The surface affinity of cations depends on both the cations and the nature of the surface

Specific ion effects at interfaces are important for a variety of thermodynamic properties of electrolyte solutions, like surface tension and the phase behavior of surfactants. We report the relative surface affinity of Na⁺ and D₃O⁺ at both the D₂O-air and the sodium dodecyl sulfate (surfactant)-covered D₂O surface by studying the alignment of interfacial D₂O, using vibrational sum frequency generation spectroscopy. The surface propensity of ions is found to be a function of both the nature of the ion and the nature of the surface. Specifically, for the charged, surfactant-covered interface, Na⁺ has a higher affinity than D₃O⁺. In contrast, D₃O⁺ has a higher affinity than Na⁺ at the air-D₂O interface. The relative surface affinity of cations thus depends on both details of the cation and the type of interface.