Ellipsometric study of depletion at oil-water interfaces

Ellipsometry is exquisitely sensitive to density variations across a fluid-fluid interface. The coefficient of ellipticity at the interface between water and a series of nonpolar and polar oils is the opposite sign to that predicted for an interface roughened by thermal capillary waves. For pure hydrocarbons, the coefficient of ellipticity is correlated with the refractive index of the oil, but is largely independent of the molecular architecture of the oil phase, ruling out molecular alignment at the interface as the major cause of the deviation from the capillary-wave model. The introduction of a "drying" layer between the oil and water can explain the experimental data. The thickness of the drying layer, modeled as a slab with a relative permittivity of unity, was only 0.3-0.4 angstrom, which is close to that expected simply from the hard sphere repulsion of a hydrocarbon surface. For polar oils, the coefficient of ellipticity decreases as the interfacial tension decreases, consistent with the reduction in thickness of the hard-sphere exclusion region on account of the formation of hydrogen bonds to water.