ELECTROCHEMISTRY WITH STATIONARY DISK AND RING-DISK MILLIELECTRODES IN MAGNETIC-FIELDS

The most well-known effect of the magnetic field on electrochemical sy stems is hydrodynamic convection (stirring) of the electrolytic soluti on. The basic hydrodynamic equations governing mass transport under th e magnetic force are well-understood. However, owing to the nonlinear character of those equations and the fact that neither the velocity no r the concentration profile near the electrode is known a priori, rigo rous analytical solutions are not available. Retreating to a semiempir ical treatment of mass transport, we took the approach of letting the rigorous hydrodynamic equations guide us to the system parameters that should control the steady-state mass-transport-limited current, and s ubsequently to vary all those parameters systematically using conventi onal millimeter-sized disk electrodes, and a range of compounds and so lvents. To our knowledge, this study comprises the first of its kind, and we concluded that the limiting current i(1) = 4.31 x 10(3) n(f+1)F A(3/4)B(1/3)Dv(-1/4)C(bulk)(4/3), where n is the number of electrons involved in the redox process, F is the Faraday constant, A is the ele ctrode area, B is the magnetic field strength, D is the diffusion coef ficient, C-bulk is the bulk concentration of the redox-active species, v is the kinematic viscosity of the electrolyte, and f > 0. The angul ar flow profile near the electrode surface was mapped using an electro chemical generation/collection method.