| Abstract: | Contrary to “common sense” impression, modest pressures often have quite large effects on reactions in solution.—The volume profile of a chemical reaction in solution is easily measurable with considerable precision by means of the effect of pressure on the rate and equilibrium constant. The factors that govern the magnitude of these pressure effects are similar to those that affect the entropy changes and there is a rough correlation between them; however, the volume parameters are much less subject to apparently random fluctuations, have much greater appeal to the solution chemist's intuition, and most important, the activation volume is the only transition state property that can readily be determined in absolute terms (rather than as a difference value). In this paper we outline the experimental approach to the measurement of volume changes in wet chemical reactions, interpret the volume quantities, discuss a number of simple model equilibria and reactions, point out a number of contributions in both mechanistic and synthetic chemistry, and make an attempt to foresee future developments. |
