The activation energy of combined reactions

• Consider that each of the rate constants of the following reactions

A + A → A* + A (E1)
A + A* → A + A (E1’)
A* → P (E2)
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 ( E1  E 2  E1' ) / RT
 e
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:
 Chain reactions
• Chain reactions: a reaction intermediate produced in one
step generates an intermediate in a subsequent step, then that
intermediate generates another intermediate, and so on.

• Chain carriers: the intermediates in a chain reaction. It could be

radicals (species with unpaired electrons), ions, etc.

• Initiation step:
• Propagation steps:
• Termination steps:
 23.1 The rate laws of chain
reactions
• Consider the thermal decomposition of acetaldehyde
CH3CHO(g) → CH4(g) + CO(g)
v = k[CH3CHO]3/2
it indeed goes through the following steps:
1. Initiation: CH3CHO → . CH3 + .CHO ki
v = ki [CH3CHO]
2. Propagation: CH3CHO + . CH3 → CH4 + CH3CO. kp
Propagation: CH3CO. → .CH3 + CO k’p
3. Termination: .CH3 + .CH3 → CH3CH3 kt

• The. net rates of change of the intermediates are:

d [ CH 3 ]
 ki [CH 3CHO]  k p [ .CH 3 ][CH 3CHO]  k ,p [CH 3CO. ]  2kt [ .CH 3 ]2
dt
d [CH 3 CO . ]
 k p [ .CH 3 ][CH 3 CHO ]  k ,p [CH 3CO . ]
dt
• Applying the steady state approximation:
0  k i [CH 3 CHO]  k p [ .CH 3 ][CH 3 CHO]  k ,p [CH 3 CO . ]  2k t [ .CH 3 ]2

0  k p [ .CH 3 ][CH 3CHO ]  k ,p [CH 3CO . ]

• Sum of the above two equations equals:

k i [CH 3CHO ]  2k t [.CH 3 ]2  0

• thus the steady state concentration of [.CH3] is:

1/ 2
 k 
[.CH 3 ]   i  [CH 3CHO ]1 / 2
 2k t 

• The rate of formation of CH4 can now be expressed as

1/ 2
d [CH 4 ]  k 
 k p [ .CH 3 ][CH 3CHO ]  k p  i  [CH 3CHO ]3 / 2
dt  2k t 

the above result is in agreement with the three-halves order

observed experimentally.
• Example: The hydrogen-bromine reaction has a complicated rate
law rather than the second order reaction as anticipated.
H2(g) + Br2(g) → 2HBr(g)
Yield
k[ H 2 ][ Br2 ]3 / 2
v
[ Br2 ]  k '[ HBr ]

The following mechanism has been proposed to account for the above
rate law.
1. Initiation: Br2 + M → Br. + Br. + M ki
2. Propagation: Br. + H2 → HBr + H. kp1
H. + Br2 → HBr + Br. kp2
3. Retardation: H. + HBr → H2 + Br. kr
4. Termination: Br. + Br. + M → Br2 + M* kt
derive the rate law based on the above mechanism.
• The net rates of formation of the two intermediates are
d[ H . ]
 k p1 [ Br . ][ H 2]  k p 2 [ H . ][ Br2 ]  k r [ H . ][ HBr ]
dt
d [ Br . ]
 2k i [ Br2 ][ M ]  k p1 [ Br . ][ H 2 ]  k p 2 [ H . ][ Br2 ]  k r [ H . ][ HBr ]  2k t [ Br . ]2 [ M ]
dt
• The steady-state concentrations of the above two intermediates can
be obtained by solving the following two equations:
k p1 [ Br . ][ H 2]  k p 2 [ H . ][ Br2 ]  k r [ H . ][ HBr ]  0

2k i [ Br2 ][ M ]  k p1 [ Br . ][ H 2 ]  k p 2 [ H . ][ Br2 ]  k r [ H . ][ HBr ]  2k t [ Br . ]2 [ M ]  0

1/ 2
k 
[ Br . ]   i  [ Br2 ]1 / 2
 kt 

. k p1 (k i / k t )1 / 2 [ H 2 ][ Br2 ]1 / 2
[H ] 
k p 2 [ Br2 ]  k r [ HBr ]

