本文从超额Helmholtz自由能的热力学一般关系式出发,给出了一个以无穷压力为参考态的,具有良好理论基础的超额自由能混合规则.该混合规则考虑了混合物分子体积大小差异的影响,通过引入一个经验参数f,减少了计算中自由能项和对数项的双重影响.该混合规则结合PR立方型状态方程及NRTL活度系数模型,对16种非极性体系、非极性-极性体系、极性与极性体系的汽液相平衡数据进行了关联,与实验数据显示了良好的一致性.与原WS混合规则相比,精度有了一定的提高,且该混合规则只包括活度系数模型参数.
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