Mechanism of reaction of the hydrated electron with ozone, perbromate, andother strongly oxidizing inorganic oxocompounds

Citation
Uk. Klaning et al., Mechanism of reaction of the hydrated electron with ozone, perbromate, andother strongly oxidizing inorganic oxocompounds, J PHYS CH A, 103(26), 1999, pp. 5055-5060
Citations number
36
Categorie Soggetti
Physical Chemistry/Chemical Physics
Journal title
JOURNAL OF PHYSICAL CHEMISTRY A
ISSN journal
10895639 → ACNP
Volume
103
Issue
26
Year of publication
1999
Pages
5055 - 5060
Database
ISI
SICI code
1089-5639(19990701)103:26<5055:MOROTH>2.0.ZU;2-W
Abstract
A model is proposed for the mechanism of reaction of the hydrated electron with strongly oxidizing inorganic oxocompounds, according to which such rea ctions comprise three steps: (1) a primary split-off of O- occurring immedi ately upon the transfer of the electron to the oxocompound, (2) after which O- becomes fully solvated, acquiring properties as in the bulk phase, and (3) finally, the solvated O- either escapes from the cage or forms an elect ron adduct by reacting back within the cage with its partner. The model is based on studies of the photochemistry of aqueous solution of the oxoanions O-3(-) and ClO3- (Walhaut, P. K.; Silva, C.; Barbara, P. F. J. Phys. Chem. 1996, 100, 5188. Klaning, U. K.; Sehested, K. J. Phys. Chem. 1991, 95, 740 .), which suggest that solvation of the photoproduct O- precedes cage-back reactions. Measurements of the reactions of the hydrated electron with the perbromate ion and the periodate ion and of the reactions of O- with the br omate and iodate ion support the model by verifying that no electron adduct is formed unless O- and its partner react in the bulk phase at a diffusion -controlled rate.