Surface Adsorption in Ternary Surfactant Mixtures above the Critical Micelle Concentration: Effects of Asymmetry on the Composition Dependence of the Excess Free Energy.

The composition of the adsorbed layer of a ternary surfactant mixture at the air-water interface has been studied by neutron reflectivity. The adsorption of the ternary mixture of octaethylene monododecyl ether (CE) sodium dodecyl 6-benzene sulfonate (LAS), and sodium dioxyethylene glycol monododecyl sulfate (SLES), as well as each of the binary mixtures, at solution concentrations greater than the mixed critical micelle concentration is highly nonideal. In the ternary mixture, the surface adsorption is dominated by CE and LAS, and there is little SLES at the interface. The departure from ideality in the binary mixtures can be quantitatively described by applying the pseudophase approximation with quadratic and cubic terms in the excess free energy of mixing (G) both at the surface and in the micelles. The same parameters that describe the binary interactions give a quantitative fit to the adsorbed fractions in the ternary mixture over a wide range of composition. A similar analysis is effective for the mixture containing sodium dodecyl sulfate instead of SLES. Of the set of six G required to fit the ternary data, one is ideal (SLES-LAS) and three, LAS-CE (micelle) and CE-SLES (micelle and surface), have minima occurring at a composition (mole fraction) of the anionic species of 1/3.