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    Vapor−Liquid Interfacial Properties of Mutually Saturated Water/1-Butanol Solutions
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    Contribution from the Center for Molecular Modeling and Department of Chemistry, University of Pennsylvania, 231 S. 34th Street, Philadelphia, Pennsylvania 19104-6323, and Department of Chemistry and Department of Chemical Engineering and Materials Science, University of Minnesota, 207 Pleasant Street SE, Minneapolis, MN 55455-0431
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    Cite this: J. Am. Chem. Soc. 2002, 124, 41, 12232–12237
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    https://doi.org/10.1021/ja027130n
    Published September 21, 2002
    Copyright © 2002 American Chemical Society
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    Adsorption and ordering at the vapor−liquid interfaces of mutually saturated water/1-butanol solutions at a temperature of 298.15 K were investigated using configurational-bias Monte Carlo simulations in the Gibbs ensemble and compared to the surface properties of neat water and 1-butanol liquids. A dense 1-butanol monolayer is observed at the surface of the water-rich phase, which results in a substantial decrease of its surface tension. In contrast, there is no enrichment of water molecules at the surface of the butanol-rich phase, and its surface tension is not significantly changed. Analysis of the interfacial structures reveals that these systems exhibit orientational ordering and composition heterogeneity. Analysis of the hydrogen-bonding distributions suggests that the formation of the 1-butanol monolayer is driven by an excellent match between water and the primary alcohol; that is, additional hydrogen bonds are formed between the excess free hydrogens of surface water and the excess hydrogen-bond acceptor sites of 1-butanol.

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     To whom correspondence should be addressed. E-mail:  binchen@ cmm.chem.upenn.edu.

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     University of Pennsylvania.

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     University of Minnesota.

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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2002, 124, 41, 12232–12237
    Click to copy citationCitation copied!
    https://doi.org/10.1021/ja027130n
    Published September 21, 2002
    Copyright © 2002 American Chemical Society
    Request reuse permissions

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