KINETICS

• Collision theory

• Transition theory

• Consecutive and parallel

reactions
 Rate of the reaction
A chemical reaction can be represented by:

where 𝜈𝑖 is the stoichiometric number of Bi.

The extent of reaction 𝜉 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 𝑣 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 𝑣𝑓 = backward rate 𝑣𝑏 ).
 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 𝛼 and 𝛽 is referred to as the order of the reaction with respect to
reactant A and B respectively; and are independent of concentration and time.

• 𝛼 and 𝛽 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 𝛼 + 𝛽.

 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 𝐸𝑎 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 =
1
𝑑1 + 𝑑2 = 𝑑12
2

Collision velocity
Impact
parameter

Intermolecular
Molecules are considered as hard spheres potential (V) 0
1
For distances ≥ 𝑑1 + 𝑑2 , V = 0.
2 1
1 𝑑 + 𝑑2
For distances < 𝑑1 + 𝑑2 , V = ∞. 2 1
2
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 𝑒 −𝐸/(𝑅𝑇) .
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 𝑍12 (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 𝑍11 :

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

Avogardo’s number
 = Mean relative speed

Reduced mass

Mean relative speed can be written as

 Substituting for 𝜌𝑖 and 𝑣12 we have:

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

collision number multiplied by the Arrhenius factor 𝑒 −𝐸/(𝑅𝑇) gives the rate in terms
of the no. of molecules formed per unit volume and per unit time.

Hence reaction rate 𝑣 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 𝑧12 is same as rate constant k, which is per
unit concentration per unit time.
Rate constant from collision theory for the reaction B1+B1products

d diameter of B1; mmass of B1

Note: Here too units of collision frequency factor 𝑧11 is same as rate constant k.
Drawbacks of collision theory

• P can’t be evaluated in a satisfactory manner.

• If factors other than orientation are involved, they can’t again be estimated easily

• It is not consistent with 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 𝐾 = 𝑒 Δ𝑆 /𝑅 𝑒 −Δ𝐻 /𝑅𝑇
 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.
a) Enthalpy of freezing of water at −10 °C is −5619 J mol-1 and entropy of
freezing of water is −20.54 J K−1mol-1 at −10 °C. What is the Gibbs energy
of freezing of water at −10 °C?

b) A sample of water vapor of 200 °C is compressed isothermally from 300 cm3 to

100 cm3. Assume water vapor behaves ideally. What is the change in molar Gibbs
energy?

What is the standard enthalpy of a reaction for which the equilibrium constant is
doubled when the temperature is increased by 10 K from 298 K? R=8.314
J/K/mol