH3
+CH3
CH3
+M
CH3
+CH3
CH3
+CH2
3.6 Consumption
CH4
+H
CH4
+O
CH4
+OH
CH4
+HO2
CH4
CH4
+CH2
CH4
+CH

of CH2
=CH
>CO
>CO
>CO2
of CH2O
=CHO
=CHO
=CHO
=CHO
=CHO
=CHO
of CH3
=CH2
=CH2O
>CH2O
>CH2O
>CH2O
=C2H6
=CH2
>C2H4
>C2H4
of CH4
=H2
=OH
=H2O
=H2O2
=CH3
=CH3
=C2H4

4. C2 Mechanism
4.1 Consumption of
C2H
+O
C2H
+H2
C2H
+O2
4.2 Consumption of
C2HO
+H
C2HO
+O
4.3 Consumption of
C2H2
+O
C2H2
+O
C2H2
+OH
C2H2
+M
4.4 Consumption of
CH2CO
+H
CH2CO
+O
CH2CO
+OH
CH2CO
+M*
4.5 Consumption of
C2H3
+H
C2H3
+O
C2H3
+O2
C2H3
4.6 Consumption of
CH3CO
+H
CH3CO
+O
CH3CO
+CH3
CH3CO
4.7 Consumption of
C2H4
+H
C2H4
+O
C2H4
+OH
C2H4
+CH3
C2H4
+M*
4.8 Consumption of
CH3CHO
+H
CH3CHO
+O
CH3CHO
+OH
CH3CHO
+HO2

C2H
=CO
=C2H2
=C2HO
CH-CO
=CH2
>CO
C2H2
=CH2
=C2HO
=H2O
=C2H
CH2-CO
=CH3
=CHO
=CH2O
=CH2
C2H3
=H2
=CH2CO
>CH2O
=C2H2
CH3-CO
=CH2CO
=CH3
=C2H6
=CH3
C2H4
=C2H3
>CH3CO
=C2H3
=C2H3
=C2H2
CH3-CHO
=CH3CO
=CH3CO
=CH3CO
=CH3CO

+H2
+H
+OH
+H
+H2
+OH
+H2O
+H2O2
+CH4
+H
+H2
+H
+H
+H2
+H

+H
+H
+H

8.40E+09
8.00E+13
6.50E+12
6.50E+12

1.50
0.00
0.00
0.00

1.4
0.0
6.3
6.3

(
(
(
(

63, 64)
65
)
66
)
67
)

+M*

2.50E+13
3.50E+13
3.00E+13
1.00E+12
1.00E+11
1.40E+17

0.00
16.7
( 68, 69)
0.00
14.6
( 70, 71)
0.00 5.0
( 72, 73)
0.00
33.5
( 74, 75)
0.00
25.5
( 76, 77)
0.00
320.0
( 78, 79)

1.80E+14 0.00
7.00E+13 0.00
9.00E+14 0.00
8.00E+12 0.00
1.50E+13 0.00
7.47E+52-11.90
1.00E+16 0.00
1.00E+16 0.00
1.00E+13 0.00

63.0
0.0
64.8
0.0
120.0
80.2
380.0
134.0
0.0

(
(
(
(
(
(
(
(
(

+CH3
+CH3
+CH3
+CH3
+H
+CH3
+H

2.20E+04 3.00
1.20E+07 2.10
1.60E+06 2.10
4.00E+12 0.00
3.20E+34 -6.00
1.30E+13 0.00
3.00E+13 0.00

36.6
31.9
10.3
81.2
457.5
39.9
-1.7

( 93, 94)
( 95, 96)
( 97, 98)
( 99,100)
(101,102)
(103,104)
(105,106)

+CH
+H
+O

1.00E+13
1.10E+13
5.00E+13

0.00
0.00
0.00

0.0
12.0
6.3

(107,108)
(109,110)
(111,112)

+H

3.00E+13
1.00E+14

0.00
0.00

0.0
0.0

(113,114)
(115
)

+M

4.10E+08
4.30E+14
1.00E+13
3.60E+16

1.50
0.00
0.00
0.00

7.1
50.7
29.3
446.0

(116,117)
(118,119)
(120,121)
(122,123)

+M*

7.00E+12
1.80E+12
1.00E+13
1.00E+16

0.00
0.00
0.00
0.00

12.6
5.6
0.0
248.0

(124,125)
(126,127)
(128,129)
(130,131)

