Atmospheric Chemistry and Physics Discussions
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10.5194/acpd-9-21647-2009
http://www.atmos-chem-phys-discuss.net/9/21647/2009/
http://www.atmos-chem-phys-discuss.net/9/21647/2009/acpd-9-21647-2009.html
http://www.atmos-chem-phys-discuss.net/9/21647/2009/acpd-9-21647-2009.pdf
21647
21668
2009-10-15
Heterogeneous ozonation kinetics of 4-phenoxyphenol in presence of photosensitizer
S. Net
L. Nieto-Gligorovski
S. Gligorovski
saso.gligorovski@univ-provence.fr
H. Wortham
Universités d'Aix-Marseille I, II, III – CNRS, UMR 6264: Laboratoire Chimie Provence, Equipe Instrumentation et Réactivité Atmosphérique, Case courrier 29, 3 place Victor Hugo, 13331 Marseille Cedex 03, France
In this work we have quantitatively measured the degradation of
4-phenoxyphenol adsorbed on silica particles following oxidative
processing by gas-phase ozone. This was performed under dark
conditions and in presence of 4-carboxybenzophenone under simulated
sunlight irradiation of the particles surface.
<br><br>
At mixing ratio of 60 ppb which corresponds to strongly ozone
polluted areas, the first order decay of 4-phenoxyphenol is
<i>k</i><sub>1</sub>=9.95×10<sup>−6</sup> s<sup>−1</sup>. At very high ozone
mixing ratio of 6 ppm the first order rate constants for
4-phenoxyphenol degradation were the following:
<i>k</i><sub>1</sub>=2.86×10<sup>−5</sup> s<sup>−1</sup> under dark
conditions and <i>k</i><sub>1</sub>=5.58×10<sup>−5</sup> s<sup>−1</sup> in
presence of photosensitizer (4-carboxybenzophenone) under light
illumination of the particles surface. In both cases the experimental
data do follow the modified Langmuir-Hinshelwood equation for surface
reactions. Langmuir-Hinshelwood and Langmuir-Rideal mechanisms are
also discussed along with the experimental results.
<br><br>
Most importantly, the quantities of the oligomers such as
2-(4-Phenoxyphenoxy)-4-phenoxyphenol and
4-[4-(4-Phenoxyphenoxy)phenoxy]phenol formed during the heterogeneous
ozonolysis of adsorbed 4-phenoxyphenol were much higher under solar
light irradiation of the surface in comparison to the dark conditions.
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