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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
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Advanced Thermodynamics - Semester 2 2017 - Lecture Notes
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.
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
2
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.
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.
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
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
H + H + M H2 + M
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 ]
5
Advanced Thermodynamics - Semester 2 2017 - Lecture Notes
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.