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Experimental Validation of Marcus Theory for Outer‐Sphere Heterogeneous Electron‐Transfer Reactions: The Oxidation of Substituted 1,4‐Phenylenediamines
Author(s) -
Clegg Antony D.,
Rees Neil V.,
Klymenko Oleksiy V.,
Coles Barry A.,
Compton Richard G.
Publication year - 2004
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200400128
Subject(s) - marcus theory , electron transfer , reaction rate constant , electrochemistry , chemistry , electrode , transfer (computing) , thermodynamics , electron , computational chemistry , steady state (chemistry) , constant (computer programming) , chemical physics , kinetics , classical mechanics , physics , quantum mechanics , parallel computing , computer science , programming language
Rate constants depend on molecular size: Results are presented to validate the relationship between molecular size and the standard electrochemical rate constant predicted by Marcus theory (see graphic). Measurement of hydrodynamic radii and electron‐transfer rates for substituted 1,4‐phenylenediamines have been made under steady‐state conditions using both hydrodynamic and stationary electrodes.