论文标题

麦克斯韦跨界和范德华的状态方程

The Maxwell crossover and the van der Waals equation of state

论文作者

Liu, Hongqin

论文摘要

著名的麦克斯韦结构[1](相等的区域,耳朵)是针对蒸气液平平衡(VLE)计算的,它使用范德华(VAN der Waals(VDW)方程)[2]设计。 EAR在饱和液体和蒸气量之间产生中间体积。共存区域中中间体积的轨迹在此定义为麦克斯韦跨界,称为M线,与EOS无关。对于VDW或任何立方[3] EOS,中间体积对应于非物理根,而其他两个分别对应于蒸气和液相的饱和体。由于其非物理性质,中间体积一直被丢弃。在这里,我们表明,事实证明,M线与共存曲线的直径[4]严格相关,它是解决几个主要问题的关键。传统上,与两个分支的共存曲线被认为是宽线线的扩展[5,6-9]。这种断言会导致三个温度,压力和体积平面的不一致。发现M线是Widom线向蒸气 - 液体共存区域的自然延伸。结果,联合的单线将整个相空间(包括共存和超临界流体区域)相干地分为所有平面中的气体和液体样式。此外,沿着M线,VDW EOS找到了一种新的观点,可以更好地与观察和现代理论保持一致的方式访问二阶过渡[10]。最后,通过使用M线的功能,我们能够为VDW EOS提供高度准确和分析的近端解决方案。

The well-known Maxwell construction[1] (the equal-area rule, EAR) was devised for vapor liquid equilibrium (VLE) calculation with the van der Waals (vdW) equation of state (EoS)[2]. The EAR generates an intermediate volume between the saturated liquid and vapor volumes. The trajectory of the intermediate volume over the coexistence region is defined here as the Maxwell crossover, denoted as the M-line, which is independent of EoS. For the vdW or any cubic[3] EoS, the intermediate volume corresponds to the unphysical root, while other two corresponding to the saturated volumes of vapor and liquid phases, respectively. Due to its unphysical nature, the intermediate volume has always been discarded. Here we show that the M-line, which turns out to be strictly related to the diameter[4] of the coexistence curve, holds the key to solving several major issues. Traditionally the coexistence curve with two branches is considered as the extension of the Widom line[5,6-9]. This assertion causes an inconsistency in three planes of temperature, pressure and volume. It is found that the M-line is the natural extension of the Widom line into the vapor-liquid coexistence region. As a result, the united single line coherently divides the entire phase space, including the coexistence and supercritical fluid regions, into gas-like and liquid-like regimes in all the planes. Moreover, along the M-line the vdW EoS finds a new perspective to access the second-order transition in a way better aligning with observations and modern theory[10]. Lastly, by using the feature of the M-line, we are able to derive a highly accurate and analytical proximate solution to the VLE problem with the vdW EoS.

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