The Three-Phase Contact Potential Difference Modulates the Water Surface Charge

The surface charge of an open water surface is crucialfor solvationphenomena and interfacial processes in aqueous systems. However, themagnitude of the charge is controversial, and the physical mechanismof charging remains incompletely understood. Here we identify a previouslyoverlooked physical mechanism determining the surface charge of water.Using accurate charge measurements of water microdrops, we demonstratethat the water surface charge originates from the electrostatic effectsin the contact line vicinity of three phases, one of which is water.Our experiments, theory, and simulations provide evidence that a junctionof two aqueous interfaces (e.g., liquid-solid and liquid-air)develops a pH-dependent contact potential difference Delta phi due to the longitudinal charge redistribution between two contactinginterfaces. This universal static charging mechanism may have implicationsfor the origin of electrical potentials in biological, nanofluidic,and electrochemical systems and helps to predict and control the surfacecharge of water in various experimental environments.