Foundations of Chemical Kinetics

Lecture 16:
Unimolecular reactions in the gas phase:
The Lindemann mechanism

Marc R. Roussel

Department of Chemistry and Biochemistry

Examples of unimolecular reactions in the gas phase

• •
•C N CH3 •N C CH 3
Isomerizations:
Decompositions:
CH 2 O CH 3

CH 2 CH 2 C C + CH 2 CH CH 2
CH 3 CH 2 O CH3 CH 3 CH 3

What makes these reactions happen?

 General behavior of unimolecular reactions

I These reactions are generally carried out with a “bath gas”

(M) for which [M]  [A] ([A] = reactant).
I At low pressures, the rate law has partial orders with respect
to A and M of 1 each, so an overall order of 2.
I At high pressures, first-order kinetics in [A] is observed.
These observations are both
1. a clue as to the mechanism, and
2. a puzzle to be solved.
 The Lindemann mechanism

k1
−−
A+M)−− A∗ + M
*
k−1
∗ k2
A −→ products
Implied potential energy profile:
A*
E

x
 The Lindemann mechanism
Rate equations

1 k
A+M−
)−
−*− A∗ + M
k−1
∗ k2
A −→ products

Rate equations:

d[A]
= −k1 [A][M] + k−1 [A∗ ][M]
dt
d[A∗ ]
= k1 [A][M] − k−1 [A∗ ][M] − k2 [A∗ ]
dt

I There is no way to solve these equations exactly.

 The Lindemann mechanism
Steady-state approximation

I There is a low barrier for reaction of A∗ , so we expect

k−1  k1 and k2  k1 [M].
I Expected time course for [A∗ ]:
1
0.9
0.8
[A*] (arbitrary units)

0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0 100 200 300 400 500
t (arbitrary units)
 The Lindemann mechanism
Steady-state approximation

I During the long, slow decline of [A∗ ],

d[A∗ ]
≈0
dt
I This is called the steady-state approximation.

d[A∗ ]
= k1 [A][M] − k−1 [A∗ ][M] − k2 [A∗ ] ≈ 0
dt
k1 [A][M]
∴ [A∗ ] ≈
k−1 [M] + k2
k1 k2 [A][M]
∴ v = k2 [A∗ ] ≈
k−1 [M] + k2
 The Lindemann mechanism

k1 k2 [A][M]
v=
k−1 [M] + k2

I Low-pressure limit:

I High-pressure limit:
 The Lindemann mechanism
Interpretation of the high-pressure limit
1k
I Suppose that the reaction A + M −
)−
−*− A∗ + M was the only
k−1
one occurring.
I When this reaction reached equilibrium, we would have
da da∗
= =0
dt dt
∴ k1 [A][M] = k−1 [A∗ ][M]
[A∗ ] k1
∴ = = K1
[A] k−1
where K1 is the equilibrium constant for this reaction.
I The high-pressure limit of the Lindemann rate equation is
therefore
v ≈ K1 k2 [A]
 The Lindemann mechanism
A slight rewrite

k1 k2 [A][M]
v= = kL [A]
k−1 [M] + k2
k1 k2 [M]
with kL = .
k−1 [M] + k2

Define k∞ = k1 k2 /k−1 (high-pressure limit of kL )

k∞ [M]
Then, kL = .
[M] + k∞ /k1
 Experimental determination of the Lindemann
parameters

k∞ [M]
kL = .
[M] + k∞ /k1

1 1 1 1
∴ = +
kL k∞ k1 [M]

A plot of kL−1 vs [M]−1 therefore allows us to recover k∞ and k1 .

Example: cis-trans isomerization of 2-butene at 740 K

CH3 CH3 H CH3

C C C C

H H CH3 H

[2-butene]/10−5 mol L−1 0.25 0.3 0.6 1.2 5.9

k/10−5 s−1 1.05 1.14 1.43 1.65 1.82

Note: The theory is the same even if the “bath gas” is the
reactant itself.
Example: cis-trans isomerization of 2-butene at 740 K
(continued)

0.9

0.8
k /10 s
-1 5

0.7

0.6

0.5
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
[2-butene]-1/105L mol-1
Example: cis-trans isomerization of 2-butene at 740 K
(continued)

slope = 0.106 mol s L−1

1
∴ k1 = = 9.4 L mol−1 s−1
slope
intercept = 0.53 × 105 s
∴ k∞ = 1.9 × 10−5 s−1
 The value of k1

I If we vary the temperature, we can get the preexponential

factor and activation energy corresponding to k1 .
I We might guess that k1 (rate constant for A + M → A∗ + M)
is collision limited.
We should therefore be able to predict the pre-exponential
factor from collision theory.
Collision-theory preexponential factor for the collisional
activation of cyclopropane at 760 K

I The hard-sphere radius of cyclopropane is 2.2 Å.

I σ = π(2r )2 = 6.1 × 10−19 m2
I The mean relative speed of cyclopropane molecules is
s
8RT
v̄r =
πµm
s
8(8.314 472 J K−1 mol−1 )(760 K)
=
π(70.134 × 10−3 kg mol−1 )
= 479 m s−1 .

I Act = σv̄r L = 1.75×108 m3 mol−1 s−1 ≡ 1.75×1011 L mol−1 s−1

I Experimental value: 9 × 1018 L mol−1 s−1
 Curved Lindemann plots

0.4

0.35

0.3

0.25
k /10 s
5

0.2
-1

0.15

0.1

0.05

0
0 50 100 150 200 250 300 350 400
p-1/torr-1

Lindemann plot for the decomposition of cyclobutane to ethene at

449 ◦ C
Source: Butler and Ogawa, JACS 85, 3346 (1963).
Summary: the two problems with Lindemann theory

1. The rate constant k1 exceeds the collision theory value, which

should be an upper limit according to the theory studied so
far.
2. Plots of k −1 vs p −1 , which should be straight, deviate from
linearity at low pressures.