Explaining Kinetic/Thermodynamic Control

Given a starting material S and two potential products P1 and P2 via transition states T1 and T2, if the relative energies of S, P1, P2, T1 and T2 are such that the kinetic product (fastest formed) is P1 and the thermodynamic product (most stable) is P2, and the back reactions are slow, then there is potential for thermodynamic/kinetic control of the reaction. Kinetic Control: Exploit the slow formation of equilibrium: do something with the major product P1 before the product distribution shifts to a majority of P2. The slow back reactions mean that the window of time available in which to do this is practically long:
!=0 !

P1 predominates Want P1: practically long time Want P2: impractically long time Thermodynamic control:

P2 predominates

Wait till equilibrium is reached, then do something with the major product P2: the initial formation of P1 in the majority is not a problem if you have enough time to burn waiting. The problem is that equilibrium may take a very long time to be established perhaps years! Instead of waiting, fast-forward the reaction by increasing the temperature T so that equilibrium is reached (P2 makes up the majority) within a practical amount of time (conversely As T increases the window of time available in which to do something with P1 decreases until it is impractically small):
!=0 !

P1

P2 predominates

Want P1: Impractically short time Want P2: Practically short time

Joshua Smith 15/5/2011