KINETICS

Collision theory
Transition theory
Consecutive and parallel
reactions

Rate of the reaction

A chemical reaction can be represented by:

where is the stoichiometric number of Bi.

The extent of reaction is the same for each reactant and product, and

the initial amount of

reactant i.

Hence we have:

By convention the rate of the reaction is defined in terms of the rate of

change of the concentration of a reactant or product so that

The rate of the reaction for: A + 2B = X

The same rate of reaction is obtained, no matter which reactant or product is studied.

The rate of reaction does depend on how the stoichiometric equation is written.
If the reaction goes in the forward direction, the rate of reaction is positive. If the reaction
goes in the backward direction, the rate of reaction is negative. If the reaction is at
equilibrium, the rate of reaction is zero (i.e. forward rate = backward rate ).

Order of the reaction

At constant temperature the rate of reaction depends on the concentrations of
reactants and products, in absence of catalysts and inhibitors. If the reaction
A + 2B = X
goes essentially to completion to the right, the rate of reaction may be experimentally
found to be:

rate
constant

The exponent and is referred to as the order of the reaction with respect to
reactant A and B respectively; and are independent of concentration and time.
and are not the stoichiometric numbers in the balanced chemical equation, but
have to be obtained from rate experiments.

the overall order of the reaction is + .

Arrhenius rate equation

An empirical equation for rate constant was proposed by Arrhenius for dependence
of rate constants on temperature over a limited range as

where A is the pre-exponential factor and is the activation energy.

This implies rate increases with increase in temperature.

Logarithmic form:

Definition of activation
energy (differential form)

On integrating the differential form:

Collision Theory
Collision
diameter
Relative velocity

Collision velocity

= 2 1 + 2 = 12

Impact
parameter

Molecules are considered as hard spheres

1
2
1
<2

For distances

1 + 2 , V = 0.

For distances

1 + 2 , V = .

Intermolecular
potential (V) 0

1
+ 2
2 1

Intermolecular
distance

Postulates of Collision theory

Molecules are considered as rigid hard spheres having translational energy

Activation energy is restricted only to translational energy. Collisions that are
sufficiently energetic to supply the activation energy produce reaction.
For a reaction to occur the molecules must collide and if they posses energy equal
to or greater than threshold energy, their collision result in the product of the
reaction.
Only small fraction of collisions are effective, which is given by the Boltzmann
factor /() .

Suppose reaction occurs with collision between molecules of type 1 and type 2.
B1 + B2 = Product
From collision theory of hard spheres:
The number of collisions of molecules of type 1 with molecules of type 2 per unit
time per unit volume 12 (collision density or collision number):

The number of collisions of molecules of type 1 with other molecules of type 1 per
unit time per unit volume 11 :

= no. of molecules of type i per unit volume and is given as:

Avogardos number

= Mean relative speed

Reduced mass
Mean relative speed can be written as

Substituting for and 12 we have:

According to hard-sphere collision theory Lewis and Trautz formulated that,

collision number multiplied by the Arrhenius factor /() gives the rate in terms
of the no. of molecules formed per unit volume and per unit time.
Hence reaction rate in moles of collisions between molecules of type 1 and
type 2 per unit volume per unit time is given as

fraction of collisions that provide

energy greater than E.

Rate constant:
Collision frequency factor
Collision cross section
Deviations from this theory are encountered with solution reactions between
ions or dipolar substances.
Remedy: Two molecules must also come together with such mutual orientation
that necessary bonds can be broken and made. Rate constant can be written as:

P = Steric factor = fraction of total number of collisions that have the right mutual
orientation.
Note: Units of collision frequency factor 12 is same as rate constant k, which is per
unit concentration per unit time.

Rate constant from collision theory for the reaction B1+B1products

d diameter of B1; mmass of B1

Note: Here too units of collision frequency factor 11 is same as rate constant k.

Drawbacks of collision theory

P cant be evaluated in a satisfactory manner.
If factors other than orientation are involved, they cant again be estimated easily
It is not consistent wit the fact that at equilibrium the ratio of rate constants in the
forward and backward directions is the equilibrium constant

Lacks entropy term that should appear in

expression for K as = / /

Potential Energy Surfaces

For the reaction
where A, B, and C are atoms

Suppose nuclei are constrained

to a line.
Reaction coordinate

The highest point along the reaction

coordinate is a saddle point. The reaction
system at this point is said to be in the
transition state.