Heterogeneous ozonation kinetics of 4-phenoxyphenol in the presence of photosensitizer

Sopheak Net (1) , L. Gligorovski (2) , S. Gligorovski (2) , H. Wortham (2)

1 LASIRE - Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516
2 LCE - Laboratoire Chimie de l'environnement

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 the presence of 4-carboxybenzophenone under simulated sunlight irradiation of the particles surface. At the mixing ratio of 60 ppb which corresponds to strongly polluted ozone areas, the first order of decay of 4-phenoxyphenol is k 1 =9.95×10 −6 s −1. At a very high ozone mixing ratio of 6 ppm the first order rate constants for 4-phenoxyphenol degradation were the following: k 1 =2.86×10 −5 s −1 under dark conditions and k 1 =5.58×10 −5 s −1 in the presence of photosensitizer (4-carboxybenzophenone) under light illumination of the particles surface. In both cases, the experimental data follow the modified Langmuir-Hinshelwood equation for surface reactions. The Langmuir-Hinshelwood and Langmuir-Rideal mechanisms for bimolecular surface reactions are also discussed along with the experimental results. 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.

Domaines: Autre; Physique Atmosphérique et Océanique [physics.ao-ph]

Sopheak Net, L. Gligorovski, S. Gligorovski, H. Wortham. Heterogeneous ozonation kinetics of 4-phenoxyphenol in the presence of photosensitizer. Atmospheric Chemistry and Physics, 2010, 10 (4), pp.1545-1554. ⟨10.5194/acp-10-1545-2010⟩. ⟨hal-01912532⟩