The electrification of hydrophobic surfaces is an intensely debated subject in physical chemistry. We theoretically study the ζ potential of hydrophobic surfaces for varying pH and salt concentration by solving the Poisson–Boltzmann and Stokes equations with individual ionic adsorption affinities. Using the ionic surface affinities extracted from the experimentally measured surface tension of the air–electrolyte interface, we first show that the interfacial adsorption and repulsion of small inorganic ions such as H3O+, OH–, HCO3–, and CO32– cannot account for the ζ potential observed in experiments because the surface affinities of these ions are too small. Even if we take hydrodynamic slip into account, the characteristic dependence of the ζ potential on pH and salt concentration cannot be reproduced. Instead, to explain the sizable experimentally measured ζ potential of hydrophobic surfaces, we assume minute amounts of impurities in the water and include the impurities’ acidic and basic reactions with water. We find good agreement between our predictions and the reported experimental ζ potential data of various hydrophobic surfaces if we account for impurities that consist of a mixture of weak acids (pKa = 5–7) and weak bases (pKb = 12) at a concentration of the order of 10–7 M.
