2.

Chemical Kinetics
Introduction:
• Thermodynamic laws allow determination of the
equilibrium state of a chemical reaction system.
• If one assumes that the chemical reactions are fast
compared to the other transport processes like
- diffusion,
- heat conduction, and
- flow,
• then, thermodynamics describe the system locally.

2. Chemical Kinetics 1 AER 1304–ÖLG

Introduction (Cont’d):
• In most combustion cases, however, chemical reac-
tions occur on time scales comparable with that of
the flow and the molecular transport processes.
• Then, information is needed about the rate of
chemical reactions.
• Chemical reaction rates control pollutant forma-
tion, ignition, and flame extinction in most com-
bustion processes.

2. Chemical Kinetics 2 AER 1304–ÖLG

 Global & Elementary Reactions
• An elementary reaction is one that occurs on a
molecular level exactly in the way which is de-
scribed by the reaction equation.
OH + H2 → H2 O + H

• The equation above is an elementary reaction. On

the contrary, the following is not an elementary
reaction:
2H2 + O2 → 2H2 O
• Above reaction is global or overall reaction.

2. Chemical Kinetics 3 AER 1304–ÖLG

 • A general global reaction mechanism involving
overall reaction of a moles of oxidizer with one
mole of fuel to form b moles of products:

F + aOx → bPr (2.1)

• Experimental observations yield the rate at which

fuel is consumed as

d[F]
= −kG (T )[F]n [Ox]m (2.2)
dt

2. Chemical Kinetics 4 AER 1304–ÖLG

 • [X] denotes molar concentration of X, e.g.
kmol/m3 .
• kG (T ) is the global rate coefficient.
• n and m relate to the reaction order.
• According to Eqn 2.2, reaction is
- nth order with respect to fuel,
- mth order with respect to oxidant, and
- (m + n)th order overall.
• m and n are determined from experimental data
and are not necessarily integers.

2. Chemical Kinetics 5 AER 1304–ÖLG

 • Use of global reactions to express chemistry is
usually a black box approach and has limited use
in combustion.
• It does not provide a basis for understanding what
is actually happening.
• Let’s consider the following global reaction:
2H2 + O2 → 2H2 O (2.3)

• It implies that two moles of hydrogen molecule

react with one mole of oxygen to form one mole
of water, which is not strictly true.

2. Chemical Kinetics 6 AER 1304–ÖLG

 • In reality many sequential processes occur that
involve several intermediate species. Following
elementary reactions, among others, are important
in conversion of H2 and O2 to water:

H2 + O2 → HO2 + H (2.4)

H + O2 → OH + O (2.5)
OH + H2 → H2 O + H (2.6)
H + O2 + M → HO2 + M (2.7)

2. Chemical Kinetics 7 AER 1304–ÖLG

 • Radicals or free radicals or reactive species are
reactive molecules, or atoms, that have unpaired
electrons.
• To have a complete picture of the combustion of
H2 with O2 , more than 20 elementary reactions
can be considered.
• Reaction mechanism is the collection of elemen-
tary reactions to describe the overall reaction.
• Reaction mechanisms may involve a few steps or
as many as several hundred (even thousands).
• (State-of-the-art).

2. Chemical Kinetics 8 AER 1304–ÖLG

 Elementary Reaction Rates
- Using the concept of elementary reactions has
many advantages.
- Reaction order is constant and can be experimen-
tally determined.
- molecularity of the reaction: number of species
that form the reaction complex.
- Unimolecular
- Bimolecular
- Trimolecular / Termolecular

2. Chemical Kinetics 9 AER 1304–ÖLG

Bimolecular Reactions & Collision Theory
• Most combustion related elementary reactions are
bimolecular:
A+B→C+D (2.8)

• The rate at which the reaction proceeds is

d[A]
= −kbimolec [A][B] (2.9)
dt
• kbimolec ∝ f (T ) and has a theoretical basis, unlike
kG , rate coefficient of a global reaction.

