eCPA: An ion-specific approach to parametrization

Anders Schlaikjer*, Kaj Thomsen, Georgios M. Kontogeorgis

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review

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Abstract

Abstract The eCPA equation of state has been shown to be a promising electrolyte model, for which several applications have been demonstrated. The model at its current status is, however, limited by the use of salt-specific parameters for the interactions between salts and water. Having salt-specific parameters limit the applicability to simple systems of ions, as it can only be applied when a common ion is found between the salts in the solution. For more complex systems of multiple ions/salts this may not work well. In this work the main goal is to eliminate this limitation by parametrizing the model with an ion-specific parameter set. The ion-specific parameters are estimated by a simultaneous fitting of parameters for 17 ions, consisting of 10 cations and 7 anions, and with data for 55 salts. The parameters are fitted to osmotic coefficient and mean ionic activity coefficient data in a wide temperature range from 273.15 K to above 500 K and up to an ionic strength of 6 molal. The parameters are found to yield similar deviations as the salt-specific parameters, however, for a few salts cation-anion interaction parameters were needed in order to obtain reasonable accuracy. The parameters are applied to a series of systems, which include mixed salt osmotic coefficients, solid-liquid equilibrium and vapor-liquid equilibrium of water-methanol-salt, illustrating the applicability of the ion-specific parameters. Modelling of mixed salt osmotic coefficients illustrate that the parameters work well in salt mixtures, while the phase equilibria alsv o illustrate the extension to mixed solvent systems.
Original languageEnglish
JournalFluid Phase Equilibria
Volume470
Pages (from-to)176-187
ISSN0378-3812
DOIs
Publication statusPublished - 2018

Keywords

  • Equation of state
  • CPA
  • Debye-hückel
  • Electrolytes
  • Parametrization

Cite this

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title = "eCPA: An ion-specific approach to parametrization",
abstract = "Abstract The eCPA equation of state has been shown to be a promising electrolyte model, for which several applications have been demonstrated. The model at its current status is, however, limited by the use of salt-specific parameters for the interactions between salts and water. Having salt-specific parameters limit the applicability to simple systems of ions, as it can only be applied when a common ion is found between the salts in the solution. For more complex systems of multiple ions/salts this may not work well. In this work the main goal is to eliminate this limitation by parametrizing the model with an ion-specific parameter set. The ion-specific parameters are estimated by a simultaneous fitting of parameters for 17 ions, consisting of 10 cations and 7 anions, and with data for 55 salts. The parameters are fitted to osmotic coefficient and mean ionic activity coefficient data in a wide temperature range from 273.15 K to above 500 K and up to an ionic strength of 6 molal. The parameters are found to yield similar deviations as the salt-specific parameters, however, for a few salts cation-anion interaction parameters were needed in order to obtain reasonable accuracy. The parameters are applied to a series of systems, which include mixed salt osmotic coefficients, solid-liquid equilibrium and vapor-liquid equilibrium of water-methanol-salt, illustrating the applicability of the ion-specific parameters. Modelling of mixed salt osmotic coefficients illustrate that the parameters work well in salt mixtures, while the phase equilibria alsv o illustrate the extension to mixed solvent systems.",
keywords = "Equation of state, CPA, Debye-h{\"u}ckel, Electrolytes, Parametrization",
author = "Anders Schlaikjer and Kaj Thomsen and Kontogeorgis, {Georgios M.}",
year = "2018",
doi = "10.1016/j.fluid.2017.12.008",
language = "English",
volume = "470",
pages = "176--187",
journal = "Fluid Phase Equilibria",
issn = "0378-3812",
publisher = "Elsevier",

}

eCPA: An ion-specific approach to parametrization. / Schlaikjer, Anders; Thomsen, Kaj; Kontogeorgis, Georgios M.

In: Fluid Phase Equilibria, Vol. 470, 2018, p. 176-187.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - eCPA: An ion-specific approach to parametrization

AU - Schlaikjer, Anders

AU - Thomsen, Kaj

AU - Kontogeorgis, Georgios M.

PY - 2018

Y1 - 2018

N2 - Abstract The eCPA equation of state has been shown to be a promising electrolyte model, for which several applications have been demonstrated. The model at its current status is, however, limited by the use of salt-specific parameters for the interactions between salts and water. Having salt-specific parameters limit the applicability to simple systems of ions, as it can only be applied when a common ion is found between the salts in the solution. For more complex systems of multiple ions/salts this may not work well. In this work the main goal is to eliminate this limitation by parametrizing the model with an ion-specific parameter set. The ion-specific parameters are estimated by a simultaneous fitting of parameters for 17 ions, consisting of 10 cations and 7 anions, and with data for 55 salts. The parameters are fitted to osmotic coefficient and mean ionic activity coefficient data in a wide temperature range from 273.15 K to above 500 K and up to an ionic strength of 6 molal. The parameters are found to yield similar deviations as the salt-specific parameters, however, for a few salts cation-anion interaction parameters were needed in order to obtain reasonable accuracy. The parameters are applied to a series of systems, which include mixed salt osmotic coefficients, solid-liquid equilibrium and vapor-liquid equilibrium of water-methanol-salt, illustrating the applicability of the ion-specific parameters. Modelling of mixed salt osmotic coefficients illustrate that the parameters work well in salt mixtures, while the phase equilibria alsv o illustrate the extension to mixed solvent systems.

AB - Abstract The eCPA equation of state has been shown to be a promising electrolyte model, for which several applications have been demonstrated. The model at its current status is, however, limited by the use of salt-specific parameters for the interactions between salts and water. Having salt-specific parameters limit the applicability to simple systems of ions, as it can only be applied when a common ion is found between the salts in the solution. For more complex systems of multiple ions/salts this may not work well. In this work the main goal is to eliminate this limitation by parametrizing the model with an ion-specific parameter set. The ion-specific parameters are estimated by a simultaneous fitting of parameters for 17 ions, consisting of 10 cations and 7 anions, and with data for 55 salts. The parameters are fitted to osmotic coefficient and mean ionic activity coefficient data in a wide temperature range from 273.15 K to above 500 K and up to an ionic strength of 6 molal. The parameters are found to yield similar deviations as the salt-specific parameters, however, for a few salts cation-anion interaction parameters were needed in order to obtain reasonable accuracy. The parameters are applied to a series of systems, which include mixed salt osmotic coefficients, solid-liquid equilibrium and vapor-liquid equilibrium of water-methanol-salt, illustrating the applicability of the ion-specific parameters. Modelling of mixed salt osmotic coefficients illustrate that the parameters work well in salt mixtures, while the phase equilibria alsv o illustrate the extension to mixed solvent systems.

KW - Equation of state

KW - CPA

KW - Debye-hückel

KW - Electrolytes

KW - Parametrization

U2 - 10.1016/j.fluid.2017.12.008

DO - 10.1016/j.fluid.2017.12.008

M3 - Journal article

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SP - 176

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JO - Fluid Phase Equilibria

JF - Fluid Phase Equilibria

SN - 0378-3812

ER -