Journal Details

1. Photo-oxidation Reaction of Tert-butyl Chloride with OH Radicals and Cl Atoms in the Troposphere and its Implications.

F. Joy & B. Rajakumar.  Phys. Chem. Chem. Phys., 2023, 25(11), 7901-7916.

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.