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  • 1
    ISSN: 1040-0397
    Keywords: Iodo-nitrobenzene ; Reduction ; Channel electrode ; Microdisk electrode ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reduction of m-iodo-nitrobenzene, m-I-φ-NO2, in acetonitrile solution was studied using both microdisk and channel electrodes. A voltammetric wave with a halfwave potential of -1.09 V (vs. saturated calomel reference electrode) was observed and both techniques showed that more than one electron was passed per molecule of the substrate. The rates of mass transport were varied in both electrode systems by changing either the electrode radius in the case of microelectrodes, or the electrolyte flow rate in the case of channel electrodes so as to identify the kinetics and mechanism of the electrode process. Both approaches indicated an ECE mechanism operates: where HS denotes the solvent-supporting electrolyte system. The rate constants for the decomposition of the radical anion, [m-I-φ-NO2]·, as determined by the two methods, were in excellent agreement and equal to 0.30(0.05) s-1. Comparisons between the use of microdisks and channel electrodes for such studies are reported and their relative sensitivity assessed.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Electroanalysis 4 (1992), S. 311-315 
    ISSN: 1040-0397
    Keywords: Channel electrode ; catalytic reactions ; EC′ mechanism ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A computational strategy is presented for the simulation of current-voltage curves of electrode processes with very fast coupled homogeneous kinetics at the channel electrode. The approach is illustrated by consideration of the EC′ mechanism that relates to the homogeneous catalysis of electrochemical reactions. It is shown that for fast catalytic reactions “split” voltammetric waves are observed where the two components of the wave result first from the direct reduction (oxidation) of a mediator and, secondly, to a prewave in which mediated reduction of a substrate takes place.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1040-0397
    Keywords: Aggregation ; Dyes ; Microelectrodes ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new electrochemical technique is presented for the investigation of aggregation phenomena in solution over a wide range of solution conditions. Developed nominally for dyes, the method is, in principle, applicable to any electroactive compound. The method employs microelectrodes to measure the change in the diffusion limited current, with concentration, of the aggregating species of interest. At the onset of aggregation, the relationship between this limiting current and concentration deviates from linearity. This deviation, due to the slower rate of diffusion of aggregates, is related to the degree of association of the molecule, assuming a molecular weight distribution of aggregates and using an established relationship between the effective diffusion coefficient and molecular weight. The technique is contrasted with an existing spectroscopic method.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 1040-0397
    Keywords: Flow electrolysis ; Channel electrode ; Microband arrays ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Analytical and numerical methods are used to establish concentration distributions around channel microband electrodes both in isolation and as part of multi-electrode arrays. The importance of axial diffusion in addition to convection and diffusion normal to the electrode surface is stressed. In particular, downstream depletion effects are shown to occur over many electrode lengths, so that the diffusion fields of electrodes within arrays overlap and interfere. A simple analytical expression is derived to describe this depletion and permits the design of practical arrays in which electrodes operate essentially independently of each other.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Electroanalysis 4 (1992), S. 695-700 
    ISSN: 1040-0397
    Keywords: Channel electrode ; voltammetry ; thin layer cell ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A computational approach to the calculation of irreversible and quasi-reversible current voltage curves at channel electrodes is presented. The method has generality since, in particular, no assumptions are made as to the electrode geometry or electrolyte flow rates so that both Lévěque and, with novelty, thin-layer conditions may be explored. An approximate analytical theory for the shape of current-voltage curves which predicts the flow rate dependence of the half-wave potential is presented for the latter case and found to be in good agreement with rigorous computational theory.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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