Arrest as a General Property of the Supercooled Liquid State

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• 作者：Jan H. Sluyters ; Margaretha Sluyters-Rehbach
• 刊名：Journal of Physical Chemistry B
• 出版年：2016
• 出版时间：April 21, 2016
• 年：2016
• 卷：120
• 期：15
• 页码：3735-3745
• 全文大小：575K
• 年卷期：0
• ISSN：1520-5207

文摘

Owing to the universal presence of intermolecular interactions, it has to be expected that at some well-defined lower temperature a liquid loses its dynamic properties like fluidity and self-diffusion. As a sequel to two earlier papers on the discovery of such an arrest temperature T₀ for supercooled water at 243 K, where also the coexisting vapor pressure was found to become zero, in this paper a further study is undertaken of the behavior of a selection of other liquids. At first, two simple equations of state (van der Waals and virial) are shown in principle to predict a zero vapor pressure at a finite temperature. The interaction parameters B (second virial coefficient) and μ_JT (Joule–Thomson coefficient) of the vapor are found to become virtually infinite at a temperature T_0,B, with a value equal or close to the T₀ derived from the liquid properties. Just as earlier found for water, the latter is obtained by extrapolation of several available dynamic and equilibrium data, which should produce an intersection with the temperature axis at the same T₀ value. With the exception of molten salts and liquid pure metals, this condition appears to be fulfilled quite accurately. Thus, the temperature of arrest is a general phenomenon for supercooled liquids. As an illustration, it is shown how the PVT diagram of carbon dioxide can be extended into the supercooled temperature region. It is argued that T₀ is the temperature below which the Boltzmann energy, kT, is lower than the minimal energy needed for a molecule to break the interactions with its surrounding molecules. We propose to name this minimal energy, kT₀, the multimolecular potential of the liquid object. The relationship of the liquid multimolecular potential with the pair potential, ε, of the molecular species is established for various examples and appears to be a proportionality with ε ≈ 2kT₀.