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Consider the following reaction:

The products are formed in the following ratios:
The reasons for the ratios will be explained in the
section on electrophilic substitution, however, what is important
to note here is that the underlying reason is that the more abundant
isomers simply form faster than the less abundant. This is
known as kinetic control. However, kinetic control is not
the only control of a reaction. If the conditions are correct,
it is possible to have thermodynamic control.
If a reaction is under thermodynamic control, it does
not matter how fast the products are formed, only their relative
stabilities matter; the less stable, the less abundant the product.
For kinetic control to occur, we normally need low
temperatures, and for thermodynamic control, high temperatures.
Kinetic control also normally uses harsh reagents, and thermodynamic
control less reactive ones, so that the reaction mixture may equilibrate.
The following energy profile may prove useful:
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From the diagram above, we can see that the kinetic
product forms first because it's transition state has a lower activation
energy, whereas the thermodynamic product is more stable, but its
transition state requires more activation energy. However,
it is possible that the product that forms fastest is also the most
stable, in which case it is both the kinetic and thermodynamic product. |
An example of a reaction whose product can be change
by altering the conditions to change from kinetic to thermodynamic
control is the sulphonation of napthalene.
| Thermodynamic |
Kinetic |
| 160ºC |
80ºC |
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