1.5.

3 Chemical Reaction Rate and Activation Energy

Chemical Reaction Rate : The speed of a chemical reaction may be defined as the change in
concentration of a substance divided by the time interval during which this change is observed:

Consider the following Reaction

2HI H2 + I2
The Reaction Rate V is Given by
V = d[HI]/dt = k[HI]
Where [ HI ] is the Concentration Of HI k is the reaction Rate constant . Which Can be
experimentally determined by using the Arrhenius Equation.:
ln k =a-bT
k=exp(a).exp(b/t)
Arrhenius Equation : The Arrhenius equation is a simple but remarkably accurate formula for

the temperature dependence of the reaction rate constant, and therefore, the rate of a chemical
reaction. The equation was first proposed by Svante Arrhenius in 1884.
The equation relates k, the rate constant for a given chemical reaction, with the temparature
T, the activation energy for the reaction, Ea , , and the universal gas constant, R.
High temperature and low activation energy favor larger rate constants, and therefore speed
up the reaction.

 The equation is a combination of the concepts of activation energy and the MaxwellBoltzmann distribution.

The statistical theory of Boltzman and Maxwell shows that the number of molecules with an
energy greater than Ea is proportional to exp(Ea /RT) As Shown in fig 1.5.1
The Arrhenius equation shows that the probability of the HI molecules undergoing dissociation
is proportional to the number of molecules with energy greater than the threshold energy Ea
When the Free energy of the HI molecules exceeds Ea temperature T .
HI molecules assumed to approach within a certain distance enabling them to collide and form
the new bonds of H2 and I2 This energy Ea is called the Activation Energy
The Reaction Rate is limited by the probability that the reading molecule will have a free energy
exceeding the activation energy
Using this concept the reaction rate V can be expressed by the following Arrhenius Reaction
V= Aexp (-Ea /RT)
Where A is the basic Constant for the Reaction Rate.

In case of chemical reaction involving free energy states G1 to G2 as shown in fig 1.5.2
The Reaction G1 to G2 take place
State G1 Must be raised to the activation state Ga
Where Ga=G1 + Ea
The reaction rate in this case is determined by equation The chemical Reaction from G2 to G1
the reaction rate is given by
V = Aexp( (-Ea+G)/RT)

Then the net reaction rate of the system is

V - V =Aexp (-Ea /RT).[1-exp(-G/RT)

If G>0, then V>V and the reaction proceeds from state G1 TO G2

In a Electro chemical reaction , ionized atoms in the reacting liquids are accelerated by the
external electric field to a kinetic energy corresponding to the activation energy for reaction the
mean free path of the ions becomes longer than in ordinary Bronian Motion and the

probability that the reactive atoms will collide with each other increases .thus the Reaction rate
in the electric field is higher than that in the absence of an electric field.