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Advanced Thermodynamics - Semester 2 2017 - Lecture Notes

CHAPTER 3

CHEMICAL KINETICS
Chemical equilibrium provides information on equilibrium compositions but does not tell us how long it
needs to reach the equilibrium. The latter is answered by chemical kinetics which deals with chemical
reaction rates.

Considering only chemical equilibrium could be misleading. The example for NO formation at the end
of Chap. 2 indicates that practical conditions may not allow enough time for the reaction to reach
equilibrium. Another example is H2 oxidation. H2 oxidation has very high chemical potentials and thus
enormous equilibrium constant at room temperature, K P (298K ) = 1.2 x1040 , which means that the
equilibrium mixture is dominated by water. However, the reaction rate of H2 oxidation is extremely
3 3
slow at 298 K. For [H2] = 1 mol/cm and [O2] = 0.5 mol/cm , the reaction rate at 298 K is
d[H2 0]
= 2.77 x10 13 mol / (cm3 s) , which means that reaching equilibrium will take 114,622 years!
dt

1. Global vs. Elementary Reactions


The reaction for 1 mole of fuel and a mole of oxidizer can be written as
F + aOx =
bPr
This is a highly simplified expression of the actual reaction process because it considers all fuel and
oxidants react in one step to form products. Such reactions are called global reaction.
The rate of a global reaction can be written as
d[Prod ]
= k(T )[F ]n [Ox ]m
dt
3
where [Prod], [F], and [Ox] is the molar concentration (mol/m ) of the product, fuel and oxidant,
respectively; n and m are the reaction order for fuel and oxidizer, respectively, which are not
necessarily integers; and k(T) is the reaction rate coefficient or rate constant for the global reaction.
3 1-n-m
Note that the unit of rate constant k is (mol/m ) /s.
A global reaction usually consists of multiple elementary reactions. An elementary reaction is a
chemical reaction in which one or more of the chemical species react directly to form the products in a
single reaction step.

For example, hydrogen oxidation reaction


2H2 + O2 2H 2 O
includes the following important elementary reactions
H2 + O2 HO2 + H
H + O2 OH + O
OH + H2 H2O + H
H + O2 + M HO2 + M
These reactions involve free radicals, H, O, OH and HO2, as the intermediates. Free radicals are
reactive atoms or molecules that have unpaired electrons. Almost all combustion reactions are
free radical reactions. Note free radicals are different from ions because they dont carry electronic
charge.

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Advanced Thermodynamics - Semester 2 2017 - Lecture Notes

2. Elementary Reaction Rates


Chemical reactions are collisions in essence. An elementary reaction is the collision of two
species (atom, molecule or radical) to break one bond and form another.

Similar to a global reaction, the rate of an elementary reaction of two molecules


A+BC +D
can be written as
d[ A]
k[ A][B]
=
dt
Note that because it is an elementary reaction, i.e. two species literately collide and react, the reaction
order is 2 overall and 1 with respect to A or B.

The rate constant, k, can be considered to be the product of three factors:


rate of rate Probability that

reacting = of . a collision leads
collisions collisions to reaction

The rate of collisions between A and B, ZAB, can be derived from a simple collision theory as follows
1/2
8 kBT
Z AB = NAV
2
AB

23
where NAV is the Avogadro number, 6.022 x 10 molecules/mol
AB is the mean molecular radius of A and B, ( A + B ) / 2
-23
kB is the Boltzmann constant, 1.381 x 10 J/K
is the reduced mass for species A and B, mA mB / ( mA + mB ) .

The probability that a collision leads to reaction can be expressed as a product of two factors: an
energy factor, exp(Ea / RuT ) , which expresses the fraction of collisions that occur with an energy
above the threshold required for reaction, Ea, and a geometrical or steric factor, p, that takes into
account the geometry of collision between A and B.

Ea is called activation energy, the physical meaning of which can be shown in the figure below.

Energy Activation energy

Reactant Energy released

Product
Progress of Reaction

Collisions between the two reactants, A and B, need be hard enough to overcome the energy barrier
represented by Ea in order to form the products. Collisions with energy lower than of Ea will simply not
lead to a reaction.

Combined these expressions, the rate constant for an elementary reaction involving A and B can be
written as

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Advanced Thermodynamics - Semester 2 2017 - Lecture Notes

1/2
8 kBT
=k(T ) pNAV
2
AB exp(Ea / RuT )

It should be pointed out that collision theory is based on an overly simplified model and has many
shortcomings. However, it demonstrates the essence of collision for chemical reactions, and yields an
expression for rate constant that is similar to the empirical Arrhenius equation. For cases where the
temperature range of interest is not too large, the rate constant can be expressed in same way as the
Arrhenius equation:
k(T ) A exp(Ea / RuT )
=
where A is called pre-exponential factor or the (collision) frequency factor.

A more general form considering the temperature factor in A can be written as


k(T ) AT b exp(Ea / RuT )
=
where A, b, and Ea can all be empirically determined.

An elementary reaction involving two species, as in this example, is called bimolecular reaction. The
overall reaction order for all bimolecular reactions is 2. Similarly, an elementary reaction involving one
or three species is called unimolecular or termolecular reaction, and the overall reaction order is 1
and 3, respectively. Elemental reactions involving more than three molecules are very rare,
considering the impossibility of a collision of four species.

3. Reaction Rates for Multistep Mechanisms


As mentioned, global reactions often consist of multiple elementary reactions. The collection of
elementary reactions necessary to describe a global reaction is called a reaction mechanism.
In a multistep system, forming or consuming a certain species involve more than one elementary
reaction. The net production rate can be quite complicated.
Lets go back to the H2-O2 reactions (R1 to R4) at the beginning of the Chapter.
k

H2 + O2
f1
HO2 + H R1
k r1

kf 2

H + O2
OH + O R2
k r2

k

OH + H2
f3
H2O + H R3
k r3

k

H + O2 + M
f4
HO2 + M R4
k r4

Note that they are all reversible reactions. The product rate of hydrogen atom can be written as

d[H ]
= k f 1 [H2 ][O2 ] + kr 2 [OH ][O] + k f 3 [OH ][H2 ] + kr 4 [HO2 ][M]
dt
kr 1 [HO2 ][H ] k f 2 [H ][O2 ] kr 3 [H2O][H ] k f 4 [H ][O2 ][M]

Note that this expression is based on the only four reactions being considered; the RHS would
become increasingly longer should more reactions are included.

The compact notion for a reaction mechanism including N species and L reactions can be written as
N kf N

=i 1 =
ij' Xi ij" Xi
kr i 1
i = 1, 2, , N species j = 1, 2, , L reaction

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Advanced Thermodynamics - Semester 2 2017 - Lecture Notes

Where ij' and ij" are stoichiometric coefficient on the reactants and products side of the equation,

respectively, for ith species and jth reaction. For example, for H atom in R1, H' ,1 = 0 and H" ,1 = 1 ; in
R2, H' ,2 = 1 and H" ,2 = 0 , and so on.

The net production rate of ith species, i (= d[ X i ] / dt ) , in a multistep mechanism can be compactly
written as
L
i = ij q j for i = 1, 2, , N
j =1

where =
ij ij" ij'
N N
ij' ij"
=
and q j k fj [ X i ] krj [ X i ]
=i 1 =i 1

which is defined as the rate-of-progress variable for jth reaction.

4. Relation between Rate Constants and Equilibrium Constants


For reversible reactions, the rate constants of the forward reaction and the reverse reaction are
inherently related via the equilibrium constant.
Consider reaction
kf

A + B C + D
k r
At equilibrium, the forward reaction rate must equal the reverse reaction rate, so we have
d[ A]
k f [ A][B] + kr [C ][D] =
= 0
dt
After rearrangement,
k f (T ) [C ][D]
=
kr (T ) [ A][B]
Recall the equilibrium constant can be expressed in terms of molar concentration, [Xi], as
[C ] C [D] D
KC (T ) = A B
[ A] [B]
where the superscripts are the stoichiometric coefficients for the reaction, and for the elementary
reaction here they are all 1. Therefore we have

k f (T )
KC (T ) =
kr (T )
This relation indicates that for elementary reactions, knowing any two of kf, kr and KC will enable us to
know the third. In practice, rate constants of elementary reactions are usually difficult to determine,
while equilibrium constant can be readily calculated from tabulated thermal properties. Therefore the
standard practice is to use the equilibrium constant and the most accurate experimental rate constant
to derive the rate constant of the opposition reaction.

