Photo-oxidation reaction of tert-butyl chloride with OH radicals and Cl atoms in the troposphere and its implications?

Physical Chemistry Chemical Physics Pub Date: 2023-02-23 DOI: 10.1039/D2CP03503K

Abstract

In the present work, the temperature-dependent kinetics for the reaction of tert-butyl chloride (TBC) with OH radicals and Cl atoms were determined experimentally between 268 and 363 K, and theoretically between 200 and 400 K. Pulsed laser photolysis-laser induced fluorescence (PLP-LIF) and relative rate (RR) methods were used to obtain the rate coefficients for the reaction of TBC with OH radicals and Cl atoms, respectively. The Arrhenius equations Image ID:d2cp03503k-t1.gif and Image ID:d2cp03503k-t2.gif were obtained for both reactions based on the experimentally measured rate coefficients. The theoretical rate coefficients were determined at the CCSD(T)/aug-cc-pVTZ//M06-2X/6-31+G(d,p) level for the reaction of TBC with OH radicals and at the CCSD(T)/cc-pVDZ//MP2/6-311+G(d,p) level for the reaction with Cl atoms with incorporated tunnelling corrections. The product analysis of both reactions in the presence of oxygen (O2) was carried out, and a degradation pathway for TBC was proposed. The potential implications of these reactions in the atmosphere were discussed using the obtained kinetic parameters.

Graphical abstract: Photo-oxidation reaction of tert-butyl chloride with OH radicals and Cl atoms in the troposphere and its implications
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