Rate constants for the reaction of cl with a series of C4 to C6 ketones using the relative rate method.
Rate constants for the reaction of cl with a series of C4 to C6 ketones using the relative rate method.
复制标题
使用相对速率法计算 cl 与一系列 C4 至 C6 酮反应的速率常数。
DOI：
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发表时间：
2007
影响因子：
2.9
通讯作者：
T. Wallington
中科院分区：
文献类型：
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作者：
E. Kaiser;T. Wallington
测定了常温下氯气与8种酮的反应速率常数与丙烷在约900托氮气中的反应速率常数。实验是在吡喃合成塔中进行的，用气相色谱分析了酮和丙烷的消耗。氯原子是通过用黑光蓝荧光灯照射初始混合物中的Cl2而产生的。实验测得的速率常数(10~(-11)cm~3分子~(-1)S~(-1))为：丁酮(3.8+/-0.3)；2-戊酮(11.6+/-1.0)；3-戊酮(8.3+/-0.7)；2-己酮(19.4+/-1.9)；3-己酮(15.3+/-1.1)；环戊酮(10.4+/-0.9)；3-甲基-2-丁酮(6.2+/-0.5)；和4-甲基-2-戊酮(12.8+/-1.0)。2-戊酮、3-戊酮、2-己酮、3-己酮、3-甲基-2-丁酮和4-甲基-2-戊酮的结果显著高于之前两个绝对率研究报告的结果(2-己酮的系数为3)。对这种差异的可能解释进行了讨论。
Rate constants for the reaction of Cl with eight ketones were measured relative to the rate constant of propane in approximately 900 Torr of N2 at ambient temperature. Experiments were carried out in a Pyrex reactor with GC analysis of the consumption of the ketones and propane. Chlorine atoms were generated by irradiation of Cl2 in the initial mixture using a black-light-blue fluorescent lamp. The rate constants determined in these experiments (10-11 cm3 molecule-1 s-1) are: butanone (3.8 +/- 0.3); 2-pentanone (11.6 +/- 1.0); 3-pentanone (8.3 +/- 0.7); 2-hexanone (19.4 +/- 1.9); 3-hexanone (15.3 +/- 1.1); cyclopentanone (10.4 +/- 0.9); 3-methyl-2-butanone (6.2 +/- 0.5); and 4-methyl-2-pentanone (12.8 +/- 1.0). The results for 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, 3-methyl-2-butanone, and 4-methyl-2-pentanone are significantly higher (by a factor of 3 for 2-hexanone) than reported in two previous absolute rate studies. The likely explanation for this discrepancy is discussed.