A Comparative Analysis of Empirical Equations Describing Pressure Dependence of Equilibrium and Reaction Rate Constants

General properties of the empirical analytical functions used to describe the effect of pressure on rate and equilibrium constants in solution are reviewed and the effects of experimental errors on the accuracy of activation and reaction volumes predicted by these equations are compared. When the error levels are low (1-2%) and pressure ranges are small (0-1kbar) all functions perform well, but when fitting data with high error or extending to higher pressures special care must be taken in order to obtain reliable results. Analysis of the results from fitting the equations to simulated data as well as experimental data for Diels-Alder, Menshutkin, and methanolysis reactions allows us to propose a set of general recommendations when using these equations as a tool for obtaining accurate activation and reaction volumes.The accepted manuscript in pdf format is listed with the files at the bottom of this page. The presentation of the authors' names and (or) special characters in the title of the manuscript may differ slightly between what is listed on this page and what is listed in the pdf file of the accepted manuscript; that in the pdf file of the accepted manuscript is what was submitted by the author