Download Biological Electrochemistry by Glenn Dryhurst (Auth.) PDF
By Glenn Dryhurst (Auth.)
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Extra info for Biological Electrochemistry
Sample text
The overall picture of the process shown in Fig. 18 was complicated by a report by Parker [68], who found that under cyclic voltammetric conditions up to five different electrode processes may be observed for the p-benzohydroquinone-p-benzoquinone system in acetonitrile at a platinum electrode. The nature of the reduction processes was found to be highly dependent on electrode history. 5 V vs. , identical to that shown in Fig. 34 V vs. SCE and a new oxidation peak on the next cycle (peak ll a) at E p = - 0 .
Because of the disagreements between the results of Parker [68] and those of Eggins and Chambers [66,69], a further, more detailed investigation of the electrochemistry of various quinone-hydroquinone systems in nonaqueous solvents was carried out by Eggins and Chambers [71]. A typical slow-sweep cyclic voltammogram for p-benzohydroquinone in acetonitrile is shown in Fig. 24. , exactly the same as proposed by Parker [68] (see equation for peak l a in Fig. 21). 0 ^ — 1 T. 0 Potential (Vvs. SCE) Fig.
Consideration of the cyclic voltammogram shown in Fig. 38 reveals that reduction peak l l c is somewhat smaller than peak l c . Cauquis and Marbach [84] also noted that reproducible cyclic voltammograms 1 could not be obtained at sweep rates below 67 mV s~ . In particular, reduction peak ll c could not be observed below the latter sweep rate. These observations have been rationalized by the influence of residual water in the solvent. Thus, it was proposed [84] that the primary peak l c product, a radical anion (Q~), undergoes partial protonation by this residual water to give a neutral radical (QH-).