Summary of Lecture VI

Transition state theory (TST) Derivation

The rate constant of the elementary reaction gas reaction
A+B Products
(i)
is derived.
From the Assumptions:* the reaction goes through an activated
complex :
that produces products at a rate
State of the system at transition state (at the top of the
barrier)structure that is in the process of change in the
direction of the products, but not an intermediate
product.
Rate of the elementary gas reaction is:
d[C]/dt= k[A][B]=

(1)

Note that the rate in Eq. (1) is the rate at which A and B passes
the barrier without turning back according to TST. The first
equality in Eq. (1) is due to rxn. (i) and second equality is due
to TST assumption as shown in rxn. (ii).
Hence second order rate constant k, is written
as
Frequency of that special vibration of the activated complex
that makes it unstable
inverse of time spent at TS (transition state).
Equilibrium constant for the formation of the
activated complex.

 is calculated from statistical mechanics as:

partition function per unit volume

evaluated using energies relative to the
zeropoint energy of the molecule.

Zero point energy

of molecule i

For rxn. (ii):

= Difference in zero point energies of the

activated complex and the reactants.

From Assumption (iii) : it is permissible to separate the motion

of the system (activated complex) over the barrier from other
motions of the activated complex. Hence

From Eqs. (4-5), rate constant k in Eq. (2) is written as

Exercise: For an arbitrary mth order reaction the rate constant

k is:

Note that for an elementary reaction such as rxn (i) order

and molecularity are equal.
*Assumptions of TST

1. Molecular systems that have surmounted the potential

barrier in the direction of products cannot turn back and
form reactant molecules again.
2. Energy distribution among the reactant molecules is in
accordance with Maxwell Boltzmann distribution. Even when
the whole system is not in equilibrium the concentration of
activated complex that form products can be calculated using
equilibrium theory.
3. It is permissible to separate the motion of system over the
barrier from other motion associated with the activated
complex.
4. A chemical reaction can be satisfactorily treated in terms of
classical motion over the barrier. Quantum effects being
ignored