2. Chemical Kinetics 10 AER 1304–ÖLG

 • Collision theory for bimolecular reactions has sev-
eral shortcomings.
• Approach is important for historical reasons and
may provide a simple way to visualize bimolecular
reactions.
• Uses the concepts of wall collision frequency,
mean molecular speed, and mean free path.
• The simpler approach is to consider a single
molecule of diameter σ travelling at constant
speed v and experiencing collisions with identi-
cal, but stationary molecules.

2. Chemical Kinetics 11 AER 1304–ÖLG

 • If the distance travelled (mean free path) between
colisions is large, then moving molecule sweeps
out a cylindrical volume of vπσ 2 ∆t.
• For random distribution of stationary molecules
with number density n/V , number of collisions
collisions
Z≡ = (n/V )vπσ 2 (2.10)
per unit time

• For Maxwellian velocity distribution for all

molecules √
Zc = 2(n/V )πσ 2 v̄ (2.11)

2. Chemical Kinetics 12 AER 1304–ÖLG

 • Eqn.2.11 applies to identical molecules. For dif-
ferent molecules, we can use σA + σB ≡ 2σAB
√ 2
Zc = 2(nB /V )πσAB v̄A (2.12)

which expresses frequency of collisions of a single

A molecule with all B molecules.
• For all A molecules
2 2 2 1/2
ZAB /V = (nA /V )(nB /V )πσAB (v̄A + v̄B )
(2.13)

2. Chemical Kinetics 13 AER 1304–ÖLG

 If we express mean molecular speed in terms of
temperature,

8kB T 1/2
2
ZAB /V = (nA /V )(nB /V )πσAB
πµ
(2.14)
kB = Boltzmann constant.
µ = (mA mB )/(mA + mB ) = reduced mass.
T = absolute temperature.

2. Chemical Kinetics 14 AER 1304–ÖLG

 • We can relate ZAB /V to reaction rates

No. of collisons Probability that

d[A] A and B molecules a collision
− = per unit volume · leads to
dt per unit time reaction

kmol of A
· (2.15a)
No. of molecules of A
or
d[A] −1
− = (ZAB /V )PNAV (2.15b)
dt

2. Chemical Kinetics 15 AER 1304–ÖLG

 • The probability that a collision will lead to a reac-
tion can be expressed as a product of two factors:
- an energy factor

exp [−EA /(Ru T )]

which expresses the fraction of collisions that

occur with an energy above the activation
energy
- a geometrical or steric factor p, that takes
into account the geometry of collisions be-
tween A and B.

2. Chemical Kinetics 16 AER 1304–ÖLG

 • With substitutions nA /V = [A]NAV and nB /V =
[B]NAV , Eqn.2.15b becomes

d[A] 8πk T 1/2

2 B
− =pNAV σAB ·
dt µ (2.16)
exp [−EA /(Ru T )][A][B]

• Comparing Eqn. 2.16 with 2.9

8πkB T 1/2 −EA

2
k(T ) = pNAV σAB exp
µ Ru T
(2.17)

2. Chemical Kinetics 17 AER 1304–ÖLG

 • Collision theory is not capable of providing any
means to determine EA or p.
• More advanced theories do allow calculation of
k(T ) from first principles to a limited extent.
• If the temperature range of interest is not too
large, kbimolec can be expressed by the semi-
empirical Arrhenius form
−EA
k(T ) = A exp (2.18)
Ru T
where A is a constant termed pre-exponential fac-
tor or frequency factor.

2. Chemical Kinetics 18 AER 1304–ÖLG

 • Most of the time the experimental values for rate
coefficients in Arrhenius form expressed as

b −EA
k(T ) = AT exp (2.19)
Ru T

where A, b, and EA are three empirical constants.

• The standard method for obtaining EA is to graph
experimental rate constant data versus inverse of
temperature, i.e. log k vs 1/T . The slope gives
EA /Ru .

