Direct Resolution of the Interactions of a Hydrocarbon Gas with Adsorbed Surfactant Monolayers at the Water/Air Interface Using Neutron Reflectometry

We have directly resolved in the present work the interfacial composition during and after the interactions of a saturated atmosphere of oil vapor with soluble surfactant solutions at a planar water/air interface for the first time. Experiments were conducted on interactions of hexane vapor with solutions of alkyltrimethylammonium bromides and sodium dodecyl sulfate to observe the balance between cooperativity and competition of the components at the interface. In all cases, hexane adsorption was strongly enhanced by the presence of the surfactant, even at bulk surfactant concentrations four orders of magnitude below the critical micelle concentration. Cooperativity of the surfactant adsorption was observed only for sodium dodecyl sulfate at intermediate bulk concentrations, yet for all four systems, competition set in at higher concentrations, as hexane adsorption reduced the surfactant surface excess. The data fully supported the complete removal of hexane from the interface following venting of the system to remove the saturated atmosphere of oil vapor. These results help to identify future experiments that would elaborate and could explain the cooperativity of surfactant adsorption, such as on cationic surfactants with short alkyl chains and a broader series of anionic surfactants. This work holds relevance for oil recovery applications with foam, where there is a gas phase saturated with oil vapor.