CHEMICAL KINETICS: 2

Molecularity
Elementary
Reaction

Mechanism
Steady-state
Approximation

Rate law for elementary reaction

Law of Mass Action applies:

rate of rxn product of active masses of

reactants
active mass molar concentration raised to
power of number of species
Examples:

A P + Q
A + B C + D

rate = k1 [A]1
rate = k2 [A]1 [B]1

2A + B E + F + G

rate = k3 [A]2 [B]1

Molecularity of elementary reactions?

Unimolecular (decay) A P

d [ A]

k1[ A]
dt
Bimolecular (collision) A + B P

d [ A]

k2 [ A][ B]
dt

Termolecular (collision) A + B + C P

d[ A]

k3[ A][ B][C ]

dt
No other are feasible! Statistically highly
3

unlikely.

Reversible reactions (small DrG)

A

k1
k-1

Rate:

Assume first order, elementary rxn in both directions

d [ A]

k1[ A] k1[ B]
dt

Conservation of Mass: [ A]0 [ B]0 [ A] [ B]

[ B] [ A]0 [ B]0 [ A]

d [ A]

k1[ A] k1 [ A]0 [ B]0 [ A]

dt

AB
[A]o

[B]o initial

If [B]o =0, so:

[A]o[A] + [B]
If [B]o0, so:
[A]o + [B] o [A] + [B]

Integrate:

k1[ A]t k1 [ A]0 [ B]0 [ A]t

(k1 k1 )t
ln
k1[ A]0 k1[ B]0

At equilibrium
A
At equilibrium

k1
k-1

d [ A]

0
dt

d [ A]

k1[ A] k1[ B]
dt

k1[ A]eq k1[ B]eq

The forward rate equals the
reverse at equilibrium.

What is the equilibrium constant for this reaction?

In terms of rate constants?

k1
K eq
k 1

K eq

[ B]eq
[ A]eq

Elementary Consecutive Reactions

Mother/daughter Radiactive decay, an example:
k1
k2
239
239
U
Np
Pu

239

Consecutive unimolecular reaction:

k1
k2
A
B
C

The rate of decomposition of A is:

d [ A]
k1[ A]
dt
The intermediate B is formed from A, but also decays to C. The net
formation rate of B is therefore:

d [ B]
k1[ A] k2 [ B]
dt

The reagent C is produced from the unimolecular decay of B:

d [C ]
k 2 [ B]
dt

 Integrated solution for the first order reaction (A) is:

[ A] [ A]0 e k1t
Then one gets a new expression for the reactant B:

d [ B]
k1[A]0 e-k1t k2 [ B]
dt
the integrated solution for the above equation is:

[ B]
when assuming [B]0 = 0.

k1
(e k1t e k2t )[ A]0
k2 k1

Based on the conservation law [A] + [B] + [C] = [A]0

k1e k2t k2e k1t

[C ] 1
[ A]0
k2 k1

 k1e k2t k2e k1t

[C ] 1
[ A]0
k2 k1

C A0 A0e

k1t

k1 A0 k1t k2t

e e
k2 k1

We get different kinetic

behaviour depending on the
ratio of the rate constants
k1 and k2

Rate Determining Step

Example the use of QSSA

Evaluate the integrated rate law for
decomposition of N2O5
Reaction:
2 N 2O5 ( g ) 4 NO2 ( g ) O2 ( g )

v k[ N 2O5 ]

Based on the reaction below :

ka

N 2O5 ( g ) NO2 ( g ) NO3 ( g )

ka '
NO2 ( g ) NO3 ( g )
N 2O5 ( g )
kb

NO2 ( g ) NO3 ( g ) NO2 ( g ) O2 ( g ) NO ( g )

kc

NO ( g ) N 2O5 ( g ) 3NO2 ( g )

Example the use of QSSA

If

NO = x
NO2 = y
NO3 = z
N2O5 = w

Then, we have:
1) kbyz kcxw = 0
2) kaw kayz - kbyz = 0
3) dw/dt = kaw + kayz kcxw
4) From (1) kbyz = kcxw
5) From (2) kcxw =kaw kayz
6) (5) to (3) dw/dt = kaw + kayz kcxw
7) dw/dt = kaw + kayz kaw + kayz
= 2kaw + 2kayz

Example the use of QSSA

Then, we have:
8) From (2) kaw = kayz + kbyz
= yz (ka+ kb)
yz = (kaw)/ (ka+ kb)
9) (8) into (7) dw/dt = 2kaw + 2kayz
= 2kaw + 2ka[(kaw)/ (ka+ kb)]

dw 2k a k a ' w 2k a kb w 2k a k a ' w

dt
k a ' kb
dw 2k a kb w

v kw k[ N 2O5 ]
dt
k a ' kb

Pre-Equilibrium Reaction

A B

ka
ka

kb

C P
Intermediate Product

Since we assume A, B, and C in equilibrium,

so,
ka
[C ]
K
, with K
[ A][ B]
ka '

Two possibilities,
1. We also assume that reaction of C become P is
too slow to affect the pre-equilibrium reaction of
A,B, and C.

