Kavli Affiliate: Rudolf Podgornik
| First 5 Authors: Bin Zheng, Shigeyuki Komura, David Andelman, Rudolf Podgornik,
| Summary:
Onsager’s variational principle is generalized to address the diffusive
dynamics of an electrolyte solution composed of charge-regulated macro-ions and
counterions. The free energy entering the Rayleighian corresponds to the
Poisson-Boltzmann theory augmented by the charge-regulation mechanism. The
dynamical equations obtained by minimizing the Rayleighian include the
classical Poisson-Nernst-Planck equations, the Debye-Falkenhagen equation, and
their modifications in the presence of charge regulation. By analyzing the
steady state, we show that the charge regulation has an important impact on the
non-equilibrium macro-ion spatial distribution and their effective charge,
deviating significantly from their equilibrium values. Our model, based on
Onsager’s variational principle offers a unified approach to the diffusive
dynamics of electrolytes containing components that undergo various charge
association/dissociation processes.
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