Small-angle X-ray scattering and near-infrared vibrational spectroscopy of water confined in aerosol-OT reverse micelles.
The state of water confined in Aerosol-OT-hydrocarbon-water reverse micelles with cyclohexane, n-pentane, n-octane, and n-dodecane as apolar solvents is investigated by small-angle X-ray scattering and near-infrared vibrational spectroscopy of the first overtone of the OH stretching mode of water. The experiments focus on water/AOT molecular ratios W(0)=2-20, where water is strongly affected by the confinement and surface-water interactions. The pair-distance distribution functions derived from the small-angle scattering patterns allows a detailed characterization of the topology of these systems, and they indicate deviations from monodisperse, spherical water pools for some of these hydrocarbon systems. In contrast to a common assumption, the pool size does not scale linearly with W(0) in going from dry reverse micelles (W(0)-->0) to essentially bulk-like water (W(0)>20). The first overtone of the OH-stretching vibration exhibits highly structured spectra, which reveal significant changes in the hydrogen bonding environment upon confinement. The spectra are rationalized by a core/shell model developed by Fayer and co-workers. This model subdivides water into core water in the interior of the micelle and shell water close to the interface. Core water is modelled by the properties of bulk water, while the properties of shell water are taken to be those of water at W(0)=2. The model allows the representation of the spectra at any hydration level as a linear combination of the spectra of core and shell water. Different approaches are critically reviewed and discussed as well.
Balakrishnan
Sangeetha
S
Physical Chemistry II, Ruhr-University Bochum,D-44780 Bochum, Germany.
Javid
Nadeem
N
Weingärtner
Hermann
H
Winter
Roland
R
D004143:Dioctyl Sulfosuccinic Acid / Q000737:chemistry*; D006860:Hydrogen Bonding; D008823:Micelles; D053838:Scattering, Small Angle; D019265:Spectroscopy, Near-Infrared; D014867:Water / Q000737:chemistry*; D014961:X-Ray Diffraction
D008823:Micelles; D014867:Water; D004143:Dioctyl Sulfosuccinic Acid