Rale constant electron transfer

An absorption (1030 nun) found in the near-infrared spectrum of this complex arises from a mixed valence transition. Light-induced meial-to-metal charge transfer was predicted by Hush56 for systems of this type before it was observed experimentally. Further, his theory relates the energy of absorption to that required for thenral electron transfer (hv = 4 x Ec) and from this it is possible to calculate the thermal electron transfer rale constant (5 x (08 s-1).57... 

Sharma and Millero (1988) determined the corresponding second-order rate constants k 0 = 2.1 104 and iCi=8.7 102 A/-1s-1 in sea water. The di and ii iehlorocomplexes were not sufficiently reactive to produce detectable rate constants. Thus the chloride ion, which stabilizes the soft reactant Cu(I) inhibits the oxygenation, whereas OH, which stabilizes the product Fe(III), accelerates i lie rale of Fe(II) oxidation. The reaction of Cu(I) with 02 represents an interesting test case because the reverse reaction has been measured by pulse tadiolysis. We may therefore apply the principle of microscopic reversibility to the electron-transfer step ... 

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