2. Chemical Kinetics 19 AER 1304–ÖLG

Unimolecular Reactions:
• Involves single species

A→B (2.20)

A→B+C (2.21)

- Examples: O2 → O + O; H2 → H + H.
- First order at high pressures
d[A]
= −kuni [A] (2.22)
dt

2. Chemical Kinetics 20 AER 1304–ÖLG

 - At low pressures, the reaction rate may also de-
pend a third molecule that may exist within the
reaction volume
d[A]
= −k[A][M] (2.23)
dt
Termolecular Reactions:
A+B+M→C+M (2.24)

• Termolecular reactions are third order

d[A]
= −kter [A][B][M] (2.25)
dt

2. Chemical Kinetics 21 AER 1304–ÖLG

 Multistep Mechanisms
Net Production Rates
• Consider some of the reactions in H2 -O2 system
kf 1
H2 + O2 kr1
HO2 + H (R.1)
kf 2
H + O2 kr2
OH + O (R.2)
kf 3
OH + H2 kr3
H2 O + H (R.3)
kf 4
H + O2 + M kr4
HO2 + M (R.4)

2. Chemical Kinetics 22 AER 1304–ÖLG

 • The net production rate of any species, say X,
involved is the sum of all of the individual ele-
mentary rates producing X minus all of the rates
destroying X.
• Net production rate of O2 is then,

d[O2 ]
=kr1 [HO2 ][H] + kr2 [OH][O]
dt
(2.26)
+ kr4 [HO2 ][M] − kf 1 [H2 ][O2 ]
− kf 2 [H][O2 ] − kf 4 [H][O2 ][M]

2. Chemical Kinetics 23 AER 1304–ÖLG

 • Net production rate for H atoms:
d[H]
=kf 1 [H2 ][O2 ] + kr2 [OH][O]
dt
+ kf 3 [OH][H2 ] + kr4 [HO2 ][M] (2.27)
− kr1 [HO2 ][H] − kf 2 [H][O2 ]
− kr3 [H2 O][H] − kf 4 [H][O2 ][M]
d[Xi ](t)
= fi {[X1 ](t), [X2 ](t), ......[Xn ](t)}
dt
[Xi ](0) = [Xi ]0
(2.28)

2. Chemical Kinetics 24 AER 1304–ÖLG

Compact Notation:
• Since mechanisms may involve many elementary
steps and many species, a generalized compact
notation has been developed for the mechanism
and the individual species production rates.
• For the mechanism,
N N
νji Xj νji Xj for i = 1, 2, ...L (2.29)
j=1 j=1

where νji and νji are stoichiometric coefficients

of reactants and products, respectively.

2. Chemical Kinetics 25 AER 1304–ÖLG

 N L
j Species i Reaction
1 O2 1 R.1
2 H2 2 R.2
3 H2 O 3 R.3
4 HO2 4 R.4
5 O
6 H
7 OH
8 M

2. Chemical Kinetics 26 AER 1304–ÖLG

 • Stoichiometric coefficient matrices:
 
1 1 0 0 0 0 0 0
1 0 0 0 0 1 0 0
νji =   (2.30a)
0 1 0 0 0 0 1 0
1 0 0 0 0 1 0 1
 
0 0 0 1 0 1 0 0
0 0 0 0 1 0 1 0
νji =   (2.30b)
0 0 1 0 0 1 0 0
0 0 0 1 0 0 0 1

2. Chemical Kinetics 27 AER 1304–ÖLG

 • Net production rate of each species in a multistep
mechanism:
L
d[Xj ]/dt ≡ ω̇j = νji qi for j = 1, 2, .....N
i=1
(2.31)
where
νji = (νji − νji ) (2.32)
N N
I II
νji νji
qi = kf i [Xj ] − kri [Xj ] (2.33)
j=1 j=1

2. Chemical Kinetics 28 AER 1304–ÖLG

 • For example, qi (= q1 ) for reaction R.1 is

qi =kf 1 [O2 ]1 [H2 ]1 [H2 O]0

[HO2 ]0 [O]0 [H]0 [OH]0 [M]0
− kr1 [O2 ]0 [H2 ]0 [H2 O]0 (2.34)
[HO2 ]1 [O]0 [H]1 [OH]0 [M]0
= kf 1 [O2 ][H2 ] − kr1 [HO2 ][H]

• Writing similar expressions for i = 2, 3, and 4

and summing completes the total rate expression
for ω̇j .

