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Electrooxdation of Tricarbonyl( N,N ‐Diphenylcyclohexadienecarboxamide)Iron Complexes. Reversibility of Electron Transfer and Free Energy Change
Author(s) -
Hwang WenShu,
Lee Liangshiu,
Yu WeiRen
Publication year - 1993
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.199300040
Subject(s) - chemistry , electron transfer , reaction rate constant , cyclic voltammetry , kinetic energy , electrochemistry , marcus theory , electron , voltammetry , range (aeronautics) , analytical chemistry (journal) , kinetics , electrode , organic chemistry , physics , materials science , quantum mechanics , composite material
Qualitative and quantitative criteria of irreversibility of electron transfer in cyclic voltammetry (CV) of tricarbonyl( N,N ‐diphenylcyclohexadienecarboxamide)iron complexes were investigated. The measurement of the heterogeneous rate constants for electron transfer according to CV data over an extended range of free energy change ( ΔG) for these complexes are described. Kinetic analyses of the electrochemical technique demonstrates that when the applied potential exceeds the standard potential E°, the experimental rate constant k e represents an accurate measurement of the intrinsic rate constant k 1 for electron transfer. However, as the applied potential is less than E°, the reversibility of the electron‐transfer process becomes increasingly more important, and the rate constants for reverse electron transfer k ‐t and decomposition k 2 of the electrogenerated intermediate have to be taken into account.