Surface activity of octanoic acid in ethanol-water solutions from molecular simulation and experiment

The surface activity of a typical surfactant, octanoic acid (OA), in ethanol-water solutions is investigated with a combined experimental and molecular simulation approach. The experiments show that OA reduces the surface tension of ethanol-water solutions at low ethanol concentration, but the effectiveness decreases with increasing ethanol concentration and vanishes for ethanol concentrations above 60%. Molecular dynamics simulations are used to obtain free energy landscapes for OA as a function of the distance from the surface. The free energy driving force pushing OA to the surface decreases with increasing ethanol concentration, and becomes insignificant (i.e., less than kT) for ethanol concentrations above 70%. Thus, the decrease in the effectiveness of OA in reducing the surface tension at higher ethanol concentrations can be attributed to the decrease in the free energy driving force keeping OA at the surface. We expect these results to apply generally to hydrocarbon-based surfactants.