The number of collisions that takes place per second per unit volume of
the reaction mixture is called collision frequency. The value of collision
frequency is generally very high. Under ordinary conditions of
temperature and pressure in a gaseous system, the collision frequency of
binary collisions is of the order 1025 to 1028
This theory explains that how chemical reactions take place and why
rates of reaction changes. For a reaction to occur, the reactant particles
must collide. Only a certain fraction of the total collisions results in the
formation of products. Such collisions are called effective or successful
collisions.
For the reacting species to make effetive collisions they should have
sufficient energy to break the chemical bonds in the reacting molecules.
The minimum amount of energy which the colliding moleccules must
possess is known as threshold energy. This means that only those
collisions of reactants which possess energies greater than threshold
energy will give products.
Orientation barrier :
The colliding molecules should also have proper orientation so that the
old bonds may break and new bonds are formed.
During this reaction, the products are formed only when the colliding
molecules have proper orientationat the time of collisions .These are
called effective collisions.
On the other hand when molecules are not properly orientedat the of
collision,they result in ifeffective collisionsand donot form products.
Take another example ,the reaction between bromoethane with OH- ions
to form methanol. The OH- ions must attack the positively charged
carbon to form an intermediate whch changes to product after
elimination of Br- ion. If OH- does not get proper site for attack, the
reaction will not occur.
Effective collisions:
The reacting molecuels having energy less than threshold energy will
not undergo effective collisions and are not able to form products. Thus
the energy of collisions determines the possibility of a reaction.
There are some collisions which are highly energetic while others are
not. This can be understood by taking an example . As we know that all
the molecules in a substance don’t possess the same kinetic energy
because of the collision between the moving molecuels.
The fraction of molecules having very low or very high energies is very
small. The peak of the graph shows that most of the molecules have
intermediate kinetic energies. E corresponds to the minimum or
threshold energy required for the effective collisions.
It may be noted that Lower the value of activation energy larger will be
the fraction of colliding molecules for effective collisions.This will
increase the rate of reaction.
From the graph we can get that at high temperature the curve is shifted
towards the right which indicates that at high temperature the molecules
have higher energies.
And it is also clear that the curve at high temperature is flatter than at
lower temperature. This means that the number of molecules with higher
energy have increased .
The number of molecules having energies equal to or greater than
threshold energy is proportional to the area abcd at temperature T1 and
area abef at temperature T2. The area abef is roughly twice as large as
abcd.
Catalyst provides a new path for the reaction in which reactants are
converted to products quickly. Catalyst forms a new activated complex
of lower potential energy. This means that for the catalyzed reactions
the activation energy is lower than that for the uncatalyzed reaction.
As a result the fraction of total number of collisions possessing lower
activation energy is increased and hence the rate of reaction also
increases. This can be explained with the help of a figure.
Photochemical reactions:
There are certain reactions where the rate of chemical reaction is affected
by certain radiation. The photons of these radiations having frequencies
possess sufficient energy to overcome the activation barriers. Such types
of reactions, which are initiated by absorption of radiation, are called
photochemical reactions. There are various examples like preparation of
HCl, photosynthesis, polymerization, photography, sterilization of
water, photo etching etc.
Generally ultraviolet and visible radiations are used for carrying out
such types of reactions because their photons possess energies
approximately of the order of 420 kJ/mole, which is comparable to most
of the bond energies.
4) In some cases the molecule that absorbs light may transfer it’s
energy to another molecule, which undergoes a reaction. This is
called photosensitizations
2) The chlorine atom formed in the first step attacks the hydrogen
molecule and forms HCl and hydrogen atom.
5) There are some reactions, which remove the active species needed
for the propagation of the reaction. This called chain-terminating
step.
Differences between photochemical reaction and thermo chemical
reaction:
Photosensitization:
There are some reactions which don’t get initiated directly when
exposed to the radiations. For the initiations of such type of reactions a
small amount of a foreign material, which can absorb light, is added to
the reaction mixture. The added substance does not undergo any
chemical change but absorbs energy and transfers the excess energy to
one of the reactants. Such a substance which when added to the reaction
mixture helps to start a photochemical reaction without itself
undergoing any chemical change is called photosensitiser. The reaction
carried by the presence of photo sensitizer is called a photosensitization
reaction. For example, the dissociation of X2 can occur in the presence of
a photo sensitizer as:
ii)
Recently many new techniques have been developed to study
the fast reactions. These are flow methods, relaxation methods
and many spectrophotomeric techniques. For example,
photosynthesis reaction was studied by flash photolysis.