Journal of Physical Chemistry B, Vol.113, No.29, 9779-9785, 2009
The Role of Ionic Pair Association on Micellization and Counterion Binding in Ionic Micelles
The onset in the micellization of ionic surfactants and the binding of counterions onto ionic micelles can be related to ionic pair effects using Bjerrum's correlation. Two magnitudes are defined to calculate such effects. One is a characteristic dimension for the volume element occupied by a single ion d(ev)(S) = 0.5 x (10(24) nm(3) l(-1)/(N-A[S]))(1/3), and the other is an "interaction control volume" ratio Phi(i) = X-Si(Z(Si) d(ev)(Si))(3)/[Sigma(j=1,n)(X-sj Z(sj) d(ev)(Sj))(3)]. It is shown that in both the case of the onset of micellization and the binding of counterion onto micelles there are two situations: when the concentration and charge of a polyvalent cation i present is such that Phi(i) > 0.5 and otherwise. When Phi(i) is above 0.5, the critical micelle concentration (CMC) and the binding of ions onto micelles are dependent on d(ev)(S) of the polyvalent cation. Below (Phi(i) = 0.5, both the CMC and the binding ratios are related to the contributions of both monovalent and polyvalent species weighed by their "interaction control volume" ratio. As a consequence, it is proposed that ionic groups formed by a counterion and three or four surfactant ions are the building blocks of ionic micelles.