Application of the Thermodynamics of Small Systems to Micellar Solutions

Abstract

The theoretical treatments of micelle formation have been based mainly on the mass-action and phase-separation models, even though the phase-separation model is inconsistent with the degrees of freedom of the phase rule. In addition, the two models merge asymptotically with increasing micellar aggregation number. As discussed in the preceding chapters, the mass-action model requires knowledge of all of the stepwise association constants from monomer to micelles, a requirement difficult to fulfill. This model therefore has such defects as the assumption that the micelle aggregation number is monodisperse (in spite of its actual polydispersity) or the fact that some numerical values for micellization constants are assumed when estimating the dispersion of micellar size.