22.

6 Elementary reactions
Elementary reactions: reactions which involve only a small number
of molecules or ions.
A typical example:
H + Br2 HBr
+ Br
Molecularity: the number of molecules coming together to react in
an elementary reaction.
Molecularity and the reaction order are different !!!
Reaction order is an empirical quantity, and is obtained from
the experimental rate law;
Molecularity refers to an elementary reaction proposed as an
individual step in a mechanism. It must be an integral.

 An elementary bimolecular reaction has a second-order rate law:

A + B P
d [ A]
k[ A][B]
dt

If a reaction is an elementary bimolecular process, then it has

second-order reaction kinetics; However, if the kinetics are secondorder, then the reaction might be complex.

22.7 Consecutive elementary

reactions

An example:
239U

239Np 239Pu

Consecutive unimolecular reaction

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] k 2 [ B]
dt

The substance 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 k 2 [ B]
dt

the integrated solution for the above equation is:

[ B]

k1
(e k1t e k2t )[ A]0
k 2 k1

when assuming [B]0 = 0.

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

k1e k2t k2e k1t

[C ] 1
[ A]0
k

2
1

Example. In an industrial batch process a substance A produces the desired

compound B that goes on to decay to a worthless product C, each step of
the reaction being first-order. At what time will B be present in the greatest
concentration?
Solution: At the maximum value of B
d [ B]
0
dt

Using the integrated solution of B and taking derivatives with respect to t:

k1 [ A]0 (k1e k1t k 2 e k2t )
d [ B]

dt
k 2 k1

In order to satisfy

d [ B]
0
dt
k1e k1t k2e k2t

tmax =

=0

k
1
ln 1
k1 k 2 k 2

The maximum concentration of B can be calculated by plugging the tmax into

the equation.

Steady State Approximation

Assuming that after an initial induction period, the rates of change of
concentrations of all reaction intermediates are negligibly small.
d [ B]
0
dt

Substitute the above expression back to the rate law of B

0 k1[ A] k2[ B]
[B] = (k1/ k2)[A]
Then

d [C ]
k 2 [ B] k1 [ A]
dt

d[C ]
k1[ A]0 e k1t
dt

The integrated solution of the above equation is

C (1 e k t )A0
1

In a batch reactor, steady state approximation can only be applied to intermediate

products, not the final product!

Self-test 22.8 Derive the rate law for the decomposition of ozone in the
reaction 2O3(g) 3O2(g) on the basis of the following mechanism
O3 O2 + O
k1
O2 + O O 3
k1
O + O3 O 2 + O 2
k2
Solution:
First, write the rate law for the reactant O3 and the intermediate product O
d[O3 ]
k1[O3 ] k1' [O2 ][O] k2 [O][O3 ]
dt
d [O ]
dt

k1[O3 ] k1' [O2 ][O ] k 2 [O ][O3 ]

Applying the steady state approximation to [O]

0 k1[O3 ] k1' [O2 ][O] k2 [O][O3 ]

Plug the above relationship back to the rate law of [O3]

d[O3 ]
k1[O3 ] (k1' [O2 ] k 2 [O3 ])
dt

Rate determining step

Simplifications with the rate determining step

Suppose that k2 >> k1,

then k2 k1 k2

e k2t e k1t

therefore concentration C

k1e k2t k2e k1t

[C ] 1
[ A]0
k2 k1

can be reorganized as
[C] (1 - e k t)[A]0
1

The above result is the same as obtained with steady state approximation

Kinetic and thermodynamic control

of reactions
Consider the following two reactions
A + B P1 rate of formation of P1 = k1[A][B]
A + B P2 rate of formation of P2 = k2[A][B]

[P1]/[P2] = k1/k2 represents the kinetic

control over the proportions of products.

Problems 22.6 The gas phase decomposition

of acetic acid at 1189 K proceeds by way of
two parallel reactions:

(1) CH3COOH CH4 + CO2, k1 = 3.74 s-1

(2) CH3COOH H2C=C=O + H2O, k2 = 4.65 s-1

What is the maximum percentage yield of the

ketene CH2CO obtainable at this temperature.

