Abstract
It has been suggested that the pressure coefficient of the rate constant of some reactions may be influenced by the formation of intermolecular or intramolecular conformations prior to reaction. This has been examined theoretically and the relevant experimental evidence has been discussed. No examples of an effect in which the conformations are at equilibrium are known with certainty, but the effect of pressure on termination in the polymerization of styrene appears to be an example of a conformational effect when the conformations are not at equilibrium.The pressure coefficient of the rate constant for the isomerization of citraldehyde to 3,8-carvomenthenediol is not consistent with a unimolecular slow step, but it is consistent with either a bimolecular or a termolecular slow step. It is pointed out that the pressure coefficient of rate constants may be very useful in determining the molecularity of some reactions.
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