Application of a solvent-coupled model to a calculation of partial molar isobaric heat capacities of neutral and ionic solutes in aqueous solution. Estimates of isobaric heat capacities of activation

Abstract

Partial molar isobaric heat capacities and volumes of apolar and ionic solutes in water have been examined using the Lumry–Frank two-state model for water in conjunction with the Grunwald extrathermodynamic assumption describing the impact of a solvent equilibrium on the properties of a solute. The analysis has been extended to a consideration of isobaric heat capacities of activation. The predicted dependence of the latter parameter on temperature for a first-order unimolecular reaction resembles that calculated using the Albery–Robinson mechanism for solvolytic reactions.