Effect of surfactant shape on solvophobicity and surface activity in alcohol-water systems

Here we study the relationship between a surfactant's molecular shape and its tendency to partition to the interface in ethanol-water mixtures. In general, finding surfactants that are effective in alcohol-water mixtures is more challenging than finding ones that are effective in pure water. This is because the solvophobic effect that partitions surfactants from bulk solution to the interface becomes weaker as ethanol concentration increases. We use experiments and molecular dynamics to observe the effects of increasing surfactant tail length or width. The results show that increasing surfactant tail length causes the surfactant to partition to the surface better in low ethanol concentrations, but not at high ethanol concentrations. In comparison, increasing surfactant tail width causes the surfactant to partition to the surface better at higher concentrations of ethanol. We examine the liquid structure to elucidate the mechanisms that weaken the partitioning effect as ethanol concentration increases. Ethanol-water mixtures are nanoscopically heterogeneous with protic and aprotic regions in the bulk solution. We see that the surfactant tail is most likely to be solvated in the aprotic regions where it perturbs fewer hydrogen bonds.