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

Surface Tension Measurements with the Drop Profile Analysis Tensiometry—Consideration of the Surfactant Mass Balance in a Single Drop

In drop profile analysis tensiometry, the ratio of drop surfaces area S to volume V is large, i.e., S/V >> 1. In such a case, the concentration of a surfactant within the drop bulk decreases due to adsorption at the drop surface. In contrast, in bubble profile analysis tensiometry, we have S/V << 1 so that depletion due to adsorption is negligible. A protocol is presented to determine the correct adsorption parameters of surfactants from surface tension data measured by bubble and drop profile analysis tensiometry. The procedure is applied to experimental data measured for selected surfactants of different adsorption activities: C10OH, CTAB, Tween 20, and the equimolar mixture SDS + DoTAB. The results show that for surfactants with higher surface activity, the differences between the surface tensions measured with the drops and bubbles profile analysis tensiometry, respectively, are larger, while for less surface-active surfactants, such as SDS, the results obtained from drop and bubble profile experiments are very close. The correction procedure is based on the same set of adsorption parameters used to fit both the experimental data obtained from drop-based measurements (which involve the depletion effects) and those data measured in a way that depletion effects are negligible

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

Surface Tension Measurements with the Drop Profile Analysis Tensiometry—Consideration of the Surfactant Mass Balance in a Single Drop

In drop profile analysis tensiometry, the ratio of drop surfaces area S to volume V is large, i.e., S/V >> 1. In such a case, the concentration of a surfactant within the drop bulk decreases due to adsorption at the drop surface. In contrast, in bubble profile analysis tensiometry, we have S/V << 1 so that depletion due to adsorption is negligible. A protocol is presented to determine the correct adsorption parameters of surfactants from surface tension data measured by bubble and drop profile analysis tensiometry. The procedure is applied to experimental data measured for selected surfactants of different adsorption activities: C10OH, CTAB, Tween 20, and the equimolar mixture SDS + DoTAB. The results show that for surfactants with higher surface activity, the differences between the surface tensions measured with the drops and bubbles profile analysis tensiometry, respectively, are larger, while for less surface-active surfactants, such as SDS, the results obtained from drop and bubble profile experiments are very close. The correction procedure is based on the same set of adsorption parameters used to fit both the experimental data obtained from drop-based measurements (which involve the depletion effects) and those data measured in a way that depletion effects are negligible