CRITICAL LINES AND PHASE-EQUILIBRIA IN BINARY VANDERWAALS MIXTURES
CRITICAL LINES AND PHASE-EQUILIBRIA IN BINARY VANDERWAALS MIXTURES
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DOI：
10.1098/rsta.1980.0266
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发表时间：
1980-01-01
期刊：
影响因子：
5
通讯作者：
SCOTT, RL
中科院分区：
文献类型：
--
作者：
VANKONYNENBURG, PH;SCOTT, RL
相平衡的研究历来是研究非电解质液体及其混合物中分子间力性质的最重要的信息来源之一。在本世纪初，气-液和液-液相行为的许多主要特征已经在实验中得到了很好的表征，但是对各种各样的物质在很大的压力和温度范围内的相平衡的理论解释却远远落后。本文介绍了符合范德华方程的二元混合物相平衡的理论研究，特别是在高压下可能发生的液-液平衡。二元混合物中发生的流体相行为的变化可以根据临界点附近热力学性质的变化进行定性讨论。当温度升高时，非均相（两相）体系变为均相（单相）体系时，就会出现较高的临界溶液温度。恒压下沿温度摩尔分数（T, x）共存曲线的最高温度为该压力下的UCST。当温度升高时，均相体系变为两相体系时，临界溶液温度（LCSTs）降低。lst处于t， x共存曲线的最小值。对混合函数曲率的临界点屈服要求的热力学考虑。
The study of phase equilibria is historically one of the most important sources of information about the nature of intermolecular forces in non-electrolyte liquids and their mixtures. Many of the main features of vapour-liquid and liquid-liquid phase behaviour were already well characterized experimentally during the early part of this century, but the theoretical explanation of phase equilibria for a wide variety of substances and over a large range of pressures and temperatures has lagged far behind. This paper presents theoretical studies of phase equilibria in binary mixtures obeying the van der Waals equation, especially liquid-liquid equilibria that can occur at high pressures. The variety of fluid phase behaviour that occurs in binary mixtures can be qualitatively discussed in terms of the changes in thermodynamic properties near critical points. Upper critical solution temperatures (UCSTs) occur when a heterogeneous (two-phase) system becomes a homogeneous (one-phase) system when the temperature is raised. The maximum temperature along the temperature-mole fraction (T, x) coexistence curve for constant pressure is the UCST at this pressure. Lower critical solution temperatures (LCSTs) occur when a homogeneous system becomes a two-phase system when the temperature is increased. The LCST is at the minimum of theT, xcoexistence curve. Thermodynamic considerations of critical points yield requirements for the curvature of the mixing functions plotted againstx.