+C2H2
+H
+CHO
+H

2.00E+13 0.00
3.00E+13 0.00
1.50E+12 0.00
1.60E+32 -5.50

0.0
0.0
0.0
193.5

(132,133)
(134,135)
(136
)
(137,138)

+H2
+CO2
+CO
+CO

2.00E+13 0.00
2.00E+13 0.00
5.00E+13 0.00
2.30E+26 -5.00

0.0
0.0
0.0
75.2

(139,140)
(141,142)
(143,144)
(145,146)

+H2
+H
+H2O
+CH4
+H2

1.50E+14
1.60E+09
3.00E+13
4.20E+11
2.50E+17

0.00
1.20
0.00
0.00
0.00

42.7
3.1
12.6
46.5
319.8

(147,148)
(149
)
(150,151)
(152,153)
(154,155)

4.00E+13
5.00E+12
8.00E+12
1.70E+12

0.00
0.00
0.00
0.00

17.6
7.5
0.0
44.8

(156,157)
(158,159)
(160,161)
(162,163)

+H
+H2
+H

+CO
+CO
+CO
+H
+C2H
+H
+CO
+CHO
+CHO
+CO

+H
+O
+M

+M*

+H2
+OH
+H2O
+H2O2

26

80,
82,
84
85
86
87,
89,
91
92

81)
83)
)
)
)
88)
90)
)
)

CH3CHO
+CH2
=CH3CO
+CH3
2.50E+12 0.00
15.9
(164,165)
CH3CHO
+CH3
=CH3CO
+CH4
8.50E+10 0.00
25.1
(166,167)
CH3CHO
=CH3
+CHO
2.00E+15 0.00
331.0
(168,169)
4.9 Consumption of C2H5
C2H5
+H
=CH3
+CH3
3.00E+13 0.00
0.0
(170,171)
C2H5
+O
=CH3CHO +H
5.00E+13 0.00
0.0
(172,173)
C2H5
+O2
=C2H4
+HO2
2.00E+12 0.00
20.9
(174,175)
C2H5
+CH3
=C3H8
7.00E+12 0.00
0.0
(176,177)
C2H5
+C2H5
=C2H4
+C2H6
1.40E+12 0.00
0.0
(178,179)
C2H5
=C2H4
+H
1.00E+43 -9.10
224.1
(180,181)
4.10 Consumption of C2H6
C2H6
+H
=H2
+C2H5
5.40E+02 3.50
21.8
(182,183)
C2H6
+O
=OH
+C2H5
3.00E+07 2.00
21.4
(184,185)
C2H6
+OH
=H2O
+C2H5
6.30E+06 2.00
2.7
(186,187)
C2H6
+HO2
=H2O2
+C2H5
6.00E+12 0.00
81.2
(188,189)
C2H6
+CH3
=C2H5
+CH4
5.50E-01 4.00
34.7
(190,191)
C2H6
+CH2
=CH3
+C2H5
2.20E+13 0.00
36.3
(192,193)
C2H6
+CH
=H
+C3H6
1.10E+14 0.00
-1.1
(194,195)
------------------------------------------------------------------------. b.
k
= A T exp(-E/RT); A (cm, mol, s), b (-), E (kJ/mol)
.
.
.
.
.
.
[M*] = [H2]+6.5 [H2O]+0.4 [O2]+0.4 [N2]+0.75 [CO]+1.5 [CO2]+3.0 [CH4]

6.3 Quasi-Steady States

Consider the following reactions: S1

12

S2

23

S3

The rate laws for the different species are:

d[S1 ]
d[S2 ]
d[S3 ]
= k12 [S1 ]
= k12 [S1 ] k23 [S2 ]
= k23 [S2 ]
dt
dt
dt
It shall be assumed that S2 is a very reactive species and thus has a short live time (k23 >> k12). Then the

rate rate of consumption of S2 is approximately equal to the rate of formtaion of S2, such that it can be written
as an approximation :
(quasi-steady state assumption):

d[S2 ]
= k12 [S1 ] k23 [S2 ] 0
dt

If one is interested in the rate of formation of the product S3, the rate law for S3 is difficult to interpret,
because only the concentration of the intermediate S2 appears in the rate law for S3. However, using the
quasi-steady state assumption, one obtains the simple relationship

d[S3 ]
= k12 [S1 ]
dt

[S3 ] = [S1 ]0 1 exp( k12 t ) + [S3 ]0

and thus:

