5.

111 Lecture Summary #32 Monday, December 1, 2014

Reading for Today: 14.7-14.8, 14.10 in 5th ed and 13.7-13.8, 13.10 in 4th ed
Reading for Lecture #33: 14.11-14.13 in 5th ed and 13.11-13.13 in 4th ed

Topic: Kinetics
I. Investigating Reaction Mechanisms

I. Investigating Reaction Mechanisms. To describe how a reaction takes place, we

propose a reaction mechanism, which is the series of steps (or )
that take place to convert reactants to products. We then examine whether the
mechanism is consistent with experimental data. Since the mechanism can affect the
overall rate of the reaction, it is important to understand which steps are slow and
which are fast.

Example 1: 2NO (g) + O2 (g) → 2NO2 (g)

It is experimentally determined that the rate of formation of NO2 is kobs [NO]2[O2]

Overall order = Is a one step mechanism likely?

molecular reactions are rare
Proposed mechanism
k1
Step 1 NO + NO N2O2 forward rate =
k -1
order= molecular
reverse rate =

order= m olecular
k2
Step 2 O2 + N2O2 → NO2 + NO2 rate =

order= molecular

What is the rate of NO2 formation? NO2 is formed in step 2 and the rate equals:

rate of formation of NO2 = 2k2 [O2][N2O2]

(The factor of 2 appears because two molecules of NO2 are formed; so the concentration
of NO2 increases twice as fast as the concentration of N2O2 decreases).

but this rate law includes an intermediate, [N2O2], and intermediates must not appear in
a final rate law. We must solve for [N2O2] in terms of reactants, products, and rate
constants.

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net rate of formation of N2O2 =

At this point, we use the steady-state approximation.

Steady-state approximation: the rate of formation of intermediates rate

of decay of intermediates.

Net rate = ______ = k1 [NO]2 – k-1 [N2O2] - k2 [N2O2][O2]

Solving for [N2O2]:

Substituting into rate of formation of NO2 = 2k2 [O2][N2O2]

rate of formation of NO2 = 2 k1 k2 [O2] [NO]2

k-1 + k2 [O2]

This would be the answer if the mechanism had no fast or slow steps. The above rate
law is inconsistent with the experimentally determined rate law (kobs [NO]2[O2]), so the
mechanism must have steps.

What if the first step is fast and reversible, and the second step is slow?
k1
Step 1 NO + NO N2O2
( k -1
)
k2
Step 2 O2 + N2O2 → NO2 + NO2
( )

The slowest elementary step in a sequence of reactions is called the rate determining
step (RDS).

A rate determining step is so much slower than the rest of the steps that it
the rate of the overall reaction.

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Given this proposal about fast and slow steps, we can simplify based on the
consideration that the decomposition of N2O2 is faster than the consumption of N2O2.

k-1 [N2O2] >>> k2 [N2O2][O2]

rate of is rate of consumption

decomposition faster
of [N2O2] than

with k-1 >> k2 [O2] and the term "k2 [O2]" drops out

[N2O2] = k1 [NO]2 (original expression)

k-1 + k2 [O2]

Leaving:

[N2O2] = k1 [NO]2 or [N2O2] = k1 = equilibrium expression for the 1st step

k-1 [NO]2 k-1

When a reversible fast step is followed by a slow step, the first step approaches
equilibrium. Not much of the product is being siphoned off by the second step, so an
equilibrium-like condition is reached.

Figure by MIT OpenCourseWare.

Now we can substitute k1 [NO]2 or K1 [NO]2 for [N2O2]

k-1

rate = 2k2 [O2][N2O2] = 2k1k2 [O2][NO]2 or 2K1k2 [O2][NO]2

k -1

kobs = 2K1k2 kobs is the observed rate constant

rate = kobs [O2][NO]2 agrees with experimental data (first step must be fast and
reversible, and that must be followed by a slow step)

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Example 2: The following mechanism has been proposed for 2NO + Br2 → 2NOBr
If the experimental rate law is kobs [NO][Br2], determine which step is slow.
k1
st
1 NO + Br2 NOBr2 ratef=
k -1
rater=

k2
nd
2 NOBr2 + NO → 2NOBr rate=

rate of formation of NOBr = 2k2 [NOBr2][NO] but [NOBr2] is an intermediate

Solve for intermediate in terms of rate constants, reactants and/or products:

change in [NOBr2] =

Steady state approximation: 0 = k1 [NO][Br2] – k -1 [NOBr2] - k2 [NOBr2][NO]

Rearranging:

k -1 [NOBr2] + k2 [NOBr2][NO] = k1 [NO][Br2]

[NOBr2] (k -1 + k2 [NO])= k1 [NO][Br2]

[NOBr2 ] = k1 [NO][Br2 ] Substitute back into 2k2 [NOBr2][NO] to get:

k-1 + k2 [NO]

rate of formation of NOBr = 2k1 k2 [NO] 2 [Br2 ]

k-1 + k2 [NO]

If first step is slow k2[NO] >> k-1 rate =

and second step is fast
rate =

overall order =

If first step is fast k-1 >> k2[NO] rate =

and second step is slow
rate =

overall order =

The experimental rate law kobs [NO][Br2] is consistent with a slow first step and a fast
second step.

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Example 3: Write the rate law for 2O3 → 3O2 given that the first step is fast and
reversible, and the second step is slow.

k1
Step 1 O3 O2 + O ratef=
(fast k -1
reversible) rater=
k2
Step 2 O + O3 → O2 + O2 rate=
(slow)

The rate is determined by the slowest step

The rate of formation of O2 is equal to 2 times the rate of the slow step (k2[O][O3]), since
two molecules of O2 are formed.

Thus, rate of formation of O2 = 2k2[O][O3], but “O” is an intermediate, solve for “O” in
terms of products and reactants and rate constants.

Since the first step is fast and reversible and the second step is slow, the first step is in
equilibrium and we can write

[O 2][O] = k1 = K1 or [O] = k1 [O 3]
[O 3] k -1 k -1 [O 2]

Substituting:

rate = 2k2 k1 [O3 ]2

k-1 [O2]

rate = kobs [O3]2

[O2]

What is the order in O3? double O3/rate will?

What is the order in O2? double O2/

What is the overall order? double both O3 and O2/

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5.111 Principles of Chemical Science

Fall 2014

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