12.

5 REACTION MECHANISMS
 Kinetics  gives us information about steps involved in a
reaction (reaction mechanism)
Example: NO2(g) + CO(g)  NO(g) + CO2(g)
Experimentally: Rate = k [NO2]2
Proposed mechanism
K1
NO2(g) + NO2(g)  NO3(g) + NO(g) (1st elementary step)
slow
K2
NO3(g) + CO(g)  NO2(g) + CO2(g) (2nd elementary step)
fast
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NO2(g) + CO(g)  NO(g) + CO2(g) (overall reaction)

NO3(g) is an intermediate, mechanism is composed of

elementary steps.
Intermediate: a species that is neither a reactant nor a product but is
formed and consumed during the reaction sequence.
Elementary step: a reaction whose rate law can be written from its
molecularity (coefficients in balanced equation).

Slow-step: it is the rate-determining step (RDS).

Requirements for a proper mechanism:
1. The sum of the elementary steps must give the overall balanced
equation for the reaction.
2. The mechanism must agree with the experimentally determined rate
law.
Example: 2NO2(g) + F2(g)  2NO2 F(g)
Experimentally: Rate = k [NO2] [F2]

Suggested mechanism
k1
NO2(g) + F2(g)  NO2 F(g) + F (slow)

k2
F(g) + NO2(g)  NO2 F(g) (fast)

Is this an acceptable mechanism?

Answer: Check the two requirements for a proper mechanism:

1. The sum of elementary steps gives the overall reaction:

2NO2(g) + F2(g)  2NO2 F(g) (overall reaction) ✓

2. Rate law from slow step == experimental rate law ✓
∴ Yes, this is an acceptable mechanism.
Example: Write the rate law for the elementary reactions:
A) O3 + NO  O2 + NO2 (bimolecular reaction: two reactants)
B) CH3NC  CH3CN (unimolecular reaction: one reactant)

Answer: Since the two given reactions are elementary, the rate raw can
be written from their molecularity.

A) O3 + NO  O2 + NO2 Rate = k [O3] [NO]

B) CH3NC  CH3CN Rate = k [CH3NC]
Example: A proposed mechanism for a reaction is:

C4H9Br  C4H9+ + Br - (slow)

C4H9+ + H2O  C4H9OH2+ (fast)

C4H9OH2+ + H2O  C4H9OH + H3O+ (fast)

A) Write rate law for this mechanism.

B) Write overall reaction.
C) What are the intermediates?
Answer:
A) Slow step is RDS (1st step)  Rate = k [C4H9Br]
B) C4H9Br + 2H2O  Br - + C4H9OH + H3O+
C) C4H9+ and C4H9OH2+