Desolvation of redox species and ions accompany many technological electrochemical processes, including bubble formation, metal deposition and ion intercalation. This presentation presents a model system using scanning electrochemical cell microscopy for quantitatively measuring the kinetics and energetics associated with solvation/desolvation during coupled electron- and phase-transfer reactions (CEPhT). Examples include CEPhT reactions occurring at the three-phase boundary between a dielectric phase (toluene, alkanes, air), an aqueous electrolyte, and a carbon electrode. Electric field spillover at the three-phase boundary is shown to drive electron- and phase-transfer.
