Association‐based activity coefficient model for electrolyte solutions

Lin, Yu‐Jeng; Hsieh, Cheng‐Ju; Chen, Chau‐Chyun

doi:10.1002/aic.17422

Title: Association‐based activity coefficient model for electrolyte solutions

Journal Article · 17 September 2021 · AIChE Journal

DOI: https://doi.org/10.1002/aic.17422 · OSTI ID:1820687

^[1]; Hsieh, Cheng‐Ju ^[1];

^[1]

Department of Chemical Engineering Texas Tech University Lubbock Texas USA

Abstract This work presents an association‐based activity coefficient model that explicitly considers the solution nonideality due to associations among ions and solvent species. Built upon the electrolyte nonrandom two‐liquid (eNRTL) model, the model greatly improves the accuracy of eNRTL model for strongly associating electrolyte solutions due to presence of ionic species with high surface charge density. The model successfully correlates mean ionic activity coefficients of 46 aqueous single‐salt systems from 10 cations and 5 anions at 298.15 K up to their solubility limits. With the ion‐specific association parameters identified, the model accurately predicts activity and osmotic coefficients for aqueous mixed‐salt systems at 298.15 K. The temperature dependence of the model results has also been examined at 273–373 K. With superior accuracy over a wide range of concentration and temperature, the model represents a major advancement over eNRTL model and has a great potential to be a next‐generation model for electrolyte solutions.

View Accepted Manuscript (Publisher)

Cite

Export

Save

Sponsoring Organization:: USDOE

Grant/Contract Number:: NONE; EE0007888

OSTI ID:: 1820687

Journal Information:: AIChE Journal, Journal Name: AIChE Journal Journal Issue: 2 Vol. 68; ISSN 0001-1541

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: United States

Language:: English

References (48)