Example: Combustin of hydrogen with chlorine

(1)

Cl2 + M

Cl

+ Cl + M

(2)
(3)

Cl
H

+ H2
+ Cl2

HCl
HCl

+ H
+ Cl

(4)

Cl

+ Cl

Cl2

+ M

+ M

Using the steady-state assumption , the rate law for the intermediates H and Cl is given by:
1
1
k
d[HCl]
= 2 k2 1 [Cl 2 ] 2 [H 2 ] = kgesamt [Cl] 2 [H 2 ]
k4
dt

27

The concept of the quasi-steady state assumption simplifies the mathematical treatment of the rate laws.
The reaction of hydrogen with chlorine is an example which shows that the rate law of the overall reaction
H 2 + Cl 2 2HCl does not have the reaction order 2 (as one would naively expect), but the order 1.5.

6.5 Partial Equilibrium

An analysis of experiments or simulations shows that at high temperatures (T > 1800 K bei p = 1 bar)
the reaction rates of forward and backward reactions are so fast that for the reactions
(1,2)
H + O2 = OH + O
O + H2 = OH + H
(3,4)
OH+ H2

H2O+ H .

(5,6)

k2 [OH] [O]

are in so-called partial equilibria.

k1 [H] [O2]

k3 [O] [H2] =
k5 [OH] [H2] =

k4 [OH] [H]
k6 [H2O] [H] .

This equation system can be solved for [O],[H] and [OH] yielding:
1

[H]

k k k 2 [O ][H ]3 2
= 1 3 5 2 2 22
k2 k4 k6 [H 2 O]

[O] =

k1k5 [O 2 ][H 2 ]
k2 k6 [H 2 O]

[OH]

kk
2
= 1 3 [O 2 ][H 2 ]

k2 k4

The concentration of these unstable species can be expressed in terms of the concentration of the stable
species H2, O2 and H2O.
%
1.5

T/K
C3H 8

1800

1600
1400
1.0
1200

O (partial equilibrium)

C3H 8

O (detailed mechanism)

0.5

O (equilibrium)

z / mm

0
0

0.5

1.0

1.5

Mole fractions of O in a premixed stoichiometric C3H8-air-flame at p = 1 bar, Tu = 298 K, calculated

using a full mechanism, the partial equilibrium assumption, and the assumption of a complete
equilibrium (essential for the understanding of thermal NO formation)

28

7. Laminar Premixed Flames

7.1 Flame Structures

acetylene-oxygen flame at a pressure of 100 mbar; concentration profiles are determined using mass
spectroscopy, temperature measured using Na-D-line reversal

7.2 Flame Velocities

Pressure dependence

Pressure dependence of vl in stoichimetric CH4-air-mixtures

29

A simple expression for the flame velocity is given by the theory of Zeldovich for a single step reaction:
vl

n
1
2

E
2 R Tb

Where n denotes the reaction order, E the activation energy and Tb the burnt gas temperature.
The figure above clearly shows the weakness of the single-step model: The reaction order 2 or 3 of the
rate-limiting steps (see next paragraph) predicts no pressure dependence or even a positive pressure
dependence; the numerical results, however, show a negative pressure dependence.
Concentration dependence
-1
v
cm.ss -1 )
vLL // (cm

C2 H4
80

60

C4 H8
C6 H6

C3 H6
C 2 H5 OH

CH 3OH

40

20

Vol-%
fuel
% fuel

0
0

10

15

-1
vvL // c
m. s -1
L (cm s )

80

C4 H10
n-C 7 H16 C 3 H8

60

C 2 H6

CH 4

C2 H2 (vu /2)

40

20

Vol-%
fuel
% fuel

0
0

10

15

Laminar flame velocitiy vl for hydrocarbon-air-mixtures at p = 1 bar, Tu = 298 K. Points:

experiments, Lines: detailed simulations

30

7.3 Sensitivity Analysis

The rate laws for a reaction mechanism consisting of R reactions among S species can be written as a system
of first order ordinary differential equations dci / dt = Fi (c1 ,K, cS ; k1 ,K, k R ) ; i = 1,L, S The time t is the
independet variable, The concentrations ci of species i are dependent variables, and kr the parameters of
the system. The dependence of the solution ci on the parameters kr is called sensitivity:
ci
kr

Ei , r

bzw.

