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Réactivité de radicaux inorganiques, CO3 ·- et Cl·/Cl2 ·- en solution aqueuse

Abstract : In natural water, humic substances are a source of reactive species production, in the presence of light and oxygen, such as singlet oxygen, superoxide, hydroxyl radicals, hydrogen peroxide but also a plurality of inorganic radicals such as the carbonate and chlorine radicals. The reactivity of these is unknown. This work aims to study the reactivity of carbonate and chorine radicals with pesticide ofphenylurea type and identify the products of degradation. The carbonate radical was generated by the photolysis of [Co(NH3)5CO3]+, by photosensitization from 4-carboxybenzophenone, from 1-nitronaphtalene and from duroquinone and by UV excitation of hydrogen peroxide. The chlorine radical was generated by UV excitation of hydrogen peroxide. The rate constants for reaction with the carbonate and chlorine radicals with the pesticides were determined after validation of competitive kinetic or kinetic modeling. These constants are included of the carbonate radical in the range 0.35-3.5x107 mol-1 L s-1, and in the range fron 1,2-3,9x108 mol-1 L s-1 for the chlorine radical. The comparison between the reactivity of the carbonate and chlorine radicals with the hydroxyl radicals, shows a factor 1000 for the carbonate radical and 100 for the chorine radical for the reactivity of hydroxyl radicals. Several degradation products were identified from the carbonate radical. These products were the hydroxylation of the aromatic ring, the products of demethylation, a derivative quionone imine for fenuron, the breaking of the bridge dissulfure for metsulfuron methyl. The comparison of the degradation products formed with carbonate and hydroxyl radicals show some common products to both processes, and others products are more specific. The products from the carbonate radical are fewer in number than those resulting from the hydroxyl radical.
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Submitted on : Friday, April 4, 2014 - 4:02:09 PM
Last modification on : Wednesday, December 15, 2021 - 3:09:15 AM
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  • HAL Id : tel-00973851, version 1


Natacha Arlie. Réactivité de radicaux inorganiques, CO3 ·- et Cl·/Cl2 ·- en solution aqueuse. Autre. Université Blaise Pascal - Clermont-Ferrand II, 2012. Français. ⟨NNT : 2012CLF22329⟩. ⟨tel-00973851⟩



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