On the propagation of concentration polarization from microchannel-nanochannel interfaces. Part I: Analytical model and characteristic analysis.

We develop two models to describe ion transport in variable-height micro- and nanochannels. For the first model, we obtain a one-dimensional (unsteady) partial differential equation governing flow and charge transport through a shallow and wide electrokinetic channel. In this model, the effects of electric double layer (EDL) on axial transport are taken into account using exact solutions of the Poisson-Boltzmann equation. The second simpler model, which is approachable analytically, assumes that the EDLs are confined to near-wall regions. Using a characteristics analysis, we show that the latter model captures concentration polarization (CP) effects and provides useful insight into its dynamics. Two distinct CP regimes are identified: CP with propagation in which enrichment and depletion shocks propagate outward, and CP without propagation where polarization effects stay local to micro- nanochannel interfaces. The existence of each regime is found to depend on a nanochannel Dukhin number and mobility of the co-ion nondimensionalized by electroosmotic mobility. Interestingly, microchannel dimensions and axial diffusion are found to play an insignificant role in determining whether CP propagates. The steady state condition of propagating CP is shown to be controlled by channel heights, surface chemistry, and co-ion mobility instead of the reservoir condition. Both models are validated against experimental results in Part II of this two-paper series.