2,3-Dimethyl-2-butene (TME) Ozonolysis: Pressure Dependence of Stabilized Criegee Intermediates and Evidence of Stabilized Vinyl Hydroperoxides

被引：50

作者：

Drozd, Greg T. ^{[1
]}

Kroll, Jesse ^{[2
]}

Donahue, Neil M. ^{[1
]}

机构：

[1] Carnegie Mellon Univ, Pittsburgh, PA 15213 USA

[2] MIT, Cambridge, MA 02139 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2011年 / 115卷 / 02期

关键词：

OZONE-ALKENE REACTIONS; GAS-PHASE OZONOLYSIS; WATER-VAPOR; OH RADICALS; HYDROXYMETHYL HYDROPEROXIDE; CARBONYL OXIDES; HOX FORMATION; FORMIC-ACID; MECHANISM; PROMPT;

D O I：

10.1021/jp108773d

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：

We present measurements of the pressure dependence of stabilized Criegee intermediate (SCI) formation utilizing a hexafluoroacetone scavenger. SCI yields in the ozonolysis of 2,3-dimethyl-2-butene (TME) were measured in a high pressure flow reactor within a range of 50-710 Torr. Within this pressure range, SCI yields increase linearly with pressure. A zero pressure intercept of about 15% indicates that a significant fraction of CI are formed below the barrier to isomerization. By comparison of our results of the pressure dependence of SCI formation and both prompt and long-time OH yields, our results indicate that OH formation from ozonolysis proceeds via at least two intermediates, the SCI and presumably a vinylhydroperoxide (VHP).

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收藏

页码：161 / 166

页数：6

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