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1458 Journal of Chemical Education Vol. 76 No. 10 October 1999 JChemEd.chem.wisc.edu

The idea of zero-order kinetics frequently produces as-
tonishment the first time it is presented to students because
it is difficult to imagine a reaction as being independent of
the concentration of all the species involved. This situation,
when mentioned in texts, is seldom illustrated with examples,
so that reactions following zero-order kinetics are sometimes
considered chemical curiosities (1).
To clarify the authentic meaning of zero-orders kinetics
the following simple analogy can be used.
Imagine a room in which there is a box with stressed
mice attempting to escape. The box is not perfectly sealed so
that mice can escape, although the exit is not visible to them.
Also in the room are cats, hungry and efficient hunters, who
have detected the existence of mice and are on the watch so
that those that escape are immediately captured (see figure).
In this reaction the reagents are mice (M) and hungry cats
(C), the product is the pair formation MC, the room is the
scenario of the reaction, and the reaction is over when each
cat has obtained one mouse.
Applying common sensedespite its subjective compo-
nentit is reasonable to admit that:
1. The higher the number of mice in the box, the higher
the probability of one mouse finding the exit; that is,
therateat which miceescapedependson their number
(concentration) in the box.
2. The rate of disappearance of hungry cats, the same as
the absolute value of the rate of mousecat pairs
formed, is independent of their number because they
must wait for free mice in order to capture them.
Consequently, the rate law for the reaction, with respect to
C and MC, can be expressed as
d[C]/dt = d[(MC)]/dt = k[M]
x
[C]
0
= k[M]
x
The overall order of the reaction is x and the partial orders
are x (unknown; however, constant for a particular run) with
respect to [M] and 0 with respect to [C] (2).
In kinetics the rate of a reaction is measured under a
variety of conditionsto obtain asmuch information aspossible,
and care is required to interpret the results from different runs
to draw coherent conclusions. Imagine a run starting with 500
mice and 5 cats and three observers examining variations in
M, C, and MC, respectively.
The first observer concludesthat the rate of disappearance
of mice iszero (d[M]/dt = 0) because it isnot possible to detect
the small change from 500 to 495 in the group of running
mice (1% resolution is associated with most measurements).
Of course, the correct conclusion from thisobservation should
be: the fact that we are unable to appreciate changes in a
system is not a sufficient condition to conclude that nothing
is happening in it.
The second observer concludes that the rate of disap-
pearance of cats is constant (d[C]/dt = constant) because
the time required by the fifth mouse to escape (when the mice
are 496) isimperceptibly longer than that required by the first
(at 500). The third observer comes to a similar conclusion:
d[MC]/dt = constant.
Thus, in runs starting from a large excess of mice over
cats, the above rate law transforms into
d[C]/dt = d[MC]/dt = k[M]
x
[C]
0
= k
obs
and the reaction seems to follow zero-order kinetics. It is said
that the reaction has run in pseudo-zero-order conditions. It
should be noted that distinct values for k
obs
are obtained for
runs of this kind starting from different numbers of mice.
In conclusion, pseudo-zero-order kinetics can eventually
be established when measuring the variation in concentration
of the limiting reagent in the presence of a large excess of
others(in fact, overall first-order reactionsinvolving more than
one species might run under pseudo-zero-order conditions).
If so, the mousecat analogy can be useful in shedding light
on the problem, in the same way that mice inside the box
are unreactive and become very reactive once they escape.
This is analogous to a reagent that requires an initial trans-
formation (isomerization, dissociation,) to become reac-
tive (slow step) so that the resulting species reacts immedi-
ately (fast step) as it forms.
Acknow ledgment
To Jose A. Olivares for helpful comments.
Litera ture Cited
1. Hindmarsh, K.; House, D. A. J. Chem. Educ. 1996, 73, 585.
2. For the terminology on kineticssee Reeve, J. C. J. Chem. Educ.
1991, 68, 728 and referencestherein.
Mice in the Box for Zero-Order Kinetics
Francisco J . Arniz
Laboratorio de Qumica Inorgnica, Universidad de Burgos, 09001 Burgos, Spain; *farnaiz@cid.cid.ubu.es
Applications and Analogies
edited by
Ron DeLorenzo
Middle Georgia College
Cochran, GA 31014