A Focus on Two Electrokinetics Issues

This review article intends to communicate the new understanding and viewpoints on two fundamental electrokinetics topics that have only become available recently. The first is on the holistic approach to the Poisson–Boltzmann equation that can account for the effects arising from the interaction between the mobile ions in the Debye layer and the surface charge. The second is on the physical picture of the inner electro-hydrodynamic flow field of an electrophoretic particle and its drag coefficient. For the first issue, the traditional Poisson–Boltzmann equation focuses only on the mobile ions in the Debye layer; effects such as charge regulation and the isoelectronic point arising from the interaction between the mobile ions in the Debye layer and the surface charge are left to supplemental measures. However, a holistic treatment is entirely possible in which the whole electrical double layer—the Debye layer and the surface charge—is treated consistently from the beginning. While the derived form of the Poisson–Boltzmann equation remains unchanged, the zeta potential boundary condition becomes a calculated quantity that can reflect the various effects due to the interaction between the surface charges and the mobile ions in the liquid. The second issue, regarding the drag coefficient of a spherical electrophoretic particle, has existed ever since the breakthrough by Smoluchowski a century ago that linked the zeta potential of the particle to its mobility. Due to the highly nonlinear mathematics involved in the electro-hydrodynamics inside the Debye layer, there has been a lack of an exact solution for the electrophoretic flow field. Recent numerical simulation results show that the flow field comprises an inner region and an outer region, separated by a rather sharp interface. As the inner flow field is carried along by the particle, the measured drag is that at the inner/outer interface rather than at the solid/liquid interface. This identification and its associated physical picture of the inner flow field resolves a long-standing puzzle regarding the electrophoretic drag coefficient.

From electrodiffusion theory to the electrohydrodynamics of leaky dielectrics through the weak electrolyte limit

The Taylor–Melcher (TM) model is the standard model for describing the dynamics of poorly conducting leaky dielectric fluids under an electric field. The TM model treats the fluids as ohmic conductors, without modelling the underlying ion dynamics. On the other hand, electrodiffusion models, which have been successful in describing electrokinetic phenomena, incorporate ionic concentration dynamics. Mathematical reconciliation of the electrodiffusion picture and the TM model has been a major issue for electrohydrodynamic theory. Here, we derive the TM model from an electrodiffusion model in which we explicitly model the electrochemistry of ion dissociation. We introduce salt dissociation reaction terms in the bulk electrodiffusion equations and take the limit in which the salt dissociation is weak; the assumption of weak dissociation corresponds to the fact that the TM model describes poor conductors. Together with the assumption that the Debye length is small, we derive the TM model with or without the surface charge convection term depending upon the scaling of relevant dimensionless parameters. An important quantity that emerges is the Galvani potential (GP), the jump in voltage across the liquid–liquid interface between the two leaky dielectric media; the GP arises as a natural consequence of the interfacial boundary conditions for the ionic concentrations, and is absent under certain parametric conditions. When the GP is absent, we recover the TM model. Our analysis also reveals the structure of the Debye layer at the liquid–liquid interface, which suggests how interfacial singularities may arise under strong imposed electric fields. In the presence of a non-zero GP, our model predicts that the liquid droplet will drift under an imposed electric field, the velocity of which is computed explicitly to leading order.