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.
Keywords: Poisson-Boltzmann equation; electrophoresis; electrophoretic drag coefficient; holistic approach; inner flow field vortices.