Contributions to ionic activity coefficients: A review and comparison of equations of state with molecular simulations
Résumé
Advanced Equations of State for electrolyte solutions (e-EoS) consist of many contributions stemming from
different intermolecular forces, e.g. repulsion, dispersion, hydrogen bonding, as well as ionic interactions between ions, ion solvation and possibly others. It is difficult to establish a priori which is the correct balance of the
various contributions, and different parameter estimation strategies may result in similar performance of models
having entirely different trends with respect to the contribution of the various terms. The first part of this work is
a literature review on the balance of forces exhibited by existing electrolyte models, both activity coefficient
models and e-EoS. In the second part of this work, the activity coefficients and the contributions of the various
terms calculated by molecular simulation (MS) based on the recent studies by Saravi and Panagiotopoulos are
analyzed and compared to their e-EoS counterparts at 25 ◦C and 1 bar. We have considered three e-EoS from
literature, namely the eSAFT-VR Mie, ePPC-SAFT and e-CPA. MS studies have been presented in literature both
using the so-called implicit and explicit simulations, but only the latter are considered here where water is
treated as a molecule, as these are in closer agreement to experimental data. Although correspondence between
MS contributions and e-EoS terms is not fully established, some conclusions related to the performance of e-EoS
are obtained.
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SupplementaryMaterial_Contributions_To_Ionic.pdf (908)
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