Molecular Reaction Dynamics

(Theories of Reaction Rates)

Basic Theories: Collision theory

Complex theory (transition state theory)

- Molecular encounters make then excited (collisions or energy can

be taken from surroundings-solutions)

Assumptions
- Hard spheres
- Molecules must collide
- Reactions occur only if molecules are energetic
- Collisions should transfer certain minimum energy

Steric factor is difficult to evaluate

P: order of 10-6
One case where P is large for the reaction
K+Br2
KBr + Br
P= 4.8
harpoon mechanism

Reactions in solution
Cage effect
Activation energy, encounter pair

A+ B
AB
AB

AB
A+B
P

rate=kd[A][B]
rate=kd [AB]
rate=ka[AB]

Simplest chemical reaction: H+H2

H2 + H

Figure adapted from Science, 331 411-412 (2011)