QUESTION 1 – Complex Kinetics

The gas phase reaction between bis(fluoroxy)difluoroethane CF 2(OF)2 and carbon monoxide, CO, at
temperatures in the range 383 – 413 K has the following overall reaction:
CF2(OF)2(g) + 2CO(g) = 2CF2O(g) + CO2(g)
and the experimental rate equation takes the form:
J = kR [CF2(OF)2][CO]
1. Using only the “overall reaction” and the “experimental rate equation” explain why the reaction is not
an elemental process.
The mechanism representing the overall reaction is a complicated radical chain reaction. Below is
an approximated and simplified mechanism for you to consider (If you add all five elementary
reactions you will not obtain the overall reaction; it does not matter for the purpose of this test):

CF2(OF)2 + CO k 1 FCO• + CF2OOF•

→

FCO• + CF2(OF)2 k 2 CF2O + CF2OOF•

→

CF2OOF• + CO k 3 CO2 + CF2OF•

→

CF2OF• + CO k 4 CF2O + FCO•

→

FCO• + CF2OF• k 5 CF2O

→

2. Based on the radical chain reaction mechanism write down an expression for the rate of loss of
bis(fluoroxy)difluoroethane CF2(OF)2 (i.e. −d[CF2(OF)2] / dt).

3. Based on the radical chain reaction mechanism write down expressions for the rate of formation of
the intermediates (i.e. d[FCO•]/dt, d[CF2OOF•]/dt, and d[CF2OF•]/dt).

4. By applying the steady state approximation to the 3 rates of formation of the intermediates (answers
from part 3), derive an expression for [CF2OF•] in terms of [CF2(OF)2], [CO] and k1, and k5.

5. It can also be shown that [C F2 OF •]=k 2 [ FCO •]¿ ¿ (you do not need to derive or prove this, it is
given to you!). Combine the two equations for [CF 2OF•] (i.e. the one you derived in Q4 and the one
given here) to derive an expression for [FCO•] in terms of [CO] and k1, k2, k4 and k5.

6. Substitute your answer to Q5 (i.e. the expression for [FCO•]) into the expression you wrote down in
Q2 (i.e. the rate of loss of bis(fluoroxy)difluoroethane CF 2(OF)2) and explain how this is equivalent to
the experimental rate equation given above.

7. What does the constant kR in the experimental rate equation represent in terms of k1, k2, k3, k4 and
k5?

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QUESTION 2 - ENZYME KINETICS

The velocity () of an enzyme-catalysed reaction was measured at different concentrations of

substrate, [S]. Data provided in the table below:

[S] / 10−6 M  / 10−3 M s−1

0.0833 1.666
0.1250 2.000
0.2500 2.500

1 KM 1 1
1. Construct a Lineweaver-Burk plot ( = ∙ + ) from the data provided. Label the axes
ν ν max [ S ] ν max
and show trend line (appropriately) on a graph paper (provided below) or you can plot it in excel
(the graph should be of good quality). Show the values plotted in a table.

2. Determine the Michaelis-Menten constant (KM), and the maximum velocity of the reaction (max)
from the intercept and the slope of your graph. Show your working out.

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Solution

CF2(OF)2 + 2CO → 2CF2O + CO2

r = k [CO] [CF2(OF)2] -------------(1)
From the given reactions,

CF2(OF)2 + CO k 1 FCO• + CF2OOF•

→

FCO• + CF2(OF)2 k 2 CF2O + CF2OOF•

→

CF2OOF• + CO k 3 CO2 + CF2OF•

→

CF2OF• + CO k 4 CF2O + FCO•

→

FCO• + CF2OF• k 5 CF2O

→

We get,
-rCF2(OF)2 = k1 [CF2(OF)2] [CO] - k1 [FCO*] [CF2 (OF)2] -------------(2)
- r(FCO*) = k2[FCO*][CF2 (OF)2] + k5 [FCO*][CF2OF*] – k1[CF2 (OF) 2] [CO]

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