Determination of Activation and Reaction Volumes of Polar and Isopolar Reactions Using Rule of Noncrossing of Curves ln(kP/kP=1) = f(P)

Data on the influence of high hydrostatic pressure on the rate constants (equilibrium constants) of polar and isopolar reactions were collected and analyzed. An equation was derived for determination of the activation volume (reaction volume) from only two values of the rate constants (equilibrium constants) at atmospheric pressure and 1000 bar. The differences between experimental activation (reaction) volumes and those calculated using the equation derived are within the standard errors of experimental determination of this volume parameter.