Pre-equilibrium
Consider the reaction:
A + B I P
when k1 >> k2, the intermediate product, I, could reach an
equilibrium with the reactants A and B.
Knowing that A, B, and I are in equilibrium, one gets:
and K k1
[I ]
K
[ A][ B ]

k1'

When expressing the rate of formation of the product P in terms of

the reactants, we get
d[ P ]
k 2 [ I ] k 2 K [ A][ B]
dt

Self-test 22.9: Show that the pre-equilibrium mechanism in which 2A

I followed by I + B P results in an overall third-order reaction.
A+ AI
I+BP

Solution:

k 1,

k1

k2

write the rate law for the product P

d[ P ]
k 2 [ I ][ B]
dt
Because I, and A are in pre-equilibrium
K

[I ]
[ A]2

[I] = K [A]2

so

d[ P ]
k 2 K [ A]2 [ B]
dt

Therefore, the overall reaction order is 3.

Kinetic isotope effect

Kinetic isotope effect: the decrease in the rate of a chemical
reaction upon replacement of one atom in a reactant by a heavier
isotope.
Primary kinetic isotope effect: the kinetic isotope effect observed
when the rate-determining step requires the scission of a bond
involving the isotope:
~
k (C D)
CH 1 / 2

hc
v
(C H )
with
e

)
1 (
k (C H )

2kT

CD

Secondary kinetic isotope effect: the variation in reaction rate

even though the bond involving the isotope is not broken to form
product:
k (C D)
e
k (C H )

with

CH 1 / 2
hc{v (C H ) v (C H )}

)
1 (
2kT
CD

Kinetic isotope effect

22.8 Unimolecular reactions

The Lindemann-Hinshelwood mechanism

A reactant molecule becomes energetically excited by collision with
another reactant molecule:
A + A A* + A
d[ A*]
k1[ A]2
dt

The energized molecule, A*, may lose its excess energy by colliding
with another molecule:
A + A* A + A
d [ A*]
k1' [ A][ A*]
dt

The excited molecule may shake itself apart to form product P

A* P
d[ A*]
k 2 [ A*]
dt

The net rate of the formation of A* is

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

[ A*]

k1[ A]2
k1' [ A] k2

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 k1' [ A] k2
d [ P ] k1 k 2
' [ A]
dt
k1
'
in case k1[ A] k2

d[ P ]
k1 [ A]2
dt

 The equation
reorganized into

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

can be

d [ P]
k1k 2 [ A]
( '
)[ A]
dt
k1[ A] k 2

Using the effective rate constant k to represent

k

k1k 2 [ A]
k1' [ A] k 2

Then one has

'

1
k1

k
k1k2

k1[ A]

The Rice-Ramsperger-Kassel
(RRK) model
Reactions will occur only when enough of required energy
has migrated into a particular location in the molecule.

P 1
E

s 1

s 1

E
kb
kb ( E ) 1
E

s is the number of modes of motion over which the energy

may be dissipated, kb corresponds to k2

The activation energy of combined reactions

Consider that each of the rate constants of the following reactions
A + A A* + A
A + A* A + A
A* P
has an Arrhenius-like temperature dependence, one gets
k1 k 2 A1e E1/ RT A2 e E2 / RT

'
k1'
A1' e E1 / RT

A1 A2
A1'

e ( E1 E2 E1 ) / RT
'

Thus the composite rate constant also has an Arrhenius-like form

with activation energy,
E = E1 + E2 E1
Whether or not the composite rate constant will increase with
temperature depends on the value of E,
if E > 0, k will increase with the increase of temperature

Combined activation energy

 Theoretical problem 22.20

The reaction mechanism
A2 A + A (fast)
A + B P (slow)
Involves an intermediate A. Deduce the
rate law for the reaction.
Solution: