Cardona Alejandro L, Gibilisco Rodrigo G, Blanco María B, Wiesen Peter, Teruel Mariano
LUQCA-Instituto de Investigaciones en Fisicoquímica de Córdoba, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba Ciudad Universitaria 5000 Córdoba Argentina
Institute for Atmospheric and Environmental Research, Bergische Universität Wuppertal 42097 Wuppertal Germany.
RSC Adv. 2019 Jul 22;9(39):22618-22626. doi: 10.1039/c9ra04051j. eCollection 2019 Jul 17.
Relative rate coefficients and product distribution of the reaction of 2-butanethiol (2butSH) with OH radicals and Cl atoms were obtained at atmospheric pressure and 298 K. The experiments were performed in a 480 L borosilicate glass photoreactor in synthetic air coupled to a long path "" FTIR spectrometer. The rate coefficients obtained by averaging the values from different experiments were: = (2.58 ± 0.21) × 10 cm per molecule per s and = (2.49 ± 0.19) × 10 cm per molecule per s. The kinetic values were compared with related alkyl thiols and homologous alkyl alcohols, where it was found that thiols react faster with both oxidants, OH radicals and Cl atoms. SO and 2-butanone were the major products identified for the reactions of 2-butanethiol with OH radicals and Cl atoms. The product yield of the reaction of 2-butanethiol and OH radicals were (81 ± 2)%, and (42 ± 1)% for SO and 2-butanone, respectively. For the reactions of 2-butanethiol with Cl atom, yields of SO and 2-butanone were (59 ± 2)% and (39 ± 2)%, respectively. A degradation mechanism was proposed for the pathways that leads to formation of identified products. The product distribution observed indicated that the H-atom of the S-H group abstraction channel is the main pathway for the reaction of OH radicals and Cl atoms with 2-butanethiol.
在常压和298 K条件下，获得了2-丁硫醇（2butSH）与羟基自由基和氯原子反应的相对速率系数及产物分布。实验在一个480 L的硼硅酸盐玻璃光反应器中进行，该反应器置于合成空气中，并与一台长路径傅里叶变换红外光谱仪相连。通过对不同实验值进行平均得到的速率系数为：与羟基自由基反应的速率系数(k_{OH} = (2.58 ± 0.21) × 10^{-12}) (cm^{3}) 每分子每秒，与氯原子反应的速率系数(k_{Cl} = (2.49 ± 0.19) × 10^{-12}) (cm^{3}) 每分子每秒。将这些动力学值与相关的烷基硫醇和同系烷基醇进行了比较，发现硫醇与两种氧化剂（羟基自由基和氯原子）的反应都更快。二氧化硫（SO）和2-丁酮是2-丁硫醇与羟基自由基和氯原子反应中鉴定出的主要产物。2-丁硫醇与羟基自由基反应生成二氧化硫和2-丁酮的产物产率分别为(81 ± 2)%和(42 ± 1)%。对于2-丁硫醇与氯原子的反应，二氧化硫和2-丁酮的产率分别为(59 ± 2)%和(39 ± 2)%。针对导致形成已鉴定产物的途径提出了一种降解机制。观察到的产物分布表明，S-H基团的氢原子提取通道是羟基自由基和氯原子与2-丁硫醇反应的主要途径。
