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- W1992128155 abstract "Using ESR-line broadening the rate constants of electron self exchange between five substituted p-phenylenediamines, semiquinonediimines, and quinonediimines in six aprotic solvents are measured in the temperature range 230 K < T < 360 K. A linear dependence of ln k on the solvent parameter γ = 1/n2 - 1/ϵ (n = refractive index, ϵ = permittivity) is observed for each temperature as expected from Marcus' theory, also a linear dependence of ln kT−1/2 on T−1 for each solvent. The experimental surface ln k(γ, T), however, is not in agreement with Marcus' theory, the resulting activation energies and -entropies being proportional to γ and increasing from negative values at low γ (extrapolated) to positive at high γ. The deviations are explained by a temperature-dependent reaction distance and a preceding association between the radical cations and the counterions which increases strongly with decreasing polarity of the solvent." @default.
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- W1992128155 date "1984-04-01" @default.
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- W1992128155 title "ESR-Spectroscopic Investigation of the Homogeneous Electron Transfer Reactions between Substituted p-Phenylenediamines and Quinonediimines, and the Validity of Marcus' Theory. II. Temperature Dependence and Activation Parameters" @default.
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- W1992128155 doi "https://doi.org/10.1002/bbpc.19840880404" @default.
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