Generalized electrolyte-NRTL model for mixed-solvent electrolyte systems Chen, Chau-Chyun; Song, Yuhua AIChE Journal, Vol. 50, Issue 8 https://doi.org/10.1002/aic.10151	journal	January 2004
An electrolyte CPA equation of state for mixed solvent electrolytes Maribo-Mogensen, Bjørn; Thomsen, Kaj; Kontogeorgis, Georgios M. AIChE Journal, Vol. 61, Issue 9 https://doi.org/10.1002/aic.14829	journal	August 2015
A comprehensive thermodynamic model for high salinity produced waters Tanveer, Sheik; Chen, Chau‐Chyun AIChE Journal, Vol. 66, Issue 1 https://doi.org/10.1002/aic.16818	journal	October 2019
Nonrandom two‐liquid activity coefficient model with association theory Hao, Yifan; Chen, Chau‐Chyun AIChE Journal, Vol. 67, Issue 1 https://doi.org/10.1002/aic.17061	journal	September 2020
Local composition model for excess Gibbs energy of electrolyte systems. Part I: Single solvent, single completely dissociated electrolyte systems Chen, Chau-Chyun; Britt, H. I.; Boston, J. F. AIChE Journal, Vol. 28, Issue 4 https://doi.org/10.1002/aic.690280410	journal	July 1982
A local composition model for the excess Gibbs energy of aqueous electrolyte systems Chen, Chau-Chyun; Evans, L. B. AIChE Journal, Vol. 32, Issue 3 https://doi.org/10.1002/aic.690320311	journal	March 1986
Model for describing activity coefficients in mixed electrolyte aqueous solutions: Model for Describing Activity Coefficients in Mixed Electrolyte Aqueous Solutions Lu, Xiao-hua; Maurer, G. AIChE Journal, Vol. 39, Issue 9 https://doi.org/10.1002/aic.690390912	journal	September 1993
Recent advances in modeling thermodynamic properties of aqueous strong electrolyte systems Loehe, Joseph R.; Donohue, Marc D. AIChE Journal, Vol. 43, Issue 1 https://doi.org/10.1002/aic.690430121	journal	January 1997
Use of hydration and dissociation chemistries with the electrolyte–NRTL model Chen, Chau-Chyun; Mathias, Paul M.; Orbey, Hasan AIChE Journal, Vol. 45, Issue 7 https://doi.org/10.1002/aic.690450719	journal	July 1999
A Model of Hydrogen-Bonded Liquids Luck, Werner A. P. Angewandte Chemie International Edition in English, Vol. 19, Issue 1 https://doi.org/10.1002/anie.198000281	journal	January 1980
The Debye-Hückel Theory for Hydrated Ions. I. Osmotic and Activity Coefficients of Binary Aqueous Solutions of Some 1 : 1 Electrolytes at 25°C Schönert, Hansjürgen Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 94, Issue 6 https://doi.org/10.1002/bbpc.19900940608	journal	June 1990
The Debye-Hückel Theory for Hydrated Ions. II. Osmotic and Activity Coefficients of Ternary Aqueous Solutions of Hydrogen and Alkali Halogenides at 25°C Schönert, Hansjürgen Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 94, Issue 6 https://doi.org/10.1002/bbpc.19900940609	journal	June 1990
Fluids with highly directional attractive forces. I. Statistical thermodynamics Wertheim, M. S. Journal of Statistical Physics, Vol. 35, Issue 1-2 https://doi.org/10.1007/BF01017362	journal	April 1984
Charge density-dependent strength of hydration and biological structure Collins, K. D. Biophysical Journal, Vol. 72, Issue 1 https://doi.org/10.1016/S0006-3495(97)78647-8	journal	January 1997
Physical properties from association models Michelsen, Michael L.; Hendriks, Eric M. Fluid Phase Equilibria, Vol. 180, Issue 1-2 https://doi.org/10.1016/S0378-3812(01)00344-2	journal	April 2001
Ions in water: Characterizing the forces that control chemical processes and biological structure Collins, Kim D.; Neilson, George W.; Enderby, John E. Biophysical Chemistry, Vol. 128, Issue 2-3 https://doi.org/10.1016/j.bpc.2007.03.009	journal	July 2007
ePC-SAFT revised Held, Christoph; Reschke, Thomas; Mohammad, Sultan Chemical Engineering Research and Design, Vol. 92, Issue 12 https://doi.org/10.1016/j.cherd.2014.05.017	journal	December 2014
A semi-empirical hydration model (SEHM) for describing aqueous electrolyte solutions Balomenos, Efthymios; Panias, Dimitrios; Paspaliaris, Ioannis Fluid Phase Equilibria, Vol. 243, Issue 1-2 https://doi.org/10.1016/j.fluid.2006.02.008	journal	May 2006
