Molecularity

Molecularity in chemistry is the number of molecules

that come together to react in an elementary (single-
step) reaction[1] and is equal to the sum of
stoichiometric coefficients of reactants in this
elementary reaction.[2] Depending on how many
molecules come together, a reaction can be unimolecular,
bimolecular or trimolecular.

The kinetic order of any elementary reaction or

reaction step is equal to its molecularity, and the rate
equation of an elementary reaction can therefore be
determined by inspection, from the molecularity.[1]

The kinetic order of a complex (multistep) reaction,

however, cannot be equated to molecularity since
molecularity only describes elementary reactions or
steps.

Unimolecular reactions
In a unimolecular reaction, a single molecule rearranges
atoms forming different molecules.[1] This is illustrated
by the equation

where P means Product(s). The reaction or reaction

step is an isomerization if there is only one product
molecule, or a dissociation if there is more than one
product molecule.

In either case, the rate of the reaction or step is

described by the first order rate law

where [A] is the concentration of species A, t is time,

and kr is the reaction rate constant.

As can be deduced from the rate law equation, the

number of A molecules that decay is proportional to the
number of A molecules available. An example of a
unimolecular reaction, is the isomerization of
cyclopropane to propene:
Unimolecular reactions can be explained by the
Lindemann-Hinshelwood mechanism.

Bimolecular reactions
In a bimolecular reaction, two molecules collide and
exchange energy, atoms or groups of atoms.[1]

This can be described by the equation

which corresponds to the second order rate law:

.
Here, the rate of the reaction is proportional to the
rate at which the reactants come together. An example
of a bimolecular reaction is the SN2-type nucleophilic
substitution of methyl bromide by hydroxide ion:[3]

Termolecular reactions
A termolecular[4][5] (or trimolecular)[6] reaction in
solutions or gas mixtures involves three reactant
molecules simultaneously colliding.[4] However the
term trimolecular is also used to refer to three body
association reactions of the type
Where the M over the arrow denotes that to conserve
energy and momentum a second reaction with a third
body is required. After the initial bimolecular collision
of A and B an energetically excited reaction
intermediate is formed, then, it collides with a M
body, in a second bimolecular reaction, transferring the
excess energy to it.[7]

The reaction can be explained as two consecutive

reactions:

These reactions frequently have a pressure and

temperature dependence region of transition between
second and third order kinetics.[8]
Catalytic reactions are often three-component, but in
practice a complex of the starting materials is first
formed and the rate-determining step is the reaction of
this complex into products, not an adventitious collision
between the two species and the catalyst. For example,
in hydrogenation with a metal catalyst, molecular
dihydrogen first dissociates onto the metal surface into
hydrogen atoms bound to the surface, and it is these
monatomic hydrogens that react with the starting
material, also previously adsorbed onto the surface.

Reactions of higher molecularity are not observed due

to very small probability of simultaneous interaction
between 4 or more molecules[9][4]

Difference between
molecularity and order of
reaction
It is important to distinguish molecularity from order of
reaction. The order of reaction is an empirical quantity
determined by experiment from the rate law of the
reaction. It is the sum of the exponents in the rate law
equation.[10] Molecularity, on the other hand, is
deduced from the mechanism of an elementary
reaction, and is used only in context of an elementary
reaction. It is the number of molecules taking part in
this reaction.

This difference can be illustrated on the reaction

between nitric oxide and hydrogen:

.[11]
The observed rate law is , so
that the reaction is third order. Since the order does
not equal the sum of reactant stoichiometric
coefficients, the reaction must involve more than one
step. The proposed two-step mechanism[11] has a rate-
limiting first step whose molecularity corresponds to the
overall order of 3:

(slow)
(fast)

On the other hand, the molecularity of this reaction is

undefined, because it involves a mechanism of more
than one step. However, we can consider the
molecularity of the individual elementary reactions
that make up this mechanism: the first step is
termolecular because it involves three reactant
molecules, while the second step is bimolecular because
it involves two reactant molecules.

See also
Reaction rate

References
1. Atkins, P.; de Paula, J. Physical Chemistry.
Oxford University Press, 2014
2. Temkin, O. N. State-of-the-Art in the Theory
of Kinetics of Complex Reactions. In
Homogeneous Catalysis with Metal Complexes:
Kinetic Aspects and Mechanisms, John Wiley
and Sons, ltd, 2012
3. Morrison R.T. and Boyd R.N. Organic
Chemistry (4th ed., Allyn and Bacon 1983)
p.215 ISBN 0-205-05838-8
4. J.I. Steinfeld, J.S. Francisco and W.L. Hase
Chemical Kinetics and Dynamics (2nd ed.,
Prentice Hall 1999) p.5, ISBN 0-13-737123-3
5. IUPAC Gold Book: Molecularity
6. One textbook which mentions both termolecular
and trimolecular as alternative names is J.W.
Moore and R.G. Pearson, Kinetics and
Mechanism (3rd ed., John Wiley 1981) p.17,
ISBN 0-471-03558-0
7. Text discussing rate constants for termolecular
reactions [1]
 8. IUPAC definition of Troe expression, a
semiempirical expression for the rate constant of
termolecular reactions [2]
9. Carr, R. W. Chemical Kinetics. In
Encyclopedia of Applied Physics. WILEY-
VCH Verlag GmbH & Co KGaA, 2003
10. Rogers, D. W. Chemical Kinetics. In Concise
Physical Chemistry, John Wiley and Sons, Inc.
2010.
11. Keith J. Laidler, Chemical Kinetics (3rd ed.,
Harper & Row 1987), p.277 ISBN 0-06-
043862-2

Retrieved from "https://en.wikipedia.org/w/index.php?

title=Molecularity&oldid=993030135"
 Last edited 6 days ago by Jānis Barbans

Content is available under CC BY-SA 3.0 unless otherwise

noted.