When we place conducting bodies in electrolyte solutions, their surface potential Φs appears to be much smaller in magnitude than the applied one Φ0 and normally does not obey the classical electrostatic boundary condition of a constant potential expected for conductors. In this paper, we demonstrate that an explanation of these observations can be obtained by postulating that diffuse ions condense at the "wall" due to the reduced permittivity of a solvent. For small values of Φ0, the surface potential responds linearly.
View Article and Find Full Text PDFWhen electrolyte solutions are confined in micro- and nanochannels their conductivity is significantly different from those in a bulk phase. Here we revisit the theory of this phenomenon by focusing attention on the reduction in the ion mobility with the concentration of salt and a consequent impact to the conductivity of a monovalent solution, from bulk to confined in a narrow slit. We first give a systematic treatment of electrophoresis of ions and obtain equations for their zeta potentials and mobilities.
View Article and Find Full Text PDFMotivated by recent observations of anomalously large deviations of the conductivity currents in confined systems from the bulk behavior, we revisit the theory of ion transport in parallel-plate channels and also discuss how the wettability of a solid and the mobility of adsorbed surface charges impact the transport of ions. It is shown that depending on the ratio of the electrostatic disjoining pressure to the excess osmotic pressure at the walls two different regimes occur. In the thick channel regime this ratio is small and the channel effectively behaves as thick, even when the diffuse layers strongly overlap.
View Article and Find Full Text PDFAn electrokinetic (zeta) potential of charged permeable porous films on solid supports generally exceeds their surface potential, which often builds up to a quite high value itself. Recent work provided a quantitative understanding of zeta potentials of thick, compared to the extension of an inner electrostatic diffuse layer, porous films. Here, we consider porous coatings of thickness comparable to or smaller than that of the inner diffuse layer.
View Article and Find Full Text PDFWe discuss osmotic equilibria between soft permeable particles, of radius R and volume charge density ρ, and bulk electrolyte solutions of inverse Debye length κ. Existing models are based on a simplified assumption of weakly charged particles. Here we derive analytical approximations for the distribution of potentials, ions and pressure in a system, suitable even when ρ is quite large.
View Article and Find Full Text PDFHydrophobic surfaces with large slip lengths have the potential to enhance electro-osmotic flows. Existing theories of electroosmosis in hydrophobic channels postulate immobile surface charges and/or make a number of simplifying assumptions by considering mostly weakly charged surfaces and thin diffuse layers compared to channel dimension. In this paper, we extend prior models by focusing on planar and cylindrical nanochannels.
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