Multichannel Reaction of C2Cl3 + O2 Studied by Time-Resolved Fourier Transform Infrared Emission Spectroscopy

详细信息    查看全文

• 作者：Tiancheng Xiang ; Kunhui Liu ; Shaolei Zhao ; Hongmei Su ; Fanao Kong ; Baoshan Wang
• 刊名：Journal of Physical Chemistry A
• 出版年：2007
• 出版时间：September 27, 2007
• 年：2007
• 卷：111
• 期：38
• 页码：9606 - 9612
• 全文大小：178K
• 年卷期：v.111,no.38(September 27, 2007)
• ISSN：1520-5215

文摘

The multichannel reaction of the C₂Cl₃ radical with O₂ has been studied thoroughly by step-scan time-resolvedFourier transform infrared emission spectroscopy. Vibrationally excited products of Cl₂CO, CO, and CO₂ areobserved and three major reaction channels forming respectively ClCO + Cl₂CO, CO + CCl₃O, and CO₂ +CCl₃ are identified. The vibrational state distribution of the product CO is derived from the spectral fitting,and the nascent average vibrational energy of CO is determined to be 59.9 kJ/mol. A surprisal analysis isapplied to evaluate the vibrational energy disposal, which reveals that the experimentally measured COvibrational energy is much more than that predicted by statistical model. Combining previous ab initiocalculation results, the nonstatistical dynamics and mechanism are characterized to be barrierless addition-elimination via short-lived reaction intermediates including the peroxy intermediate C₂Cl₃OO* and a crucialthree-member-ring COO intermediate.