中性(C2H4)、极性(H2O)和离子型([bmim][BF4]、[bmim][PF6]、[pmmim][Tf2N])液体的状态方程

V. Rogankov, V. Levchenko
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引用次数: 2

摘要

在离子液体的工作温度范围内,尽管实验工作者付出了相当大的努力,但迄今为止还没有观察到非常小压力下气液共存和高压下液固共存的可靠现象。低温稳定液体中高压性质的测量相对较少,而它们的一致性对相平衡预测的强烈影响是显而易见的。在这项工作中,我们讨论了波动热力学方法和相应的状态方程的适用性,以关联任何(中性,极性,离子)液体的性质,因为我们的最终目标是简单的参考预测模型,以描述含有上述成分的混合物的汽-液,液-液和液-固平衡。结果表明,在波动-热力学状态方程的框架下,现有的体积测量结果之间的不一致性以及力学性质,特别是热衍生性质对所选择的拟合实验数据的函数的形状的强烈依赖可以得到解决。为了说明所得结果,并与已知的[bmim][BF4]和[bmim][PF6]的实验数据以及格流状态方程和热力学积分方法进行了比较。它证实了预测的热力学一致性和在广泛压力范围内推导性质的良好相关性。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Towards the Equation of State for Neutral (C2H4), Polar (H2O), and Ionic ([bmim][BF4], [bmim][PF6], [pmmim][Tf2N]) Liquids
Despite considerable effort of experimentalists no reliable vapor-liquid coexistence at very small pressures and liquid-solid coexistence at high pressures have been until now observed in the working range of temperature / for ionic liquids. The measurements of high-pressure properties in low-temperature stable liquid are relatively scarce while the strong influence of their consistency on the phase equilibrium prediction is obvious. In this work we discuss the applicability of fluctuational-thermodynamic methodology and respective equation of state to correlate the properties of any (neutral, polar, ionic) liquids since our ultimate goal is the simple reference predictive model to describe vapor-liquid, liquid-liquid, and liquid-solid equilibria of mixtures containing above components. It is shown that the inconsistencies among existing volumetric measurements and the strong dependence of the mechanical and, especially, caloric derived properties on the shape of the functions chosen to fit the experimental data can be resolved in the framework of fluctuational-thermodynamic equation of state. To illustrate its results the comparison with the known experimental data for [bmim][BF4] and [bmim][PF6] as well as with the lattice-fluid equation of state and the methodology of thermodynamic integration is represented. It corroborates the thermodynamic consistency of predictions and excellent correlation of derived properties over the wide range of pressures /.
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