Highly hydrophobic, water-insoluble
nonionic surfactants are often considered irrelevant to the ionization
of interfaces at which they adsorb, despite observations that suggest
otherwise. In the present study, we provide unambiguous evidence for
the participation of a water-insoluble surfactant in interfacial ionization
by conducting electrophoresis experiments for surfactant-stabilized
nonpolar oil droplets in aqueous continuous phase. It was found that
the surfactant with amine headgroup positively charged the surface
of oil suspended in aqueous continuous phase (oil/water interface),
which is consistent with its basic nature. In nonpolar oil continuous
phase, the same surfactant positively charged the surface of solid
silica (solid/oil interface) which is often considered acidic. The
latter observation is exactly opposite to what the traditional <i>acid–base mechanism of surface charging</i> would predict,
most clearly suggesting the possibility for another charging mechanism