13.

8 The Rate Law and the Mechanism

The mechanism of a reaction cannot be observed directly. A mechanism is devised to
explain the experimental observations. It is like the explanation provided by a detective
to explain a crime in terms of the clues found. Other explanations may be possible, and
further clues may make one of these other explanations seem more plausible than the
currently accepted one. So it is with reaction mechanisms. They are accepted
provisionally, with the understanding that further experiments may lead you to accept
another mechanism as the more probable explanation. < An important clue in
understanding the mechanism of a reaction is the rate law. The reason for its importance
is that once you assume a mechanism, you can predict the rate law. If this prediction
does not agree with the experimental rate law, the assumed mechanism must be wrong.
Take, for example, the overall equation

If you follow the rate of disappearance of F2, you observe that it is directly proportional
to the concentration of NO2 and F2.

This rate law is a summary of the experimental data. Assume that the reaction occurs
in a single elementary reaction.

This, then, is your assumed mechanism. Because this is an elementary reaction, you
can immediately write the rate law predicted by it.

However, this does not agree with experiment, and your assumed mechanism must be
discarded. You conclude that the reaction occurs in more than one step.

Rate-Determining Step
The reaction of NO2 with F2 is believed to occur in the following steps (elementary
reactions).

The rate constant for each step has been written over the arrow. The net result of the
mechanism must be equivalent to the net result of the overall equation. By adding the
two steps together, you can see that this is the case.

The F atom is a reaction intermediate.

The mechanism must also be in agreement with the experimental rate law. Let us
look at that. Note that the second step is assumed to be much faster than the first, so
that as soon as NO2 and F2 react, the F atom that is formed reacts with an NO2 molecule
to give another NO2F molecule. Therefore, the rate of disappearance of F2 (and
therefore the rate law) is determined completely by the slow step, or rate-determining
step. The rate-determining step is the slowest step in the reaction mechanism.
To understand better the significance of the rate-determining step, suppose you
and a friend want to start a study group. You and your friend decide to send invitation
cards to some students in your class. You write a lengthy note on each card
explaining the study group, taking an average of 2.0 minutes per card. Your friend
puts the card in an envelope, affixes a computer-printed address label, seals the
envelope,
and stamps it, taking 0.5 minute per card. How long does it take to do 100 cards?
What is the average time taken per card (rate of completing the cards)?
Because you take longer than your friend to do each card, your friend can complete
the task for one card while you are working on another. It takes you a total of
(100 cards _ 2.0 min/card) to do your step in the task. When you have finished the
last card, your friend still has to place the card in the envelope, and so forth. Therefore,
you have to add an additional 0.5 min to the total time.

We have underlined the last significant figure.

The rate of completing the invitation cards is
The rate is essentially the time it takes you to compose a note. The time for your
friend to finish the task is insignificant compared with the total time. The rate for the
task equals the rate for the slower step (the rate-determining step).
The rate-determining step in the reaction of NO2 and F2 is the first step in the
mechanism, in which NO2 reacts with F2 to produce NO2F and an F atom. The rate
equation for this rate-determining step of the mechanism is

This should equal the experimental rate law (otherwise the mechanism cannot be
correct), which it does if you equate k1 to k (the experimental rate constant). This
agreement is not absolute evidence that the mechanism is correct. However, one can
perform experiments to see whether fluorine atoms react very quickly with nitrogen
dioxide. Such experiments show that they do.

Example 13.11 Determining the Rate Law from a Mechanism with an Initial Slow
Step
See Problems 13.89 and 13.90.
Ozone reacts with nitrogen dioxide to produce oxygen and dinitrogen pentoxide.

The proposed mechanism is

What is the rate law predicted by this mechanism?

Problem Strategy Consider the mechanism of the reaction and look to see whether the
first step is slow compared to the other steps. If this is the case, then the rate law can be
written on the basis of this first step.
Solution The rate law from the first step is

Answer Check Keep in mind that writing the rate law as we have done in this problem
works when the first step of the mechanism is much slower than the other steps.
Reaction
mechanisms that are not structured like this one will require different approaches to
determine
the mechanism.

Exercise 13.11 The iodide-ion-catalyzed decomposition of hydrogen peroxide,

H2O2, is believed to follow the mechanism

What rate law is predicted by this mechanism? Explain.

Problem Strategy Consider the mechanism of the reaction and look to see whether the
first step is slow compared to the other steps. If this is the case, then the rate law can be
written on the basis of this first step.
Solution The rate law from the first step is

Answer Check Keep in mind that writing the rate law as we have done in this problem
works when the first step of the mechanism is much slower than the other steps.
Reaction
mechanisms that are not structured like this one will require different approaches to
determine
the mechanism.
Exercise 13.11 The iodide-ion-catalyzed decomposition of hydrogen peroxide,
H2O2, is believed to follow the mechanism

What rate law is predicted by this mechanism? Explain.

Mechanisms with an Initial Fast Step

A somewhat more complicated situation occurs when the rate-determining step follows
an initial fast, equilibrium step. The decomposition of dinitrogen pentoxide,
which we discussed in the chapter opening section, is believed to follow this type of
mechanism.

FIGURE 13.16
Representation of the mechanism
of decomposition of N2O5, using
molecular models
Note that little atomic rearrangement occurs
during each step.

To give the overall stoichiometry, you need to multiply the first step by two. Note that
there are two reaction intermediates, NO3 and NO. Figure 13.16 represents the
mechanism by means of molecular models. Let us show that this mechanism is
consistent
with the experimentally determined rate law,

The second step in the mechanism is assumed to be much slower than the other steps
and is therefore rate-determining. Hence, the rate law predicted from this mechanism is

However, this equation cannot be compared directly with experiment because it is

written in terms of the reaction intermediate, NO3. The experimental rate law will
be written in terms of substances that occur in the chemical equation, not of reaction
intermediates. For purposes of comparison, it is necessary to re-express the
rate equation, eliminating [NO3]. To do this, you must look at the first step in the
mechanism.
This step is fast and reversible. That is, N2O5 dissociates rapidly into NO2 and
NO3, and these products in turn react to re-form N2O5. The rate of the forward reaction
(dissociation of N2O5) is

and the rate of the reverse reaction (formation of N2O5 from NO2 and NO3) is

When the reaction first begins, there are no NO2 or NO3 molecules, and the reverse
rate is zero. But as N2O5 dissociates, the concentration of N2O5 decreases and the
concentrations of NO2 and NO3 increase. Therefore, the forward rate decreases and
the reverse rate increases. Soon the two rates become equal, such that N 2O5 molecules
form as often as other N2O5 molecules dissociate. The first step has reached
dynamic equilibrium. Because these elementary reactions are much faster than the
second
step, this equilibrium is reached before any significant reaction by the second step
occurs. Moreover, this equilibrium is maintained throughout the reaction. <
At equilibrium, the forward and reverse rates are equal, so you can write

Substituting into the rate law, you get

Thus, if you identify k1k2/k_1 as k, you reproduce the experimental rate law.
In addition to correctly predicting the experimental rate law, the mechanism must
also be in agreement with the overall equation for the reaction. Although the first
step is essentially in equilibrium, the products of this step (NO 2 and NO3) are being
continuously used in the subsequent steps. Note that each of these subsequent steps
uses up a molecule of NO3. For these steps to proceed, the first step must effectively
produce two molecules of NO3. Thus, the net result of the mechanism is as follows:

The net result of the mechanism is equivalent to the overall equation for the reaction,
as it should be.