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- W4246851374 abstract "Consideration of ECE type schemes: A+1eB BC C+1eD involving a chemical reaction interposed between two electron-transfer steps has been very successful in explaining the occurrence of the multi-electron processes so often encountered in organic electrochemistry. As soon as the second electron transfer is regarded as easier than the first one the interference of the disproportionation reaction: B+CA+D in the overall kinetics must however be considered. Besides the ECE case two other limiting mechanisms DISP1 and DISP2 are thus also obtainable corresponding respectively to reaction [2] or reaction [4] being the r.d.s. The polarization problem is stated and solved under “pure kinetic” conditions, i.e., when a stationary state deriving from mutual balance of diffusion and chemical reaction is established. The results are applied to peak location and peak shape analysis in linear sweep voltammetry. It is shown that the effect of the experimental parameters: rate and equilibrium constants, sweep rate and initial concentration can be rationalized with the use of only two dimensionless parameters in the general case. A finite difference approach is described in the genral case whereas in most of the particular cases (pure mechanisms, or transition between two of the limiting cases) integral equations are obtainable. A kinetic zone diagram is then constructed in the space of the two dimensionless parameters. It allows to predict how a variation in each of the experimental parameter shifts the system from one limiting mechanism to the other." @default.
- W4246851374 created "2022-05-12" @default.
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- W4246851374 date "1977-12-09" @default.
- W4246851374 modified "2023-10-01" @default.
- W4246851374 title "ECE and disproportionation Part V. Stationary state general solution application to linear sweep voltammetry" @default.
- W4246851374 doi "https://doi.org/10.1016/0368-1874(77)80446-2" @default.
- W4246851374 hasPublicationYear "1977" @default.
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