Exercises 7

1. The thermal isomerization of cyclopropane to propene in the gas phase has a

rate constant of k = 5.95 x 10−4 s-1 at 500 ˚C. Calculate the value of G‡ for the
reaction.

2. El factor preexponencial y la energía de activación para la reacción

unimolecular:

CH3 NC( g ) ⎯⎯
→CH3CN( g )

Son 4.0 x 1013 s-1 y 272 kJ  mol-1 respectivamente. Calcule los valores para
H ‡ , S ‡ y G‡ a 300 K.

3. The rate of electron-exchange reaction between naphthalene ( C10 H 8 ) and its

anion radical ( C10 H 8− ) are diffusion controlled

C10 H 8− + C10 H 8 C10 H 8 + C10 H 8−

The reaction is bimolecular and second order. The rate constants are

T (K ) 307 299 289 273

k /109 (M s-1 ) 2.71 2.40 1.96 1.43

Calculate the values of E A , H ‡ , S ‡ y G ‡ at 307 K for the reaction

4. The decomposition of urea in 0.1 M of HCl occurs according to the reaction

NH 2CONH 2 + 2 H 2O → 2 NH 4+ + CO32−

The first-order rate constant for this reaction was measured as a function of
temperature, with the following results
Expt. T / ˚C k x 106 / min-1
1 61.0 7.13
2 71.2 27.7

Calculate the entropy of activation at 71.2 ˚C for the reaction of decomposition

of urea. Make the assumptions you need.
Hint: use the Arrhenius equation to calculate the activation entropy