Preferential Orientations and Anomalous Interfacial Tensions in Aqueous Solutions of Alcohols

Abstract

Literature studies on interfacial tension versus temperature between normal alcohols and water show that it increases with temperature and exhibits a maximum value at a given temperature depending on the molecular weight of the alcohol. This very unusual behavior is supposedly accompanied by the formation of monolayers of alcohol molecules oriented preferentially at the interface, a structural issue not confirmed until now. We use molecular-based models for water and alcohols in combination with molecular dynamics simulations to provide physical insights, from a molecular perspective, into the structural and thermodynamic behavior at the liquid–liquid interfaces of aqueous solutions of alcohols.