5.

TOPIC: 5.4 ELEMENTARY REACTIONS

ENDURING UNDERSTANDING:
TRA-4 There is a relationship between the speed of a reaction and the collision frequency of particle
collisions.
LEARNING OBJECTIVE:
TRA-4.A Represent an elementary reaction as a rate law expression using stoichiometry.
ESSENTIAL KNOWLEDGE:
TRA-4.A.1 The rate law of an elementary reaction can be inferred from the stoichiometry of the molecules
participating in a collision.
TRA-4.A.2 Elementary reactions involving the simultaneous collision of three or more particles are rare.
EQUATION(S):
N/A

NOTES:
An elementary reaction is a single step within the reaction mechanism.
Consider the reaction below:
2 NO (g) + O2 (g) → 2 NO2 (g)
It is very unlikely for three particles to collide at the same time and in the correct orientation for a reaction to
occur. This reaction actually takes place in two steps, or elementary reactions.

First the two NO molecules react to form an unstable intermediate*, N2O2, as shown here:
2 NO (g) → N2O2 (g)

Then the N2O2 intermediate reacts with the O2, to form the final products.
N2O2 (g) + O2 (g) → 2 NO2 (g)

The net equation is formed by combining the two reactions and cancelling the intermediate, N2O2.
2 NO (g) → N2O2 (g)
N2O2 (g) + O2 (g) → 2 NO2 (g)
2 NO (g) + O2 (g) → 2 NO2 (g)

Notice that the sum of the elementary steps is the same as the overall balanced equation. This must be true.

*The term intermediate describes species that are neither reactants nor products; they are formed during the
reaction and are then consumed by the reaction.

The molecularity of the reaction describes the number of molecules that have to collide in an elementary step.
Both elementary steps are bimolecular as they have two colliding molecules. Unimolecular reactions involve only
one particle, these might be decomposition, nuclear decay or isomerization. Termolecular reactions involve three
colliding particles; they are very rare because it is highly unlikely for three particles to collide simultaneously in
the correct orientations. You can know how difficult this is if you have ever attempted the three person high-five!

The rate law can be inferred from an elementary step based on the number of molecules that must collide. For
example in the reaction above, the rate law for the first step could be:
Rate = k [NO]2
As there are two particles of NO that must collide, it would be second order.

The rate law for step 2 only would therefore be:

Rate = k [N2O2][O2]

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Sometimes you are given information about the speed of the elementary step in the reaction. The slowest step is
known as the rate determining step, because it limits how fast the reaction can go.

Imagine that you work at a chocolate shop. It takes you 15 minutes to make a chocolate, 8 hours for it to cool and 5
minutes to box the chocolate. The step in this example that limits how fast you can make the chocolates is the
cooling step. Speeding up either of the other steps wouldn’t significantly change how quickly you can prepare the
chocolate.

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 (fast)
B + C → D (slow)
Rate = k [A]2[C]
*In 5.9 we discuss in more depth when the rate determining step is not the first step.

I DO:
Given the following elementary steps, what is the overall reaction and what is the rate law for elementary step 1?
2 HI(g) → H2I2(g)
H2I2(g) → H2(g) + I2(g)
Overall reaction: 2 HI(g) → H2(g) + I2(g)
Rate law for elementary step 1: Rate= k[HI]2

WE DO:
Gaseous cyclobutane, C4H8, breaks into two gaseous ethylene, C2H4, molecules via a single-step
unimolecular reaction. Write the balanced equation for this reaction and then write the rate law
for the reaction based on the stoichiometry of the elementary step.

YOU DO:
1) The reaction: 2 ChAp (g) → Ch2 (g) + Ap2 (g) occurs in a single elementary step. Write the rate law for this
reaction.

2) Write the rate law for a reaction that takes place for this elementary reaction:
O3 + NO → NO2 + O2

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3) Scientists have suggested two different mechanisms for the same reaction. The elementary steps for
each suggestion are shown below:

Proposal 1) Proposal 2)

(1) 2 A → C (1) 2 A + E → A2
(2) C + D → A + B (2) A2 + D → A + B + E

A) What is the overall balanced equation for this reaction?

B) What is (are) the intermediate(s) in this reaction?

Proposal 1) Proposal 2)

C) What is the predicted rate law for proposal 1, elementary step 1?

D) What is the predicted rate law for proposal 1, elementary step 2?

E) What is the predicted rate law for proposal 2, elementary step 1?

F) What is the predicted rate law for proposal 2, elementary step 2?

G) If the observed rate law for this reaction was found to be Rate = k [A]2, which proposal is correct and which
step is the slow step?

4) Scientists have suggested two reaction mechanisms for the reaction: 2 ICl + H2 → 2 HCl + I2
A) 2 ICl + H2 → 2 HCl + I2 (Single step)

B) (1) ICl + H2 → HI + HCl (slow)

(2) HI + ICl → HCl + I2 (fast)

A. Why is choice B a more likely reaction mechanism? Explain

B. Write the predicted rate law for this reaction.