Effect of surface conduction-induced electromigration on current monitoring method for electroosmotic flow measurement.

Current monitoring method for measurement of EOF in microchannels involves measurement of time-varying current while an electrolyte displaces another electrolyte having different conductivity due to EOF. The basic premise of the current monitoring method is that an axial gradient in conductivity of a binary electrolyte in a microchannel advects only due to EOF. In the current work, using theory and experiments, we show that this assumption is not valid for low concentration electrolytes and narrow microchannels wherein surface conduction is comparable with bulk conduction. We show that in presence of surface conduction, a gradient in conductivity of binary electrolyte not only advects with EOF but also undergoes electromigration. This electromigration phenomenon is nonlinear and is characterized by propagation of shock and rarefaction waves in ion concentrations. Consequently, in presence of surface conduction, the current-time relationships for forward and reverse displacement in the current monitoring method are asymmetric and the displacement time is also direction dependent. To quantify the effect of surface conduction, we present analytical expressions for current-time relationship in the regime when surface conduction is comparable to bulk conduction. We validate these relations with experimental data by performing a series of current monitoring experiments in a glass microfluidic chip at low electrolyte concentrations. The experimentally validated analytical expressions for current-time relationships presented in this work can be used to correctly estimate EOF using the current monitoring method when surface conduction is not negligible.