Tutorial on Monday and

Wednesday

• No. 2 (Chapter 22: The rates of chemical

reactions) by Bryan Lucier

• March 7 & 9 (from 2:30 to 3:50pm, Essex

Hall room 182)
 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 2kT   CD 
Kinetic isotope effect
(primary)
Kinetics isotope effect
(secondary)
 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]  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
 d [ P] k1k2 [ A]2
• The equation dt
 k2 [ A*]  '
k1[ A]  k2
can be
reorganized into
d [ P] k1k 2 [ A]
( ' )[ 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 (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

A1' e  E1 / RT
' '
k1

A1 A2 ( E1  E2  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 → CH CH kt
3 3

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

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

• Sum of the above two equations equals:

ki [CH 3CHO ]  2kt [.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 (ki / kt )1 / 2 [ H 2 ][ Br2 ]1 / 2
[H ] 
.
k p 2 [ Br2 ]  kr [ 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 k 1, k 1’

(2) NO2 + NO3 → NO2 + O2 + NO k2
(3) NO + N2O5 → NO2 + NO2 + NO2 k3