A simplified model of oscillating electrolytes.

Abstract

Unstable electrophoretic transport leading to oscillations in concentration profiles occur in certain electrolyte systems known as oscillating electrolytes whose eigenmobilities are complex valued. The study of the nonlinear behavior of such systems is of great interest but is constrained due to a high degree of complexity in the governing equations. Here we present a simplified model of unstable electrophoretic transport in a binary system that reduces the governing equations to two partial differential equations only and does away with other equations that characterize acid-base dissociation reactions and electroneutrality. We present analytical expressions for electromigration fluxes and validate the model with full nonlinear simulations. The model exhibits similar nonlinear behavior as the actual unstable electrophoretic system under various initial disturbances. For comparison, we also show that similar modeling for a stable system predicts concentration profiles that quantitatively agree with its nonoscillating dynamics. Moreover, the unique feature of electromigration flux in oscillating electrolytes that unfolds from the modeling led us to find an elegant explanation of the instability mechanism. Our theory gives a qualitative understanding of the existence and growth of large oscillation patterns in oscillating electrolytes.