Practice problems:

k1
1. For a reversible reaction A ⇌ P, k1 = 4.0 × 10-2 s-1 and k2 is half of k1 . Initial
K2
concentration of A is 20 mol dm-3 at what time the concentration of P will be 1.0 mol dm-3
Hint: (1) Find the equilibrium concentration
(2) Then get the time at P is 1.0 mol dm-3

2. For a reaction A2+B2 ⇌ 2AB, Ea = 15.5 kJ mol-1 and A= 10.9× 1010 dm3 mol-1 s-1,
Calculate Δ≠H and Δ≠S0 at 1000 K
Hint: (i) Use the relation between Δ≠H0 and Ea
(ii) TST expression for preexponential factor

3. At 298K, Calculate the preexponential factor (A) for the H2 + I2 → [H2I2]≠ reaction.
While the partition function for each
translational degree of freedom = 5× 109 dm-1
vibrational degree of freedom = 5
rotational degree of freedom = 50.
Calculate the preexponential factor.

Hint: (i) Find out the no. of the translational, rotational, and vibrational degree of
freedom for the above system.
(ii) Use it to calculate the k

4. Use the following data of an unimolecular decomposition to determine the k1 and k2

which appear in the Lindemann mechanism. Assume k-1 = 5× 1010 dm3 mol-1 s-1.
Determine the mean life time of the activated molecule.

[A]× 106 10 15 20 40 100 200 400

mol dm-3
first
k obs (s-1) 0.333 0.391 0.426 0.495 0.625 0.781 0.952

5. The k≠ for the dissociation of methane CH4 → CH3 + H is 1016 s-1, and Ea = 400 kJ mol-
1
. Using RRK theory, calculate the unimolecular rate constant for methane at an
excitation energy of 500 kJ mol-1.