Langmuir, Vol.12, No.2, 487-493, 1996
Electrochemical Studies of a Redox-Active Surfactant - Correlation Between Electrochemical Responses and Dissolved States
Electrochemical studies of a nonionic surfactant, alpha-(ferrocenylundecyl)-omega-hydroxy-oligo(ethylene oxide) (FPEG), have been conducted in 0.16 M NaCl aqueous solution at a glassy carbon electrode. The correlation between electrochemical responses and dissolved states has been examined in detail. Cyclic voltammograms (upsilon = 10 mV/s) of the FPEG solutions change with the concentration; below the critical micelle concentration (cmc), the voltammetric shape is of a typical surface-confined species, while above the cmc the diffusion-controlled waves are superimposed at the cathodic side of the surface waves, and far above the cmc the voltammetric shape is of a typical diffusion-controlled species. FPEG in the aqueous solutions adsorbs onto the glassy carbon electrode surface to form a monolayer because of its surface activity. The adsorption isotherm has been represented by the Frumkin isotherm, which includes the repulsive interaction between the adsorbed FPEG molecules. Above the cmc, FPEG forms micelles. Chronoamperometrically determined apparent diffusion coefficients of the micellar solutions decrease with increasing concentrations. This has been interpreted in terms of the change in the diffusion species by disruption of the micelles into monomers at the cmc in the concentration gradient in diffusion layers. Cyclic voltammetric peak potentials of the micellar solutions shift toward the anodic side with the concentration. This behavior has been explained as the electrochemical reaction coupled with a preceding disassembled reaction of the micelles.
Keywords:ELECTRON-TRANSFER REACTIONS;PHTHALOCYANINE THIN-FILMS;IONIC MICELLAR SYSTEMS;FERROCENYL MOIETY;REVERSIBLE FORMATION;VESICLE FORMATION;ORDERED SYSTEMS;DISRUPTION;MONOLAYERS;EQUILIBRIUM