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首页> 外文期刊>RSC Advances >Gas-phase degradation of 2-butanethiol initiated by OH radicals and Cl atoms: kinetics, product yields and mechanism at 298 K and atmospheric pressure
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Gas-phase degradation of 2-butanethiol initiated by OH radicals and Cl atoms: kinetics, product yields and mechanism at 298 K and atmospheric pressure

机译：由OH基团和CL原子引发的2-丁硫醇的气相降解：动力学，产量和298k和大气压的机制

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摘要

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 "in situ" FTIR spectrometer. The rate coefficients obtained by averaging the values from different experiments were: k(OH) = (2.58 +/- 0.21) x 10(-11) cm(3) per molecule per s and k(Cl) = (2.49 +/- 0.19) x 10(-10) cm(3) 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. SO2 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 SO2 and 2-butanone, respectively. For the reactions of 2-butanethiol with Cl atom, yields of SO2 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.
机译：在大气压力下获得的相对速率系数和2-丁硫醇（2butSH）与OH自由基和Cl原子的反应产物的分布和在耦合到一个长路径合成空气480大号硼硅酸盐玻璃光反应器中进行298个K.实验“原位”FTIR光谱仪。通过平均从不同的实验中的值所获得的速率系数分别为：K（OH）=（2.58 +/- 0.21）×10（-11）厘米（3）每个分子每S和K（氯）=（2.49 +/-每分子为0.19）×10（-10）厘米（3）。将动力学值与相关的烷基硫醇和同源烷基醇进行比较，发现硫醇与氧化剂，oh基团和Cl原子更快地反应。 SO2和2-丁酮是用OH基团和CL原子的2-丁硫醇反应鉴定的主要产物。 2-丁硫醇和OH基团反应的产物产量分别为SO2和2-丁酮的（42 +/- 1）％。对于2-丁硫醇与Cl原子的反应，SO2和2-丁酮的产率分别为（59 +/- 2）％和（39 +/- 2）％。提出了导致鉴定产物形成的途径的降解机制。观察到的产品分布表明，S-H组抽象通道的H原子是OH基团和Cl原子与2-丁硫醇反应的主要途径。

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  • 来源
    《RSC Advances》 |2019年第39期|共9页
  • 作者

    Cardona Alejandro L.; Gibilisco Rodrigo G.; Blanco Maria B.; Wiesen Peter; Teruel Mariano;

  • 作者单位

    Univ Nacl Cordoba Fac Ciencias Quim LUQCA Inst Invest Fis Quim Cordoba Ciudad Univ RA-5000 Cordoba Argentina;

    Berg Univ Wuppertal Inst Atmospher &

    Environm Res D-42097 Wuppertal Germany;

    Univ Nacl Cordoba Fac Ciencias Quim LUQCA Inst Invest Fis Quim Cordoba Ciudad Univ RA-5000 Cordoba Argentina;

    Berg Univ Wuppertal Inst Atmospher &

    Environm Res D-42097 Wuppertal Germany;

    Univ Nacl Cordoba Fac Ciencias Quim LUQCA Inst Invest Fis Quim Cordoba Ciudad Univ RA-5000 Cordoba Argentina;

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