The dielectric constant and the viscosity of water at the interface of hydrophilic surfaces differ from their bulk values, and it has been proposed that the deviation is caused by the strong electric field and the high ion concentration in the interfacial layer. We calculate the dependence of the dielectric constant and the viscosity of bulk electrolytes on the electric field and the salt concentration. Incorporating the concentration and field-dependent dielectric constant and viscosity in the extended Poisson-Boltzmann and Stokes equations, we calculate the electro-osmotic mobility. We compare the results to literature experimental data and explicit molecular dynamics simulations of OH-terminated surfaces and show that it is necessary to additionally include the presence of a subnanometer wide interfacial water layer, the properties of which are drastically transformed by the sheer presence of the interface. We conclude that the origin of the anomalous behavior of aqueous interfacial layers cannot be found in electrostriction or electroviscous effects caused by the interfacial electric field and ion concentration. Instead, it is primarily caused by the intrinsic ordering and orientation of the interfacial water layer.
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
- Surfaces, Coatings and Films
- Materials Chemistry