Study of tert-butyl bromide hydrolysis in the 1-propanol/water system using the fundamental thermodynamic equation of chemical reactivity

Abstract

In previous work we have demonstrated the viability of the fundamental thermodynamic equation of chemical reactivity and have outlined the procedure for analyzing intrinsic activation parameters using this equation. We have recently developed a three-step interpolation technique for evaluating the functional dependencies of these parameters in terms of the system (state) variables. In this work we apply this technique to the hydrolysis reaction of tert-butyl bromide in the 1-propanol/water solvent system, and we use the Kirkwood–Onsager equation to model the electrostatic term in the fundamental equation. Analyses under isobaric conditions show that the intrinsic activation entropy and Kirkwood–Onsager parameter depend strongly on the system variables, particularly the relative permittivity. We also analyze the standard (non-intrinsic) activation entropies and enthalpies for iso-mole fraction and isodielectric conditions. These analyses provide a fundamental thermodynamic platform for distinguishing solvation-shell and bulk electrostatic effects on reaction rates.