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(a) For a one-electron reaction, the value for the separation of peak potentials approaches a limit of 2.219RT/F (57.0 mV at 298 K) as the standard electron-transfer rate constant increases (reversibility) and the distance between the switching potential and reversible formal potential increases. This fact can be deduced from the data presented in Tables 1 and 2 of ref 8b. For switching potentials 100 and 200 mV removed from the reversible potential, the values at 298 K are 64 and 60 mV, respectively.
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34
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85033054952
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(a) For comparison, experimental activation enthalpies for heterogeneous electron-transfer reactions of species with small inner reorganization energies typically fall in the range 5-7 kcal/mol. See ref 9b for benzophenone and ref 9c for nitromesitylene.
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