5.

TOPIC: 5.9 PRE-EQUILIBRIUM APPROXIMATION

LEARNING OBJECTIVE:
5.9.A Identify the rate law for a reaction from a mechanism in which the first step is not rate limiting
ESSENTIAL KNOWLEDGE:
5.9.A.1 If the first elementary reaction is not rate limiting, approximations (such as pre-equilibrium) must
be made to determine a rate law expression.
EQUATION(S):
N/A
NOTE: This was previously titled “Steady State Approximation”
NOTES:
When the first step of a reaction is fast, (not the slow step/rate determining step), we need to approximate the
reaction rate, through a process that College board describes as “Pre-equilibrium approximation”.

This idea was introduced in 5.4.

The slowest step of the reaction determines the rate of the reaction. If the first step is slow, then the overall rate
for the reaction will be based on the stoichiometry of the first elementary reaction.
Example:
A + A → B (slow)
B + C → D (fast)
Rate = k [A]2

If a subsequent elementary reaction is slow, then you have to add all the reactants up to the slowest step and
cancel any intermediates to determine the rate of reaction.

Example:
A + A ⇌ B (equilibrium, fast)
B + C → D (slow)
Observed Rate = k [A]2[C]

In cases where the slow step is not the first step of the reaction, when we write the rate law that is predicted by
this rate limiting step if may contain reaction intermediates. However, an intermediate should not appear in the
overall reaction equation therefore it should not appear in the rate law for the reaction. To solve this problem, we
can express the concentration of the intermediates in terms of the reactants and substitute.

If you look at the first step in this mechanism the reaction is fast which means that the B is formed quickly and
starts to accumulate. As the amount of B increases, some of the B reacts and reforms the A reactants. This is called
an equilibrium reaction and is designated with a double-headed arrow. As long as the first step of the reaction is
fast, there B is available for the second step. Since the second step is consumes B slowly, the amount of the B
intermediate remains fairly constant over the course of the reaction.

𝑘1
A + A ⇌ B (equilibrium, fast)
𝑘−1
When the rate of the forwards reaction is equal to the rate of the reverse reaction, then we can say that equilibrium
has been reached.
First we need to be sure that the mechanism is valid. To do that we will add the two equations together and cancel
the intermediates.
A+A⇌B
B+C→D
Overall Reaction= 2A + C → D
Observed Rate = k [A]2[C]
1 TOPIC: 5.9 Pre-Equilibrium Approximation by Emily Miller is licensed under CC BY-NC-SA 4.0. To view a copy of this license, visit http://creativecommons.org/licenses/by-nc-sa/4.0/.
 5.9
Since the second step is rate limiting, we can write the rate law for that step.

Rate = k2[B][C]

However, as B is an intermediate, we must substitute so that it is not in the rate law, expressing the concentration
of intermediate, B, in terms of the concentration of the reactants, A.

At equilibrium:
Rate (forward) = Rate (reverse)

k1[A]2 = k-1[B]

𝑘1 [𝐴]2
[B] = 𝑘−1
Now substitute this new expression for [B]:
𝑘2 𝑘1 [𝐴]2 [𝐶]
Rate = 𝑘−1

And then combine all the k values into a single k constant.

Rate = k[A]2[C]

I DO:
Ozone naturally decomposes into oxygen according to the following reaction:
2 O3(g) → 3 O2 (g)
The experimentally observed rate law for this reaction is:
𝑘[𝑂3 ]2
Rate =
[𝑂2 ]
The reaction occurs in two steps, which is the rate limiting step?
Step 2 (because the rate if it were step 1 would be Rate = k1 [O3])

𝑘1
O3 (g) ⇌ O2 (g) + O (g)
𝑘−1
𝑘2
O (g) + O3 (g) → 2 O2 (g)
Show that the rate law for the slow step agrees with the experimentally observed rate law.
Step 2: Rate law = k2 [O][O3]
Substitute to remove intermediate.
k1 [O3] = k-1 [O2][O]

[O] = k1 [O3]
k-1 [O2]

Rate law = k2 k1 [O3][O3]

k-1 [O2]

Rate law = k [O3]2

[O2]

2 TOPIC: 5.9 Pre-Equilibrium Approximation by Emily Miller is licensed under CC BY-NC-SA 4.0. To view a copy of this license, visit http://creativecommons.org/licenses/by-nc-sa/4.0/.
 5.9
WE DO:
The mechanism shown here is proposed for the reaction:
2A→2B+C

𝑘1
2A ⇌ B+D (Fast, equilibrium)

It
𝑘−1
B+D→E+C (Slow)
E →2B (Fast)
Propose a rate law consistent with the mechanism.

JK.CAT K
YOU DO: CBJCDJ fTJR
1) A reaction is proposed to take place in the following elementary steps.
(1) AB + C → D
(2) D + C → E KCABJCC3Z
(3) E + AB → F
If the rate law for this reaction was found experimentally to be: Rate = k [AB]2[C]2, which step must be the slow
step? (You can assume that steps that occur before the slow step are fast, equilibrium)

Thethirdstep R K AB C
2) Given the following two-step mechanism:
Step 1) NO2 (g) + Cl2 (g) → ClNO2 (g) + Cl (g)
Step 2) NO2 (g) + Cl (g) → ClNO2 (g)
a) Identify the intermediate

Cl
b) What is the overall reaction?

2NOzigitclaig 7201002cg
c) If the first step is the slow step, what is the predicted rate law?

I
d) If the second step is the slow step, what is the predicted rate law?
(YouRKCNODCCI
can assumeRKCNOICC.la
that the first step is fast, equilibrium)

3) Step 1) A ⇌ B + C (Fast, equilibrium)

Step 2) C → D + E (slow)
Write a rate law that is consistent with this mechanism.
step2vatelaw R
hoco.tk
KCCJJY
What is the overall reaction?
F bR
BtDtEKCA A
3 TOPIC: 5.9 Pre-Equilibrium Approximation by Emily Miller is licensed under CC BY-NC-SA 4.0. To view a copy of this license, visit http://creativecommons.org/licenses/by-nc-sa/4.0/.