Abstract
The reaction mechanisms for oxidation of CH3CCl2 and CCl3CH2 radicals, formed in the atmospheric degradation of CH3CCl3 have been elucidated. The primary oxidation products from these radicals are CH3CClO and CCl3CHO, respectively. Absolute rate constants for the reaction of hydroxyl radicals with CH3CCl3 have been measured in 1 atm of Argon at 359, 376, and 402 K using pulse radiolysis combined with UV kinetic spectroscopy giving (OH + CH3CCl3) = (5.4 ± 3) 10−12 exp(−3570 ± 890/RT) cm3 molecule−1 s−1. A value of this rate constant of 1.3 × 10−14 cm3 molecule−1 s−1 at 298 K was calculated using this Arrhenius expression. A relative rate technique was utilized to provide rate data for the OH + CH3 CCl3 reaction as well as the reaction of OH with the primary oxidation products. Values of the relative rate constants at 298 K are: (OH + CH3CCl3) = (1.09 ± 0.35) × 10−14, (OH + CH3CClO) = (0.91 ± 0.32) × 10−14, (OH + CCl3CHO) = (178 ± 31) × 10−14, (OH + CCl2O) < 0.1 × 10−14; all in units of cm3 molecule−1 s−1. The effect of chlorine substitution on the reactivity of organic compounds towards OH radicals is discussed.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.