The activity coefficient is a key thermodynamic parameter, particularly in phase equilibria calculations. Different activity coefficient models have been developed to date, including empirical, correlative, predictive, and pure predictive. In this study, a predictive group contribution activity coefficient model based on the Wilson model was developed, which is called the Wilson Functional Activity Coefficient (Wilson-FAC). High-quality and critically evaluated vapor–liquid phase equilibria (VLE) data was used in the optimization procedure to obtain the interaction parameters between the main groups. Different thermodynamic consistency tests, including the Herington test, Van Ness test, point test, infinite dilution test, EOS test, and end point test, were applied to check the quality of the used VLE data. The interaction parameters between the 50 main groups involved in the 137 molecules were optimized using the fminsearch embedded function in MATLAB software. The developed Wilson-FAC model covers solutions with various thermodynamic behaviors, including ideal, moderately positive, and negative deviation from Raoult’s law and azeotropic systems as highly nonideal solutions. Using the obtained interaction parameters from the binary VLE data, the model can accurately predict the phase equilibria of multicomponent mixtures. The model covers the phase equilibrium behavior of all types of intermolecular interactions in binary systems well.

中文翻译：

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使用高质量和严格评估的相平衡数据开发 Wilson 功能活性系数模型


活性系数是一个关键的热力学参数，尤其是在相平衡计算中。迄今为止，已经开发了不同的活动系数模型，包括经验、相关、预测和纯预测。本研究开发了一种基于 Wilson 模型的预测组贡献活性系数模型，称为 Wilson 功能活性系数 （Wilson-FAC）。在优化过程中使用了高质量和经过严格评估的气-液相平衡 （VLE） 数据，以获得主要组之间的相互作用参数。应用不同的热力学一致性测试，包括 Herington 测试、Van Ness 测试、点测试、无限稀释测试、EOS 测试和终点测试，以检查所用 VLE 数据的质量。使用 MATLAB 软件中的 fminsearch 嵌入式函数优化了 137 个分子中涉及的 50 个主基团之间的相互作用参数。开发的 Wilson-FAC 模型涵盖了具有各种热力学行为的解，包括理想、适度正和负偏离拉乌尔定律和共沸系统作为高度非理想解。使用从二进制 VLE 数据中获得的相互作用参数，该模型可以准确预测多组分混合物的相平衡。该模型很好地涵盖了二元系统中所有类型的分子间相互作用的相平衡行为。