2. Chemical Kinetics 29 AER 1304–ÖLG

Rate Coefficients and Equilibrium Constants:
• At equilibrium forward and reverse reaction
rates must be equal.
kf
A+B kr
C+D (2.35)

• Formation rate of species A:

d[A]
= −kf [A][B] + kr [C][D] (2.36)
dt
• For equilibrium, time rate of change of [A]
must be zero. Same goes for B, C, and D.

2. Chemical Kinetics 30 AER 1304–ÖLG

 • Then, Eqn. 2.36
0 = −kf [A][B] + kr [C][D] (2.37)

arranging
[C][D] kf (T )
= (2.38)
[A][B] kr (T )
• Previously we have defined equilibrium con-
stant as,
(PC /P o )c (PD /P o )d ...
Kp = (2.39)
(PA /P o )a (PB /P o )b ...

2. Chemical Kinetics 31 AER 1304–ÖLG

 • Since molar concentrations are related to mol
fractions and partial pressures as,

[Xi ] = χi P/(Ru T ) = Pi /(Ru T ) (2.40)

we can define an equlibrium constant based on

molar concentrations, Kc and relate it to Kp ,

Kp = Kc (Ru T /P o )c+d+...−a−b... (2.41a)

or
o Σν II −Σν I
KP = Kc (Ru T /P ) (2.41b)

2. Chemical Kinetics 32 AER 1304–ÖLG

 where, Kc is defined as,

νiII
[Xi ]
[C]c [D]d ... prod
Kc = a b
= νiI
(2.42)
[A] [B] ... [Xi ]
react

• So that,
kf (T )
= Kc (T ) (2.43)
kr (T )

• For bimolecular reactions Kc = Kp .

2. Chemical Kinetics 33 AER 1304–ÖLG

Steady-State Approximation
• Analysis of reactive systems can be simplified
by applying steady-state approximation to the
reactive species or radicals.
• Steady-state approximation is justified when
the reaction forming the intermediate species is
slow, while the reaction destroying the interme-
diate species is very fast.
• As a result the concentration of the radical is
small in comparison with those of the reactants
and products.

2. Chemical Kinetics 34 AER 1304–ÖLG

 • Example (Zeldovich mechanism for NO forma-
tion):
k1
O + N2 −→ NO + N
k2
N + O2 −→ NO + O

First reaction is slow (rate limiting); while sec-

ond is fast.
• Net production rate of N atoms,
d[N]
= k1 [O][N2 ] − k2 [N][O2 ] (2.44)
dt

2. Chemical Kinetics 35 AER 1304–ÖLG

 • After a rapid transient allowing buildup of N,
d[N]/dt approaches zero.

0 = k1 [O][N2 ] − k2 [N]ss [O2 ] (2.45)

k1 [O][N2 ]
[N]ss = (2.46)
k2 [O2 ]
• Time rate of change of [N]ss is

d[N]ss d k1 [O][N2 ]
= (2.47)
dt dt k2 [O2 ]

2. Chemical Kinetics 36 AER 1304–ÖLG

Mechanism for Unimolecular Reactions
• Let’s consider a three-step mechanism:
ke ∗
A + M −→ A + M (2.48a)
∗ kde
A + M −→ A + M (2.48b)
∗ kunim
A −→ products (2.48c)
• In step 1: kinetic energy transferred to A from
M; A has increased internal vibrational and
rotational energies and becomes an energized A
molecule, A∗ .

2. Chemical Kinetics 37 AER 1304–ÖLG

 • Two possible scenarios for A∗ :
- A∗ may collide with another molecule and
goes back to A (2.48b)
- A∗ may decompose into products (2.48c)
• The rate at which products are formed:
d[products]
= kunim [A∗ ] (2.49)
dt
• Net production rate of A∗ :
d[A∗ ]
= ke [A][M] − kde [A∗ ][M] − kunim [A∗ ]
dt
(2.50)

