超出单流体近似,用于流体混合物的热力学
Anja Reimer1, Thorsten Winkler-Markert1, Joachim Gross1
1Institute of Thermodynamics and Thermal Process Engineering, University of Stuttgart, Pfaffenwaldring 9, 70569 Stuttgart, Germany.
The Journal of chemical physics
|January 7, 2026
概括
一个新的校正因子通过计算粒子大小差异来改善流体混合物的状态方程. 这增强了对各种模型和真实流体的热力学特性和相位平衡的预测.
科学领域:
- 热力学是一种热力学.
- 物理化学 物理化学
- 计算化学的计算化学
背景情况:
- 对于流体混合物的状态分析方程通常使用单流体近似.
- 这些近似简化了模型,但引入了不准确性,特别是在具有不同颗粒大小的混合物中.
研究的目的:
- 开发一个简单的代数校正因子,用于使用一流体近似的扰动理论.
- 提高流体混合物的热力学特性和相位平衡预测的准确性.
主要方法:
- 定义了一个校正因子,即赫尔姆霍尔茨能量中的严格和近似的第一阶扰动项的比.
- 利用基于基本粒子测量的符号回归来导出修正因子的封闭式表达式.
- 将校正因子应用于UV理论和PCP-SAFT状态方程.
- 为列纳德-斯混合物生成新的分子模拟数据以验证该方法.
主要成果:
- 与单流体方法相比,校正因数显著提高了模型流体预测相位平衡和热力学性能的准确性.
- 分子模拟数据证实了尺寸不对称的莱纳德-斯混合物的精度提高.
- 由于类似的物质细分尺寸,PCP-SAFT对真实流体预测的影响很小.
结论:
- 建议的校正因子有效地解决了扰乱理论的单流体近似中的不准确性.
- 该方法为更准确地预测混合物行为提供了有价值的工具,特别是当存在显著的大小不对称时.
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