Bulk electroconvective instability at high Péclet numbers

Bulk electroconvection pertains to flow induced by the action of a mean electric field upon the residual space charge in the macroscopic regions of a locally quasielectroneutral strong electrolyte. For a long time, controversy has existed in the literature as to whether quiescent electric conduction from such an electrolyte into a uniform charge-selective solid, such as a metal electrode or ion exchange membrane, is stable with respect to bulk electroconvection. While it was recently claimed that bulk electroconvective instability could not occur, this claim pertained to an aqueous, low-molecular-weight electrolyte characterized by an order-unity electroconvection Péclet number. In this paper, we show that the bulk electroconvection model transforms into the leaky dielectric model in the limit of infinitely large Péclet number. For the leaky dielectric model, conduction of the above-mentioned type is unstable, and so it is in the bulk electroconvection model for sufficiently large Péclet numbers. Such instability is sensitive to the ratio of the diffusivity of the cations to the anions. For infinite Péclet number, the case with equal ionic diffusivities is a bifurcation point separating stable and unstable regimes at the low-current limit. Further, for a cation-selective solid, when the Péclet number is finite and the anions are much more diffusive than the cations, an unreported bulk electroconvective instability is possible at low current. At higher currents and large Péclet numbers, we found that the system is unstable for all cation-to-anion diffusivity ratios, but passes from a monotonic instability to an oscillatory one as this ratio passes through unity.