ARRHENIUS EQUATION AND CALCULATION

OF ACTIVATION ENERGY
Arrhenius gave a quantitative relation between rate constant and
temperatures:

This equation is called Arrehnius equation where A is called

frequency factor. Ea is the activation energy. Both A and Ea are the
characteristics of the equation and also called Arrehnius parameters.

The factor e-Ea/RT corresponds to the fraction of molecules that have

kinetic energy greater than Ea. T is the absolute temperature and R is
the gas constant.

Taking logarithm, the equation will be written as:

It is clear that as the value of activation energy Ea increases, the value
of k decreases and, therefore the reaction rate decreases.

Calculation of activation energy:

With the help of above equation we can calculate the activation

energy of the reaction. The equation is in the form y= mx + c which
represents a straight line.

If we plot a graph between log k and 1/T we will get a straight line.

The intercept of this line is equal to log A and slope is equal to –Ea
/2.303RT.
By knowing the value of slope and gas constant R, activation energy
can be calculated as

Alternatively, Ea and A can be determined by measuring the value of

rate constant at two different temperatures.

Let k1 and k2 are the rate constants for the reaction at two different
temperaturesT1andT2respectively.

Then,
Concept of activation energy and transition theory

There are various reactions like burning of coal, combustion of

hydrogen and oxygen gases that require some extra energy for the
completion of reaction. By absorbing this extra energy their energies
become equal to the minimum energy called threshold energy.

The excess energy (over and above the average energy of the
reactants) that must be supplied to the reactants to undergo chemical
reactions is called activation energy. Ea

It is equal to the difference threshold energy needed for the reaction

and average kinetic energy of all the reacting molecules.

Activation Energy = Threshold energy-Average Kinetic energy

Every reaction has a definite value of Ea (activation energy). This
energy decides the fraction of total collisions, which are effective. If
the value of activation energy for the reaction is low, then there will
be large number of molecules that have this energy and the fraction
of effective collisions (f,) will be large. The reaction will proceed at
high rate.

Activated complex state:

When the kinetic energy of the colliding molecules is equal to

activation energy Ea then the configuration of the reacting species
formed at this stage is different from the original reactant as well as
the product. This stage is called activation state or Transition state.

The reacting species with specific configuration at the activated state

is called activated complex or intermediate. This can be explained by
taking an example of the reaction between H2 (g) and I2 (g).

The activated complex has configuration in which H - H and I – I are

breaking and H – I are formed.

This activated or transition state is unstable which is in between the

reactants and the products. Its life period is very short because of
instability and splits into the products to acquire stable state of lower
energy.
Progress of a reaction:

According to the concept of activation energy, products are not

directly formed from reactants or in other words the reactants don’t
change into the products. The reactants first absorb energy equal to
activation energy and then activated complex is formed.

At this state the molecules have energy equal to the minimum energy
(Threshold energy) required to form products. It means that there
must be some energy barrier that has to be overcome before the
formation of products. This energy barrier is called activation energy
barrier.

Graphically it can be explained, as the energy barrier represented in

the graph obtained is the energy hump, which has to be crossed
before the formation of products from reactants.

Consider a general equation,

Average energy of the reactants is represented as Er and for products

it is Ep

The reaction between A (g) and B2 (g) will proceed only if the
colliding reactants must possess sufficient energy to reach the top of
the energy barrier and form activated complex. The energy required
to form the activated complex is called activation energy. The
activated complex can be represented as [A---- B].

This complex has very short life span and thus splits up into
products. It can be represented as

Activation energy plays an important role in comparing the rates of

reactions.

Activation energy and reversible reactions:

Consider a reversible reaction

A+B ↔ C+D

Just as activation energy is required for the forward reaction similarly

it is also required for backward reaction. During the progress of the
reaction the reactant molecules in the forward direction and product
molecules in the backward direction follow the same path and from
same activated complex but with a different activation energy.

This is represented graphically in the figure for both exothermic and

endothermic reactions.
From the graph it is clear that both the reactant molecules and the
product molecules in forward and backward direction respectively
has to pass through the transition state even though the activation
energies for both o the reactions are different.

Similarly

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