Chapter 2. Exercise
Chapter 2. Exercise
Chapter 2. Exercise
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
REFERENCES
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?
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 -.
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
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
2.15. On doubling the concentration of reactant, the rate of reaction triples. Find
the reaction order.
NO* + NO: A 2 ~ 0 ~
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,]
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
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?