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Week 5 Tutorial Problem Set

1. Derive the rate law for the decomposition of ozone in the overall reaction
2 O3(g) → 3 O2(g)
on the basis of the following reaction mechanism:
O3 → O2 + O ka
O2 + O → O3 k’a
O + O3 → 2 O2 kb

2. The enzyme carbonic anhydrase catalyses the hydration of CO2 in red blood cells to
give bicarbonate ion:
𝐶𝑂2 (𝑔) + 𝐻2 𝑂(𝑙) → 𝐻𝐶𝑂3− (𝑎𝑞) + 𝐻 + (𝑎𝑞)
The following data were obtained for the reaction at pH = 7.1, 273.5K, and an
enzyme concentration of 2.3 nmol/L
[CO2] (mmol/L) 1.25 2.5 5 20
Rate (mmol/L s) 2.78×10-2 5.00×10-2 8.33×10-2 1.67×10-1
Determine the catalytic efficiency of carbonic anhydrase at 273.5 K.

3. The condensation reaction of propanone, (CH3)2CO, in aqueous solution is catalysed


by bases, B, which react reversibly with propanone to form the carbanion C3H5O-.
The carbanion then reacts with a molecule of propanone to give the product. A
simplified version of the mechanism is:
(1) 𝐴𝐻 + 𝐵 → 𝐵𝐻 + + 𝐴−
(2) 𝐴− + 𝐵𝐻 + → 𝐴𝐻 + 𝐵
(3) 𝐴𝐻 + 𝐴− → 𝑝𝑟𝑜𝑑𝑢𝑐𝑡
Where AH stands for propanone and A- denotes its carbanion. Use the steady-state
approximation to find the concentration of the carbanion and derive the rate equation
for the formation of the product.

4. The enzyme-catalysed conversion of a substrate at 25 °C has a Michaelis-Menton


constant of 0.035 mol/L. The rate of the reaction is 1.15×10-3 mol/L·s when the
substrate concentration is 0.110 mol/L. What is the maximum velocity of the
enzymolysis?

5. Hydrogen bromide gas is formed from the following chain reaction mechanism with
hydrogen gas and bromine gas:
Overall: 𝐵𝑟2 + 𝐻2 → 2𝐻𝐵𝑟

Initiation: 𝐵𝑟2 + 𝑀 → 2𝐵𝑟 ∙ + 𝑀


Propagation: 𝐻2 + 𝐵𝑟 ∙ → 𝐻 ∙ + 𝐻𝐵𝑟
𝐵𝑟2 + 𝐻 ∙ → 𝐵𝑟 ∙ + 𝐻𝐵𝑟
Retardation: 𝐻 ∙ + 𝐻𝐵𝑟 → 𝐵𝑟 ∙ + 𝐻2
Termination: 𝑀 + 𝐵𝑟 ∙ + 𝐵𝑟 ∙ → 𝐵𝑟2 + 𝑀
From this information, derive the rate equation for the system.
6. Polystyrene is an important industrial polymer and is synthesized using a free radical
chain polymerisation process. Using 1 mmol/L concentration of
azobisisobutyronitrile (AIBN) as a thermal initiator at 60 °C (t1/2 = 22hr, f = 0.8) in
bulk styrene (10 mol/L concentration), your boss wants to know what the maximum
molecular weight of the polystyrene would be in a reactor run under the above
conditions. You have the following kinetic data, and you also know that polystyrene
terminates solely by coupling.

A Ea (kJ/mol)
Propagation of 4.5×106 L/mol-sec 26
Styrene
Termination of 5.8×107 L/mol-sec 8
Styrene

7. What is the molecular weight of styrene when the temperature is increased to 100 °C
and all of the concentrations are held the same as the above reaction?

8. The typical polyester polymer is formed by the step-growth condensation


polymerization shown below:
O O O O

n HO CH2
10
OH + n
HO CH2 OH HO CH2 O
C
CH2
C
O H
4 n H2O 10 4

In order to be useful for the production of polyester fibres, the polymer must have a
number average molecular weight ( ̅̅̅̅𝑀𝑛 ) of 500,000 g/mol. The diol and diacid are
combined in the reactor vessel in equal portions. Calculate:
a) The number average degree of polymerization (𝑋 ̅̅̅𝑛̅)
b) The conversion, p, for this system
c) The initial concentration of either reactant, [𝐴]0 , needed to obtain this
molecular weight in 5 hrs when the uncatalyzed rate constant is 7.5×10-5
L∙mol-1∙s-1
d) The initial concentration, for the same 5 hr span, when the acid catalyzed rate
constant is 1.6×10-3 L∙mol-1∙s-1