Kinetic and product studies of Cl atoms reactions with a series of branched Ketones  

作　　者：Yangang Ren Jinhe Wang Benoit Grosselin Veronique Daele Abdelwahid Mellouki 

机构地区：[1]Institut de Combustion, Aerothermique, Reactivite et Environnement (/CARE), CNRS (UPR 3021), 1C Avenue de la Recherche Scientifique,45071 Orleans Cedex 2, France [2]School of Municipal and Environmental Engineering, Shandong Jianzhu University, Jinan 250101, China

出　　处：《Journal of Environmental Sciences》2018年第9期271-282,共12页环境科学学报（英文版）

基　　金：supported by Labex Voltaire (ANR-10-LABX-100-01), ARD PIVOTS program (supported by the Centre-Val de Loire regional council);the European Union's Horizon 2020 Research and Innovation Programme through the EUROCHAMP2020 Infrastructure Activity under grant agreement No. 730997;the China Scholarship Council for the financial support;supported by the Natural Science Foundation of China (No. 41305124)

摘　　要：The rate constants for the C1 atom reaction with three branched ketones have been measured at 298 ± 2 K and 760 Torr using the relative rate method in the absence of NO. The rate constants values obtained （in units of 10^-10 cm^3/（molecule.sec）） are： k（2-methyl-3-pentanone） = 1.07 ± 0.26, k（3-methyl-2-pentanone） =1.21 ± 0.26, and k（4-methyl-2-pentanone） = 1.35 ± 0.27. Combining the chemical kinetic data obtained by this study with those reported for other ketones, a revised Structure Activity Relationship （SAR） parameter and R group reactivity （kR of R（O）R＇ and CHx （x = 1, 2, 3） group reactivity （kCHx） toward C1 atoms were proposed. In addition, the products from the three reactions in the presence of NO were also identified and quantified by using PTR-ToF-MS and GC-FID, and the yields of the identified products are： acetone （39% ± 8%） ＋ ethanal （78% ± 12%）, 2-butanone （22% ± 2%） ＋ ethanal （75% ± 10%） ＋ propanal （14% ± 1%） and acetone （26% ± 3%） ＋ 2-methylpmpanal （24% ± 2%）, for C1 atoms reaction with 2-methyl-3-pentanone, 3-methyl-2-pentanone and 4-methyl-2-pentanone, respectively. Based on the obtained results, the reaction mechanisms of C1 atoms with these three ketones are proposed.The rate constants for the C1 atom reaction with three branched ketones have been measured at 298 ± 2 K and 760 Torr using the relative rate method in the absence of NO. The rate constants values obtained （in units of 10^-10 cm^3/（molecule.sec）） are： k（2-methyl-3-pentanone） = 1.07 ± 0.26, k（3-methyl-2-pentanone） =1.21 ± 0.26, and k（4-methyl-2-pentanone） = 1.35 ± 0.27. Combining the chemical kinetic data obtained by this study with those reported for other ketones, a revised Structure Activity Relationship （SAR） parameter and R group reactivity （kR of R（O）R＇ and CHx （x = 1, 2, 3） group reactivity （kCHx） toward C1 atoms were proposed. In addition, the products from the three reactions in the presence of NO were also identified and quantified by using PTR-ToF-MS and GC-FID, and the yields of the identified products are： acetone （39% ± 8%） ＋ ethanal （78% ± 12%）, 2-butanone （22% ± 2%） ＋ ethanal （75% ± 10%） ＋ propanal （14% ± 1%） and acetone （26% ± 3%） ＋ 2-methylpmpanal （24% ± 2%）, for C1 atoms reaction with 2-methyl-3-pentanone, 3-methyl-2-pentanone and 4-methyl-2-pentanone, respectively. Based on the obtained results, the reaction mechanisms of C1 atoms with these three ketones are proposed.

关 键 词：KETONES Cl atoms Rate constants PRODUCTS Mechanism 

分 类 号：X701[环境科学与工程—环境工程]