Chemistry 360

Spring 2015
Dr. Jean M. Standard
April 24, 2015

Mechanism Case Study: Gas Phase Decomposition of Ozone

Introduction: Experimental Rate Law

The overall reaction for the gas phase decomposition of ozone is

2 O3 "
" 3 O 2 . (1)

Note that the stoichiometry of an overall reaction does not necessarily reflect the molecularity of the mechanism.
For example, if the mechanism of the overall
reaction shown above for ozone decomposition actually corresponded
to a bimolecular reaction of two ozone molecules, then the expected rate law would be second-order in ozone,

1 d [O 3 ] 2
= k [O 3 ] , (2)
2 dt

Solving for the ozone rate, this becomes

d [O 3 ] 2
= 2k [O 3 ] . (3)
dt

However, the rate law suggested by Eq. (3) is not correct. The actual rate law for ozone decomposition, deduced
from experimental studies, is given in
Eq. (4).

d [O 3 ] 2 1
Experimental Rate Law : = k exp [O 3 ] [O 2 ] . (4)
dt

The experimental rate law shows that the reaction is indeed second order in ozone. However, the reaction is also
dependent uponthe product concentration (O2) with an order of 1, suggesting that there is more going on in the
mechanism than just a simple bimolecular reaction.

Proposed Mechanism
A more complicated mechanism has been proposed for the gas phase decomposition of ozone. The proposed
mechanism is

k
""1
Step 1 : O3 O2 + O (5a)
"
k
"
1

k
Step 2 : O3 + O ""2 2 O2 . (5b)

The overall reaction is therefore in agreement with the expected result,

2 O3 "
" 3 O2 . (5c)

In the proposed mechanism, O atom acts as an intermediate: it is a species that appears in one or more of the

mechanistic steps, but does not appear in the overall reaction.
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Verifying the Proposed Mechanism

In order to verify whether or not the proposed mechanism provides a rate law that is consistent with the
experimental result, the following procedure is employed. (1) The rate law is constructed from the mechanistic steps
proposed for the reaction. (2) The steady-state approximation is applied to any intermediates in order to eliminate
them from the rate law. (3) Further approximations are made in the rate law to account for any known rate-
determining steps. The procedure is described in more detail for the ozone example below.

(1) Construction of the Rate Law

From the two steps of the mechanism proposed in Eq. (5), the rate law for ozone may be written as

d [O 3 ]
= k1 [O 3 ] + k 1 [O 2 ][O] k 2 [O 3 ][O] . (6)
dt

Note that this rate law includes the intermediate, O atom, in two of the terms. In addition, the rate law does not at
this point appear to match the experimental rate law given in Eq. (4).

(2) Application of the Steady-State Approximation
In order to obtain a rate law for the proposed mechanism to compare with the experimental rate law, any
intermediates present in the rate law should be eliminated from the equation if possible. In order to do this, the
steady-state approximation is applied to any intermediates that appear in the rate law. The steady-state
approximation states that the concentration of an intermediate is generally small and slowly varying; as a
result, the time dependence of an intermediate I is approximated to be zero,

d [ I] (7)
Steady State Approximation : 0.
dt

In this case, to apply the steady-state approximation to the intermediate O atom, the rate law for O is obtained from
the mechanism in Eq. (5) and the steady-state approximation is applied by setting the rate equal to zero,

d [O]
= k1 [O 3 ] k 1 [O 2 ][O] k 2 [O 3 ][O] 0 . (8)
dt

Next, Eq. (8) is solved for [O],

k1 [O 3 ] = ( k1 [O 2 ] + k 2 [O 3 ])[O] ,
k1 [O 3 ]
or [ O] = . (9)
k 1 [O 2 ] + k 2 [O 3 ]

And finally, the expression for the concentration of the intermediate O is substituted into the rate law for ozone
given in Eq. (6),

d [O 3 ]
= k1 [O 3 ] + k 1 [O 2 ][O] k 2 [O 3 ][O]
dt
= k1 [O 3 ] + ( k 1 [O 2 ] k 2 [O 3 ])[O]
$ k1 [O 3 ] '
= k1 [O 3 ] + ( k1 [O 2 ] k 2 [O 3 ]) & )
% k 1 [O 2 ] + k 2 [O 3 ] (
2 2
k1k 1[O 3 ][O 2 ] k1k 2 [O 3 ] + k1k 1[O 2 ][O 3 ] k1k 2 [O 3 ]
=
k 1 [O 2 ] + k 2 [O 3 ]
2
d [O 3 ] 2k1k 2 [O 3 ]
= . (10)
dt k 1 [O 2 ] + k 2 [O 3 ]

At this point, the predicted rate law still does not match the experimental rate law, but there is one more step.

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(3) Inclusion of Information About Rate-Determining Step

The final step in the process of checking a proposed mechanism is to include information about the rate-determining
step (RDS), if known. The rate-determining step is defined as the slowest step in the mechanism; i.e., it is the
bottleneck in the reaction. Such information is sometimes available from experimental studies.

Knowledge of the rate-determining step may be used to further simplify the predicted rate law. For example, in the
case of the gas phase ozone decomposition, it is known from experiment that both the forward and reverse portions
of Step 1 (Eq. 5a) are fast compared to Step 2 (Eq. 5b); that is, Step 2 is the RDS. This allows us to make predictions
about the rate constants for those steps (the faster the reaction, the larger the rate constant),

k1 >> k 2 and k 1 >> k 2 . (11)

Therefore, in the predicted rate law, Eq. (10), information about the magnitudes of the rate constants may be used to
simplify the denominator,

Since k1 >> k 2 , k 1[O 2 ] >> k 2 [O 3 ] .
Therefore, k 1[O 2 ] + k 2 [O 3 ] k 1[O 2 ] . (12)

Using this to simplify the predicted rate law in Eq. (10) leads to the expression
2
d [O 3 ] 2k1k 2 [O 3 ]
=
dt k 1 [O 2 ] + k 2 [O 3 ]
2
2k1k 2 [O 3 ]
=
k 1 [O 2 ]
d [O 3 ] # 2k k &
= % 1 2(
[O 3 ] 2 . (13)
dt $ k 1 ' [O 2 ]

The predicted rate law now matches the experimental rate law since it is second order in O3 and also has an order 1
for O2. From comparison of Eq. (4) and Eq. (13), we also see that the experimental rate constant may be expressed

in terms of the rate constants for the individual steps,

2k1k 2
k exp = . (14)
k 1