Cross-over between first-order and critical wetting at the liquid-vapour interface of n-alkane/methanol mixtures: tricritical wetting and critical prewetting

Details Cross-over between first-order and critical wetting at the liquid-vapour interface of n-alkane/methanol mixtures: tricritical wetting and critical prewetting Cross-over between first-order and critical wetting at the liquid-vapour interface of n-alkane/methanol mixtures: tricritical wetting and critical prewetting

2001-11-11

arxiv.org/abs/cond-mat/0111206v2

Physics

Condensed Matter

Soft Condensed Matter

52 pages, 17 figures, to appear in Journal of Statistical Physics. The tex file has been revised after refereeing. The figures

Scientific paper

A mean-field theory is presented which describes the basic observations of recent experiments revealing rich wetting behaviour of n-alkane/methanol mixtures at the liquid-vapour interface. The theory, qualitative and in part heuristic, is based on a microscopic lattice-gas model from which a Cahn-Landau approach is distilled. Besides the physics associated with the short-range components of the intermolecular interactions, effects of the long-range tails of the net van der Waals forces between interfaces are also taken into account. Including weak long-range forces which favour wetting in the theory does not visibly alter the critical wetting transition for the nonane/methanol mixture, in contrast with the generic expectation of first-order wetting for such systems, but in good agreement with experiment. For decane/methanol weak long-range forces bring the transition very close to the prewetting critical point, leading to an adsorption behaviour closely reminiscent of short-range tricritical wetting, observed experimentally for alkane chain length between 9.6 and 10. Finally, for undecane/methanol the transition is clearly of first order. First-order wetting is also seen in the experiment.

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