A semi-empirical hydration model (SEHM) for describing aqueous electrolyte solutions Balomenos, Efthymios; Panias, Dimitrios; Paspaliaris, Ioannis Fluid Phase Equilibria, Vol. 247, Issue 1-2 https://doi.org/10.1016/j.fluid.2006.06.001	journal	September 2006
Water-Mediated Ion Pairing: Occurrence and Relevance van der Vegt, Nico F. A.; Haldrup, Kristoffer; Roke, Sylvie Chemical Reviews, Vol. 116, Issue 13 https://doi.org/10.1021/acs.chemrev.5b00742	journal	April 2016
Nonrandom Two-Liquid Segment Activity Coefficient Model with Association Theory Hao, Yifan; Chen, Chau-Chyun Industrial & Engineering Chemistry Research, Vol. 58, Issue 28 https://doi.org/10.1021/acs.iecr.9b02078	journal	June 2019
Thermodynamic Modeling of Aqueous Electrolyte Systems: Current Status May, Peter M.; Rowland, Darren Journal of Chemical & Engineering Data, Vol. 62, Issue 9 https://doi.org/10.1021/acs.jced.6b01055	journal	March 2017
Cation Hydration and Ion Pairing in Aqueous Solutions of MgCl ₂ and CaCl ₂ Friesen, Sergej; Hefter, Glenn; Buchner, Richard The Journal of Physical Chemistry B, Vol. 123, Issue 4 https://doi.org/10.1021/acs.jpcb.8b11131	journal	January 2019
Ion Pairing Marcus, Yizhak; Hefter, Glenn Chemical Reviews, Vol. 106, Issue 11 https://doi.org/10.1021/cr040087x	journal	November 2006
Perturbed-Chain SAFT: An Equation of State Based on a Perturbation Theory for Chain Molecules Gross, Joachim; Sadowski, Gabriele Industrial & Engineering Chemistry Research, Vol. 40, Issue 4 https://doi.org/10.1021/ie0003887	journal	February 2001
New reference equation of state for associating liquids Chapman, Walter G.; Gubbins, Keith E.; Jackson, George Industrial & Engineering Chemistry Research, Vol. 29, Issue 8 https://doi.org/10.1021/ie00104a021	journal	August 1990
Modeling of Aqueous Electrolyte Solutions with Perturbed-Chain Statistical Associated Fluid Theory Cameretti, Luca F.; Sadowski, Gabriele; Mollerup, Jørgen M. Industrial & Engineering Chemistry Research, Vol. 44, Issue 9 https://doi.org/10.1021/ie0488142	journal	March 2005
Ten Years with the CPA (Cubic-Plus-Association) Equation of State. Part 1. Pure Compounds and Self-Associating Systems Kontogeorgis, Georgios M.; Michelsen, Michael L.; Folas, Georgios K. Industrial & Engineering Chemistry Research, Vol. 45, Issue 14 https://doi.org/10.1021/ie051305v	journal	July 2006
Inclusion of Ionic Hydration and Association in the MSA-NRTL Model for a Description of the Thermodynamic Properties of Aqueous Ionic Solutions: Application to Solutions of Associating Acids Simonin, Jean-Pierre; Krebs, Stéphane; Kunz, Werner Industrial & Engineering Chemistry Research, Vol. 45, Issue 12 https://doi.org/10.1021/ie051312j	journal	June 2006
Symmetric Electrolyte Nonrandom Two-Liquid Activity Coefficient Model Song, Yuhua; Chen, Chau-Chyun Industrial & Engineering Chemistry Research, Vol. 48, Issue 16 https://doi.org/10.1021/ie9004578	journal	August 2009
Prediction of Vapor−Liquid Equilibria of Associating Mixtures with UNIFAC Models That Include Association Fu, Yuan-Hao; Orbey, Hasan; Sandler, Stanley I. Industrial & Engineering Chemistry Research, Vol. 35, Issue 12 https://doi.org/10.1021/ie950545f	journal	January 1996
Thermodynamics of multicomponent, miscible, ionic systems: theory and equations Pitzer, Kenneth S.; Simonson, John M. The Journal of Physical Chemistry, Vol. 90, Issue 13 https://doi.org/10.1021/j100404a042	journal	June 1986
Thermodynamics of electrolytes. I. Theoretical basis and general equations Pitzer, Kenneth S. The Journal of Physical Chemistry, Vol. 77, Issue 2 https://doi.org/10.1021/j100621a026	journal	January 1973
Ionic solvation numbers from compressibilities and ionic vibration potentials measurements Bockris, J. O'M.; Saluja, P. P. S. The Journal of Physical Chemistry, Vol. 76, Issue 15 https://doi.org/10.1021/j100659a014	journal	July 1972
