Nonlinear electrostatics: the Poisson-Boltzmann equation
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double-layer free energieselectric double layerGibbs variational principleinter-plate forces in electrolytesPoisson-Boltzmann theory
Boltzmann equations (35Q20) PDEs in connection with optics and electromagnetic theory (35Q60) Ionized gas flow in electromagnetic fields; plasmic flow (76X05) Research exposition (monographs, survey articles) pertaining to optics and electromagnetic theory (78-02) Electro- and magnetostatics (78A30) Composite media; random media in optics and electromagnetic theory (78A48) Electrochemistry (78A57) Statistical mechanics of plasmas (82D10)
Abstract: The description of a conducting medium in thermal equilibrium, such as an electrolyte solution or a plasma, involves nonlinear electrostatics, a subject rarely discussed in the standard electricity and magnetism textbooks. We consider in detail the case of the electrostatic double layer formed by an electrolyte solution near a uniformly charged wall, and we use mean-field or Poisson-Boltzmann (PB) theory to calculate the mean electrostatic potential and the mean ion concentrations, as functions of distance from the wall. PB theory is developed from the Gibbs variational principle for thermal equilibrium of minimizing the system free energy. We clarify the key issue of which free energy (Helmholtz, Gibbs, grand,...) should be used in the Gibbs principle; this turns out to depend not only on the specified conditions in the bulk electrolyte solution (e.g., fixed volume or fixed pressure), but also on the specified surface conditions, such as fixed surface charge or fixed surface potential. Despite its nonlinearity the PB equation for the mean electrostatic potential can be solved analytically for planar or wall geometry, and we present analytic solutions for both a full electrolyte, and for an ionic solution which contains only counterions, i.e. ions of sign opposite to that of the wall charge. This latter case has some novel features. We also use the free energy to discuss the inter-wall forces which arise when the two parallel charged walls are sufficiently close to permit their double layers to overlap. We consider situations where the two walls carry equal charges, and where they carry equal and opposite charges.
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Cited in
(18)- Refined derivation, exact solutions, and singular limits of the Poisson- Boltzmann equation
- Poisson-Fermi formulation of nonlocal electrostatics in electrolyte solutions
- Perturbation solutions for the nonlinear Poisson-Boltzmann equation with a high-order-accuracy Debye-Hückel approximation
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