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Voltammetry under high mass transpor conditions

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The improvement of electrochemical techniques using High Speed Channel Electrodes (HSCE) recently introduced by Compton et al, and their application in combination with spectroscopic methods 'in situ' to study electroorganic reactions is pursued.
The HSCE methods allow the determination of rate constants of fast electrode reactions usually masked by the mass transport. The technique is also suitable to identify the nature of the short-time living intermediates in electrode mechanisms when combined with spectroscopic techniques. The HSCE will be applied to mechanistic problems related to electrode reactions of some organic compounds in which both the group in Oxford and in Seville are interested. First the oxidation of ferrocene will be studied preventing the formation of passivating overlayers. Then, the method will be adapted for photoelectrochemical measurements in order to study the fast light induced decomposition of electrogenerated radical anions of halonitrobenzenes. The analysis of the first electron transfer in the reduction of nitromethane and the characterization of the radical formed will be attempted combining HSCE with ESR and UV spectroscopies 'in situ'.

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The Chancellor, Masters and Scholars of the University of Oxford
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