22.

5 The temperature dependence

of reaction rates
• Arrhenius equation:

k  A e  Ea / RT
A is the pre-exponential factor; Ea is the activation energy.
The two quantities, A and Ea, are called Arrhenius parameters.

• In an alternative expression Ea

lnk = lnART-
one can see that the plot of lnk against 1/T gives a
straight line.
Example: Determining the Arrhenius parameters from the following data:
T/K 300 350 400 450 500
k(L mol-1s-1) 7.9x106 3.0x107 7.9x107 1.7x108 3.2x108

Solution:
1/T (K-1) 0.00333 0.00286 0.0025 0.00222 0.002
lnk (L mol-1s-1) 15.88 17.22 18.19 18.95 19.58

25

20

15

Series1

10

0
0 0.0005 0.001 0.0015 0.002 0.0025 0.003 0.0035

The slope of the above plotted straight line is –Ea/R, so Ea = 23 kJ mol-1.

The intersection of the straight line with y-axis is lnA, so A = 8x1010 L mol-1s-1
 The interpretation of the Arrhenius
parameters
• Reaction coordinate: the collection of
motions such as changes in
interatomic distance, bond angles, etc.

• Activated complex

• Transition state

• For bimolecular reactions, the

activation energy is the minimum
kinetic energy that reactants must
have in order to form products.
 Applications of the Arrhenius principle
Temperature jump-relaxation method:
consider a simple first order reaction:
A↔B
at equilibrium:ddt[ A]  0
d [ A]
  k a '[ A]  k b' [ B ]
dt

k a '[ A]  k [ B ]
'
eq
'
b
'
eq

After the temperature jump the system has a new

equilibrium state. Assuming the distance between the
current state and the new equilibrium state is x, one gets
[A] = [A]eq + x; [B] = [B]eq - x;
 22.6 Elementary reactions
• Elementary reactions: reactions which involves 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 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 second-
order, then the reaction might be complex.
 22.7 Consecutive elementary
reactions
• An example:
239
U → 239Np →239Pu
• Consecutive unimolecular reaction
A → B → C
The rate of decomposition of A is:
d [ A]
  k 1 [ 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 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  k 2 [ B ]
dt

the integrated solution for the above equation is:

k1
[ B]  (e k1t  e k2t )[ A]0 when assuming [B]0 = 0.
k 2  k1

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

 k1e  k2t  k 2e  k1t 
[C ]  1  [ A]0
 k 2  k1 
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 equation 25.7.6 and taking derivatives with respect to t:

d[ B] k1 [ A]0 (k1e  k1t  k 2 e  k2t )

dt k 2  k1
d[ B]
In order to satisfy 0
dt

k1e  k1t  k2e  k2t =0

1 k
tmax = 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

e  k1t
[C] ≈ (1 - )[A]0
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 → O 2 + O k1
O2 + O → O 3 k1’
O + O 3 → O2 + 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 ]  k 2 [O ][O3 ]
dt
d [O ]
 k1[O3 ]  k1' [O2 ][O ]  k 2 [O ][O3 ]
dt

Applying the steady state approximation to [O]

0  k1 [O3 ]  k1' [O2 ][O ]  k 2 [O ][O3 ]

k1 [O3 ]
 [O ] 
k1' [O ]  k 2 [O3 ]

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

d [O3 ] k [O ]
  k1 [O3 ]  (k1' [O2 ]  k 2 [O3 ]) ' 1 3
dt k1[O ]  k2 [O3 ]
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  k 2e  k1t 
[C ]  1  [ A]0
 k 2  k1 

can be reorganized as
k t
[C] ≈ (1 - )[A]e0 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:

K
[I ] and K  k1'
[ 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.

Solution: write the rate law for the product P

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

so [I] = K [A]2

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)  with hc v (C  H )   CH 1 / 2 
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  hc {v  (C  H )  v (C  H )}   CH 1 / 2 
k (C  H )  1  ( ) 
with 2 kT   CD 
Kinetic isotope effect
 22.8 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*]
  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*]  k 2 [ 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] k1k 2 [ A]2
 k 2 [ A*]  '
dt k1[ A]  k 2

Further simplification could be obtained if the deactivation of A* is

'
much faster than A*  P, i.e., k1 [ A ][ A*]  k 2 [ A*] then k1' [ A]  k2
d [ P ] k1 k 2
 ' [ A]
dt k1
'
in case k1[ A]  k 2
d[ P ]
 k1 [ A]2
dt
 d [ P] k1k 2 [ A]2
• The equation dt
 k 2 [ A*]  ' can
k1[ A]  k 2
be
reorganized into
d [ P] k k [ A]
( ' 1 2 )[ A]
dt k1[ A]  k 2

• Using the effective rate constant k to represent

k1k 2 [ A]
k
k1' [ A]  k 2

• Then one has

'
1 k1 1
 
k k1k 2 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.

s 1
 E 
*
P  1  
 E 
s 1
 E 
*
kb ( E )  1   kb
 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  E 1/ RT A2 e  E2 / RT

k1'
'
A1' e  E1 / RT
A1 A2 '
 e ( E1  E2  E1 ) / RT
A1'

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: