The Lindemann mechanism is not empirical (it does not derive directly from experimental unlike, for

example, the Arrhenius equation, or the ideal gas law). It does not predict rates because although it
provides an expression for a rate constant it does not predict any values for that rate constant. It
does however explain why reactions such as dissociations or isomerization may look as though they
are behaving unimolecularly (i.e. as though a single molecule in isolation is falling apart or
isomerizing).

RRK theory
If we apply the steady-state approximation to the concentration of the transition state species we
can find an expression for k2 (the rate constant for the rate determining step):

𝑑[𝐴ǂ ]
= 0 = 𝑘2 [𝐴∗ ] − 𝑘 ǂ [𝐴ǂ ]
𝑑𝑡
ǂ
[𝐴ǂ ]
𝑘2 = 𝑘 ∗
[𝐴 ]

This is a useful expression because an approximate value for kǂ is given by a vibrational frequency
and the concentration ratio gives the probability of the energy reaching the active mode. This
probability can be evaluated using statistics.
1. The RRK probability of energy reaching the active vibrational mode is given by:
𝐸a 𝑠−1
‡
[𝐴 ]
= (1 − )
[𝐴∗ ] 𝐸
where s is the number of relevant vibrational modes (typically s = (3N-6)/2 for an N atom molecule).
Calculate this probability if s = 3 and (a) E = 1.5Ea, (b) E = 3Ea. Repeat the calculation if s = 6. How
many degrees of vibrational freedom does cyclopropane have?

Answer:
2 5
E Ea/E (1- Ea/E) (1- Ea/E)
(Answer for s = 3) (Answer for s = 6)
2 5
1.5 Ea 2/3 (1/3) = (1/9) = 11% (1/3) = (1/243) = 0.4 %
2 5
3 Ea 1/3 (2/3) = (4/9) = 44% (2/3) = (32/243) = 13 %

For cyclopropane N = 9; 3N – 6 = 21. Therefore we expect s to be around 10 (around half the

number of vibrational modes). This is larger than the values of s used above and so we would expect
the probabilities to be smaller than those calculated in the Table. Cyclopropane is not very big – this
probability will be very small for large molecules. Therefore we expect rates of
dissociation/isomerization to be slow for large molecules as a consequence of the very low
probability of sufficient energy reaching the active mode.

𝐸a 𝑠−1
2. The RRK expression is 𝑘2 = 𝑘 ‡ (1 − ) .
𝐸

If k‡ = 1014 s-1, s = 6, E = 1.5Ea, calculate k2 and comment on your answer.

Answer
𝐸a 𝑠−1 1
From the Table above (1 − 𝐸
) = 243

Therefore k2 = 1014/243 = 4.11 × 1011 s-1

𝑘 ‡ is large and so the reaction will proceed very quickly once sufficient energy is in the active mode.
k2 is much smaller as a consequence of the low probability of sufficient energy reaching the active
mode. Because k2 << 𝑘 ‡ the overall rate is dictated by k2, which is therefore the rate determining
step.
The rate determining step is the energy redistribution step, not the break up of the transition state.

RRK theory does rely on empirical parameters because the value of s has to be adjusted to best fit
the experimental observations.

RRK theory is not based on ab initio calculations.

RRK theory makes no assumption about the geometry of the transition state.

RRK theory predicts that “unimolecular” reaction rates will be slower for large molecules than for
small molecules. This is seen in practice. Therefore RRK theory gives predictions that agree better
with experimental observations than those of the Lindemann mechanism.