Solid-Liquid Phase Transition in the Octadecanoic Acid Film Adsorbed on the Toluene-Water Interface

The structure of the soluble protonated (pH=2) octadecanoic acid film adsorbed on the saturated hydrocarbon (n-hexane) - water and aromatic hydrocarbon (toluene)-water interfaces is studied by X-ray reflectometry using synchrotron radiation. The experimental data demonstrate that a solid phase of a Gibbs monolayer (26 +/- 1) Angstrom thick, in which aliphatic tails are perpendicular to the surface and the area per molecule is A=(18 +/- 2) Angstrom^2, forms in the film at the n-hexane - water interface. The solid monolayer on the toluene - water interface in the adsorbed film melts when temperature increases, and this transition is caused by disordering the hydrocarbon tails of the acid. During the solid - liquid transition, the Gibbs monolayer thickness remains almost the same, (22 +/- 1) Angstrom. In the solid phase, we have A=(20+/- 2) Angstrom^2 and the angle of deviation of the molecular tails from the normal to the surface is about ~ 30 deg. The density of the liquid monolayer phase with A=(24 +/- 2) Angstrom^2 corresponds to liquid n-octadecane.