Surfactant Interactions and Organization at the Gas–Water Interface (CTAB with Added Salt)

We have studied adsorbed layers of cetyltrimethylammonium bromide (CTAB) at air-water interfaces in the presence of added electrolyte. Fast bubble compression/expansion measurements were used to obtain the surface equation of state, i.e., the surface tension vs CTAB surface concentration dependence. We show that while a simple model where the surfactant molecules are assumed to be noninteracting is insufficient to describe the measured response of the surfactant layer, a modified Frumkin equation where the local interactions between the molecular components depend on their surface concentration captures the response. The variation of the effective interactions in the surfactant layer in the model shows that the interactions in the surfactant layer change from effectively repulsive to attractive with increasing surface concentration. Molecular dynamics simulations are performed to probe the origins of the change in the interactions. The simulations indicate that already at low surface concentrations the surfactants aggregate as highly dynamic rafts with surfactant orientation parallel to the interface. Increasing the concentration leads to a change in the assembly morphology at the interface: the surfactant layer thickens and the surfactants sample a range of tilted orientations with respect to the interfacial plane. The change from transient raftlike assemblies to dynamical aggregates at the interface involves a clear increase in the degree of counterion binding: we speculate that the flip of the effective interaction parameter in the model used to interpret the experimental results could result from this. The work here presents basic steps toward a proper understanding of the molecular organization and interactions of surfactants at an air-water interface. This is crucially important in understanding macroscopic properties of surfactant-stabilized systems such as foams, emulsions, and colloidal dispersions.