Department of Chemistry, Acadia University, Wolfville, Nova Scotia, B4P 2R6, Canada.
J Phys Chem A. 2010 Aug 19;114(32):8369-75. doi: 10.1021/jp1037409.
The reactions of Cl with tetrahydrofuran, tetrahydropyran, and dimethyl ether have been studied as a function of temperature, pressure, and O(2) concentration. The temperature was varied from approximately 280 to 360 K, the mole fraction of O(2) ranged from zero to approximately 0.6, and the experiments were made in a bath of argon at total pressures ranging from approximately 300 to 760 Torr. The rate coefficients were measured using the relative rate method with gas chromatographic analysis. The reaction of Cl with isobutane was the reference reaction, the rate coefficients for which were calibrated against the reaction of propane with chlorine atoms as a function of temperature. The rate coefficients were unaffected by the concentration of O(2) or by variation in pressure. The rate coefficient for the reaction of Cl with isobutane increased slightly with decreasing temperature. This weak temperature dependence of the rate coefficient was in satisfactory agreement with information in the literature and is represented in Arrhenius form by k(T) = (1.02(-0.25)(+0.32)) x 10(-10) exp(99 +/- 88/T) cm(3) molecule(-1) s(-1), where the uncertainties represent two standard deviations. The rate coefficients for the reactions of Cl with the ethers did not show a statistically significant dependence on temperature. Their average values over our range of temperature are: for Cl + tetrahydrofuran, k = (2.71 +/- 0.34) x 10(-10) cm(3) molecule(-1) s(-1); for Cl + tetrahydropyran, k = (2.03 +/- 0.82) x 10(-10) cm(3) molecule(-1) s(-1); and for Cl + dimethyl ether, k = (1.73 +/- 0.22) x 10(-10) cm(3) molecule(-1) s(-1), in which the uncertainties are again two standard deviations.
已研究了 Cl 与四氢呋喃、四氢吡喃和二甲醚的反应，作为温度、压力和 O2 浓度的函数。温度从大约 280 到 360 K 变化，O2 的摩尔分数从零到大约 0.6，实验在总压力从大约 300 到 760 托的氩浴中进行。使用相对速率法和气相色谱分析测量速率系数。Cl 与异丁烷的反应是参考反应，其速率系数是根据丙烷与氯原子的反应随温度的变化来校准的。速率系数不受 O2 浓度或压力变化的影响。Cl 与异丁烷的反应速率系数随温度的降低略有增加。这种速率系数的弱温度依赖性与文献中的信息基本一致，以阿累尼乌斯形式表示为 k(T) = (1.02(-0.25)(+0.32)) x 10(-10) exp(99 +/- 88/T) cm(3) molecule(-1) s(-1)，其中不确定性表示两个标准偏差。Cl 与醚的反应速率系数没有表现出与温度有统计学意义的依赖关系。在我们的温度范围内，它们的平均值为：Cl + 四氢呋喃，k = (2.71 +/- 0.34) x 10(-10) cm(3) molecule(-1) s(-1)；Cl + 四氢吡喃，k = (2.03 +/- 0.82) x 10(-10) cm(3) molecule(-1) s(-1)；Cl + 二甲醚，k = (1.73 +/- 0.22) x 10(-10) cm(3) molecule(-1) s(-1)，其中不确定性再次为两个标准偏差。
