Pitzer and electrolyte nonrandom two‐liquid (eNRTL) models are the two most widely used electrolyte thermodynamic models. For aqueous sodium chloride (NaCl) solution, both models correlate the experimental mean ionic activity coefficient (γ_±) data satisfactorily up to salt saturation concentration, that is, ionic strength around 6 m. However, beyond 6 m, the model extrapolations deviate significantly and diverge from each other. We examine this divergence by calculating the mean ionic activity coefficient over a wide range of concentration based on molecular simulations and Kirkwood–Buff theory. The asymptotic behavior of the activity coefficient predicted by the eNRTL model is consistent with the molecular simulation results and supersaturation experimental data. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3728–3734, 2018

中文翻译：

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回顾电解质热力学模型：分子模拟的见解

Pitzer和电解质非随机二液（eNRTL）模型是两个使用最广泛的电解质热力学模型。对于氯化钠（NaCl）水溶液，两个模型都将实验平均离子活度系数（γ _±）数据令人满意，直至盐饱和浓度，即6 m左右的离子强度。但是，超过6 m时，模型外推明显偏离并且彼此不同。我们根据分子模拟和柯克伍德–巴夫理论，通过计算宽浓度范围内的平均离子活度系数，研究了这种差异。eNRTL模型预测的活度系数的渐近行为与分子模拟结果和过饱和实验数据一致。©2018美国化学工程师学会AIChE J，64：3728–3734，2018