Measuring properties of interfacial and bulk water regions in a reverse micelle with IR spectroscopy: A volumetric analysis of the inhomogeneously broadened OH band

Abstract

The water OH stretching band (3000–3600 cm −1) was analyzed for absorption contributions from the respective bulk and interfacial water regions of a reverse micelle. This analysis was performed by correlating volume changes of these regions to changes in the OH band absorption as the micelle radius grows. The volumetric analysis is based on the well established expanding core–shell model for AOT reverse micelles and yields the dimensions of the water regions and their individual spectral responses in the OH band. The interfacial shell thickness was determined to be 0.45 nm for AOT reverse micelles in i-octane. It was found that each water region absorbs at most frequencies in the OH band; however, absorption on the red side of the OH band is dominated by bulk water, while absorption on the blue side is dominated by interfacial water. The bulk spectral response was found to be more similar to pure water, while the interfacial spectrum is strongly blue-shifted reflecting the weaker hydrogen bonding in this region. AOT reverse micelles with radii in the range 2–4 nm conformed well to the volumetric model. However, it was found that determination of the bulk water spectral response is particularly sensitive to uncertainty in the micelle radius.