)
Ei(,rel
r

kr ci
ci kr

Result of a sensitivty analysis:

high values of relative sensitivities with respect to the slow (i.e., rate-limiting) reactions
low values of relative sensitivities with respect to the fast (and, thus, not rate-limiting) reactions
A sensitivity analysis can identify the rate limiting reactions! Thus sensitivity analysis is a valuable tool
for a deeper understanding of complex reaction mechanisms.
Sensitivity analyses for the flame velocity show similar results for all aliphatic hydrocarbon-air mixtures:
Relative Sensitivity

Lean Flame
Stoich. Flame
Rich Flame

2.0
1.5

1.0

0.5
0.0
-0.5
Reaction

-1.0
0

1 5 1 7 2 5 3 8 3 9 5 1 6 1 1 5 01 8 0

Sensitivity analysis for the laminar flame velocity of a CH4-air flame with respect to the rate
coefficients of the involved elementary reactions.
the results are quite independent of the equivalence ratio
reaction 1:
reaction 15:
reaction 38:

strongly rate-limiting (slowest chain branching reaction)

H + O2 OH + O
H + O2 + M HO2 + M negative sensitivity because of its chain-terminating character
CO + OH CO2 + H
governs the heat release and is rate-limiting, too

31

7.4 Reaction Flow Analysis

One considers the percentage of a species s (s=1,...,S) in the reaction r (r=1,...,R) formed (or consumed),
in which it will be integrated on over the complete reaction time. A number scheme of the following form
is given, and the reaction flows can be identified:
Species
reaction

1
2
3
.
.
.
R-1
R

.....

S-1

20%
0%
2%
.
.
.
78%
0%

3%
0%
5%
.
.
.
90%
2%

0%
0%
0%
.
.
.
100%
0%

.....
.....
.....
.
.
.
.....
.....

0%
0%
100%
.
.
.
0%
0%

0%
0%
90%

5%
5%

A reaction can be regarded as unimportant (here e.g. reaction 2) if all entries in a row are below a certain
limit.

Integral reaction flow analysis in a premixed stochiometric (left) and rich (right) CH4-air-flame at p = 1
bar, Tu = 298 K (Warnatz 1984)

32

8. NO-Formation
Problem: NO-formation is kinetically controled. It is very slow and often characteristic time scales are
longer than the residence time.
Typically the assumption of NO being in chemical equilibrium is wrong.

NO-concentrations in H2-air flames with different stoichiometries, experimental (symbols)

and computational (curves) results
How can the stable nitrogen molecule be attacked in order to react?

8.1 Thermal NO (Zeldovich-NO)

thermal because the reaction occurs only at high temperatures (the rate limiting reacrtion has a high
activation energy).
O + N2

NO + N

k1=1,81012 exp (-319 kJmol-1/RT) cm3/(mols)

N + O2

NO + O

k2=6,4109 exp (-26 kJmol-1/RT) cm3/(mols)

N + OH

NO + H

k3=3,01013 cm3/(mols)

for the rate of NO-formation we obtain:

d[NO]
= k1[O][N 2 ] + k2 [N][O 2 ] + k3 [N][OH]
dt
reactive N-atoms can be assumed to be in a quasi steady state

d[N]
= k1[O][N 2 ] k2 [N][O 2 ] k3 [N][OH] 0 i.e.
dt

k1[O][N 2 ] k2 [N][O 2 ] + k3 [N][OH]

and we obtain

d[NO]
= 2 k1[O][N 2 ]
dt

33

Problem: How can we determine [O]?

The simple method to use the equilibrium concentration can lead to results wrong by a factor of 10 (superequilibrium in the flame front).
Better choice: partial equilibrium assumption
For (T > 1800 K bei p = 1 bar) we obtain partial equilibria (forward and reverse rate are equal) for the
following reactions:
OH

+ H2

+ O2

k1
k2
k3

H2O + H

(1,2)

OH

+ O

(3,4)

OH

+ H

(5,6)

k4
k5

+ H2

k6

k1[OH][H2] = k2[H2O][H]

k3[H][O2] = k4[OH][O]

k5[O][H2] = k6[OH][H]

Solve for [H], [O], and [OH]:

1

k 2 k k [ O ][ H 2 ]3 2
[H] = 1 3 5 2
2
k2 k4 k6 [ H 2 O ]

k k [O ][H 2 ]
[O] = 1 3 2

k2 k4 [H 2 O]

k k
2
[OH] = 3 5 [O 2 ][H 2 ]
k4 k6

This means: The O-atom concentration can be calculated from the concentrations of H2O, O2 and H2. The
formulas are only valid at high temperatures (T > 1700 K, see figure below); but because the thermal NOformation is negligible anayway at lower temperatures (high activation energy), this does not matter.

