1.

Assume a cyclic reaction

X Y

The forward and reverse rate constants for X Y;Y Z and Z X reactions are
respectively k1, k-1; k2,k-2 and k3, k-3 respectively.

Assume each elementary step is first order with respect to reactants and products

(i) Apply the steady state approximation to X, Y and Z and arrive at an expression for [Z]/[X] in
terms of k1, k-1; k2,k-2 and k3, k-3

(ii) Evaluate [Z]/[X] if all rate constants are equal

(iii) Now assume each step is microscopically reversible. Write down expressions for [Y]/[X];
[Z]/[Y] and [Z]/[X].
Verify if the ratio [Z]/[X] evalued in step (i) and step (iii) are the same. If not, under what
conditions is the ratio [Z]/[X] evaluated in step (ii) and (iii) exactly equal?

(iv) What is the difference between steady state approximation and principle of microscopic
reversibility?

2. For a reaction A+B ↔ C+ D,

write down the expression for the equilibrium constant for the fwd reaction assuming X‡ is the
transition state.

Assuming A is diatomic molecule and B is an atom, how many degrees of freedom should X‡ have?
What is the molecularity of the reaction?

Write down the expression for the vibrational partition function for X‡ . From this derive the
frequency of decomposition of X‡ into products C and D. Did you make any assumptions during this
derivation? If yes, what assumption did you make?

3. NO2+CO = NO + CO2

Derive the partition functions for QNO2, QCO, QNO and QCO2 assuming qT, qR and qV are the
translational, rotational and vibrational partition functions per degree of freedom, regardless of the
nature of the molecule and TS.

With this information, derive the frequency factor from TST and compare it with that of collision
theory.

Do you see a difference? If yes, why is there a difference?

How does inclusion of statistical factors for NO2 and CO and Transition state change the rate
constant calculated by TST?
4.

Which reaction co-ordinate best describes the reaction A+BC ---> AB +C in the two
cases above?

Locate the TS in both cases.

5. A ---> B is a unimolecular reaction.

A+ M ↔ A* + M
A* ----> B
where M is an inert molecule.

A* is a vibrationally excited state of A.

(i) What is the activation energy for the de-energization reaction

A* + M → A+ M

(ii) Assume 5 quanta of energy are transferred to A due to collision, thereby exciting to a higher
vibrational energy level. If the 3 bonds in A* can be described as simple oscillators, calculate the
total number of ways in which 5 hν can be distributed between 3 oscillators.

(iii) If P (Eν) is the degeneracy of each energy level in units of hν i.e. Eν/hν, plot P (Eν) vs Eν/hν
E
and ∑ P(E ν ) vs Eν/hν for the first 3 vibrational energy levels
Eν=0
(iii) Compare the rate constants of energization calculated by Hinshelmann mechanism with that of
Lindemann and comment on why the former matches better with experiments.