5. Chain Reactions
Chain reactions involve the production of a radical species which subsequently reacts to produce one
or more radicals. Chain reactions are essential part of combustion mechanism.

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Advanced Thermodynamics - Semester 2 2017 - Lecture Notes

Chain reactions include three stages of reactions.


i. Chain initiation, where a free radical is produced from a stable species to start the chain reaction
sequence, e.g.
H2 + O2 HO2 + H
,
NO + M N + O + M
ii. Chain propagation, where a radical reacts to produce one or more radicals to sustain the chain
reaction process. If one radical is produced out of one radical, it is called chain transfer, e.g.
H2 + OH H2O + H
NO + O O2 + N
If more than one radical are produced by one radical, it is called chain branching, e.g.
H + O2 OH + O
H + NO OH + N
Chain branching reactions are the main cause of the self-propagating flames and explosions.
iii. Chain termination, where radicals lose activity by colliding with each other or with inert species
to stop the chain reaction, e.g.

H + H + M H2 + M

6. Approximations for Kinetics Simplification


A combustion mechanism often includes many elementary reactions. Given the complex nature of
solving these reactions simultaneously, some approximations are made to simplify the problem.
6.1 Steady-state approximation
When active intermediate species, e.g. free radicals, are formed in a reaction system, they typically
are consumed rapidly due to their high activity. As a result, their concentrations are relatively small
and close to constant compared to those of the reactants and products. Therefore, the production
rates of these species can be assumed to be zero.
For example, during NO formation
k
O + N2
1
NO + N
k
N + O2
2
NO + O
N atom is very active because it has three unpaired electrons. The formation of N atom is slow and
the consumption of N atom is fast. After a rapid transient allowing the buildup of N to some low
concentration, the N concentration stays nearly constant. The net production rate of N atom can be
written as

d[N]
= k1 [O][N2 ] k2 [N][O2 ]
dt
With steady-state approximation, d[N] / dt 0 , therefore
k1 [O][N2 ] k2 [N]ss [O2 ] =
0

k1 [O][N2 ]
Or [N]ss =
k2 [O2 ]

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Advanced Thermodynamics - Semester 2 2017 - Lecture Notes

6.2 Partial equilibrium approximation


Many combustion processes involves both fast and slow reactions, and the overall reaction rate is
controlled by the slow reactions. Treating the fast reactions as if they were equilibrated simplifies the
chemical kinetics by eliminating the need to write rate equations for the radical species involved. This
treatment is call partial equilibrium approximation.
For example, in H2-O2 mechanism the following chain-propagating reactions
k

H + O2
5f

OH + O R5
k 5r

k

O + H2
2f

OH + H R2
k 2r

k

OH + H2
3f

H2O + H R3
k 3r

are much faster, in both directions, than the termolecular chain-terminating reactions forming H2O, e.g.

H + OH + M H2O + M
Partial equilibrium approximation can be applied to R2, R3 and R5, which significantly simplifies the
description of the reactions.
Given equilibrium for the three reactions, we have

k f 5 (T ) [OH ][O]
K=
C 5 (T ) =
kr 5 (T ) [H ][O2 ]
k f 2 (T ) [OH ][H ]
K=
C 2 (T ) =
kr 2 (T ) [O][H2 ]
k f 3 (T ) [H2O][H ]
K=
C 3 (T ) =
kr 3 (T ) [OH ][H2 ]
At a given temperature, equilibrium constants, KC5, KC2, KC3, can be readily calculated. And
concentrations of the reactants, [H2] and [O2], and the product, [H2O], can be experimentally
determined. Therefore the three unknowns, [H], [O], [OH], can be solved from the three equations. For
example,
1/2
[O ][H ]3
[H ] = KC 5KC 2 (KC 3 )2 2 22
[H2O]
The above shows that the partial equilibrium approximation allows algebraic expressions of radical
concentrations with major species and equilibrium constants. This is important because in most cases,
radical concentrations are difficult to determine experimentally.
It is important to note that both the steady-state assumption and the partial-equilibrium assumption
allow us to solve simple algebraic equations, rather than differential equations, for radical
concentrations. However, the physical meaning behind the two assumptions is quite different: partial
equilibrium approximation forces a reaction, or sets of reactions, to be at equilibrium, while the steady-
state approximations forces the net production rate of one or more species to be essentially zero.

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