2. Chemical Kinetics 38 AER 1304–ÖLG

 • Steady-state approximation for A∗ , i.e.
d[A∗ ]/dt = 0,

∗ ke [A][M]
[A ] = (2.51)
kde [M] + kunim

• Substitute Eqn.2.51 into 2.49,

d[products] ke [A][M]
= (2.52)
dt (kde /kunim )[M] + 1

2. Chemical Kinetics 39 AER 1304–ÖLG

 • Another form of writing the overall rate of pro-
duction of products for the overall reaction:
kapp
A −→ products (2.53)
d[A] products
− = = kapp [A] (2.54)
dt dt
kapp is an apparent unimolecular rate coef.
• Equating Eqns.2.52 and 2.54 yields
ke [M]
kapp = (2.55)
(kde /kunim )[M] + 1

2. Chemical Kinetics 40 AER 1304–ÖLG

 • Eqn.2.55 lets us to explain pressure depen-
dence of unimolecular reactions:
- At high enough pressures (kde [M]/kunim ) >> 1
because [M] increases as the pressure is in-
creased; then

kapp (P → ∞) = kunim ke /kde (2.56)

- At low enough pressures (kde [M]/kunim ) << 1,

then
kapp (P → 0) = ke [M] (2.57)

2. Chemical Kinetics 41 AER 1304–ÖLG

Chain and Chain-Branching Reactions:
• Chain reactions produce one or more radical
species that subsequently react to produce an-
other radical(s).
• To learn some of the features of chain reac-
tions, we consider a hypothetical chain mecha-
nism, which is globally represented as
A2 + B2 −→ 2AB
• Chain initiation:
k1
A2 + M −→ A + A + M (C.1)

2. Chemical Kinetics 42 AER 1304–ÖLG

 • Chain-propagating reactions involving free radi-
cals A and B:
k2
A + B2 −→ AB + B (C.2)
k3
B + A2 −→ AB + A (C.3)

• Chain-terminating reaction is
k4
A + B + M −→ AB + M (C.4)

where AB is the stable product.

2. Chemical Kinetics 43 AER 1304–ÖLG

 • Concentrations of A and B are small through-
out the course of reaction, so is AB at initial
stages; thus we ignore reverse reactions and
determine reaction rates for stable species as:
d[A2 ]
= −k1 [A2 ][M] − k3 [A2 ][B] (2.58)
dt
d[B2 ]
= −k2 [B2 ][A] (2.59)
dt
d[AB]
= k2 [A][B2 ] + k3 [B][A2 ] + k4 [A][B][M]
dt
(2.60)

2. Chemical Kinetics 44 AER 1304–ÖLG

 • If we use the steady-state approximation for
free radicals A and B:
d[A]
= 2k1 [A2 ][M] − k2 [A][B2 ]
dt (2.61)
+ k3 [B][A2 ] − k4 [A][B][M] = 0

d[B]
= k2 [A][B2 ]
dt (2.62)
− k3 [B][A2 ] − k4 [A][B][M] = 0
• Simultaneous solution of Eqns. 2.61 and 2.62
for A:

2. Chemical Kinetics 45 AER 1304–ÖLG

 k1 [M][A2 ] k3 [A2 ]
[A] = + ·
2k2 [B2 ] k4 [M]
2 1/2 (2.63)
k1 k4 [M]2
1+ −1
2k2 k3 [B2 ]

• A similar expression can be written for [B].

• With the steady-state values for [A] and [B],
d[A2 ]/dt, d[B2 ]/dt, and d[AB]/dt
can be found for initial values of [A2 ] and [B2 ].

2. Chemical Kinetics 46 AER 1304–ÖLG

 • If we consider the simplest of the three,
d[B2 ]/dt:
d[B2 ] k1 k2 k3 [A2 ][B2 ]
= − [A2 ][M] −
dt 2 k4 [M]
2 1/2
k1 k4 [M]2
1+ −1
2k2 k3 [B2 ]
(2.64)
• The last two Eqns can be further simplified:
k1 k4 [M]2 /(2k2 k3 [B2 ]) << 1

2. Chemical Kinetics 47 AER 1304–ÖLG

 since k2 and k3 must be much larger than k1
and k4 for steady-state approximation to apply.
• Eqns. 2.63 and 2.64 can be approximated as:

k1 [M][A2 ] k12 k4 [M]3 [A2 ]

[A] ≈ + 2 (2.65)
2k2 [B2 ] 8k2 k3 [B2 ]2

d[B2 ] k1 k12 k4 [M]3 [A2 ]

≈ − [A2 ][M] − (2.66)
dt 2 4k2 k3 [B2 ]

• First term in both Eqns. dominates at low

pressures.

