Dielectric spectroscopy by differential measurements in trasmission lines on sodium dodecyl sulfate micelles in water

Aqueous sodium dodecyl sulfate micellar solutions were nvestigated by a recently developed double-differential dielectric spectroscopy technique in the frequency range 100 MHz­3 GHz at 22 C, in the surfactant concentration range 29.8­524 mM, explored for the first time above 104 mM. The micellar contribution to dielectric spectra was analyzed according to three models containing, respectively, a single Debye relaxation, a Cole­Cole relaxation and a double Debye relaxation. The single Debye model is not accurate enough. Both Cole­Cole and double Debye models fit well the experimental dielectric spectra. With the double Debye model, two characteristic relaxation times were identified: the slower one, in the range 400­900 ps, is due to the motion of counterions bound to the micellar surface (lateral motion); the faster one, in the range 100­130 ps, is due to interfacial bound water. Time constants and amplitudes of both processes are in fair agreement with Grosse's theoretical model, except at the largest concentration values, where interactions between micelles increase. For each sample, the volume fraction of bulk water and the effect of bound water as well as the conductivity in the low frequency limit were computed. The bound water increases as the surfactant concentration increases, in quantitative agreement with the micellar properties. The number of water molecules per surfactant molecule was also computed. The conductivity values are in agreement with Kallay's model over the whole surfactant concentration range.