TITLE:
Taking into Account Density Fluctuations in a Solvent in a Model of Dissolution
AUTHORS:
I. A. Ar’ev
KEYWORDS:
Solubility, Solvent-Induced Spectral Shift, Microscopic Balance of Volumes, Fluctuation Cavities, Aqueous Solvent, Solute Contraction, Hydrate Shell Strengthening
JOURNAL NAME:
Open Journal of Physical Chemistry,
Vol.9 No.4,
October
31,
2019
ABSTRACT: Earlier it was shown by different authors that there are cavities (vacancies, holes) in any liquid. The cavities should play a prominent role in dissolution processes. Nevertheless this fact was ignored in previous model of dissolution. The sizes of the cavities in different solvents containing benzene molecules were determined using solvent induced spectral shift method. The measurements of S1←S0 benzene transition spectral shifts permit to conclude that 1) macroscopic excess volumes play an almost negligible role in processes of benzene dissolution in very different solvents and 2) the minimal size of the cavity in water able to accommodate benzene molecule coincides with the solute size. Generalization of this conclusion to other nonpolar aromatics leads to evaluation contraction of the solutes under aqueous solvent influence permits to predict the solubility values of other aromatics in water and to evaluate effect of enhancement hydrate cell around these molecules on solubility.