Magnetic field effects on electric behavior of (Fe(CN) 6 ) 3 at bare and membrane-coated electrodes

The cyclic voltammetric behavior of [Fe(CN)6]3− was investigated under homogeneous magnetic fields perpendicular to the electrode surface in order to determine the effects of magnetic fields on the distribution of an Fe2+/Fe3+ redox couple. The cathodic current was enhanced much more than the anodic current by a homogeneous magnetic field, suggesting that the concentration gradient of paramagnetic [Fe(CN)6]3− and diamagnetic [Fe(CN)6]4− formed at an electrode surface may also contribute to the asymmetric current. The apparent diffusion coefficient of the redox couple increased by over 30% in both cathodic and anodic processes upon applying a magnetic field. For a gold electrode coated with dioctadecyldimethylammonium, the application of a magnetic field perpendicular to the surface increased the peak-to-peak separation, and enhanced the asymmetric current. It is inferred that the application of a magnetic field promotes the electron-tunneling process by tilting chain molecules in the barrier membrane.