論文

査読有り 筆頭著者 責任著者
2020年8月21日

Theory of electrolytes including steric, attractive, and hydration interactions

The Journal of Chemical Physics
  • Ryuichi Okamoto
  • ,
  • Kenichiro Koga
  • ,
  • Akira Onuki

153
7
記述言語
掲載種別
研究論文(学術雑誌)
DOI
10.1063/5.0015446

© 2020 Author(s). We present a continuum theory of electrolytes composed of a waterlike solvent and univalent ions. First, we start with a density functional F for the coarse-grained solvent, cation, and anion densities, including the Debye-Hückel free energy, the Coulombic interaction, and the direct interactions among these three components. These densities fluctuate obeying the distribution ∞exp(-F/kBT). Eliminating the solvent density deviation in F, we obtain the effective non-Coulombic interactions among the ions, which consist of the direct ones and the solvent-mediated ones. We then derive general expressions for the ion correlation, the apparent partial volume, and the activity and osmotic coefficients up to linear order in the average salt density ns. Second, we perform numerical analysis using the Mansoori-Carnahan-Starling-Leland model [J. Chem. Phys. 54, 1523 (1971)] for three-component hardspheres. The effective interactions sensitively depend on the cation and anion sizes due to competition between the steric and hydration effects, which are repulsive between small-large ion pairs and attractive between symmetric pairs. These agree with previous experiments and Collins' rule [Biophys. J. 72, 65 (1997)]. We also give simple approximate expressions for the ionic interaction coefficients valid for any ion sizes.

リンク情報
DOI
https://doi.org/10.1063/5.0015446
PubMed
https://www.ncbi.nlm.nih.gov/pubmed/32828079
Scopus
https://www.scopus.com/inward/record.uri?partnerID=HzOxMe3b&scp=85089794457&origin=inward
Scopus Citedby
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ID情報
  • DOI : 10.1063/5.0015446
  • ISSN : 0021-9606
  • eISSN : 1089-7690
  • ORCIDのPut Code : 79050433
  • PubMed ID : 32828079
  • SCOPUS ID : 85089794457

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