Study of the micelle formation and the effect of additives on this process in reversed micellar systems by positron annihilation techniques

The positron annihilation technique was applied to the study of the micelle formation process in reversed micellar systems, Aerosol OT and dodecylammonium propionate in apolar solvents, such as benzene, isooctane, and cyclohexane. The results indicate that the positronium formation probability responds very sensitively to microphase changes in reversed micellar solutions. The abrupt changes in positronium formation probability observed at certain surfactant concentrations appear to coincide with variations in the aggregation state of the surfactant molecules in solutions, as postulated by the modified pseudophase model which considers the possibility of conformational changes between premicellar aggregates, and the surfactant concentrations at which they occur may be interpreted as operational critical micelle concentrations. Additives or probe molecules can affect these changes and shift them to lower surfactant concentrations. The additions of H2O and its solubilization in form of clusters inside the reverse micelle leads to microphase changes also detectable by the positron annihilation technique. From a comparison of the rate constants between positronium and probe molecules observed in the neat solvents and in the corresponding micellar solutions, it was concluded that the probe molecules are attracted to various degrees by the reverse micelles, the nature of the surfactant and solvent determining the relative distribution of the probe molecule in the outer hydrocarbon layer and in the bulk apolar solvent of the reversed micelles