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• W2069782875 endingPage "1387" @default.
• W2069782875 startingPage "1377" @default.
• W2069782875 abstract "In a previous work (J. Phys. Chem. B 2003, 107, 9837), we reported liquid−liquid-phase splitting at negative pressures in mixtures of H2O + D2O + 3-methylpyridine (3-MP) at the limit of pure H2O as the solvent, thus extending for the first time the L−L phase diagrams to this metastable region. We showed that there is an intimate relation between pressure and solvent deuterium content. Isotopic substitution (H/D) in water provokes subtle entropic effects that, in turn, trigger a significant pressure shift, opening a pressure-wide miscibility window of as much as 1600 bar. Isotope effects are quantum in origin. Therefore, a model that is both pressure-dependent and considers quantization constitutes a necessary tool if one wishes to fully describe the p, T, x critical demixing in these systems. In the current work, the statistical-mechanical theory of isotope effects is combined with a compressible pressure-dependent model. This combination enabled us to predict successfully the overall L−L phase diagram via differences in the vibrational mode frequencies of water on its transfer from the pure state to that of dilution in 3-MP: each of the three librational modes undergo a calculated red-shift of −(250 ± 30) cm-1, while the overall internal frequencies contribution is estimated as a total +(400 ± 25) cm-1 blue-shift." @default.
• W2069782875 created "2016-06-24" @default.
• W2069782875 creator A5013329498 @default.
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• W2069782875 date "2005-12-31" @default.
• W2069782875 modified "2023-09-24" @default.
• W2069782875 title "A Simple Quantum Statistical Thermodynamics Interpretation of an Impressive Phase Diagram Pressure Shift upon (H/D) Isotopic Substitution in Water + 3-Methylpyridine" @default.
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• W2069782875 doi "https://doi.org/10.1021/jp0556207" @default.
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• W2069782875 hasPublicationYear "2005" @default.
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