Reaction Kinetics

Steric effect- particles must approach in a particular orientation.

Collision Theory
For particles to react, they must:
 Collide with sufficient energy
 Collide in the correct orientation (steric effect)
In ineffective Collisions, the particles would just bounce of each other. In Effective
collisions, the reactant particles would get converted into product particles.

Activation Energy and Threshold Energy

In normal orientation, some molecules have high energy while some molecules have very low
energy and most have average energy. Threshold energy is the minimum amount of energy
required for the reaction to start off.
To start the reaction, we supply the activation energy. Activation energy is the minimum
amount of energy supplied to the substance for effective collisions. After the activation
energy is supplied, a higher number of molecules reach the threshold energy level.
When heat is supplied to a mixture, the threshold energy and the activation energy of the
mixture remain constant. Note that these two energies values are fixed boundaries. The
kinetic energy of the particles increases and then meet the threshold energy requirement.
In summary,
Activation energy= Threshold Energy- Internal energy.

A collision will speed up if:

 Frequency of collision increases (more molecules collide in unit time)
 The proportion of particles with energy more than the threshold energy increases.
As seen in the maxwell-Boltzmann distribution curve, only a smaller number of particles
have energy equal to the threshold energy.

The line marked from the x-axis to the top represents the threshold energy.
The line from the reactant to the peak will be activation energy
Effect of temperature on the reaction
The maxwell Boltzmann distribution curve shows the number of molecules in the y-axis and
the energy of the particles in the x-axis. The conclusions draw from this are:
- No particles have zero energy/velocity
- Some particles have energy equal to or above the threshold energy
- Some particles really have low energy
- Most particles have intermediate energy.
The notable conclusion is that only less particles have energy equal to the threshold energy.
During heating, it is to be noted that the area beneath the curve is same, as it denotes the
number of particles.
When the mixture is heated:

As the mixture is heated. Every particle gain energy, the overall energy increases, thus the
curve shifts right. The curve spreads more as particles gets more energy. More proportion of
particles exceed threshold energy, so the height of the curve at the right increases.
However, note that the threshold energy barrier will remain the same.
When the mixture is cooled:

Every particle loses energy, so the peak moves towards left. The peak height increases
because the spread of values is less. Less particles have energy equal to or greater than
the threshold value.

To conclude, increasing the temperature:

- Particles gain more kinetic energy and move faster
- Increased frequency of collisions (more collisions in unit time)
- The proportion of successful collisions increase as greater proportion of particles have
kinetic energy greater than activation energy.
If mixture heated:
- Peak shifts right
- Curve flattens out
- Right end height more
If mixture cooled:
- Peak shifts left
- Curve points up
- Right end height less
The area under the curve always
stays constant.
Effect of concentration on rate of reaction:
This is in only applicable to mixtures which are in aqueous state or liquid state.
Increasing the concentration:
 More number of particles per unit volume
 More frequency of successful collisions.

Effect of pressure on rate of reaction

This only applies to gaseous mixtures.
 More gas molecules per unit volume
 More frequency of successful collisions.

Effect of Catalysts
Catalyst increases the rate of a reaction, as they shift the reaction to an alternate pathway
which requires lower activation energy.

In the distribution curve; The threshold energy region increases, as the particles will now
have to achieve less energy to successfully react. Naturally, more number of particles will
meet this requirement.

Note: The enthalpy change using a catalyst is same, as without using a catalyst.
Most of the time, the enthalpy change and the activation energy are not the same.
When number of collisions increases,the rate of reaction increases.

Catalyst is a species that decreases the activation energy of the mixture, so that more molecules
have successful collisions. This influence is done by making an alternative route to the reaction.
Heterogenous catalyst- reactants and catalyst are in different phase
Eg: phosphoric acid in hydration

Vanadium pentoxide in contact process

Enzymes are biological catalyst

Only applicable to gas

Concentration applicable only for solution