Some important relations:

Arrhenius rate equation:

Emprical relation proposed by Arrhenius Rate constant k is given as

A: Pre-exponential factor Ea: Activation energy

Collision rate theory:

Rate constant from collision theory for the reaction B1+B2products

P: steric factor z12: collision frequency factor E*= Minimum collision energy along the line of centers. = Requisite energy to produce reaction.

Drawbacks:
P cant be evaluated satisfactorily If factors other than orientation are involved, they cant again be evaluated satisfactorily It is not consistent with the fact that at equilibrium the ratio of rate constants is the equilibrium constant because k1/k-1 (from collision theory) lacks the entropy term in the exponential

Transition state theory (TST)

The rate constant of the elementary reaction gas reaction A+B C is derived. Assumption : the reaction goes through an activated complex that produces C at a rate State of the system at transition state (at the top of the barrier)structure that is in the process of change in the direction of the products, but not an intermediate product. Rate of the elementary gas reaction is d[C]/dt= k[A][B]= (4) : (ii) (i)

Note that the rate in Eq. (4) is the rate at which A and B passes the barrier without turning back according to TST. The first equality in Eq. (4) is due to rxn. (i) and second equality is due to TST assumption as shown in rxn. (ii). Hence second order rate constant k, is written as

Frequency of that special vibration of the activated complex that makes it unstable inverse of time spent at TS (transition state). Equilibrium constant for the formation of the activated complex.

For rxn. (ii):

Difference in zero point energies of the activated complex and the reactants.

Assumption : it is permissible to separate the motion of the system (activated complex) over the barrier from other motions of the activated complex. Hence

From Eqs. (7-8), rate constant k in Eq. (5) is written as

Exercise: For an arbitrary mth order reaction the rate constant k is:

Note that for an elementary reaction such as rxn (i) order and molecularity are equal.

Thermodynamic treatment of TST

Key relations:

Eq. 11 is obtained by substituting

in Eq. (1 0) .

Eq. (12) can be derived from the following:

Similarly

Taking logarithm on each side and differentiating w.r.t T on both sides of Eq. (13), one obtains Eq. (12) after identifying

Note:

(as discussed in the class) (for unimolecular reactions)

(for bimolecular reactions)