Concentration and medium micellar kinetic effects caused by morphological transitions.

The reaction methyl naphthalene-2-sulfonate + Br(-) was investigated in several alkanediyl-α-ω-bis(dodecyldimethylammonium) bromide, 12-s-12,2Br(-) (with s = 2, 3, 4, 5, 6, 8, 10, 12), micellar solutions in the absence and in the presence of various additives. The additives were 1,2-propylene glycol, which remains in the bulk phase, N-decyl N-methylglucamide, MEGA10, which forms mixed micelles with the dimeric surfactants, and 1-butanol, which distributes between the aqueous and micellar phases. Information about the micellar reaction media was obtained by using conductivity and fluorescence measurements. In all cases, with the exception of water-1,2-prop 12-5-12,2Br(-) micellar solutions, with 30% weight percentage of the organic solvent, a sphere-to-rod transition takes place upon increasing surfactant concentration. In order to quantitatively explain the experimental data within the whole surfactant concentration range, a kinetic equation based on the pseudophase kinetic model was considered, together with the decrease in the micellar ionization degree accompanying micellar growth. However, theoretical predictions did not agree with the experimental kinetic data for surfactant concentrations above the morphological transition. An empirical kinetic equation was proposed in order to explain the data. It contains a parameter b which is assumed to account for the medium micellar kinetic effects caused by the morphological transition. The use of this empirical equation permits the quantitative rationalization of the kinetic micellar effects in the whole surfactant concentration range.