Chapter 20 E

Most reactions occur in a sequence of steps called elementary reactions,
each of which involves only a small number of molecules or ions.
Molecularity:
Molecularity of an elementary reaction is the number of molecules coming
together to react in an elementary reaction.
• In a unimolecular reaction, a single molecule shakes itself apart or its
atoms into a new arrangement, as in the isomerization of cyclopropane to
propene.
• In a bimolecular reaction, a pair of molecules collide and exchange energy,
atoms, or groups of atoms, or undergo some other kind of change.
It is most important to distinguish molecularity from order:
• reaction order is an empirical quantity, and obtained from the

experimentally determined rate law;
• molecularity refers to an elementary reaction proposed as an

individual step in a mechanism.
A→B Unimolecular
B+C→D Bimolecular
D+A→E Bimolecular
+__________________
2A + C → E This is NOT an elementary reaction

Consecutive elementary reactions
Some reactions proceed through the formation of an intermediate (I), as in

the consecutive unimolecular reactions
An example of this type of mechanism is the radioactive decay.

The rate of unimolecular decomposition of A is :
The net rate of formation of ntermediate (I) is:
The rate for formation of product P is :

At all times [A] + [I] + [P] = [A]0
The steady-state approximation
It is assumed that; the concentrations of intermediates rise from zero and during the
major part of the reaction, the rates of change of concentrations of all reaction
intermediates are negligibly small (means they stay constant)
Rate:
The rate of unimolecular decomposition of A is : d[P]/dt=kb [I]
Steady-State Appr.
The net rate of formation of intermediate (I) is :
The rate for formation of product P is :

Intermediates: NO and NO3-
Final equation:
Rate:
The rate-determining step
• In general, the rate-determining step (RDS) is the slowest step in a
mechanism and controls the overall rate of the reaction.
• The rate-determining step is not just the slowest step: it must be slow and be a
crucial gateway for the formation of products.
• If the first step in a mechanism is rate-

determining, then the rate of the overall
reaction is equal to the rate of the first step.
• All subsequent steps are so fast that once the
first intermediate is formed, it immediately
goes to formation of products.
• Slowest step is the one with the highest
activation energy.
Pre-equilibria
From a simple sequence of consecutive reactions we now turn
to a slightly more complicated mechanism in which an intermediate
reaches an equilibrium with the reactants A and B:
ka kb
ka’
• The rate constants are ka and ka′ for the forward and reverse
reactions of the equilibrium and kb for the final step.
• This scheme involves a pre-equilibrium, in which an intermediate is
in equilibrium with the reactants.
• The condition is possible when ka′ ≫ kb
In writing these equations, we are presuming that the rate of reaction of I to
form P is too slow to affect the maintenance of the pre-equilibrium.
We are also ignoring the fact that the standard concentration (co ) should
appear in the expression for K to ensure that it is dimensionless.
The rate of formation of P may now be written:

ka kb
ka’
RDS
Method Begin by writing the net rates of change of the
concentrations of the substances and then invoke the steady-
state approximation for the intermediate I.
Use the resulting expression to obtain the rate of change of
the concentration of P.
when the rate constant for the decay of I into products is much
smaller than that for its decay into reactants, kb ≪ ka ′.
For a reaction with a pre-equilibrium, there are three activation energies to take
into account: two referring to the reversible steps of the pre-equilibrium and one for
the final step.
The relative magnitudes of the activation energies determine whether the overall
activation energy is (a) positive or (b) negative.
ka kb
Temperature dependency ka’
RDS
Suppose that each rate constant exhibits an temperature
dependency, then we can apply Arrhenius equation for each:
The effective activation energy of the reaction is:
This activation energy is positive if E +E >E

a,a a,b a,a′
negative if E >E +E
a,a′ a,a a,b
Kinetic and thermodynamic control of reactions
In some cases reactants can give rise to a variety of products, as in nitrations of
mono-substituted benzene, when various proportions of the ortho-, meta-, and
para-substituted products are obtained, depending on the directing power of the
original substituent.
Suppose two products, P1 and P2, are produced by the following competing reactions:
The relative proportion in which the two products have

been produced at a given stage of the reaction (before it
has reached equilibrium) is given by the ratio of the two
rates, and therefore of the two rate constants:
Consequently, the ratio
[P2]/[P1] increases with
increasing temp before
equilibrium is reached.
Checklist of concepts
1. The mechanism of reaction is the sequence of elementary steps that leads from
reactants to products.
2. The molecularity of an elementary reaction is the number of molecules coming
together to react.
3. An elementary unimolecular reaction has first-order kinetics; an elementary
bimolecular reaction has second-order kinetics.
4. The rate-determining step is the slowest step in a reaction mechanism that
controls the rate of the overall reaction.
5. In the steady-state approximation, it is assumed that the concentrations of all
reaction intermediates remain constant and small throughout the reaction.
6. Pre-equilibrium is a state in which an intermediate is in equilibrium with the
reactants and which arises when the rates of formation of the intermediate and its
decay back into reactants are much faster than its rate of formation of products.
7. Provided a reaction has not reached equilibrium, the products of competing
reactions are controlled by kinetics.

Chapter 20 E

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Chapter 20 E

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Most reactions occur in a sequence of steps called elementary reactions,

each of which involves only a small number of molecules or ions.

• reaction order is an empirical quantity, and obtained from the

• molecularity refers to an elementary reaction proposed as an

2A + C → E This is NOT an elementary reaction

Some reactions proceed through the formation of an intermediate (I), as in

An example of this type of mechanism is the radioactive decay.

The net rate of formation of ntermediate (I) is:

The rate for formation of product P is :

The rate for formation of product P is :

• If the first step in a mechanism is rate-

The rate of formation of P may now be written:

Temperature dependency ka’

The effective activation energy of the reaction is:

This activation energy is positive if E +E >E

The relative proportion in which the two products have

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