Calculated O-atom-concentrations in a propane-air flame

Thermal NO is formed if
N2 is present
the temperature is high (above app. 1700 K)
the O-atom concentration is high

34

8.2 Prompt NO (Fenimore-NO)

The mechanism of prompt NO formation (also named Fenimore-NO after Fenimore, who postulated this
mechanism) is associated with the CH-radical. CH reacts with molecular nitrogen to form HCNwhich then
reacts fast to NO:

d[N 2 ]
= k[CH][N 2 ]
dt

CH + N2 (HCN + N) NO

rate coefficient of the rate limiting step CH + N2 is not know very well.
activation energy of CH + N2 (HCN + N) NO is only 57 kJ/mol (cf. 319 kJ/mol for thermal NO)
Therefore prompt NO occurs also at lower temperatures (down to 1000 K).

CH-radicals are formed by decomposition of C2H2, which itself is formed under rich conditions.
In non-premixed combustion: Even for globally lean mixtures locally rich conditions exist
Therefore prompt NO-formation is important in non-premixed flames.
Prompt NO is formed if:
N2 is present
rich conditions are present at least locally (leading to a sufficiently large CH-radical-concentration)

35

ppm NO
120
Thermal + prompt NO

100
80
60
40
20
0

Thermal NO

0.4

0.6

0.8

1.0

1.2

1.4

1.6

NO-formation in a stirred reactor; dependence on air equivalence ratio = 1/ (Bartok et al. 1972, Glarborg et
al. 1986)

8.3 NO-formation via N2O

at high pressures NO formation via N2O becomes important
N2O + M

+ N2O

NO

+ NO

+ N2O

N2

+ O2

+ N2

O
O

+ M

Ea = 97 kJ/mol

note the two competing reactions

O + N2
O + N2

+ M

NO

+ N

N2O

+ M

d[N 2 ]
= ka [O][N 2 ] p 2
dt
d[N 2 ]
= ka [O][N 2 ][M] p3
dt

thermal NO

8.4 Conversion of fuel-nitrogen to NO

imortant in coal combustion, because coal contains about 1% nitrogen, which, during the degasification
is transfered into the gas phase and leads to NO-formation.
reaction to species like NH3 and HCN is fast and not rate limiting, oxidation to NO is rate limiting
NH 3
Fuel Nitr ogen

HCN
CN

OH

O2

HNCO
NCO

HCN

NH2
NH

CH i

O2 , OH
NO

NO

NH i

N2

CH i

model system: propane-air flame doped with 2400 ppm CH3-NH2 (methylamine)
lean conditions ( < 1.0): about 2/3 of the N transformed into NO, rest is transformed into N2.
rich conditions ( > 1.0): NO-formation decreases, but HCN (cyanic acide) and NH3 (ammonia) are
formed, which are finally oxidized to NO in the atmosphere.
minimum of pollutants at = 1.4 (maximum conversion to N2).

36

rate limiting reactions (according to a sensitivity analysis):

N

OH

NO

NO

N2

The rate coefficients of these reactions are known quite well. Thus, fuel nitrogen conversion can be
calculated reasonably well.

8.5 NO-Reduction by primary methods

staged combustion
1. rich combustion (at about = 1,4) yields a maximum of N2
2. lean combustion (to get an overall stoichiometric combustion)
N2 formed during the first stage is not transformed into NO, because the temperature is kept low
additional reduction possible if the second stage is very lean, and in a third stage fuel is added to get an
overall stoichiometric combustion (in this way NO is reduced by the reaction NO + CH3 products
(reburn).

Zone of high NO production

Tstoich.

Final
products

Nonpremixed

Tfinal
RQL

RQL

LPC

T0
0
Air

final stoich.

