On the Multi-Layered Adsorption of Alcanols in the Vicinity of Liquid–Vapor Transition at the Saturated Hydrocarbon–Water Interface

Structure of adsorption layer of long-chain monoatomic alcohols: 1-dodecanol and 1-tetracosanol at the interfaces n-hexane – water and n-hexadecane – water in the vicinity of “liquid – vapor” thermotropic phase transition is investigated by the method of X-ray reflectometry at synchrotron source. Model-independent structural data obtained on the adsorption layers under investigation deviate considerably from the structural parameters which have been proposed previously within a model-based representation and discussed in previous publications on said systems. It is shown that in the low-temperature mesophase the adsorption film consists of a Gibbs monolayer, a transitional liquid region with thickness of two to three monolayers ~50 Å and an extended (wide up to 200 Å) layer of micelles. Presence of a plane of the closest approach of micellar layer to the adsorption film at the interface is established. Transition to the high-temperature mesophase is followed by liquefying and partial evaporation of alcanol film along with observed depletion of micellar layer down to its complete disappearance.