Bimolecular Reactions

The most common type of elementary process is a

bimolecular reaction that results from the collision of two
molecules, atoms or ions.
Eg: 2 NO2 collision N2O4

The characteristic feature of a bimolecular elementary

reaction is a collision between two species, giving a
collision complex that result in a rearrangement of
chemical bonds (breaking of old bonds in reactants and
formation of new bonds in products).

Collision theory of a bimolecular reaction

Collision theory qualitatively explains how chemical

reactions occur and why reaction rates differ for different
reactions.
Reactant particles must collide, but only a certain
fraction of the total collisions have the energy to
connect effectively and cause the reactants to
transform into the products.

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 Only a portion of the molecules have enough energy
and the right orientation during to break any existing
bonds and form new ones.
The minimal amount of energy needed is known as
activation energy, Ea.

Note:

o If the elements react with each other, the collision is

called successful / effective collisions.
o If the concentration of at least one of the elements is
too low, there will be fewer particles for the other
elements to react with and the reaction will happen
much more slowly.
o As temperature increases, the average kinetic energy
and speed of the molecules increase but this only
slightly increases the number of collisions.
o The rate of the reaction increases with temperature
because a higher fraction of the collisions is able to
overcome the Ea.

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Under the collision theory, three aspects of achieving
effective collision:
a) encounter rate
b) minimum energy requirement
c) steric requirement

Rate Constant

The rate constant for a bimolecular gas phase reaction, as

predicted by collision theory is:

where:
Z = collision frequency.
= steric factor.
Ea = activation energy of the reaction.
T = absolute temperature (K).
R = gas constant.

The collision frequency is:

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where:
NA = Avogadro's number
AB = reaction cross section
kB = Boltzmann's constant
AB = reduced mass of the reactants.

From Maxwell Boltzmann distribution it can be 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]

The product Z is equivalent to the pre-exponential factor

of the Arrhenius equation.

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Validity of the theory and steric factor

Once a theory is formulated, its validity must be tested, by

comparing its predictions with the results of the
experiments.

When the expression form of the rate constant is

compared with the rate equation for an elementary
bimolecular reaction, Rate = k [A] [B],

That expression is similar to the Arrhenius equation, and

gives the first theoretical explanation for the Arrhenius
equation on a molecular basis.

The weak temperature dependence of the pre-exponential

factor is so small compared to the exponential factor that
it cannot be measured experimentally.

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Steric factor

o If the values of the predicted rate constants are

compared with the values of known rate constants, it
is noticed that collision theory fails to estimate the
constants correctly and the more complex the
molecules are, the more it fails.
o The reason for this is that particles have been
supposed to be spherical and able to react in all
directions - that is not true, as the orientation of the
collisions is not always the right one.

o For example in the hydrogenation reaction of

ethylene, the H2 molecule must approach the bonding
zone between the atoms, and only a few of all the
possible collisions fulfill this requirement.

o To alleviate this problem, a new concept must be

introduced: the steric factor, .
o Steric factor is defined as the ratio between the
experimental value and the predicted one (or the ratio
between the frequency factor and the collision
frequency). It is most often less than unity.

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o Usually, the more complex the reactant molecules,
the lower the steric factor.
o Nevertheless, some reactions exhibit steric factors
greater than unity: the harpoon reactions, which
involve atoms that exchange electrons, producing
ions.
o The deviation from unity can have different causes:
the molecules are not spherical - different geometries
are possible; not all the kinetic energy is delivered
into the right spot; the presence of a solvent (when
applied to solutions), etc.

Experimental rate constants compared to the ones

predicted by collision theory for gas phase reactions
A Z
Reaction (frequency (collision (Steric
factor) frequency) factor)
2NOCl 2Cl + 2NO 9.4 x 109 5.9 x 1010 0.16
2ClO Cl2 + O2 6.3 x 107 2.5 x 1010 2.5 x 10-3
H2 + C2H4 C2H6 1.24 x 106 7.3 x 1011 1.7 x 10-6
Br2 + K KBr + Br 1 x 1012 2.1 x 1011 4.8

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For the reaction Br2 + K KBr + Br, is > 1 (4.8),
the distance of approach at which reaction occurs
appears to be considerably larger than the distance
needed for deflection of the path of the approaching
molecules in a non-reactive collision.
the reaction proceeds by a harpoon mechanism.

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 Harpoon Mechanism, > 1

K + Br2 KBr + Br

Process:
i. K atom approaching a Br2 molecule, when the two
are close enough, the valence electron (the harpoon)
flips across from K to Br2. Such a transfer is possible
even when the reactants are far apart (5 10 ).
ii. In place of two neutral particles, there are now two
ions, and so there is a strong Coulombic attraction
between them: this attraction is the line on the
harpoon.
iii. Under its influence the ions move together, the
reaction takes place, and KBr + Br emerge.

Harpoon Mechanism:

K+ .e- Br2 K+ Br2-

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The attractive force creates a larger cross-sectional
reactive area than predicted by collision theory.

Before: K+ .e- Br2, energy = E

After: K+ Br2- (electrostatic attraction), energy
= E

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.

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There are three energies contribute to the charge transfer
process:
a) Ionization energy of K = IE.
The IE must be low enough so that the valence
electron is easily donated.
b) Electron affinity of Br2 = EA.
The EA must be high enough for better acceptance of
electron from the donor.
c) Coulombic interaction energy between the ions = -
, where e = electronic charge q+q-, 0 =
permittivity of vacuum.
The Coulombic interaction must be strong enough to
attract the two different charges together.

The charge transfer occurs when the difference between

IE and EA is balanced by the Coulombic interaction
energy:

= IE EA = E

Rx = the critical distance at which charge transfer takes

place.
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 the nearest distance at which K+ ion meets with Br2-
ion.
Rx depends on the three energy contributions.

Therefore, in the Harpoon mechanism, the collision cross-

section can be obtained as, * = Rx2. While in normal
bimolecular collisions, = d2. [Rx d; d = (dA + dB)]
In order for the Harpoon mechanism to occur, E is
negative.

This mechanism, which has been worked out

quantitatively, explains why the reaction occurs far more
readily than might be expected taking into account only
mechanical collisions between the alkali-metal atoms and
halogen molecules.

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