Abstract
IN molecular liquids that may form dimers, for example by hydrogen-bonding, direct evaporation of dimers is possible when these form stable molecules. A gradual change from monomer to dimer evaporation would be expected at pairwise molecular bond energies of intermediate strength—that is, ~ 0.01–1 eV, a range of values that is typical of hydrogen-bond strengths in liquids. Here we use molecular-beam techniques to study the evaporation of large fractions of acetic and formic acid dimers from the pure liquids and from solutions. We find that their velocity distributions are non-maxwellian, and that the average dimer energies exceed the temperature of the liquid surface by 100–200 K. These unexpected effects may be qualitatively explained by a crude model in which surface-tension forces act upon non-wetting, twin-hydrogen-bond dimer inclusions within an extended, monomeric hydrogen-bonded 'sheet' at the liquid surface.
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Faubel, M., Kisters, T. Non-equilibrium molecular evaporation of carboxylic acid dimers. Nature 339, 527–529 (1989). https://doi.org/10.1038/339527a0
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DOI: https://doi.org/10.1038/339527a0
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