Salt and solvent effects on the kinetics of the oxidation of the excited state of the [Ru(bpy)3]2+ complex by S2O8(2-).
J Phys Chem A
; 110(12): 4196-201, 2006 Mar 30.
Article
in En
| MEDLINE
| ID: mdl-16553370
ABSTRACT
The title reaction was studied in different reaction media aqueous salt solutions (NaNO3) and water-cosolvent (methanol) mixtures. The observed rate constants, k(obs), show normal behavior in the solutions containing the electrolyte, that is, a negative salt effect. However, the solvent effect is abnormal, because a decrease of the rate constant is observed when the dielectric constant of the reaction medium decreases. These effects (the normal and the abnormal) can be explained using the Marcus-Hush treatment for electron transfer reactions. To apply this treatment, the true, unimolecular, electron-transfer rate constants, k(et), have been obtained from k(obs) after calculation of the rate constants corresponding to the formation of the encounter complex from the separate reactants, k(D), and the dissociation of this complex, k(-D). This calculation has been carried out using an exponential mean spherical approach (EMSA).
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Collection:
01-internacional
Database:
MEDLINE
Main subject:
Sulfates
/
2,2'-Dipyridyl
/
Sodium Compounds
/
Methanol
/
Nitrates
Language:
En
Journal:
J Phys Chem A
Journal subject:
QUIMICA
Year:
2006
Document type:
Article
Affiliation country:
Spain