J Phys Chem B 2021 Oct 26. Epub 2021 Oct 26.
Department of Chemical Engineering, University of Florida, Gainesville, Florida 32611, United States.
We analyzed the consistency, or lack thereof, of the conjectured connection between the sign of Jones-Dole's B-coefficient, or its isobaric-temperature derivative, and the structure-making/breaking ability of a solute in a dilute solution. We sought to shed light on some crucial issues, including (i) whether Jones-Dole's B-coefficient contains any embedded microstructural information, (ii) whether we can either assign any definite foundation to the widely used assumption about the sign of the B-coefficient and its structure-making/breaking trend or provide a rational justification for its use as a structure-making/breaking marker, and (iii) whether we actually need Jones-Dole's B-coefficient and its isobaric-temperature derivative as markers for the interpretation of structure-making/breaking trends. Thus, we first addressed the fundamental (statistical mechanical) microscopic to (thermodynamic) macroscopic foundations of a rigorous approach to the structure-making/breaking ability of a solute, regardless of the type of solvent or nature of the solute-solvent intermolecular interaction asymmetries, and its exact relationships to the resulting solution thermodynamics. Read More