1
Fuel

NO-reduction strategies: LPC = lean premixed combustion, RQL = rich-quick-lean

37

low combustion temperatures

addition of "inert gases"
problem: stability

exhaust gas recirculation

catalytically supported combbustion

8.6 NO-Reduction by secondary methods

selective homogeneous reduction of NO (SHR, thermal DeNOx)
addition of ammonia (NH3) to the exhaust gases
at high enough temperatures this NH3 reacts with OH to NH2, which reduces the NO to water and N2

high temperatures lead to an oxidation of NH2 to NO SHR only possible within a narrow temperature
window

ratio of NH3 and NO must be low ([NH3]/[NO] < 1,5), because otherwise NH3-gets into the atmosphere
where it is again oxidized to NOx
good mixing necessary (e.g. by fast injection of the ammonia together with water vapor)
selective catalytic reduction (SCR) of NO: use of a catalytic converter
advantage: temperature window is no longer critical
disadvantage: high cost, sensitivity
catalytic converter in cars: operation at stoichiometric conditions

38

9. Unburned Hydrocarbons and Soot

9.1 Flame extinction due to strain
Flames may extinguish due to intensive turbulence which perturbs the flames.
Lean and rich flames are particularly sensitive with respect to strain (reason for high UHC emissions of
lean engines)

9.2 Flame extinctions at walls and in gaps

Extinction of a flame front parallel to a wall
quenching distance of the order of the flame thickness
reason for quenching: low temperature, destruction of radicals
flame position [mm]
0,16
0,14
0,12
0,10
0,08
0,06
0,04

moving flame front

0,02
0,00
-0,3

wall

t - t q [ms]
-0,2

-0,1

0,0

0,1

0,2

0,3

After extinction the unburned mixture diffuses into the burned gases and is thus finally burned. Therefore
this effect does not contribute much to the formation of unburned hydrocarbons
Extinction of a flame front perpendicular to a wall
Extinction in Gaps
Most important contribution to unburned hydrocarbons

moving flame front

moving flame front

Weiter Spalt

wall
narrow gap

39

9.3 Formation of polycyclic aromatic hydrocarbons (PAH)

Higher hydrocarbons are decomposed into small fragments during combustion (C1- and C2-species).
A subsequent build-up of higher hydrocarbons can take place polycyclic aromatic hydrocarbons
precursor: acetylen (C2H2) which is formed under fuel rich conditions
% Acetylen

0.6

0.8

1.0

1.2

1.4

dependence of C2H2-formation in CH4-O2 flames on the equivalence ratio (Wagner 1979)

reaction of CH or CH2 with C2H2 leads to C3H3, which can recombine and form the first ring (benzene)
H 2C

CH

2 C3 H3

CH
C

H 2C

further addition of C2H2 leads to a growth of the ring structures

40

+ C2H

-H

Pi,3

Pi,1
Pi,2
+ C2H2, - H

-H

+ C2H2

Pi,5

Pi,4

log x

log x

-2

-2

-3

-3

-4

-4

-5

-5

-6

-6

-7

-7

z / cm

z / cm
0

0.5

1.0

0.5

1.0

Measuresd (Bockhorn et al. 1983, left) and calculated (Frenklach and Warnatz 1987, right) PAH-profiles in a rich
laminar premixed C2H2-O2-Ar-Flamme at low pressure

41

9.4 Soot Formation

Soot is formed by a continuous growth of the PAH. Freshly formed soot consists of polyaromatic structures
with a molar ration of H/C of about 1; aging leads to a higher carbon content
Reaction time

d 50 nm
Coagulation
Surface growth
and coagulation
Particle inception
Particle zone

d 0.5 nm

H2
CO2

CO

O2
H 2O

Molecular zone
Premixed fuel and oxidizer
mechanism of soot formation (Bockhorn 1994)

Picture of a soot particle in a non-premixed flame (Dobbins and Subramaniasivam 1994)

42

dependence of sooting limits on C/O-ratio at 1800 K (Haynes und Wagner 1981)

Combustion system
CH4-O2
C2H6-air
C3H8 -air
C2H4-air
C2H4-O2
C4H8-air
C2H2-air
C2H2-O2 (T 3000 K)
C6H6 -air
C6H6-O2
C11H10-air

Bunsen
burner

Well stirred
reactor

0.48
0.47
0.61

0.52
0.83
0.95
0.57

0.42

0.70

0.68

0.57

0.50

Flat flame
1 bar 26 mbar
0.45
0.47
0.53
0.60
0.71

0.65

0.95

0.74

use: as color in printers, in tires

soot formation starts at 1500 K. High temperatures cause a decomposition of the precursors, at low
temperatures precursors are not formed

43