Problems Unit 2 Physical Chemistry II 2019/2020

2.1. The cis-trans isomerization of 1,2-dimethylcyclopropane at 453 ºC is a reversible first order reaction.
The composition of the mixture depending on time is given by the following data:
t (s) 0 45 90 225 270 360 495 585 ∞
% cis 100 89.2 81.2 62.3 58.2 50.7 43.5 39.9 30
Calculate k1, k-1 y Keq.
Answer. k1 = 0.00231 s-1, Keq = 2.333, k-1 = 0.001 s-1.

2.2. For a reversible first order reaction, A↔B, k1 = 10-2 s-1 and [B]eq/[A]eq = 4. If [A]0 = 0.01 mol/l and [B]0 =
0, What is the concentration of B after 30 seconds?
Answer. 0.0025 mol/l.

2.3. In the nitration of nitrobenzene in a sulfuric acid medium and an excess of HNO 3, a mixture of isomers
ortho, meta and para dinitrobenzene is obtained. Using the following data verify that the order with respect
to nitrobenzene is one and calculate the corresponding rate constants for the three twin reactions.

t (min) [nitro-Bz] (mol/l) [ortho] (mol/l) [meta] (mol/l)

0 0.256 0 0
5 0.2334 0.0014 0.0209
20 0.1768 0.0050 0.0732
60 0.0844 0.0109 0.1586
100 0.0403 0.0136 0.1994
200 0.0063 0.0158 0.2308
400 0.0002 0.0161 0.2364
∞ 0 0.0161 0.2366

Answer. kortho = 0.001133 min-1, kmeta = 0.016576 min-1, kpara = 0.000226 min-1.

2.4. The gas phase decomposition of acetic acid at 1189 K takes place by two parallel reactions, both of
first order. Calculate the maximum yield of CH2CO (in %) that can be obtained at this temperature.
k
(1) CH3COOH 
 CH4 + CO2
1
k1 = 3.74 s-1
k
(2) CH3COOH 
CH2=C=O + H2O
2
k2 = 4.65 s-1
Answer. 55.4%
Problems Unit 2 Physical Chemistry II 2019/2020

2.5. Given the following data, where [B] is given in mmol / L, an time t in seconds, represent the variation of
the concentration of B versus time and obtain the rate constants for the processes:

k k
A 

1
B B 
  C,
2

if [A]0=0.137 M

t(s) 0 25 75 100 125 150 175 225 275 325 375 440 500 625

[B](mM) 0 24 52 60 65 68 69 66 60 54 47 39 32 21

Answer. k1 ≅ 7.99 10-3 s-1 ; k2 = 3.92 10-3 s-1

2.6. In aqueous perchloric acid solution, the mechanism of the reaction 2 Cu + H2

2+
 + +
2 Cu + 2 H can be
the following:
k1
Cu 2  H2  CuH   H 
k1

CuH   Cu 2 
k
2 Cu   H 
2

Find the rate equation by applying the approximation of the steady state.

k1k 2 H2  Cu 2  
2

v
   
Answer.
k 2 Cu 2  k 1 H 

2.7. The reaction NO2Cl  NO2 + 1/2 Cl2 is of first order and seems to follow the mechanism:

k
NO2 Cl 
NO2  Cl
1

k
NO2 Cl  Cl 
NO2  Cl2
2

Assuming steady state concentration of chlorine atoms, show that the empirical constant of the first order
can be identified with 2k1.
Problems Unit 2 Physical Chemistry II 2019/2020

2.8. The reaction between carbon monoxide and chlorine to form phosgene, Cl2  CO  Cl2 CO , follows the
rate equation:
d Cl2 CO
 k Cl2
3/ 2
CO
dt
Show that the following mechanism is consistent with the rate law:

𝐶𝑙2 + 𝑀 ↔ 2𝐶𝑙 + 𝑀 (𝑓𝑎𝑠𝑡 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚)

𝐶𝑙 + 𝐶𝑂 + 𝑀 ↔ 𝐶𝑙𝐶𝑂 + 𝑀 (𝑓𝑎𝑠𝑡 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚)
𝐶𝑙𝐶𝑂 + 𝐶𝑙2 → 𝐶𝑙2 𝐶𝑂 + 𝐶𝑙 (𝑠𝑙𝑜𝑤)

2.9. a) The reaction 2 NO + O2  2 NO2 is of order three. Assuming a small amount of NO3 on a fast
reversible equilibrium with NO and O2 and that the rate determining step is the slow bimolecular reaction
NO3 + NO  2 NO2, obtain the rate equation for this mechanism.
b) Another possible mechanism for this reaction is:
k
NO  NO 
 N2 O2 1

k
N 2 O2 
2 NO 2

k
N 2 O2  O2 
 2 NO2 3

Apply steady-state approximation to [N2O2] and obtain the rate law for d[NO2]/dt.

c) How could the suggested mechanisms be experimentally distinguished?

𝑘1 𝑘2 𝑘1 𝑘3 [𝑁𝑂]2 [𝑂2 ]
Answer. a) 𝑣 = [𝑁𝑂]2 [𝑂2 ] b) 𝑣 = c) O2 does not follows any order in (b).
𝑘−1 𝑘2 +𝑘3 [𝑂2]