The Unique Molecular Behavior of Water at the Chloroform–Water Interface

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Abstract:

The molecular bonding and orientation of water at the chloroform–water interface has been examined in this study using vibrational sum-frequency spectroscopy (VSFS). The results provide a key puzzle piece towards our understanding of the systematic changes in the interfacial bonding and orientation of water that occur with variations in the polarity of the organic phase, especially when compared with previous studies of different liquid–liquid interfacial systems. In these VSFS studies the OH spectral responses of interfacial water molecules are used to characterize the interactions between water and the organic phase. The spectral analysis, aided by isotopic dilution studies, shows that the moderate polarity of the chloroform phase results in a mixed interfacial region with stronger organic–water bonding and fewer bonding interactions between adjacent water molecules than was previously found for studies of non-polar organic liquid–water interfaces. Even with the more mixed interfacial region and stronger organic–water interactions, interfacial water retains a significant amount of orientational ordering. These results are compared with recent predictions from molecular dynamics simulations about how molecules behave at the chloroform–water interface.

Keywords: HYDROGEN BONDING; HYDROPHOBIC SURFACES; LIQUID–LIQUID INTERFACES; VIBRATIONAL SUM-FREQUENCY SPECTROSCOPY; VSFS; WATER

Document Type: Research Article

DOI: http://dx.doi.org/10.1366/000370210792434288

Affiliations: 1: Department of Chemistry, University of Oregon, 1253 University of Oregon, Eugene, Oregon 97403, USA 2: Department of Chemistry, University of Oregon, 1253 University of Oregon, Eugene, Oregon 97403, USA richmond@uoregon.edu

Publication date: September 1, 2010

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