The molecular clusters in a supercritical fluid–solid system should be considered as a phase—thermodynamic principle and evidence

Literature Information

Publication Date 2013-04-09
DOI 10.1039/C3CP44670K
Impact Factor 3.676
Authors

Minqiang Hou, Jianling Zhang, Buxing Han, Qingqing Mei, Hui Ning, Dezhong Yang


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Abstract

In this work we propose a new thermodynamic principle in which a supercritical fluid (SCF)–solid system is divided into a solid phase, a cluster phase, and a bulk fluid phase, i.e., the molecular clusters in the system are considered as an individual phase. The phase equilibria of various SCF–solid systems are calculated using this principle in combination with Monte Carlo simulation and the Peng–Robinson equation of state (PR-EOS). It is shown that in the critical region of the supercritical (SC) solvents where the clustering is significant, the results calculated using this thermodynamic principle are much more consistent with the experimental data than those calculated using the conventional thermodynamic principle, confirming the validity of the principle proposed in this work.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
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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.

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