Chapter 2. Exercise

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Problems 33

neering design, this kind of information should not be relied on and experimen-
tally found rates should be used in all cases. Thus, theoretical studies may be
used as a supplementary aid to suggest the temperature sensitivity of a given
reaction from a similar type of reaction, to suggest the upper limits of reaction
rate, etc. Design invariably relies on experimentally determined rates.

RELATED READING

Jungers, J. C., et al., Cinttique chimique appliqute, Technip, Paris, 1958.


Laidler, K. J., Chemical Kinetics, 2nd ed., Harper and Row, New York, 1987.
Moore, W. J., Basic Physical Chemistry, Prentice-Hall, Upper Saddle River, NJ, 1983.

REFERENCES

Lindemann, F. A., Trans. Faraday Soc., 17,598 (1922).


Michaelis, L., and Menten, M. L., Biochem. Z., 49,333 (1913). This treatment is discussed
by Laidler (1987), see Related Readings.

PROBLEMS

2.1. A reaction has the stoichiometric equation A + B = 2R. What is the order
of reaction?

2.2. Given the reaction 2N0, + -21 0, = N205,what is the relation between
the rates of formation and disappearance of the three reaction components?

1
2.3. A reaction with stoichiometric equation - A
2
+B = R + -21 S has the
following rate expression

What is the rate expression for this reaction if the stoichiometric equation
is written as A + 2B = 2R + S?

2.4. For the enzyme-substrate reaction of Example 2, the rate of disappearance


of substrate is given by

What are the units of the two constants?


34 Chapter 2 Kinetics of Homogeneous Reactions

2.5. For the complex reaction with stoichiometry A + 3B + 2R + S and with


second-order rate expression

are the reaction rates related as follows: r, = r, = r,? If the rates are not
so related, then how are they related? Please account for the signs, + or -.

2.6. A certain reaction has a rate given by

-r, = 0.005C2, mol/cm3. min

If the concentration is to be expressed in mollliter and time in hours, what


would be the value and units of the rate constant?

2.7. For a gas reaction at 400 K the rate is reported as

(a) What are the units of the rate constant?


(b) What is the value of the rate constant for this reaction if the rate
equation is expressed as

2.8. The decomposition of nitrous oxide is found to proceed as follows:

What is the order of this reaction with respect to N,O, and overall?

2.9. The pyrolysis of ethane proceeds with an activation energy of about 300
kJImol. How much faster is the decomposition at 650°C than at 500"C?

2.10. A 1100-K n-nonane thermally cracks (breaks down into smaller molecules)
20 times as rapidly as at 1000 K. Find the activation energy for this decompo-
sition.

2.11. In the mid-nineteenth century the entomologist Henri Fabre noted that
French ants (garden variety) busily bustled about their business on hot
Problems 35

days but were rather sluggish on cool days. Checking his results with Oregon
ants, I find

Runningspeed,m/hr 150 160 230 295 370


Temperature, "C 1 3 16 22 24 28

What activation energy represents this change in bustliness?

2.12. The maximum allowable temperature for a reactor is 800 K. At present


our operating set point is 780 K, the 20-K margin of safety to account for
fluctuating feed, sluggish controls, etc. Now, with a more sophisticated
control system we would be able to raise our set point to 792 K with the
same margin of safety that we now have. By how much can the reaction
rate, hence, production rate, be raised by this change if the reaction taking
place in the reactor has an activation energy of 175 kJ/mol?

2.13. Every May 22 I plant one watermelon seed. I water it, I fight slugs, I pray,
I watch my beauty grow, and finally the day comes when the melon ripens.
I then harvest and feast. Of course, some years are sad, like 1980, when a
bluejay flew off with the seed. Anyway, six summers were a pure joy and
for these I've tabulated the number of growing days versus the mean
daytime temperature during the growing season. Does the temperature
affect the growth rate? If so, represent this by an activation energy.

I
1976 1977 1982 1984 1985 1988
Growing days 87 85 74 78 90 84
Mean temp, "C
liar 22.0 23.4 26.3 24.3 21.1 22.7

2.14. On typical summer days, field crickets nibble, jump, and chirp now and
then. But at a night when great numbers congregate, chirping seems to
become a serious business and tends to be in unison. In 1897,A. E. Dolbear
(Am. Naturalist, 31,970) reported that this social chirping rate was depen-
dent on the temperature as given by

(number of chirps in 15 s) + 40 = (temperature, OF)


Assuming that the chirping rate is a direct measure of the metabolic rate,
find the activation energy in kJ/mol of these crickets in the temperature
range 60430°F.

2.15. On doubling the concentration of reactant, the rate of reaction triples. Find
the reaction order.

For the stoichiometry A +B -+ (products) find the reaction orders with


respect to A and B.
36 Chapter 2 Kinetics of Homogeneous Reactions

2.18. Show that the following scheme

NO* + NO: A 2 ~ 0 ~

proposed by R. Ogg, J. Chem. Phys., 15,337 (1947) is consistent with, and


can explain, the observed first-order decomposition of N205.

2.19. The decomposition of reactant A at 400°C for pressures between 1 and


10 atm follows a first-order rate law.
(a) Show that a mechanism similar to azomethane decomposition, p. 21,

is consistent with the observed kinetics.


Different mechanisms can be proposed to explain first-order kinetics. To
claim that this mechanism is correct in the face of the other alternatives
requires additional evidence.
(b) For this purpose, what further experiments would you suggest we run
and what results would you expect to find?

2.20. Experiment shows that the homogeneous decomposition of ozone proceeds


with a rate

(a) What is the overall order of reaction?


(b) Suggest a two-step mechanism to explain this rate and state how you
would further test this mechanism.

2.21. Under the influence of oxidizing agents, hypophosphorous acid is trans-


formed into phosphorous acid:

H,P02 -
oxidizing agent
H3PO3
Problems 37
The kinetics of this transformation present the following features. At a
low concentration of oxidizing agent,

rH3P03
= k [oxidizing agent] [H,PO,]

At a high concentration of oxidizing agent,

To explain the observed kinetics, it has been postulated that, with hydrogen
ions as catalyst, normal unreactive H3P02is transformed reversibly into
an active form, the nature of which is unknown. This intermediate then
reacts with the oxidizing agent to give H3P03.Show that this scheme does
explain the observed kinetics.

2.22. Come up with (guess and then verify) a mechanism that is consistent with
the experimentally found rate equation for the following reaction

2A + B -+A2B with +rAzB= k[A] [B]


2.23. Mechanism for enzyme catalyzed reactions. To explain the kinetics of en-
zyme-substrate reactions, Michaelis and Menten (1913) came up with the
following mechanism, which uses an equilibrium assumption

kl
A+E-X
with K = - and with
k2
[Eo] = [El + [XI
[A1[El '
XL+R
E
k

and where [E,] represents the total enzyme and [El represents the free
unattached enzyme.
G. E. Briggs and J. B. S. Haldane, Biochem J., 19, 338 (1925), on the
other hand, employed a steady-state assumption in place of the equilibrium
assumption

kl
A+E-X
k2 with d[Xl = 0, and [Eo] = [El + [XI
dt
xk3-R+E
What final rate form -rA in terms of [A], [E,], k,, k,, and k, does
(a) the Michaelis-Menten mechanism give?
(b) the Briggs-Haldane mechanism give?

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