The interface between water and mixed surfactant solutions of CH 3(CH 2) 19OH and CF 3(CF 2) 7(CH 2) 2OH in hexane was studied with interfacial tension and X-ray reflectivity measurements. Measurements of the tension as a function of temperature for a range of total bulk surfactant concentrations and for three different values of the molal ratio of fluorinated to total surfactant concentration (0.25, 0.28, and 0.5) determined that the interface can be in three different monolayer phases. The interfacial excess entropy determined for these phases suggests that two of the phases are condensed single surfactant monolayers of CH 3(CH 2) 19 OH and CF 3(CF 2) 7(CH 2) 2OH. By studying four different compositions as a function of temperature, X-ray reflectivity was used to determine the structure of these monolayers in all three phases at the liquid-liquid interface. The X-ray reflectivity measurements were analyzed with a layer model to determine the electron density and thickness of the headgroup and tailgroup layers. The reflectivity demonstrates that phases 1 and 2 correspond to an interface fully covered by only one of the surfactants (liquid monolayer of CH 3(CH 2) 19OH in phase 1 and a solid condensed monolayer of CF 3(CF 2) 7(CH 2) 2OH in phase 2), This was determined by analysis of the electron density profile as well as by direct comparison to reflectivity studies of the liquid-liquid interface in systems containing only one of the surfactants (plus hexane and water). The liquid monolayer of CH 3(CH 2) 19- OH undergoes a transition to the solid monolayer of CF 3(CF 2) 7(CH 2) 2OH with increasing temperature. Phase 3 and the transition regions between phases 1 and 2 consist of a mixed monolayer at the interface that contains domains of the two surfactants. In phase 3 the interface also contains gaseous regions that occupy progressively more of the interface as the temperature is increased. The reflectivity determined the coverage of the surfactant domains at the interface. A simple model is presented that predicts the basic features of the domain coverage as a function of temperature for the mixed surfactant system from the behavior of the single surfactant systems.
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
- Surfaces, Coatings and Films
- Materials Chemistry