Ion-Specific Effects at the Surface of Water

Abstract

We studied the interaction between salts and surfactants on the water surface using heterodyne-detected vibrational sum frequency generation (HD-VSFG) spectroscopy. We used sodium dodecyl sulfate (SDS) as a prototype surfactant system at 75 micromolar bulk concentration in water. The vibrational response of the OH band of near-surface oriented water molecules and the CH bands of the hydrophobic tails of the surfactant are measured. We observed a dramatic enhancement of the surface density of the negatively charged SDS (DS-) within a narrow range of added salt concentrations. We demonstrated this increase is strongly ion-specific, and induced by the screening of the lateral Coulomb repulsion of the sulfate headgroups by the added cations, followed by strong hydrophobic interactions (hydrophobic collapse) when the DS- surface density reaches a critical value. For a solution of 75 micromolar SDS, the required concentrations of CsCl, KCl, and NaCl for this transition are 2, 5, and 10 mM, respectively.