Molecularity, Mechanism and Rate Law of a

Reaction
For a chemical reaction to occur, the reacting molecules should
collide with each as said by collisions theory.

Molecularity is defined as the number of reacting species (molecues,

atoms, or ions), which collide simultaneously to bring about a
chemical reaction. Depending on the number of reacting species
reactions can be unimolecular, bimolecular or trimolecular.

Unimolecular reaction:

i) The decomposition of hydrogen peroxide involves single species,

which undergoes the change to form products.

ii) Decomposition of ammonium nitrite is also unimolecular reaction

because it involves only one reacting species.
Bimolecular reactions:

When reactions involve the collision of two species, then it is called

bimolecular reactions.

Tri -molecular reactions:

When reactions involve the collision of three species, then it is called

trimolecular reactions.
In the similar way, we can expect reactions, which involve the
collision of four or more molecules. But it is observed that reactions
involving three or more molecules are uncommon due to the fact that
for these reactions simultaneous collision of three molecules is
required. It means third molecule must collide with the other two
molecules at the same time when they are in process of collision. The
chances of the occurrence of such collisions are very rare.

On this basis we can say that reactions involving three or more than
three reacting particles should be slow. However, it is observed that
some reactions involving more than three molecules are quite fast.

For example consider a following reaction

The experimental measured rate of this reaction is:

Rate = k [Br-] [BrO3-] [H+] 2

Thus the rate if a reaction is of first order with respect to Br- and
BrO3- ion and second order with respect to H+ ions and the overall
reaction is of1+1+2 =4.But from the reaction it is clear that the
reaction is to take place in single step, the 12 particles (5Br- ions, 1
BrO3- ion and 6H+ions) would have to collide simultaneously.

Similarly, taking the case of potassium chlorate with ferrous sulphate

in the presence of sulphuric acid involves ten species.

The above reaction is appears to tenth order but actually it is a second

order reaction. This means that if the reaction is to take place in single
step, the 10 particles (1KClO3, 6 FeSO4 and 3H2SO4) would have to
collide simultaneously.

Such type of reactions is very small. Reactions with large number of

collision will not occur generally. But if the reaction is found to be
quite fast, it means that even though the balanced equation involves a
large number of molecules, yet the reaction does not proceed by
simultaneous collision of all these reacting particles. It can involve
two or maximum three collisions simultaneous.

Such type of reactions which take place through a sequence of two or

more consecutive steps are called complex reactions .The detailed
description of various steps by which reactant change into products
is called mechanism of reaction. The steps which contribute to the
overall reaction are called elementary processes.

Mechanism and rate law:

In case of multi step reaction each elementary step will take place its
own distinctive rate. Some of the steps will be very fast and some of
them will be slow.

If one step takes place much more slowly than the other steps, it will
definitely control the overall reaction rate. It means that all other
steps have to wait for the slow step.

The rate of the reaction will never be less than the rate of this slow
reaction. The other reactions will under go completion and form
products only after the occurrence of the slow step reaction.

Thus, the rate of a reaction can be defined as the rate of reaction,

which is determined by the slowest step in the sequence of complex
reaction. In other words slowest step is the rate-determining step in
the given mechanism.

Consider a reaction between NO2 andF2 to form NO2F.

From the experimental observations it is found that the rate of a

reaction is proportional to the concentration of nitrogen peroxide and
fluorine. This shows that rate-determining step in the mechanism of
this reaction must be the reaction between NO2 and F2 only. So this
reaction should be present in the mechanism of the reaction.

In the above example slow step will determine the rate of reaction
Each step in the above mechanism is called elementary reaction Sum
of all the elementary reactions will give the net reaction or overall
reaction. So rate of the above reaction can be written as:

Rate = - dx/dt = k [NO2] [F2]

This is the rate law for the reaction.

Some More Examples

1)
From the experimental observations it is found that the rate of a
reaction is proportional to the square concentration of nitrogen
peroxide. This shows that rate-determining step in the mechanism of
this reaction must be independent of the concentration of CO. The
proposed mechanism of this reaction will be

The above reaction proceed in two steps but the rate of the overall
reaction is determined by the first step which is the slower step
Rate of the above reaction can be written as;

Rate = k [NO2] 2

This is the rate law for the reaction.

2) Thermal decomposition of dinitrogen pentaoxide,

Experimentally rate of the reaction is given as

Rate of reaction = k [N2O5].

If the reaction were to be taken place by the collision of two N2O5

molecules then the reaction will of second order reaction

Rate = k [N2O5] 2

But is found that rate law suggests it is of first order reaction. This
means reaction is a complex reaction and takes place by two or more
successive steps.

Expected mechanism of the above reaction is

Since slow step is the rate determining step, so above reaction of first
order reaction.

Rate = k [N2O5] 2

3) Reaction of NO and H2 as:

Experimentally determined rate of the reaction is

Rate = k [NO] 2 [H2]

The rate law expression suggest that it is a complex reaction and will
proceed in a sequence of steps which are as follows
Since slow step is the rate-determining step, so above reaction is of
third order reaction i.e.

Rate = k [NO] 2 [H2]

4) Reaction of decomposition of hypochlorite (ClO-)

Mechanism

The first step is the slow and rate determining step. Thus, the rate
of the reaction is

Rate = k [ClO-] [ClO-] =k [ClO-] 2

So the above reaction is of second order reaction.

5) Reaction of decomposition of hydrogen peroxide

The decomposition of H2O2 is catalyzed by iodide ion in alkaline

medium.
 Alkaline medium

Experimentally calculated rate of reaction is

Rate = k [H2O2][I-]

The rate of reaction is of first order with respect to both H2O2and I-

. This means that the reaction is a complex reaction and takes place
in two or more successive steps.

So the probable mechanism for the reaction will be;

Since the first step is the slow, rate determining step. Thus, the rate
of the reaction is:
Rate = k [H2O2][I-]
 Distinction between Molecularity and order of reaction

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