Structure of the submonolayer of ethanol adsorption on a vapor/fused silica interface studied with sum frequency vibrational spectroscopy.

Sum-frequency vibrational spectroscopy in the CH and OH stretch region was used to study ethanol adsorption on fused silica from vapor of different ethanol partial pressures. It was found that the adsorbed ethanol molecules were oriented with their methyl group tilted away from the surface normal by an average angle of ∼45° at low ethanol vapor pressures and ∼39° when approaching saturated vapor pressure. The spectral change with ethanol vapor pressure and the deduced adsorption isotherm show that ethanol molecules have two distinct adsorption sites on silica: One is the silanol group site to which an ethanol molecule can be strongly hydrogen-bonded, and the other is the siloxane (Si-O-Si) group site to which an ethanol molecule can be weakly bonded. The presence of water in vapor significantly reduced the surface coverage of ethanol on silica due to competitive adsorption between ethanol and water.