The modified separation of cohesive energy density (MOSCED) is a powerful tool for early stage process conceptualization and design. It is capable of making quantitative phase-equilibrium calculations, and more importantly may be used to qualitatively understand the underlying molecular level details of a system for intuitive process design. Unfortunately, its use is limited in that parameters must first be known before predictions may be made. Here we explore the use of group contribution methods (GC-MOSCED) and electronic structure calculations in the solvation model based on density (SMD) and SM8 continuum solvation models to calculate missing parameters. We demonstrate the use of GC-MOSCED to expand MOSCED using limited data, and the ability of electronic structure calculations to calculate parameters devoid of experimental data. While GC-MOSCED performs best, we demonstrate that good predictions may be made using electronic structure calculations with the SMD continuum solvation model. Application is demonstrated for limiting activity coefficients and binary isobaric azeotropic vapor–liquid equilibrium with 1,2-ethanediol.

中文翻译：

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从分子结构预测极限活度系数和相行为：使用基团贡献法和电子结构计算将MOSCED扩展为烷二醇

改进的内聚能密度分离（MOSCED）是早期过程概念化和设计的强大工具。它能够进行定量的相平衡计算，更重要的是，它可以用于定性地了解系统的基本分子水平细节，以进行直观的过程设计。不幸的是，它的使用受到限制，因为必须先知道参数，然后才能进行预测。在这里，我们探索在基于密度（SMD）和SM8连续介质溶剂化模型的溶剂化模型中使用基团贡献方法（GC-MOSCED）和电子结构计算来计算缺失参数。我们展示了使用GC-MOSCED来使用有限的数据来扩展MOSCED的能力，以及电子结构计算能够计算没有实验数据的参数的能力。尽管GC-MOSCED的性能最佳，但我们证明使用SMD连续介质溶剂化模型进行电子结构计算可得出良好的预测。证明了其可用于限制活性系数和与1,2-乙二醇的二元等压共沸汽液平衡。