REACTION MECHANISM, MOLECULARITY OF A REACTION

Learning objective:

 To understand the meaning of reaction mechanism

 To understand elementary reactions and molecularity
 To understand and explain rate determining step

Reaction mechanism
This refers to the sequence of elementary steps that take place from reactants
to the formation of product. Each step in a reaction mechanism is called the
elementary reaction, elementary step or elementary process. Elementary
Reaction involves molecules or ions in a reaction mechanism.

These elementary steps occur precisely as represented in the step equation and
they add up to yield the overall equation. Elementary reactions occur exactly as
they are written and cannot be broken down into simpler steps.

Consider the reactions

O3(g) O2(g) + O Step 1 (slow)

O + O3(g) 2O2(g) Step 2 (fast)

2O3(g) 3O2(g) Overall reaction

Step 1 and step 2 are elementary reactions. Notice that the oxygen atom produced
in the first step of this mechanism is consumed in the second step and therefore
does not appear as a product in the overall reaction. Species that are produced in
one step and consumed in a subsequent step are called intermediates. The slowest
step in a reaction mechanism is the rate determining step. It is the step that
controls the overall rate of the reaction.

A two –step reaction mechanism

Fig 1. A two-step mechanism of reaction

Source: Tro N J. (2017). Chemistry: A molecular Approach 4TH Edition. Pearson
Education Limited
Fig 1 shows the energy diagram for the mechanism of reaction. The first step has a
much larger activation energy than the second step. This greater activation energy
results in a much smaller rate constant for the first step compared to the second
step. The first step determine the overall rate of reaction.

Molecularity of a reaction
This is the number of reactant species (molecules, ions atoms) involved in a
chemical reaction in an elementary step. Unimolecular reaction involves reaction
of a single molecule to form product. This single molecule can form a new
arrangement as in the isomerization of cyclopropane into propene. Another
example of unimolecular reaction is the gas phase decomposition of cyclobutane,
C4H10 to ethylene, C2H2.

C4H8 2C2H2

d [C 4 H 8 ]
The rate law for the above unimolecular reaction is given by  k[C 4 H 8 ]
dt

Thus the rate law for a unimolecular elementary reaction is first order in the
reactant.

d[ X ]
X Z  k[ X ]
dt

Bimolecular reaction involves two reacting molecules colliding with each other
and exchanging energy, atoms, or groups of atoms, or undergo some other kind
of change to form product(s).
Thus the rate law for a bimolecular elementary reaction is second order in the
reactants.
 d[ X ]
X + Y Z   k[ X ][Y ]
dt

The difference between order of a reaction and molecularity of a reaction is that

order of a reaction is an empirical quantity, and can be derived from the rate law
experimentally while molecularity is an elementary reaction proposed as an
individual step in a mechanism.
Termolecular reactions: These are reactions that involve three reacting
molecules. These reactions are not common.
2NO(g) + O2(g) 2NO2(g)

Rate Determining Step

This is the slowest step in a reaction mechanism. It one considers the equations
above, the first elementary step (step 1) is the slow step and is referred to as the
rate determining step.