Revisiting electrolyte thermodynamic models: Insights from molecular simulations
Revisiting electrolyte thermodynamic models: Insights from molecular simulations
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DOI：
10.1002/aic.16327
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发表时间：
2018-10-01
期刊：
影响因子：
3.7
通讯作者：
Chen, Chau-Chyun
中科院分区：
文献类型：
--
作者：
Hossain, Nazir;Ravichandran, Ashwin;Chen, Chau-Chyun
Pitzer模型和电解质非随机双液（eNRTL）模型是应用最广泛的两种电解质热力学模型。对于氯化钠（NaCl）水溶液，两种模型都能令人满意地将实验平均离子活度系数（（+/-））数据与盐饱和浓度（即离子强度约6 m）相关联。然而，超过6米，模型外推偏离显着，彼此发散。我们通过计算基于分子模拟和Kirkwood-Buff理论的宽浓度范围内的平均离子活度系数来研究这种分歧。用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。(c)2018美国化学工程师学会AIChE J，64：3728-3734，2018
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 ((+/-)) 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. (c) 2018 American Institute of Chemical Engineers AIChE J, 64: 3728-3734, 2018