Ions and dipoles in electric field: Nonlinear polarization and field-dependent chemical reaction
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| Format: | Preprint |
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2024
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| _version_ | 1866910294605824000 |
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| author | Onuki, Akira |
| author_facet | Onuki, Akira |
| contents | We investigate electric-field effects in dilute electrolytes with nonlinear polarization. As a first example of such systems, we add a dipolar component with a relatively large dipole moment $μ_0$ to an aqueous electrolyte. As a second example, the solvent itself exhibits nonlinear polarization near charged objects. For such systems, we present a Ginzburg-Landau free energy and introduce field-dependent chemical potentials, entropy density, and stress tensor, which satisfy general thermodynamic relations. In the first example, the dipoles accumulate in high-field regions, as predicted by Abrashikin {\it et al}.$[$Phys.Rev.Lett. {\bf 99}, 077801 (2007)$]$. Finally, we consider the case, where Bjerrum ion pairs form a dipolar component with nonlinear polarization. The Bjerrum dipoles accumulate in high-field regions, while field-induced dissociation was predicted by Onsager $[$J. Chem. Phys.{\bf 2}, 599 (1934)$]$. We present an expression for the field-dependent association constant $K(E)$, which depends on the field strength nonmonotonically. |
| format | Preprint |
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arxiv_https___arxiv_org_abs_2401_05825 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | Ions and dipoles in electric field: Nonlinear polarization and field-dependent chemical reaction Onuki, Akira Soft Condensed Matter We investigate electric-field effects in dilute electrolytes with nonlinear polarization. As a first example of such systems, we add a dipolar component with a relatively large dipole moment $μ_0$ to an aqueous electrolyte. As a second example, the solvent itself exhibits nonlinear polarization near charged objects. For such systems, we present a Ginzburg-Landau free energy and introduce field-dependent chemical potentials, entropy density, and stress tensor, which satisfy general thermodynamic relations. In the first example, the dipoles accumulate in high-field regions, as predicted by Abrashikin {\it et al}.$[$Phys.Rev.Lett. {\bf 99}, 077801 (2007)$]$. Finally, we consider the case, where Bjerrum ion pairs form a dipolar component with nonlinear polarization. The Bjerrum dipoles accumulate in high-field regions, while field-induced dissociation was predicted by Onsager $[$J. Chem. Phys.{\bf 2}, 599 (1934)$]$. We present an expression for the field-dependent association constant $K(E)$, which depends on the field strength nonmonotonically. |
| title | Ions and dipoles in electric field: Nonlinear polarization and field-dependent chemical reaction |
| topic | Soft Condensed Matter |
| url | https://arxiv.org/abs/2401.05825 |