eCPA: An ion-specific approach to parametrization

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

VL - 470

SP - 176

EP - 187

JO - Fluid Phase Equilibria

JF - Fluid Phase Equilibria

SN - 0378-3812

ER -