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Excess chemical potentials, excess partial molar enthalpies, entropies, volumes, and isobaric thermal expansivities of aqueous glycerol at 25 degrees C

TitleExcess chemical potentials, excess partial molar enthalpies, entropies, volumes, and isobaric thermal expansivities of aqueous glycerol at 25 degrees C
Publication TypeJournal Article
Year of Publication1999
AuthorsTo, ECH, Davies, JV, Tucker, M, Westh, P, Trandum, C, Suh, KSH, Koga, Y
JournalJournal of Solution Chemistry
Volume28
Pagination1137-1157
Date PublishedOct
Type of ArticleArticle
ISBN Number0095-9782
Keywords2-BUTOXYETHANOL, aqueous glycerol, excess partial molar enthalpies and, fluctuations, MIXING SCHEME, MIXTURES, NONELECTROLYTES, normalized cross fluctuations, PERCOLATION, PRESSURES, TERT-BUTANOL, THERMAL EXPANSIVITIES, TRANSITION, vapor pressures, VOLUMES, WATER-RICH REGION
Abstract

The vapor pressures p the excess partial molar enthalpies of glycerol He,, the densities d and the thermal expansivities oc, of aqueous glycerol were measured at 25 degrees C. From the vapor pressure data, the excess chemical potential of H2O mu(W)(E) was calculated, assuming that the partial pressure of glycerol Poly is negligibly small. The excess chemical potential of glycerol mu(Gly)(E) was estimated by applying the Gibbs-Duhem relation and these data were used to calculate the excess partial molar entropies S-Gly(E). From the density data, the excess partial molar volumes of glycerol V-Gly(E) and from the thermal expansivity data, the normalized cross fluctuations (SV)Delta, introduced by us earlier, were evaluated. While the detailed manner in which glycerol modifies the molecular arrangement of H2O in its immediate vicinity is yet to be elucidated, the hydrogen bond probability in the bulk H2O away from solute molecules is reduced gradually as the glycerol composition increases to the point where putative presence of icelike patches is no longer possible. Thereupon, a qualitatively different mixing scheme seems to set in.

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