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超临界流体的气态和液态:实验结果综述

Supercritical Fluid Gaseous and Liquid States: A Review of Experimental Results.

作者信息

Khmelinskii Igor, Woodcock Leslie V

机构信息

Department of Chemistry and Pharmacy, and CEOT, University of Algarve, 8005-139 Faro, Portugal.

Department of Physics, University of Algarve, 8005-139 Faro, Portugal.

出版信息

Entropy (Basel). 2020 Apr 13;22(4):437. doi: 10.3390/e22040437.

Abstract

We review the experimental evidence, from both historic and modern literature of thermodynamic properties, for the non-existence of a critical-point singularity on Gibbs density surface, for the existence of a critical density hiatus line between 2-phase coexistence, for a supercritical mesophase with the colloidal characteristics of a one-component 2-state phase, and for the percolation loci that bound the existence of gaseous and liquid states. An absence of any critical-point singularity is supported by an overwhelming body of experimental evidence dating back to the original pressure-volume-temperature () equation-of-state measurements of CO by Andrews in 1863, and extending to the present NIST-2019 Thermo-physical Properties data bank of more than 200 fluids. Historic heat capacity measurements in the 1960s that gave rise to the concept of "universality" are revisited. The only experimental evidence cited by the original protagonists of the van der Waals hypothesis, and universality theorists, is a misinterpretation of the isochoric heat capacity . We conclude that the body of extensive scientific experimental evidence has never supported the Andrews-van der Waals theory of continuity of liquid and gas, or the existence of a singular critical point with universal scaling properties. All available thermodynamic experimental data, including modern computer experiments, are compatible with a critical divide at , defined by the intersection of two percolation loci at gaseous and liquid phase bounds, and the existence of a colloid-like supercritical mesophase comprising both gaseous and liquid states.

摘要

我们回顾了来自历史和现代文献中关于热力学性质的实验证据,这些证据表明吉布斯密度面上不存在临界点奇异性,在两相共存之间存在临界密度间断线,存在具有单组分双态相胶体特征的超临界中间相,以及界定气态和液态存在的渗流轨迹。从1863年安德鲁斯对二氧化碳进行的原始压力 - 体积 - 温度(pVT)状态方程测量,一直到目前包含200多种流体的美国国家标准与技术研究院(NIST)2019热物理性质数据库,大量的实验证据都支持不存在任何临界点奇异性这一观点。我们重新审视了20世纪60年代导致“普适性”概念产生的历史热容测量。范德瓦尔斯假设的最初支持者以及普适性理论的支持者所引用的唯一实验证据,是对等容热容的错误解读。我们得出结论,大量的科学实验证据从未支持安德鲁斯 - 范德瓦尔斯关于液体和气体连续性的理论,也不支持具有普适标度性质的奇异临界点的存在。所有现有的热力学实验数据,包括现代计算机实验,都与在临界密度处的临界划分相一致,该临界密度由气态和液态边界处两条渗流轨迹的交点定义,并且存在包含气态和液态的类胶体超临界中间相。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8edc/7516910/d17d3535edce/entropy-22-00437-g001.jpg

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