ISSN:
1572-8927
Keywords:
Aqueous glycerol
;
vapor pressures
;
excess partial molar enthalpies and volumes
;
thermal expansivities
;
normalized cross fluctuations
Source:
Springer Online Journal Archives 1860-2000
Topics:
Chemistry and Pharmacology
Notes:
Abstract The vapor pressures p the excess partial molar enthalpies of glycerol H Gly E the densities d and the thermal expansivities αp of aqueous glycerol were measured at 25°C. From the vapor pressure data, the excess chemical potential of H2O µ W E was calculated, assuming that the partial pressure of glycerol p Gly is negligibly small. The excess chemical potential of glycerol µ 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 SVΔ, 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.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1023/A:1021703725091
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