The mechanism of methoxy radical oxidation: Hydrogen abstraction versus trioxy radical formation

被引：32

作者：

Jungkamp, TPW

Seinfeld, JH

机构：

[1] Environmental Engineering Science, California Institute of Technology, Pasadena

[2] Chemical Engineering, California Institute of Technology, Pasadena

来源：

CHEMICAL PHYSICS LETTERS | 1996年 / 263卷 / 3-4期

关键词：

D O I：

10.1016/S0009-2614(96)01197-9

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The energetic profiles of the two possible pathways of formaldehyde and HO2 radical formation in the oxidation of the methoxy radical CH3O, i.e. (a) via H-abstraction or (b) as addition/elimination involving methyl trioxy radicals CH3OOO as intermediates, were calculated using G2M(RCC) and CBS-QCI/APNO model chemistries. The 298 K barrier height for path (a) is found to be 11.5 (14.8) kcal/mol at G2M(RCC) level (CBS-QCI/APNO value in parentheses). Along path (b), the HO2 elimination from cis-CH3OOO is found to have a barrier of 1.3 (8.5) kcal/mol. Therefore, oxidation of CH3O is likely to occur by forming the CH3OOO intermediate rather than by H-abstraction.

引用

页码：371 / 378

页数：8

共 15 条

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