Metastable critical lines in (acetone + polystyrene) solutions and the continuity of solvent-quality states

文献情報

出版日

DOI 10.1039/B109405J

インパクトファクター 3.676

著者

Luís P. N. Rebelo, Zoran P. Visak, Jerzy Szydlowski

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要旨

Double critical behavior of two distinct types was found in (acetone + polystyrene) liquid solutions. A quasi-monodisperse polystyrene of Mw ∼ 16 600 in perprotio-acetone presented a T–p extremum in the critical locus at low-temperature and high-pressure and a metastable p–T one at a higher temperature and a lower (and negative) pressure. The first case corresponds to a pressure-double critical point (DCP), while the latter is a metastable temperature-DCP. At the p-DCP one expects a change in the sign of the excess volume as pressure is varied, and at the T-DCP neighboring region a change in the sign of the excess enthalpy should occur with temperature change. A Berthelot-type method was used to achieve experimental absolute negative pressures of the order of −60 bar. To the best of the authors' knowledge, this constitutes the first experimental observation of a polymer solution with two types of double critical points with one penetrating the metastable region of negative pressures. A review of the pertinent literature suggests that acetone changes by virtue of applied pressure from a “non-solvent” to a “poor-solvent” and finally to a “θ-solvent” for polystyrene.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

Metastable critical lines in (acetone + polystyrene) solutions and the continuity of solvent-quality states

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Physical Chemistry Chemical Physics

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