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Classical harmonic model for the behavior of pure fluids at the critical point

机译:临界点纯净流体行为的经典谐波模型

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摘要

We present a simple model to explain the limiting behavior of many thermodynamic properties of pure classical fluids as one approaches the critical point. The model consists of four main aspects: (i) a focus on the thermodynamic properties as described by Fluctuation Solution Theory (FST); (ii) the removal of all intramolecular energy contributions from the FST expressions; (iii) particle fluctuations (and not the energy fluctuations) dominate the thermodynamics close to the critical point; and (iv) the equipartition theorem applies to the resulting low frequency collective modes of the fluid at the critical point. Using this approach, we predict and compare the thermodynamic results for 121 pure fluids as provided by accurate equations of state. The model explains why some ratios of diverging thermodynamic properties remain finite at the critical point, and reliably predicts the value of these ratios for equations of state that mimic both mean field and Ising system types, suggesting universal behavior.
机译:我们提出了一种简单的模型,以解释纯古典流体的许多热力学性质的限制行为,因为一个接近临界点。该模型由四个主要方面组成:(i)如波动解决方案理论(FST)所述的热力学性质专注于热力学性质; (ii)从FST表达中除去所有分子内能量贡献; (iii)粒子波动(而不是能量波动)主导靠近临界点的热力学; (iv)备分定理适用于临界点处的流体的低频集体模式。使用这种方法,我们预测并比较了由精确的状态方程提供的121纯净流体的热力学结果。该模型解释了为什么发散的热力学特性的一些比率在临界点处保持有限,并且可靠地预测这些比率的这些比率的值,以模仿平均场和ising系统类型的状态,表明普遍行为。

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