Pre-Equilibrium Reaction
The rate of P formation
d [ P]
kb [C ] kb K [ A][ B]
dt

ka
d [ P]
kb
[ A][ B]
dt
ka '

2nd order

=K

Pre-Equilibrium Reaction
2. The reaction of C become P cannot be
ignored and affects the pre-equilibrium
reaction of A,B, and C.

d [ P]
kb [C ] k a [ A][ B] k a '[C ] kb [C ]
dt
0 k a [ A][ B] (k a ' kb )[C ]
k a [ A][ B]
[C ]
k a ' kb

Pre-Equilibrium Reaction
d [ P]
kb [C ]
dt
k a [ A][ B]
[C ]
k a ' kb
k a [ A][ B]
d [ P]
kb
dt
k a ' kb

d [ P]
K [ A][ B]
dt

kb k a
1). K
ka '
kb k a
2). K
k a ' kb

Another example of a
reaction with fomation of
intermediate product

Michaelis-Menten
Mechanism

Pre-Equilibrium Reaction:

Michaelis-Menten Mechanism

E S

ka
ka

kb

( ES ) P E
Intermediate Product

Similar equation to the pre-equilibrium, so:

k a [ E ][ S ]
[ ES ]
, [ E ] [ ES ] [ E ]0
k a ' kb
k a [ E ]0 [ ES ][ S ]
[ ES ]
k a ' kb

Pre-Equilibrium Reaction:

Michaelis-Menten Mechanism

k a [ E ]0 [ ES ][ S ]
[ ES ]
k a ' kb
k a [ E ]0 [ S ] k a [ ES ][ S ]
[ ES ]
k a ' kb
[ ES ]k a '[ ES ]k a k a [ E ]0 [ S ] k a [ ES ][ S ]
[ ES ]k a '[ ES ]k a k a [ ES ][ S ] k a [ E ]0 [ S ]
k a [ E ]0 [ S ]
[ ES ]
k a ' k a k a [ S ]

Pre-Equilibrium Reaction:

Michaelis-Menten Mechanism

d [ P]
kb [ ES ]
dt
ka [ E ]0[ S ]
d [ P]
kb
ka ' kb ka [ S ]
dt
kb[ E ]0[ S ]
d [ P]

k a ' kb
dt
[S ]
ka

Pre-Equilibrium Reaction:

Michaelis-Menten Mechanism

kb[ E ]0[ S ]
d [ P]

k a ' kb
dt
[S ]
ka
kb[ E ]0[ S ]
d [ P]
So
k[ E ]0 , with k
k a ' kb
dt
[S ]
ka
k a ' kb
K M , Michaelis Const
ka

Unimolecular Reactions

The Lindemann-Hinshelwood mechanism

A reactant molecule A becomes energetically excited by collision with
another A molecule:
A + A A* + A
d [ A*]
k1[ A]2
dt
The energized molecule may lose its excess energy by collision with another
molecule:
A + A* A + A

d [ A*]
k1' [ A][ A*]
dt

The excited molecule might shake itself apart to form products P

A* P

d [ A*]
k2 [ A*]
dt

The net rate of the formation of A* is

d [ A*]
k1[ A]2 k1' [ A][ A*] k2 [ A*]
dt

 If the reaction step, A + A A* + A, is slow enough to be the rate

determining step, one can apply the steady-state approximation to A*, so
[A*] can be calculated as
d [ A*]
k1[ A]2 k1' [ A][ A*] k2 [ A*] 0
dt

Then

k1[ A]2
[ A*] '
k1[ A] k 2

The rate law for the formation of P could be reformulated as

d [ P]
k1k2 [ A]2
k2 [ A*] '
dt
k1[ A] k2
Further simplification could be obtained if the deactivation of A* is much
faster than A* P, i.e., k1' [ A ][ A*] k2 [ A*] then
d [ P] k1k2
k1' [ A] k2
' [ A]
dt
k1
in case

k1' [ A] k2

d [ P]
k1[ A]2
dt

 The equation

d [ P]
k1k2 [ A]2
k2 [ A*] '
dt
k1[ A] k2

reorganized into

can be

d [ P]
k1k2 [ A]
( '
)[ A]
dt
k1[ A] k 2

Using the effective rate constant k to represent

k1k2 [ A]
k '
k1[ A] k2
Then one has
'
1

1
k
1

k
k1k 2 k1[ A]

Thank You