edited by
Applications and Analogies Ron DeLorenzo
Middle Georgia College
Cochran, GA 31014
The idea of zero-order kinetics frequently produces as- In kinetics the rate of a reaction is measured under a
tonishment the first time it is presented to students because variety of conditions to obtain as much information as possible,
it is difficult to imagine a reaction as being independent of and care is required to interpret the results from different runs
the concentration of all the species involved. This situation, to draw coherent conclusions. Imagine a run starting with 500
when mentioned in texts, is seldom illustrated with examples, mice and 5 cats and three observers examining variations in
so that reactions following zero-order kinetics are sometimes M, C, and MC, respectively.
considered chemical curiosities (1). The first observer concludes that the rate of disappearance
To clarify the authentic meaning of zero-orders kinetics of mice is zero ({d[M]/dt = 0) because it is not possible to detect
the following simple analogy can be used. the small change from 500 to 495 in the group of running
Imagine a room in which there is a box with stressed mice (1% resolution is associated with most measurements).
mice attempting to escape. The box is not perfectly sealed so Of course, the correct conclusion from this observation should
that mice can escape, although the exit is not visible to them. be: the fact that we are unable to appreciate changes in a
Also in the room are cats, hungry and efficient hunters, who system is not a sufficient condition to conclude that nothing
have detected the existence of mice and are on the watch so is happening in it.
that those that escape are immediately captured (see figure). The second observer concludes that the rate of disap-
In this reaction the reagents are mice (M) and hungry cats pearance of cats is constant ({ d[C]/dt = constant) because
(C), the product is the pair formation MC, the room is the the time required by the fifth mouse to escape (when the mice
scenario of the reaction, and the reaction is over when each are 496) is imperceptibly longer than that required by the first
cat has obtained one mouse. (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