In this work, state-of-the-art ion-specific parameter sets for the ePPC-SAFT model are obtained for 15 aqueous alkali halide solutions based on extensively collected and critically evaluated databases. The association approach, which has been proven the best for accounting for the short-range interactions, is here extended to all the alkali halides. Efforts are made to improve modeling accuracy. The impact of anion association site number on modeling accuracy is investigated. Recommended parameter sets are presented. Only 7 adjustable parameters altogether are needed for the 4 salts with the same anion, e.g., NaBr, KBr, RbBr, and CsBr. It is found that Li+-water dispersion needs to be accounted for to reach the same accuracy for Li+ salts as for the other salts. Thus, 7 parameters altogether are needed for LiCl, LiBr, and LiI. The obtained model and parameter sets are very accurate for correlating the properties included in the regression, mean ionic activity coefficient, vapor-liquid equilibria, and density, and for predicting the osmotic coefficient. In all cases, maximum deviations are within a few percent. The contributions of the model terms are analyzed.
Authors
Fufang Yang, Georgios Kontogeorgis, Jean-Charles de Hemptinne
Related Organizations
- Bibliographic Reference
- Fufang Yang, Georgios Kontogeorgis, Jean-Charles de Hemptinne. Systematic Evaluation of Parameterization Approaches for the ePPC-SAFT Model for Aqueous Alkali Halide Solutions. II. Alkali Bromides, Iodides, Fluorides, and Lithium Halides. Fluid Phase Equilibria, 2023, 573, pp.113853. ⟨10.1016/j.fluid.2023.113853⟩. ⟨hal-04190136⟩
- DOI
- https://doi.org/10.1016/j.fluid.2023.113853
- European Project Title
- New Paradigm in Electrolyte Thermodynamics
- HAL Collection
- ["Sciences De l'Environnement", 'IFP Energies Nouvelles', 'OpenAIRE', 'GIP Bretagne Environnement']
- HAL Identifier
- 4190136
- Institution
- ['IFP Energies nouvelles', 'Danmarks Tekniske Universitet = Technical University of Denmark']
- Laboratory
- Center for Energy Resources Engineering
- Published in
- France
Table of Contents
- Systematic Evaluation of Parameterization Approaches for the ePPC-SAFT Model for Aqueous Alkali Halide Solutions. II. Alkali Bromides Iodides Fluorides and Lithium Halides 1
- Abstract 2
- Keywords 2
- 1 Introduction 2
- 2 Method 4
- 2.1 ePPC-SAFT 4
- 𝐴 𝐴 𝐴 𝐴 𝐴 𝐴 𝐴 4
- 𝜀 1 𝑛 5
- 𝑉 𝑑 𝑑 5
- 𝑇 1 5
- 𝑛 𝑑 5
- 0.3777 dm mol 𝑑 1403 K 5
- 2.2 Objective function and reference database 5
- 𝑝 𝑝 5
- 𝜌 𝜌 5
- T OC 7
- T x T x T x T x 7
- 298.15 0.017 7
- 298.15 0.063 7
- 298.15 0.056 7
- 298.15 0.056 7
- 298.15 383.15 0.089 7
- 298.15 0.089 7
- 298.15 0.089 7
- 298.15 0.076 7
- 298.15 0.076 7
- 298.15 0.076 7
- 298.15 0.049 7
- 298.15 0.056 7
- 298.15 0.070 7
- 298.15 0.076 7
- 298.15 0.049 7
- 2.3 Ion-specific parameterization 8
- 2.3.1 Na K Rb and Cs salts 8
- 𝜎 𝜎 8
- 𝜎 𝜎 8
- 𝜎 𝜎 8
- 𝑟 𝜎 𝜎 𝜀 𝑘 𝑟 𝜎 𝜎 8
- 𝜀 𝑘 8
- 𝜎 𝜎 𝜎 9
- 𝜎 𝜎 9
- 𝜎 𝜎 9
- 2.3.2 Li salts 11
- 𝜀 𝑘 𝜀 11
- 𝜀 𝜀 11
- 𝑟 𝜎 𝜎 𝜀 𝑘 𝜀 𝑘 𝑟 𝜎 𝜎 11
- 𝑟 𝜎 𝜎 11
- 𝑁 𝑁 11
- 3 Results and discussion 12
- 3.1 Impact of the anion association site number 12
- 𝑁 9 12
- 𝑁 6 𝑁 12
- 𝑁 9 𝑁 12
- 𝑁 𝑁 12
- 𝑁 𝜀 𝑘 14
- 𝜎 𝜎 𝜎 𝜎 𝑁 14
- 𝜀 𝑘 𝜎 𝜎 𝜎 𝜎 14
- 𝑁 𝜀 𝑘 𝜎 𝜎 14
- 𝜎 𝜎 14
- 𝑁 10 𝜎 𝜎 14
- 𝜎 𝜎 𝜎 𝜎 𝑁 14
- 𝜀 𝑘 𝑁 14
- 3.2 Ionic diameter consistency of F 14
- 𝑟 𝜎 𝜎 14
- 𝜎 𝜎 𝜎 14
- 𝜎 𝜎 𝑟 14
- 𝜎 𝑁 𝜎 𝜎 14
- 𝜎 𝜎 15
- 𝑁 𝜎 15
- 𝜎 𝜎 15
- 𝜎 𝑁 𝑟 𝜎 𝜎 0.9707 𝑟 15
- 𝜎 𝜎 2.427 𝜀 𝑘 4910 K 𝑤 0.002993 𝑤 0.2458 𝑤 0.1043 15
- 𝑤 0.8439 15
- 𝜎 𝜎 15
- 3.3 Full vs. association strategies for the Li salts 15
- 𝜀 𝑘 16
- 𝜎 𝜎 𝜎 𝜎 16
- 𝜎 𝜎 𝜎 𝜎 𝑁 7 16
- 𝜎 0.68 Å 𝜎 1.2 Å 𝜎 10 Å 16
- 3.4 ePPC-SAFT with recommended parameter set 17
- 0.073 0.31 18
- 1.0 1.3 18
- 1.0 3.5 18
- 0.68 4.2 18
- 0.77 4.0 18
- 1.6 3.5 18
- 1.4 4.7 18
- 0.82 4.2 18
- 2.8 6.6 18
- 0.60 2.1 18
- 0.38 2.5 18
- 0.10 0.34 18
- 0.53 2.3 18
- 0.88 2.6 18
- 1.1 2.9 18
- 0.44 1.8 18
- 0.97 4.5 18
- 0.85 4.2 18
- 0.77 2.0 18
- 3.5 Contributions of the terms 19
- 4 Conclusions 22
- Nomenclature 23
- 𝑟 𝜎 𝜎 23
- 𝑟 𝜎 𝜎 23
- Greek letters 23
- CRediT authorship contribution statement 24
- Fufang Yang 24
- Georgios M. Kontogeorgis 24
- Jean-Charles de Hemptinne 24
- Declaration of competing interest 24
- Acknowledgements 24
- Reference 24
