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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