Ion Association of Magnesium Sulfate in Water at 25° Atkinson, Gordon; Petrucci, Sergio The Journal of Physical Chemistry, Vol. 70, Issue 10 https://doi.org/10.1021/j100882a017	journal	October 1966
Ionic Hydration and Activity in Electrolyte Solutions Stokes, R. H.; Robinson, R. A. Journal of the American Chemical Society, Vol. 70, Issue 5 https://doi.org/10.1021/ja01185a065	journal	May 1948
Crystallographic Evidence for Oxygen Acceptor Directionality in Oxyanion Hydrogen Bonds Hay, Benjamin P.; Dixon, David A.; Bryan, Jeffrey C. Journal of the American Chemical Society, Vol. 124, Issue 2 https://doi.org/10.1021/ja0173775	journal	January 2002
Structural Criteria for the Rational Design of Selective Ligands: Convergent Hydrogen Bonding Sites for the Nitrate Anion Hay, Benjamin P.; Gutowski, Maciej; Dixon, David A. Journal of the American Chemical Society, Vol. 126, Issue 25 https://doi.org/10.1021/ja0487980	journal	June 2004
The Structure of the Hydrogen Ion (H _aq ⁺ ) in Water Stoyanov, Evgenii S.; Stoyanova, Irina V.; Reed, Christopher A. Journal of the American Chemical Society, Vol. 132, Issue 5 https://doi.org/10.1021/ja9101826	journal	February 2010
Complexity in “Simple” Electrolyte Solutions: Ion Pairing in MgSO ₄ (aq) Buchner, Richard; Chen, Ting; Hefter, Glenn The Journal of Physical Chemistry B, Vol. 108, Issue 7 https://doi.org/10.1021/jp034870p	journal	February 2004
Ion Association and Hydration in Aqueous Solutions of LiCl and Li ₂ SO ₄ by Dielectric Spectroscopy Wachter, Wolfgang; Fernandez, Šarka; Buchner, Richard The Journal of Physical Chemistry B, Vol. 111, Issue 30 https://doi.org/10.1021/jp072425e	journal	August 2007
Ion-Pair and Solvent Relaxation Processes in Aqueous Na ₂ SO ₄ Solutions Buchner, Richard; Capewell, Stephen G.; Hefter, Glenn The Journal of Physical Chemistry B, Vol. 103, Issue 7 https://doi.org/10.1021/jp983706c	journal	February 1999
SAFT-VRE: Phase Behavior of Electrolyte Solutions with the Statistical Associating Fluid Theory for Potentials of Variable Range Galindo, Amparo; Gil-Villegas, Alejandro; Jackson, George The Journal of Physical Chemistry B, Vol. 103, Issue 46 https://doi.org/10.1021/jp991959f	journal	November 1999
Thermodynamics of Electrolytes. 13. Ionic Strength Dependence of Higher-Order Terms; Equations for CaCl2 and MgCl2 Pitzer, Kenneth S.; Wang, Peiming; Rard, Joseph A. Journal of Solution Chemistry, Vol. 28, Issue 4 https://doi.org/10.1023/A:1022695525943	journal	April 1999
The unique nature of H ⁺ in water Stoyanov, Evgenii S.; Stoyanova, Irina V.; Reed, Christopher A. Chem. Sci., Vol. 2, Issue 3 https://doi.org/10.1039/C0SC00415D	journal	January 2011
Ionic solvation Bockris, J. O'M. Quarterly Reviews, Chemical Society, Vol. 3, Issue 2 https://doi.org/10.1039/qr9490300173	journal	January 1949
A first principles study on the solvation and structure of SO[sub 4][sup 2−](H[sub 2]O)[sub n], n=6–12 Gao, Bing; Liu, Zhi-feng The Journal of Chemical Physics, Vol. 121, Issue 17 https://doi.org/10.1063/1.1802011	journal	January 2004
Osmotic Coefficients and Mean Activity Coefficients of Uni‐univalent Electrolytes in Water at 25°C Hamer, Walter J.; Wu, Yung‐Chi Journal of Physical and Chemical Reference Data, Vol. 1, Issue 4 https://doi.org/10.1063/1.3253108	journal	October 1972

Similar Records

Thermodynamic modeling of aqueous lithium salt solutions with association electrolyte nonrandom two-liquid activity coefficient model

Journal Article · 2022 · Fluid Phase Equilibria · OSTI ID:2418556

Hsieh, Cheng-Ju; Kirkes, Toni E.; Lin, Yu-Jeng; +1 more

A comprehensive thermodynamic model for high salinity produced waters

Journal Article · 2019 · AIChE Journal · OSTI ID:1572116

Tanveer, Sheik; Chen, Chau‐Chyun

Osmotic and Activity Coefficients of the {xZnCl2 + (1 - x)ZnSO4}(aq) System at 298.15 K

Journal Article · 2006 · Journal of Solution Chemistry · OSTI ID:907831

Ninkovic, R; Miladinovic, J; Todorovic, M; +2 more

Title: Association‐based activity coefficient model for electrolyte solutions

Citation Formats

References (48)

Similar Records

Related Subjects