open access publication

Article, 2024

Theoretical and practical investigation of ion–ion association in electrolyte solutions

The Journal of Chemical Physics, ISSN 1089-7690, 0021-9606, Volume 160, 15, Page 154509, 10.1063/5.0198308

Contributors

Boroujeni, Saman Naseri 0000-0003-2830-8624 [1] Maribo-Mogensen, Bjørn 0000-0001-5447-412X [2] Liang, Xiaodong 0000-0002-2007-546X [1] Kontogeorgis, Georgios M 0000-0002-7128-1511 (Corresponding author) [1]

Affiliations

  1. [1] Technical University of Denmark
    2. [NORA names: DTU Technical University of Denmark; University; Denmark; Europe, EU; Nordic; OECD];
  2. [2] Hafnium Labs ApS., Vestergade 16, 3rd floor, 1456 Copenhagen, Denmark
    3. [NORA names: Denmark; Europe, EU; Nordic; OECD]

Abstract

In this study, we present a new equation of state for electrolyte solutions, integrating the statistical associating fluid theory for variable range interactions utilizing the generic Mie form and binding Debye-Hückel theories. This equation of state underscores the pivotal role of ion-ion association in determining the properties of electrolyte solutions. We propose a unified framework that simultaneously examines the thermodynamic properties of electrolyte solutions and their electrical conductivity, given the profound impact of ion pairing on this transport property. Using this equation of state, we predict the liquid density, mean ionic activity coefficient, and osmotic coefficient for binary NaCl, Na2SO4, and MgSO4 aqueous solutions at 298.15 K. Additionally, we evaluate the molar conductivity of these systems by considering the fraction of free ions derived from our equation of state in conjunction with two advanced electrical conductivity models. Our results reveal that, while ion-ion association has a minimal influence on the modification of the predicted properties of sodium chloride solutions, their impact on sodium and magnesium sulfate solutions is considerably more noticeable.

Keywords

Debye-Huckel theory, MgSO4, MgSO4 aqueous solution, Na2SO4, NaCl, activity coefficients, aqueous solution, association, binary NaCl, chloride solution, coefficient, conduction model, conductivity, conjunction, density, electrical conductivity, electrical conductivity model, electrolyte, electrolyte solution, equation of state, equations, fluid theory, form, fraction, fraction of free ions, framework, free ions, impact, impact of ion pairing, influence, interaction, investigation, ion pairs, ion-ion, ionic activity coefficients, ions, ion–ion association, liquid density, magnesium, magnesium sulfate solution, mean ionic activity coefficients, minimal influence, model, modification, molar conductance, osmotic coefficients, pairs, predictive properties, properties, properties of electrolyte solutions, range interactions, results, sodium, sodium chloride solution, solution, state, study, sulfate solution, system, theory, thermodynamic properties, thermodynamic properties of electrolyte solutions, transport, transport properties, variable range interactions

Funders

  • European Research Council
  • European Commission

Data Provider: Digital Science

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