• substitute the above results to the rate law of [HBr]

d [ HBr ]
 k p1 [ Br . ][ H 2 ]  k p 2 [ H . ][ Br2 ]  k r [ H . ][ HBr ]
dt
1/ 2 3/2
d [ HBr ] 2k p1 (k i / k t ) [ H 2 ][ Br2 ]

dt [ Br2 ]  (k r / k p 2 )[ HBr ]
continued

• The above results has the same form as the empirical rate law, and
the two empirical rate constants can be identified as
1/ 2
k  kr
k  2k p  i  k, 
 kt  k p2

• Effects of HBr, H2, and Br2 on the reaction rate based on the
equation
1/ 2 3/2
d [ HBr ] 2k p1 (k i / k t ) [ H 2 ][ Br2 ]

dt [ Br2 ]  (k r / k p 2 )[ HBr ]
• Self-test 23.1 Deduce the rate law for the
production of HBr when the initiation step
is the photolysis, or light-induced
decomposition, of Br2 into two bromine
atoms, Br.. Let the photolysis rate be v =
Iabs, where Iabs is the intensity of absorbed
radiation.
• Hint: the initiation rate of Br. ?
Exercises 23.1b: On the basis of the
following proposed mechanism, account
for the experimental fact that the rate law
for the decomposition
2N2O5(g) → 4NO2(g) + O2(g)
is v = k[N2O5].

(1) N2O5 ↔ NO2 + NO3 k1, k1’

(2) NO2 + NO3 → NO2 + O2 + NO k2
(3) NO + N2O5 → NO2 + NO2 + NO2 k3
23.2 Explosions
• Thermal explosion: a very rapid reaction arising from a rapid increase of
reaction rate with increasing temperature.

• Chain-branching explosion: occurs when the number of chain centres

grows exponentially.

• An example of both types of explosion is the following reaction

2H2(g) + O2(g) → 2H2O(g)
1. Initiation: H2 → H. + H .

2. Propagation H2 + .OH → H. + H2O kp

3. Branching: O2 + .H → .O + .OH kb1

.O + H2 → .OH + H. Kb2

4. Termination H. + Wall → ½ H2 kt1

H. + O2 + M → HO2. + M* kt2
The explosion limits of the H2 + O2
reaction
• Analyzing the reaction of hydrogen and oxygen (see preceding
slide), show that an explosion occurs when the rate of chain
branching exceeds that of chain termination.

Method: 1. Set up the corresponding rate laws for the reaction

intermediates and then apply the steady-state
approximation.
2. Identify the rapid increase in the concentration of H.
atoms.
.
d[ H ]
 v init  k p [ .OH ][ H 2 ]  k b1 [ H . ][O2 ]  k[O ][ H 2 ]  k t 1 [ H . ]  k t 2 [ H . ][O2 ][ M ]
dt

d [ .OH ]
  k p [ .OH ][ H 2 ]  k b1 [ H . ][O2 ]  k b 2 [O ][ H 2 ]
dt

d [ .O]
 kb1[ H . ][O2 ]  kb 2 [ .O][ H 2 ]
dt

Applying the steady-state approximation

 k p [ .OH ][ H 2 ]  k b1 [ H . ][Oto .OH and .O gives
2 ]  k b 2 [O ][ H 2 ]  0

k b1 [ H . ][O2 ]  k b 2 [O ][ H 2 ]  0
 kb1[ H . ][O2 ]
[ .O ] 
kb 2 [ H 2 ]

. 2kb1[ H . ][O2 ]
[ OH ] 
k p[ H 2 ]
Therefore, d[ H . ]
 v init  (2k b1 [O2 ]  k t 1  k t 2 [O2 ][ M ])[ H . ]
dt
we write kbranch = 2kb1[O2] and kterm = kt1 + kt2[O2][M], then
d[ H . ]
 v init  (k branch  k term )[ H . ]
dt
At low O2 concentrations, termination dominates branching, so kterm >
v
kbranch. Then [ H . ]  k initk (1  e ( kterm  kbranch ) t ) this solution corresponds
term branch

to steady combustion of hydrogen.

At high O2 concentrations, branching dominates termination, kbranch >

v init
kterm. Then [ H . ]  ( e ( kbranch  kterm ) t  1)
 k term  kbranch

This is an explosive increase in the concentration of radicals!!!

• Self-test 23.2 Calculate the variation in radical
composition when rates of branching and
termination are equal.
• Solution:
d[ H . ]
 v init  (k branch  k term )[ H . ]
dt

kbranch = 2kb1[O2] and kterm = kt1 + kt2[O2][M],

d[ H . ]
 vinit
dt
The integrated solution is [H.] = vinit t