The nonlinear electromigration of analytes into confined spaces.

We consider the problem of electromigration of a sample ion (analyte) within a uniform background electrolyte when the confining channel undergoes a sudden contraction. One example of such a situation arises in microfluidics in the electrokinetic injection of the analyte into a micro-capillary from a reservoir of much larger size. Here, the sample concentration propagates as a wave driven by the electric field. The dynamics is governed by the Nerst-Planck-Poisson system of equations for ionic transport. A reduced one-dimensional nonlinear equation, describing the evolution of the sample concentration, is derived. We integrate this equation numerically to obtain the evolution of the wave shape and determine how the injected mass depends on the sample concentration in the reservoir. It is shown that due to the nonlinear coupling of the ionic concentrations and the electric field, the concentration of the injected sample could be substantially less than the concentration of the sample in the reservoir.