title: Solvent Role in the Formation of Electric Double Layers with Surface Charge Regulation: A Bystander or a Key Participant?
abstract: The charge formation at interfaces involving electrolyte solutions is due to the chemical equilibrium between the surface reactive groups and the potential determining ions in the solution (i.e., charge regulation). In this Letter we report our findings that this equilibrium is strongly coupled to the precise molecular structure of the solution near the charged interface. The neutral solvent molecules dominate this structure due to their overwhelmingly large number. Treating the solvent as a structureless continuum leads to a fundamentally inadequate physical picture of charged interfaces. We show that a proper account of the solvent effect leads to an unexpected and complex system behavior that is affected by the molecular and ionic excluded volumes and van der Waals interactions.
authors.affiliation: Department of Chemical and Biological Engineering, and Center for Micro-Engineered Materials, University of New Mexico, Albuquerque, New Mexico 87131, USA.
authors.forename: Mark E
authors.initials: ME
authors.lastname: Fleharty
authors.affiliation: Department of Chemical and Biological Engineering, and Center for Micro-Engineered Materials, University of New Mexico, Albuquerque, New Mexico 87131, USA.|Sandia National Laboratories, Albuquerque, New Mexico 87185, USA.
authors.forename: Frank
authors.initials: F
authors.lastname: van Swol
authors.affiliation: Department of Chemical and Biological Engineering, and Center for Micro-Engineered Materials, University of New Mexico, Albuquerque, New Mexico 87131, USA.
authors.forename: Dimiter N
authors.initials: DN
authors.lastname: Petsev