2. Chemical Kinetics 48 AER 1304–ÖLG

 • Concentration of A depends on the ratio k1 /k2 .
• Rate at which B2 dissapears is governed by k1 .
• Increasing k2 and k3 increases radical concen-
tration, but has no effect on production rate of
products.
• [A] and [B] are directly proportional to P .
• Reaction rates of major species scale with pres-
sure squared.
- provided that second terms in Eqns.2.65
and 2.66 remain small.

2. Chemical Kinetics 49 AER 1304–ÖLG

 • At high pressures, the second terms in Eqns.
2.65 and 2.66 become important (they increase
with pressure faster than the first terms do).
• So, k4 has some influence at high pressures,
although it does not have much influence on
radical concentrations or overall reaction rate
at lower pressures.
• Chain-branching reactions involve the forma-
tion of two radical species from a reaction that
consumes only one radical.
O + H2 O −→ OH + OH

2. Chemical Kinetics 50 AER 1304–ÖLG

Chemical Time Scales:
• Magnitude of chemical times relative to con-
vective or mixing times is of importance in
combustion.
• Unimolecular reactions
kapp
A −→ products (2.53)

d[A] products
− = = kapp [A] (2.54)
dt dt
• Integrating at constant T for [A](t = 0) =[A]0 ,

2. Chemical Kinetics 51 AER 1304–ÖLG

 [A](t) = [A]0 exp [−kapp t] (2.67)

• Characteristic chemical time can be defined as

the time required for the concentration of A
to fall from its initial value to a value equal to
1/e times the initial value,

[A](τchem )
= 1/e (2.68)
[A]0

• Combining Eqns. 2.67 and 2.68 yields,

2. Chemical Kinetics 52 AER 1304–ÖLG

 1/e = exp [−kapp τchem ) (2.69)

or
τchem = 1/kapp (2.70)

• Bimolecular Reactions
kbimolec
A + B −→ C + D (2.8)

d[A]
= −kbimolec [A][B] (2.9)
dt

2. Chemical Kinetics 53 AER 1304–ÖLG

 • For this single reaction [A] and [B] are related
by stoichiometry. Any change in [A] has a cor-
responding change in [B],

x ≡ [A]0 − [A] = [B]0 − [B] (2.71)

[B] = [A] + [B]0 − [A]0 (2.72)

• Substituting Eqn.4.71 into 4.9 and integrating,

[A](t) [A]0
= exp {([A]0 − [B]0 )kbimolec t}
[B](t) [B]0
(2.73)

2. Chemical Kinetics 54 AER 1304–ÖLG

 • Substitute Eqn.2.72 into 2.73, and set:

[A]/[A]0 = 1/e when t = τchem

gives
ln [e + (1 − e)([A]0 /[B]0 )]
τchem = (2.74)
([B]0 − [A]0 )kbimolec

• If [B]0 >> [A]0 ,

1
τchem = (2.75)
[B]0 kbimolec

2. Chemical Kinetics 55 AER 1304–ÖLG

 • Termolecular Reactions
kter
A + B + M −→ C + M (2.24)

• For a simple system at constant T , [M] is con-

stant
d[A]
= (−kter [M])[A][B] (2.9)
dt
where (−kter [M]) plays the same role as
kbimolec does for a bimolecular reaction.

2. Chemical Kinetics 56 AER 1304–ÖLG

 • Then, the characteristic time for termolecular
reactions is,

ln [e + (1 − e)([A]0 /[B]0 )]
τchem = (2.77)
([B]0 − [A]0 )kter [M]

And, when [B]0 >> [A]0 ,

1
τchem = (2.78)
[B]0 (kter [M])

2. Chemical Kinetics 57 AER 1304–ÖLG