Title: Difference between unimolecular and bimolecular reaction

Elementary reactions defines as a single step reaction with a single transition state and
without intermediates. In the elementary reactions, the elementary reaction indicate exactly
which molecules, atoms, or ion participate in it. The molecularity of a reaction can be define
as the number of molecules reacting in an elementary step. Molecurarity can be defined as
unimolecular, bimolecular or trimolecular.

Unimolecular reaction is an elementary step that involves only one reacting molecule. In
a unimolecular reaction, the structure of a single particle which are molecule or ion
rearranges to form different particles as final products. Unimolecular reaction are no
intermediate steps that the reacting molecule go through the formation of final products as it
only happen in a single step. Besides, a unimolecular reaction might involve breaking a bond
and forming two molecules, or it might involve rearrangement of one isomeric structure into
another. The examples of unimolecular reactions are include radioactive decay, thermal
decomposition, ring opening, and racemization. The overall rate law for the unimolecular
elementary reaction can be expressed as:
𝑑[𝐴]
A → Product = −𝑘[𝐴]
𝑑𝑡

A unimolecular reaction always is first-order reaction because the amount of molecule

that reacts is proportional to the number of molecules that have not reacted. It also can be
explained by the Lindemann-Hinshelwood Mechanism. Lindemann-Hinshelwood mechanism
break down a unimolecular reaction into two or more elementary steps with a rate constant
for each elementary steps. The unimolecular reaction A → B can be explained by the
Lindemann-Hinshelwood mechanism in the following equation:
k1
A + M ⇌ A* + M
k-1
𝑘2
A →B
*

In this scheme, A* is an A molecule that has sufficient vibrational energy to decompose.

A* is called an energized molecule. The energized molecule A* is formed by collision of A
with M molecule in step 1. In this collision, vibrational energy of A* is transferred by kinetic
energy of M. M could be another A molecule as some M molecule can excite A to a higher
vibrational level. Once A* has been formed, it could reverse back to A in a collision or
formed product B by having the extra vibrational energy to break the chemical bond and lead
to decomposition. By applying the steady-state approximation to the energized molecule A*,
we have
𝑑[𝐴∗ ]
= 𝑘1 [𝐴] − 𝑘−1 [𝐴∗ ][𝑀] − 𝑘2 [𝐴∗ ] ≈ 0
𝑑𝑡
𝑘1 [𝐴][𝑀]
Thus, [𝐴∗ ] = 𝑘
−1 [𝑀]+ 𝑘2
The overall rate equation is
𝑑[𝐵] 𝑘1 𝑘2 [𝐴][𝑀]
=
𝑑𝑡 𝑘−1 [𝑀] + 𝑘2

There are two limiting case for unimolecular reaction. If k-1 [M] >> k2, then we can
neglected k2 and obtain:
 𝑑[𝐵] 𝑘1 𝑘2
≈ 𝑘 [𝑀], 𝑤ℎ𝑒𝑟𝑒 𝑘 = [𝐴]
𝑑𝑡 𝑘−1
This equation is first order rate law.
If k2 >> k-1 [M], this reaction become second order-order kinetics as low pressure, the rate-
determining step is the bimolecular formation of 𝐴∗ and the rate law becomes
𝑑[𝐵]
≈ 𝑘1 [𝐴][𝑀]
𝑑𝑡
The full rate law equation becomes
𝑘1 𝑘2 [𝐴] 𝑘1 𝑘2
𝑘= =
𝑘−1 [𝑀] + 𝑘2 𝑘−1 + 𝑘2 /[𝑀]
The expression for the effective rate constant, k can be arranged to
1 1 𝑘−1
= +
𝑘 𝑘1 [𝑀] 𝑘1 𝑘2
This equation which predicts that a plot 1/k against 1/P0 will be linear.
Bimolecular reaction is an elementary step that involves two molecules as reactants. In a
bimolecular reaction, two particles which are atoms, molecules or ions collide and rearrange
to form products. In a bimolecular reaction, the formation of new chemical bond between the
reactant particles, and existing bonds may be broken. Occasionally the two particles combine
to form a new, bigger one. Occasionally the original two were formed two new molecules.
The bimolecular reaction is second order reaction as the rate rely on the two molecules to
collide each other and so rely on the concentration of both molecules. The overall rate law for
the bimolecular elementary reaction can be expressed as:
𝑑[𝐴]
A + B → Product or A + A → Product = −𝑘[𝐴][𝐵]
𝑑𝑡
The rate constant for a bimolecular gas phase reaction can predicted by collision theory
which is:
−𝐸𝑎
k(T) = 𝑍𝜌exp( )
𝑅𝑇

