TY - JOUR
T1 - Thermodynamic Modeling of Aqueous LiCl, LiBr, LiI, and LiNO3 Solutions
AU - Kirkes, Toni E.
AU - Saravi, Sina H.
AU - Chen, Chau Chyun
N1 - Funding Information:
Funding support is provided by the U. S. Department of Energy under the grant DE-EE0007888. The authors gratefully acknowledge the financial support of the Jack Maddox Distinguished Engineering Chair Professorship in Sustainable Energy sponsored by the J.F Maddox Foundation.
Funding Information:
Funding support is provided by the U. S. Department of Energy under the grant DE-EE0007888. The authors gratefully acknowledge the financial support of the Jack Maddox Distinguished Engineering Chair Professorship in Sustainable Energy sponsored by the J.F Maddox Foundation.
Publisher Copyright:
© 2020
PY - 2021/3/1
Y1 - 2021/3/1
N2 - Thermodynamic models are essential to facilitate the advancement of process design, optimization, and operation of electrolyte systems. In this work, a comprehensive thermodynamic framework based on the Electrolyte Nonrandom Two-Liquid model is developed to calculate phase equilibria behavior and salt solubility of aqueous LiCl, LiBr, LiI, and LiNO3 solutions. The model describes the non-ideality of the electrolyte solutions by using two binary interaction parameters for each molecule-electrolyte pair in the system. Each binary interaction parameter is further expressed with up to three temperature coefficients which are regressed from experimental data. To take into account the hydration of lithium ion, two separate chemistries for the dissociation of lithium salts are investigated. In the first case, the lithium ion is considered as a bare ion, Li+, while in the second case hydration of the lithium ion from Li+ to Li(H2O)+ is considered. The calculated thermodynamic properties compare adequately with the experimental data for both sets of chemistries for concentrations up to saturation and temperatures from 273.15 K up to 623.15 K. Moderate to significant improvements are observed with the incorporation of the hydration chemistry for aqueous LiCl, LiBr, and LiI solutions when compared to the non-hydrated lithium ion model results.
AB - Thermodynamic models are essential to facilitate the advancement of process design, optimization, and operation of electrolyte systems. In this work, a comprehensive thermodynamic framework based on the Electrolyte Nonrandom Two-Liquid model is developed to calculate phase equilibria behavior and salt solubility of aqueous LiCl, LiBr, LiI, and LiNO3 solutions. The model describes the non-ideality of the electrolyte solutions by using two binary interaction parameters for each molecule-electrolyte pair in the system. Each binary interaction parameter is further expressed with up to three temperature coefficients which are regressed from experimental data. To take into account the hydration of lithium ion, two separate chemistries for the dissociation of lithium salts are investigated. In the first case, the lithium ion is considered as a bare ion, Li+, while in the second case hydration of the lithium ion from Li+ to Li(H2O)+ is considered. The calculated thermodynamic properties compare adequately with the experimental data for both sets of chemistries for concentrations up to saturation and temperatures from 273.15 K up to 623.15 K. Moderate to significant improvements are observed with the incorporation of the hydration chemistry for aqueous LiCl, LiBr, and LiI solutions when compared to the non-hydrated lithium ion model results.
UR - http://www.scopus.com/inward/record.url?scp=85097558079&partnerID=8YFLogxK
U2 - 10.1016/j.fluid.2020.112914
DO - 10.1016/j.fluid.2020.112914
M3 - Article
AN - SCOPUS:85097558079
VL - 531
JO - Fluid Phase Equilibria
JF - Fluid Phase Equilibria
SN - 0378-3812
M1 - 112914
ER -