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Kinetic and mechanism of the reaction between Cl and several mono-methyl branched alkanes


Maofa Ge , Yan Chen , Weigang Wang , Junling Li , Li Zhou , Bo Shi , Cici Fan , Ke Wang , Hao Zhang , Hong Li

DOI:10.1016/j.jes.2022.08.010

Received May 29, 2022,Revised , Accepted August 05, 2022, Available online August 21, 2022

Volume 36,2024,Pages 474-482

Branched alkanes are ubiquitous in the troposphere and play an important role in the chemical processes. In this work, the rate constants and products for the reaction of Cl atoms with 3-methylhexane and 2-methylheptane were measured at room temperature (298 ± 0.2 K) and atmospheric pressure using a conventional relative rate method. The rate constants of 3-methylhexane and 2-methylheptane in units of cm3/(mol·sec) are (3.09 ± 0.31) × 10−10 and (3.67 ± 0.40) × 10−10, respectively. Furthermore, the corresponding atmospheric lifetime of the studied branched alkanes with Cl was 6.92-89.90 hours and 5.82-75.69 hours, respectively. The estimated atmospheric lifetimes indicated that the reaction with Cl atoms could be the most important atmospheric degradation pathway for 3-methylhexane and 2-methylheptane. Primary gas-phase products of the reactions were identified and quantified, and particle-phase products were also obtained. The atmosphere oxidation mechanism of Cl atoms with 3-methylhexane and 2-methylheptane is proposed. The SOA yields of 3-methylhexane and 2-methylheptane from the reaction of Cl atoms were determined to be 7.96% ± 0.89% and 13.35% ± 1.50% respectively. Overall, the results reveal that the primary loss process of branched alkanes is the reaction with Cl atoms, which impacts its degradation on a regional scale.

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