Desolvation Inability of Solid Hydrates, an Alternative Expression for the Gibbs Free Energy of Solvation, and the Myth of Freeze-Drying.

The term "desolvation inability" is proposed in order to describe the alteration of the original chemical structure of a solute ("decomposition") prior to the solvent's full removal upon the heating of the solvate. This behavior has been sporadically reported; however, it is much more frequent, and it is the basis of various, seemingly unrelated, effects/processes, e.g., the vinegar syndrome of cellulose acetate cinematographic films, in thermal energy storage. An explanation and a criterion/index for the prediction of this behavior are provided based on the comparison of the Gibbs free energies of decomposition and desolvation. A new approach for the expression of the Gibbs free energy of desolvation is proposed by reversing the roles of the solute and solvent and by regarding water as the solute rather than as the solvent, while the solute is treated as a solid solvent. This approach results in lower solvation/desolvation Gibbs free energy values. Based on the above, the experimentally observed thermal behavior of three inorganic hydrates is predicted and explained. Theoretically and experimentally, it is supported that decomposition is possible at sub-zero (°C) temperatures and the regarded simultaneous drying and protection of heat-sensitive substances by freeze-drying, at least in some cases, e.g., for the case of gallic acid, is an unverified myth.