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Free energy outer-sphere cross-reaction

Marcus theory showed a good correlation between experimental and calculated rate constants using Eq. (5). The 22 value was set at 10 M sec for this purpose and is considered as an upper limit for selfexchange of the diethyldithiocarbamate radical/anion pair. From the oxidation rates it was also estimated that E (edtc /edtc ) = 0.43(3)V vs SCE. A free-energy analysis for the oxidation of diethyldithiocarbamate (edtc ) by [FeiCNlgT also showed that the initial outer-sphere oxidation of the thiolate anion to its thio radical (Eq. 36) is the main energy barrier to be crossed along the reaction coordinate. [Pg.260]

Rate constants for outer-sphere electron transfer reactions that involve net changes in Gibbs free energy can be calculated using the Marcus cross-relation (Equations 1.24—1.26). It is referred to as a cross-relation because it is derived from expressions for two different self-exchange reactions. [Pg.26]

See other pages where Free energy outer-sphere cross-reaction is mentioned: [Pg.199]    [Pg.821]    [Pg.808]    [Pg.561]    [Pg.561]    [Pg.18]    [Pg.55]    [Pg.292]    [Pg.189]    [Pg.28]    [Pg.32]    [Pg.10]    [Pg.149]    [Pg.294]    [Pg.162]    [Pg.54]    [Pg.503]    [Pg.167]    [Pg.52]    [Pg.670]   
See also in sourсe #XX -- [ Pg.200 , Pg.201 , Pg.202 , Pg.203 , Pg.204 ]



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