Hydrogen bonding and phase equilibrium

The thermodynamics of the mobile order of H-bonding in liquids considers not the various H-bonded or non-H-bonded entities present in the solution, but the fraction of time (1 − γ) during which an OH proton follows the electron-donor site of another molecule in its walk through the liquid. The influ...

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Bibliographic Details
Published in:Journal of molecular structure 1994-06, Vol.322, p.75-82
Main Authors: Huyskens, Pierre L., Seghers, Katarine
Format: Article
Language:English
Subjects:
Chemical thermodynamics
Chemistry
Exact sciences and technology
General and physical chemistry
Mixtures
Phase equilibria
Thermodynamic properties
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Summary:The thermodynamics of the mobile order of H-bonding in liquids considers not the various H-bonded or non-H-bonded entities present in the solution, but the fraction of time (1 − γ) during which an OH proton follows the electron-donor site of another molecule in its walk through the liquid. The influence of the H-bonds on the free energy of the system is given by G h = n RT ln γ. The time fraction (1 − γ) is ruled by the concentration of the sites and by equilibrium constants which may differ from those of Guldberg and Waage. Quantitative expressions are derived for the effect of solvent—solvent and solute—solvent H-bonds on the solubility of crystalline substances with carbonyl or ether groups. At 25°C the predictions agree within 10% with the experimental values.
ISSN:0022-2860
1872-8014
DOI:10.1016/0022-2860(94)87022-5