Abstract The reactions of 1-chlorocyclopentene with tropospheric oxidants, Cl, OH and O3 are studied to measure the rate coefficients at 298 K and 800 Torr of N2 using the relative rate method with butene, cyclopentene and butane as references. The concentrations of the organics are measured by Gas Chromatograpy technique. The measured average rate coefficient values of kCl, kOH and kO3 (in cm3 molecule−1 s−1) are (3.51 ± 1.26) x 10−10, (5.97 ± 1.08) x 10−11 and (1.50 ± 0.19) x 10−17, respectively. In addition, the rate coefficient for reaction of OH with 1-chlorocyclopentene at 298 K and 30 Torr was also measured using an absolute method of laser photolysis-laser induced fluorescence technique, and the kOH value is found to be (6.01 ± 0.70) x 10−11 cm3 molecule−1 s−1. The stable products formed during the reaction of Cl, OH and O3 initiated oxidation of the 1-chlorocyclopentene in presence of air are characterized by GCMS. The abstraction and addition products are identified among them, the latter are found to be major products. The experimental results are supported by molecular orbital calculations, and abstraction of the allylic hydrogen atoms is predicted to be the major abstraction channel. Calculations predict the preferential addition of chlorine atom to the carbon atom of the unsaturation center not having Cl attached to it. The rate coefficients of 1-chlorocyclopentene are compared with that of cyclopentene and substituted cyclopentene to understand the effect of substituent Cl on the reactivity. The measured rate coefficients have been used to calculate tropospheric lifetime of the compound to be 316, 2 and 26 h for Cl, OH and O3, respectively. Based on these values, the major degradation pathway of 1-chlorocyclopentene is suggested to be its reaction with OH. Atmospheric impact of these molecules is local as tropospheric lifetime (τ)

中文翻译：

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1-氯环戊烯与对流层氧化剂在 298 K 反应的速率系数

摘要 以丁烯、环戊烯和丁烷为参照，采用相对速率法，研究了1-氯环戊烯与对流层氧化剂Cl、OH和O3在298K和800Torr下的反应速率系数。通过气相色谱技术测量有机物的浓度。测得的 kCl、kOH 和 kO3 的平均速率系数值（以 cm3 分子-1 s-1 计）为 (3.51 ± 1.26) x 10-10、(5.97 ± 1.08) x 10-11 和 (1.50 ± 0.19) x 10 -17，分别。此外，还使用激光光解-激光诱导荧光技术的绝对法测量了OH与1-氯环戊烯在298 K和30 Torr反应的速率系数，发现kOH值为（6.01±0.70）x 10−11 cm3 分子−1 s−1。Cl反应过程中形成的稳定产物，在空气存在下 OH 和 O3 引发的 1-氯环戊烯氧化用 GCMS 表征。其中确定了抽象和加法产品，发现后者是主要产品。实验结果得到分子轨道计算的支持，预计烯丙基氢原子的提取是主要的提取通道。计算预测氯原子优先加到不饱和中心的碳原子上，而没有氯连接到它上面。将 1-氯环戊烯的速率系数与环戊烯和取代环戊烯的速率系数进行比较，以了解取代基 Cl 对反应性的影响。测得的速率系数已被用于计算化合物的对流层寿命，分别为 316、2 和 26 小时的 Cl、OH 和 O3。基于这些值，建议 1-氯环戊烯的主要降解途径是它与 OH 的反应。这些分子的大气影响是局部的，因为对流层寿命 (τ)