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

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 k(268-363) K (TBC thorn OH) = (8.14 f 1.35) x 10(-13) exp [(-139.5 f 50.8 )/T] cm(3) molecule(-1) s(-1)and k( K TBC thorn )(268-363)Cl = (2.90 f 0.69) x 10(-11 )exp [(-155.6 f 73.0 )/T]cm(3) molecule(-1) s(-1)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 (O-2) 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.