CH3 + CH3OCH3 的激波管研究。

Shock tube investigation of CH3 + CH3OCH3.

机构信息

Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, United States.

出版信息

J Phys Chem A. 2012 Jul 12;116(27):7287-92. doi: 10.1021/jp302761b. Epub 2012 Jun 29.

DOI:10.1021/jp302761b

PMID:22681341

Abstract

The title reaction has been investigated in a diaphragmless shock tube by laser schlieren densitometry over the temperature range 1163-1629 K and pressures of 60, 120, and 240 Torr. Methyl radicals were produced by dissociation of 2,3-butanedione in the presence of an excess of dimethyl ether. Rate coefficients for CH(3) + CH(3)OCH(3) were obtained from simulations of the experimental data yielding the following expression which is valid over the range 1100-1700 K: k = (10.19 ± 3.0)T(3.78) exp((-4878/T)) cm(3) mol(-1)s(-1). The experimental results are in good agreement with estimates by Curran and co-workers [Fischer, S. L.; Dryer, F. L.; Curran, H. J. Int. J. Chem. Kinet.2000, 32 (12), 713-740. Curran, H. J.; Fischer, S. L.; Dryer, F. L. Int. J. Chem. Kinet.2000, 32 (12), 741-759] but about a factor of 2.6 lower than those of Zhao et al. [Zhao, Z.; Chaos, M.; Kazakov, A.; Dryer, F. L. Int. J. Chem. Kinet.2008, 40 (1), 1-18].

摘要

标题反应已在无膜激波管中进行了研究，通过激光纹影密度测量法在 1163-1629 K 的温度范围内和 60、120 和 240 托的压力下进行了研究。在二甲醚过量的情况下，通过 2,3-丁二酮的离解产生了甲基自由基。通过对实验数据的模拟，得到了 CH(3) + CH(3)OCH(3) 的速率系数，得出了以下在 1100-1700 K 范围内有效的表达式：k = (10.19 ± 3.0)T(3.78) exp((-4878/T)) cm(3) mol(-1)s(-1)。实验结果与 Curran 等人的估计[Fischer, S. L.; Dryer, F. L.; Curran, H. J. Int. J. Chem. Kinet.2000, 32 (12), 713-740. Curran, H. J.; Fischer, S. L.; Dryer, F. L. Int. J. Chem. Kinet.2000, 32 (12), 741-759]非常吻合，但比 Zhao 等人的结果低约 2.6 倍[Zhao, Z.; Chaos, M.; Kazakov, A.; Dryer, F. L. Int. J. Chem. Kinet.2008, 40 (1), 1-18]。