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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Low-Pressure Study of the Reaction of Cl Atoms with Isoprene
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Low-Pressure Study of the Reaction of Cl Atoms with Isoprene

机译：Cl原子与异戊二烯反应的低压研究

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摘要

The kinetics of the reaction of chlorine atoms with isoprene (1) has been studied using the discharge-flow mass-spectrometric method: Cl + C_5H_8 (+M) → C_5H_8Cl (+M) (1a); Cl + C_5H_8 → C_5H_7 + HCl (1b). As a result of direct and relative measurements, the overall rate constant k_1 = (6.7 ± 2.0) * 10~(-11) exp{(485 ± 85)/T} cm~3 molecule~(-1) s~(-1) was obtained at a pressure of 1 Torr of helium over the temperature range 233-320 K. k_1 was found to be pressure-independent (within 10%) at T = 298 K in the pressure range 0.25-3 Torr. Both HCl and C_5H_8Cl adduct were detected as products of reaction 1. The measurement of the HCl yield as a function of temperature led to the branching fraction for the H-atom abstraction channel (1b): k_(1b)/k_1 = (1.22 ± 0.4) exp{-(595 ± 90)/T} (P = 1 Torr, T = 233-320 K); k_(1b)/k_1 = 0.169 ± 0.022 at 298 K. The results are compared with those reported in a recent study~4 carried out at 298 K. In addition, the rate coefficient has been measured for the reaction Cl + Br_2 → (2), which was used as the reference in the relative study of reaction 1. Combining the present results obtained in the range 233-320 K with those available from a previous study in the range 298-401 K~(10), the following Arrhenius expression is recommended: k_2 = (2.3 ± 0.4) * ~(-10) exp{(135 ± 60)/T} cm~3 molecule~(-1) s~(-1).
机译：氯原子与异戊二烯（1）的反应动力学已使用放电流动质谱法研究：Cl + C_5H_8（+ M）→C_5H_8Cl（+ M）（1a）; Cl + C_5H_8→C_5H_7 + HCl（1b）。通过直接和相对测量，总速率常数k_1 =（6.7±2.0）* 10〜（-11）exp {（485±85）/ T} cm〜3分子〜（-1）s〜（- 1）是在233-320 K的温度范围内以1 Torr的氦气压力获得的。在0.25-3 Torr的压力范围内，在T = 298 K时，k_1与压力无关（在10％以内）。 HCl和C_5H_8Cl加合物均被检测为反应1的产物。HCl收率的测量与温度的关系导致H原子提取通道（1b）的支化分数：k_（1b）/ k_1 =（1.22± 0.4）exp {-（595±90）/ T}（P = 1托，T = 233-320 K）;在298 K时k_（1b）/ k_1 = 0.169±0.022。将结果与在298 K时进行的最新研究〜4进行比较。此外，还测量了反应Cl + Br_2→的速率系数2），在反应1的相对研究中用作参考。结合在233-320 K范围内获得的当前结果与从先前研究298-401 K〜（10）中获得的结果，以下推荐Arrhenius表达：k_2 =（2.3±0.4）*〜（-10）exp {（135±60）/ T} cm〜3分子〜（-1）s〜（-1）。

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