Quasi-Equilibrium Hypothesis

ASSUMPTIONS:
All reversible elementary steps are in equilibrium.
All reversible steps must immediately be followed by
a rate-determining step.
The rates of all steps after the RDS are several
times faster than the rate of the RDS.

 Mechanism:
k1

N 2O5 NO2 NO3

k2

k3

NO2 NO3 NO O2 NO2

k4

NO NO3 2 NO2

(slow)

Guidelines to Formulating Reaction

Mechanisms
The most fundamental basis for mechanistic
speculation is a complete analysis of reaction
products.

Guidelines to Formulating Reaction

Mechanisms
The atomic and electronic structure of the reactants
and products may provide important clues as to the
nature of possible intermediate species.

Guidelines to Formulating Reaction

Mechanisms
All of the elementary reactions involved in a
mechanistic sequence must be feasible with respect
to bond energies.

Guidelines to Formulating Reaction

Mechanisms
A number of elementary reactions sufficient to
provide a complete path for the formation of all
observed products must be employed.

Guidelines to Formulating Reaction

Mechanisms
All of the intermediates produced by the elementary
reactions must be consumed by other elementary
reactions so that there will be no net production of
intermediate species.

Guidelines to Formulating Reaction

Mechanisms
The great majority of known elementary steps are
bimolecular, the remainder being unimolecular or
termolecular.

Guidelines to Formulating Reaction

Mechanisms
A postulated mechanism for a reaction in the
forward direction must also hold for the reverse
reaction (principle of microscopic reversibility).

Guidelines to Formulating Reaction

Mechanisms
Transitory intermediates do not react preferentially
with one another to the exclusion of their reaction
with stable species.

Guidelines to Formulating Reaction

Mechanisms
When the overall order of a reaction is greater than
three, the mechanism probably has one or more
equilibria and intermediates prior to the rate
determining step.

Guidelines to Formulating Reaction

Mechanisms
Inverse orders arise from rapid equilibria prior to the
rate determining step.

Oxidation of Arsenious Acid in

Aqueous solution

H 3 AsO3 I H 2O H 3 AsO4 3I 2H
Rate Expression:

k[ H 3 AsO3 ][ I ]
r
2

[I ] [H ]

Oxidation of Arsenious Acid in

Aqueous solution
Mechanism I

H 3 AsO3 H 2 AsO3 H

(equil)

I 3 H 2O 2 I H 2OI

(equil)

H 2OI H 2 AsO3 H 2 AsO3 I H 2O

(slow)

H 2 AsO3 I I H 2 AsO3

H 2 AsO3 H 2O H 3 AsO4 H

(fast)

Oxidation of Arsenious Acid in

Aqueous solution
Mechanism II

H 3 AsO3 H 2 AsO3 H

(equil)

I 3 H 2O 2 I H 2OI

(equil)

H 2OI H 2 AsO3 H 2 AsO3 I H 2O

(equil)

H 2 AsO3 I I H 2 AsO3

H 2 AsO3 H 2O H 3 AsO4 H

(slow)

Guidelines to Formulating Reaction

Mechanisms
Whenever a rate law contains non-integer orders,
there are intermediates present in the reaction
sequence.