From Maxwell Boltzmann distribution it can deduced that the fraction of collisions with more
energy than the activation energy is exp (−𝐸𝑎 /RT). Therefore, the rate of a bimolecular
reaction for ideal gases will be:
Rate= k [A][B]
−𝐸
r = 𝑍𝜌[A][B]exp( 𝑅𝑇𝑎 )
The product Z𝜌 is corresponding to the pre-exponential factor of the Arrhenius equation.
Steric factor is a term used in collision theory. It can be defined as the ratio between the
experimental value and the expected one or the ratio between the frequency factor and the
collision frequency. Steric factor is most often less than unity, which means it less than 1.
Generally, the more complex the reactant molecules, the lower the steric factor. Steric factor
can be expressed as an equation:
 𝐴𝑜𝑏𝑠𝑒𝑟𝑣𝑒𝑑
𝜌=
𝑍𝑐𝑎𝑙𝑐𝑢𝑙𝑎𝑡𝑒𝑑

However, there are some of the reactions that exhibit steric factors larger than unity,
which is a harpoon reactions. Harpoon reactions are a type of chemical reaction between two
substances: one is metal atom that form a cation, another one is halogen molecule that form
an anion and it refers to harpoon mechanism. Harpoon mechanism is a mechanism
recommended to explain a metal atom such as sodium or potassium and a halogen molecule
such as bromine. The chemical equation between the potassium and bromine is K + Br2 →
KBr + Br. When the potassium atom move towards the bromine molecule its valence electron
moves to the bromine molecule thus providing a ‘harpoon’. There is a strong Coulombic
attraction between the two ions. As a result the ions move together and the reaction takes
place, and KBr + Br emerges. The attractive force generates a greater cross-sectional reactive
area than predicted by collision theory. The harpoon extends the cross-section for the reactive
encounter, and the reaction rate is greatly underestimated by only taking for the collision
cross-section the value for simple mechanical contact between K + Br2. Harpoon mechanism,
which has been worked out quantitatively, explains why the reaction happens far more
readily than might be expected taking into account only mechanical collisions between the
alkali-metal atoms and halogen molecules. Harpoon mechanism are shown below:
K+ .e- →→ Br2 K+ ↔ Br-2

The difference between the unimolecular reaction and bimolecular reaction can be
explained by table:

Unimolecular vs Bimolecular Reactions

Unimolecular reaction is an elementary step Bimolecular reaction is an elementary step
that involves only one reacting molecule. that involves two molecules as reactants.
Reactants
Unimolecular reaction have only one Bimolecular reaction have two reactants.
reactant. A → Product A + B → Product or A + A → Product
Order of Rate Law
Unimolecular reactions can be explained by Bimolecular reactions can be explained by
first order of rate law. rate = k[A] second-order rate law. rate law = k[A]2
Overall Order
The whole order of the rate equation of The whole order of the rate equation of
unimolecular reactions is always 1. bimolecular reactions is always 2.

In conclusion, both of the unimolecular reactions and bimolecular reaction are reactions
and form the product in a single step. The difference between unimolecular reactions and
bimolecular reactions can be explained by reactants involved in the reaction, order of rate law
and overall order of the rate equation.
References
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