Faradaic electrochemistry at microcylinder, band, and tubular band electrodes

Current-time relationships of faradaic processes at microcylinder, band, and tubular band electrodes have been evaluated. Microcylinder electrodes were fabricated from platinum wires (5 μm radius) sealed in glass capillaries. Band and tubular electrodes were constructed with platinum sheets (∼ 20 μm width) or thin pieces of graphite (∼ 5 μm width) sealed between insulating mateials. The temporal response of the current at a microcylinder electrode for the reduction of ferricyanide in aqueous potassium chloride solutions is in excellent agreement with that predicted by equations derived for heat flux to a cylinder. An estimation of the magnitude and temporal properties of the measured current at a band electrode can be obtained when a hemicylinder geometry is assumed. The current respone is identical at band and tubular band electrodes even for the smallest tubular radius investigated, 0.54 mm. Cyclic voltammograms at electrodes of all three geometries show significant contributions from radial diffusion at slow scan rates (< 20 mV s−1). The current at a graphite tubular band electrode was found to be independent of flow of solution through the electrode at flow rates up to 3 ml min−1.

[1]  R. Adams,et al.  Electrochemical behavior very small electrodes in solution: Double potential step, cyclic voltammetry and chronopotentiometry with current reversal , 1982 .

[2]  I. Kolthoff,et al.  Voltammetry with Stationary Microelectrodes of Platinum Wire. , 1941 .

[3]  W. Blaedel,et al.  Reversible Charge Transfer at the Tubular Platinum Electrode. , 1966 .

[4]  R. Wightman,et al.  Response of microvoltammetric electrodes to homogeneous catalytic and slow heterogeneous charge-transfer reactions , 1980 .

[5]  R. Mark Wightman,et al.  Flow rate independent amperometric cell , 1982 .

[6]  M. M. Nicholson Diffusion Currents at Cylindrical Electrodes. A Study of Organic Sulfides , 1954 .

[7]  R. S. Robinson,et al.  Microsecond spectroelectrochemistry by external reflection from cylindrical microelectrodes , 1982 .

[8]  W. C. Purdy,et al.  Electrochemical detectors in liquid chromatography. A short review of detector design , 1981 .

[9]  A. Szabó,et al.  Chronoamperometric current at finite disk electrodes , 1982 .

[10]  R. Wightman,et al.  Ultrafast Voltammetry and Voltammetry in Highly Resistive Solutions with Microvoltammetric Electrodes , 1984 .

[11]  M. M. Stephens,et al.  An examination of the finite difference numerical approach to the solution of electrochemically-induced diffusive transport at stationary solid cylinder electrodes: Single sweep voltammetry of reversible systems , 1984 .

[12]  Jürgen Heinze,et al.  Diffusion processes at finite (micro) disk electrodes solved by digital simulation , 1981 .

[13]  B. Scharifker,et al.  Electrochemical kinetics at microscopically small electrodes , 1981 .

[14]  G. L. Booman,et al.  Measurement of Diffusion Currents at Clindrical Electrodes Using a Current Integrator , 1956 .

[15]  Koichi Aoki,et al.  Diffusion-controlled current at the stationary finite disk electrode: Theory , 1981 .

[16]  C. Olson,et al.  Chronoamperometry at tubular mercury-film electrodes , 1967 .

[17]  R. Wightman,et al.  Faradaic electrochemistry at microvoltammetric electrodes , 1980 .

[18]  Keith B. Oldham,et al.  Edge effects in semiinfinite diffusion , 1981 .