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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 DO at both the DO-air and the sodium dodecyl sulfate (surfactant)-covered DO surface by studying the alignment of interfacial DO, 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 DO. In contrast, DO has a higher affinity than Na at the air-DO interface. The relative surface affinity of cations thus depends on both details of the cation and the type of interface.

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