A nonlinear equation for ionic diffusion in a strong binary electrolyte.

The problem of the one dimensional electro-diffusion of ions in a strong binary electrolyte is considered. The mathematical description, known as the Poisson-Nerst-Planck (PNP) system, consists of a diffusion equation for each species augmented by transport due to a self consistent electrostatic field determined by the Poisson equation. This description is also relevant to other important problems in physics such as electron and hole diffusion across semi-conductor junctions and the diffusion of ions in plasmas. If concentrations do not vary appreciably over distances of the order of the Debye length, the Poisson equation can be replaced by the condition of local charge neutrality first introduced by Planck. It can then be shown that both species diffuse at the same rate with a common diffusivity that is intermediate between that of the slow and fast species (ambipolar diffusion). Here we derive a more general theory by exploiting the ratio of Debye length to a characteristic length scale as a small asymptotic parameter. It is shown that the concentration of either species may be described by a nonlinear partial differential equation which provides a better approximation than the classical linear equation for ambipolar diffusion but reduces to it in the appropriate limit.