Electrochemical Studies of a Redox-Active Surfactant. Correlation between Electrochemical Responses and Dissolved States

Electrochemical studies of a nonionic surfactant, α-(ferrocenylundecyl)-ω-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 (v = 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. Chronoa...