Surface and bulk phase behavior of dry and hydrated tetradecanol:octadecanol alcohol mixtures

Sloutskin, E.; Sirota, E. B.; Kraack, H.; Gang, O.; Doerr, A.; Ocko, B. M.; Deutsch, M.
May 2002
Journal of Chemical Physics;5/8/2002, Vol. 116 Issue 18, p8056
Academic Journal
Surface freezing was studied in dry and hydrated octadecanol:tetradecanol (C[sub 18]OH:C[sub 14]OH) mixtures, using surface tension and synchrotron x-ray surface diffraction techniques. Even small amounts of admixed C[sub 18]OH were found to induce surface freezing in C[sub 14]OH which does not exhibit this effect when pure. The phase diagram of the bulk was measured by calorimetry and bulk x-ray diffraction. Upon increasing the bulk mole fraction of C[sub 18]OH (φ) a sharp increase in the bulk supercooling occurs at φ ≈ 0.4 in dry mixtures, while no supercooling was observed for the hydrated mixtures. A simple thermodynamical model based on the theory of s-regular mixtures is shown to account well for the dependence of the surface freezing onset temperature of both dry and hydrated mixtures, and the hydrated bulk's freezing temperature on φ. Only a phenomenological description exists for the dry bulk's phase diagram. This study is expected to provide a baseline for the general surface and bulk behavior of long-chain alcohol mixtures.


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