Influence of solute association on the phase behavior of 12-hydroxystearic acid/n-alkane solutions

Abstract

The phase behavior of 12-hydroxystearic acid (12-HSA) in even-numbered alkanes ranging from octane (C₈) to hexatriacontane (C₃₆) was measured by visual observation of liquid + solid to liquid and liquid–liquid to liquid cloud points and liquid + solid to liquid + liquid transitions. In general solid phases were stabilized to low concentration and higher temperature with increasing alkane length. Liquid–liquid immiscibility was observed in larger alkanes starting with octadecane. The liquidus lines of shorter alkanes (octane to hexadecane) showing only liquid to liquid + solid transitions were fit with an attenuated associated solution model based on the Flory–Huggins lattice model assuming that 12-HSA forms a carboxylic acid dimer over all concentrations investigated. The fit results show that 12-HSA forms associated structures with degrees of association ranging from 3.7–4.5 dimers in the neat 12-HSA. At low concentrations, the 12-HSA is dissociated into dimers, however the free energy cost of dissociation stabilizes the solid phase giving a sharp knee at low concentrations. The role of 12-HSA association in its phase behavior and gelation behavior are discussed. More broadly, the importance of solute association in small molecule organogelators and its potential as a molecular design parameter similar to other component thermodynamic parameters, such as melting temperature and heat of fusion, is discussed.