电解质溶液相平衡热力学模型研究进展

Progress in study on applied thermodynamic models for phase equilibria of electrolyte solution

从电解质溶液理论、活度系数模型和状态方程出发,对用于电解质溶液相平衡关联、预测的成功模型及近年来应用研究的进展,以工程应用模型为重点,进行了综述。从长程静电作用和非静电作用对活度系数的贡献的角度,介绍了活度系数模型中,以Debye-Hckel理论和MSA理论为基础的长程静电作用项的进展,介绍了Pitzer方程、E-NRTL、E-UNIQUAC以及化学贡献等活度系数模型的研究与应用进展;电解质状态方程则从3个方面总结了近年来的研究进展,即:以三次型方程、微扰理论为基础的电解质溶液状态方程和高温超临界条件下电解质溶液状态方程。

Recent advances in study on some successful thermodynamic models for phase equilibria of electrolyte solution are reviewed from three aspects, i.e., electrolyte solution theory, activity coefficient model (ACM), and equation of state (EOS). In particular, attention is focused on the engineering application models. From the point of view of long range electrostatic contribution, the advances of the long range term of activity coefficient expression, which based on Debye-Hdckel theory and MSA theory, are reviewed. From the point of view of non-electrostatic contribution, the advance and application of the successful activity coefficient models i.e. Pitzer's equation, E-NRTL, E-UNI-QUAC and chemical contribution model are introduced. In electrolyte EOS, the recent equations of state for electrolyte solution are summarized from three aspects, i.e., the cubic EOS, the perturbation theory based EOS, and the EOS for high-temperature and supercritical electrolyte systems.