Surface freezing in binary mixtures of chain molecules. I. Alkane mixtures.
X-ray surface scattering and surface tension measurements are used to study surface freezing in molten mixtures of alkanes. These binary mixtures consist of protonated and deuterated alkanes, as well as of alkanes of different lengths. As for pure alkanes, a crystalline monolayer is formed at the surface a few degrees above the bulk freezing temperature. The structure of the monolayer has been determined on an angstrom scale. A simple theoretical approach is used to account for the thermodynamical observations at the surface and in the bulk. The model is based on a competition between entropic mixing and a repulsive interaction due to chain-length mismatch. The surface and bulk liquid phases are treated as ideal mixtures, while the solid phases are treated as regular mixtures. The theory is found to account well for all the mixtures studied, both hydrogenated-hydrogenated and hydrogenated-deuterated. The repulsive interaction and its dependence on the chain lengths of the components are determined from fits to the measured data.
Sloutskin
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Physics Department, Bar Ilan University, Ramat Gan 52900, Israel.
Wu
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Peterson
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Gang
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Ocko
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Sirota
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Deutsch
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