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Some Recent Approaches to the Study of Heterogeneous Redox Kinetics of Metal Complexes. Comparisons with Homogeneous Redox Processes
Author(s) -
Weaver Michael J.
Publication year - 1979
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.197900004
Subject(s) - chemistry , redox , kinetics , metal , homogeneous , electrochemistry , electrode , cobalt , chromium , half reaction , inner sphere electron transfer , thermodynamics , inorganic chemistry , ion , organic chemistry , physics , quantum mechanics
Some experimental and conceptual aspects of the electrode kinetics of metal complexes are reviewed, with emphasis on the comparison between heterogeneous and homogeneous redox behavior, using cobalt(III)/(II) and chromium(III)/(II) couples as illustrative examples. Experimental methods for determining the position of the heterogeneous reaction sites and for distinguishing between outer‐sphere and ligand‐bridged electrode reactions are examined, along with the interpretation of electrochemical activation parameters for outer‐sphere pathways. The possible roles of bridging ligands in catalyzing electrode reactions are discussed in terms of “intrinsic” and “thermodynamic” contributions to the observed rate constants.