Get Advances in Heterocycling Chemistry. Vol. 32 PDF

By Donald Bethell

ISBN-10: 0080493424

ISBN-13: 9780080493428

ISBN-10: 0120335328

ISBN-13: 9780120335329

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An alternative theory to the Butler–Volmer theory for electron transfer is provided by the Marcus–Hush theory (Marcus, 1968; Hush, 1968) which assumes a potential-dependent ␣. Since in most cases ␣ is essentially independent of potential, use of the simpler Butler–Volmer equation is usually adequate. HOMOGENEOUS CHEMICAL KINETICS It is common for homogeneous chemical reactions to accompany the electron-transfer step. Thus, an electrochemical reaction mechanism may 1 Note that charges, if any, on species A and B in (19) and subsequent equations are omitted for simplicity.

However, if the chemical step associated with the decomposition of B was sufficiently fast in both directions on the time-scale of the MODERN VOLTAMMETRY 27 voltammetric experiment, then the whole process would be termed chemically reversible. These concepts related to electrochemical and chemical reversibility can be demonstrated by considering the EC mechanism described by (19) and (27). k1 B → ← C C (27) kϪ1 • At extremely fast scan-rates the electron transfer step is electrochemically irreversible and the C step is outrun.

The final product of this overall two-electron reduction process was found to be the radical anion of nitrobenzene as evidenced by EPR spectroscopy. A simplified form of the ECE mechanism proposed for the reduction of p-iodonitrobenzene is in (48)–(50), where HS is an H atom source. E иϪ p-NO2C6H4I ϩ eϪ → ← [p-NO2C6H4I] HS (48) C [p-NO2C6H4I]иϪ → p-NO2C6H5 ϩ IϪ (49) E иϪ p-NO2C6H5 ϩ eϪ → ← [p-NO2C6H5] (50) J. C. EKLUND ET AL. 40 On continuous cycling of the potential through the two reduction processes, the magnitude of the current associated with the first reduction process gradually drops whereas that due to the second process increases.

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Advances in Heterocycling Chemistry. Vol. 32 by Donald Bethell


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