Considered one of the most versatile and widely used classical thermodynamic models to correlate phase equilibria behavior of nonideal systems, the nonrandom two‐liquid (NRTL) theory does not explicitly account for specific chemical associations such as hydrogen bonding. This deficiency has been recognized as the cause for unsatisfactory representation of association systems like methanol–alkanes binaries. This work presents a practical approach to integrate Wertheim's perturbation theory for association contribution with the classical NRTL model. Specifically, the association contribution is calculated from pre‐determined molecule‐specific association strengths while the physical interaction contribution is captured with NRTL binary interaction parameters. The resulting association NRTL model correlates fluid phase equilibria of association systems with few adjustable parameters and offers improved predictive capability for higher order systems.

中文翻译：

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关联理论的非随机两液活度系数模型

被认为是使非理想系统的相平衡行为相关的最通用和最广泛使用的经典热力学模型之一，非随机两液（NRTL）理论并未明确考虑特定的化学缔合，例如氢键。这种缺陷已被认为是导致诸如甲醇-烷烃二进制之类的缔合体系表现不佳的原因。这项工作提出了一种实用的方法，可以将Wertheim的摄动理论与经典的NRTL模型相结合来进行联想贡献。具体来说，缔合贡献是根据预先确定的分子特异性缔合强度来计算的，而物理相互作用的贡献是由NRTL二元相互作用参数捕获的。