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Answers to exercises 427

(4) (a) Mechanism 1: Cl, Cl3

Mechanism 2: Cl, COCl
(b) Mechanism 1: Initiation: Cl2(g) → 2Cl(g)
Chain propagation:

Cl(g) + Cl2(g) → Cl3(g)

Cl3(g) + CO(g) → COCl2(g) + Cl(g)

Termination: 2Cl(g) → Cl2(g)

None of the above: Cl3(g) → Cl(g) + Cl2(g)
Mechanism 2:
Initiation: Cl2(g) → 2Cl(g)
Chain propagation:

Cl(g) + CO(g) → COCl(g)

COCl(g) + Cl2(g) → COCl2(g) + Cl(g)

Termination: 2Cl(g) → Cl2(g)

None of the above: COCl(g) →Cl(g) + CO(g)
k2 k3 [CO] k1 [Cl2 ]3
(c) Mechanism 1: v =
k−2 + k3 [CO] k−1

k2 k3 [CO] k1 [Cl2 ]3
Mechanism 2: v =
k−2 + k3 [Cl2 ] k−1
The two mechanisms can be distinguished because the rates behave differently at high and
low pressures of the two reactants. For instance, mechanism 1 predicts that the order with
respect to CO will be zero at high pressure of CO, while mechanism 2 predicts first-order
behavior with respect to CO under any experimental conditions.
(5) There are two ways to go about answering this question, each of which gives a slightly different
result. If you assume that the first step is in quasi-equilibrium, we get the experimental rate law
with k = kk1−1k2 . If you make this assumption, you would conclude that the first step is fast (in both
directions) while the second step is slow.
We can also apply the steady-state approximation to the NOBr2 concentration. We get the
2 [Br ]
rate law v = k1kk−12 [NO]
+k2 [NO]
2
, which reduces to the experimental rate law if k2 [NO]
k−1 . The
correspondence between the experimental rate constant k and the rate constants appearing in
the mechanism are exactly as above, i.e. k = kk1−1k2 . We get this result by assuming that the step
controlled by k2 is slow, along with the steady-state approximation which implies that the removal
of the intermediate is fast. This means that the dissociation of NOBr2 into NO and Br2 is the
fastest process in this reaction, the other two elementary reactions being relatively slow.
(6) If we apply the steady-state approximation to the intermediate, we get a rate law

k1 k2 a 2 c
v=
k−1 + k2 c

If k−1  k2 c, this reduces to v ≈ kk1−1k2 a 2 c, which is a third-order rate law. This implies that the
degradation of the dimer B back to monomers is a fast process.

Exercise group 14.2

(1) (a) A → 3C (b) K = 4.4 × 10−3 mol2 L−2

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428 Answers to exercises

Review exercise group 14.3

k1 k2
(1) (a) v = [indole][HSO−5 ]. (b) k = k1 k2 k−1 + k−2 . (c) 7.5 × 10 s or 21 h.
4
k−1 + k−2
(2) (a) 2PAA → 2AH + O2 . (b) v = kk1−1k2 [PAA]2 [H+ ]. (c) 2nd order. (d) Increasing the pH decreases
the proton concentration, which should decrease the rate of reaction.

Exercise group 15.1

(1) From an Eadie–Hofstee plot, we can calculate vmax = 0.215 μmol L−1 s−1 and KM =
159 μmol L−1 . However, the fit to the data is very poor, suggesting that the simple Michaelis–
Menten mechanism may not be the correct model in this case.
(2) (a) KM = 5.5 mmol/L, k−2 = 12 s−1 . (b) k1 > 2.2 × 103 L mol−1 s−1 .
(3) KM = 21 μmol L−1 , specific activity = 1.8 nmol s−1 g−1
(4) (a) There is some scatter, but the Eadie–Hofstee plot is linear. This transport process therefore
displays Michaelis–Menten kinetics. (b) KM = 31.8 μmol/L, vmax = 0.903 μmol min−1 g−1 .

Exercise group 15.2

(1) (a) The vmax values are nearly constant and a plot of KM vs. i0 is linear, so the data are
compatible with competitive inhibition. (b) vmax = 10.5 μmol L−1 s−1 , KS = 3.98 mmol L−1 ,
KI = 2.31 mmol L−1 .
(2) Competitive with vmax = 745 μmol L−1 s−1 , KS = 83 μmol L−1 , KI = 18 mmol L−1
(3) I find the following for the Eadie-Hofstee plots at each of the BATA concentrations:

[BATA]/μmol L−1 slope/μmol L−1 intercept/μmol L−1 s−1

0 −8.44 0.347
1.9 −19.72 0.332
3.8 −30.22 0.320
7.6 −47.90 0.281

Both the intercept and slope are changing, so this is not an instance of competitive inhibition.
(4) If you create Eadie–Hofstee plots for each inhibitor concentration, you should get the following
data:
[E4P]/μmol L−1 vmax /μmol g−1 min−1 KM /μmol L−1
0 677 748
1.5 691 1376
3 501 954
4.5 521 2195
6 467 4284

The vmax isn’t constant, so that rules out competitive inhibition. (I would expect the vmax to show a
more consistent trend than this, so experimental errors are probably causing some trouble getting
accurate values for the intercepts of the Eadie–Hofstee plots. However, the overall trend of vmax
decreasing with increasing [E4P] is clear.) If we had uncompetitive inhibition, KM would decrease
with increasing [E4P]. However, the trend runs the other way, give or take some experimental
difficulties around 1.5–3 μmol/L E4P. Thus, it can’t be uncompetitive inhibition either. Some
other type of inhibition not studied in this course is operating here.
Incidentally, if you actually draw the Eadie–Hofstee plot (which you should), you’ll see that
the data are pretty messy. It’s often difficult to get great data in some of these experiments. I