ESR kinetic study of the photobleaching of chlorine dioxide solutions at 303, 365 and 436 nm

Initial quantum yields for the photobleaching of OClO dissolved in CCl 4 at 298 K are measured by electron spin resonance spectrometry at three wavelengths, under 1 atm of either N 2 or O 2. Yields are unaffected at 365 nm, but increase by about 45% at 303 and 436 nm, when O 2 is replaced by N 2. Th...

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Bibliographic Details
Published in:Chemical physics letters 1995-01, Vol.232 (3), p.237-241
Main Authors: Churio, M.S., Brusa, M.A., Perissinotti, L.J., Ghibaudi, E., Coronel, M.E.J., Colussi, A.J.
Format: Article
Language:English
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Summary:Initial quantum yields for the photobleaching of OClO dissolved in CCl 4 at 298 K are measured by electron spin resonance spectrometry at three wavelengths, under 1 atm of either N 2 or O 2. Yields are unaffected at 365 nm, but increase by about 45% at 303 and 436 nm, when O 2 is replaced by N 2. These results, at variance with gas-phase photolysis, suggest a qualitative change in the mechanism of photofragmentation at ≈365 nm. We show that OClO solvatochromic shifts are controlled by the dynamic polarization of the medium, rather than by a modification of the energies of the states involved.
ISSN:0009-2614
1873-4448
DOI:10.1016/0009-2614(94)01355-Y