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Issue 26, 2013
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Directly measuring reaction kinetics of ˙QOOH – a crucial but elusive intermediate in hydrocarbon autoignition

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Abstract

Hydrocarbon autoignition has long been an area of intense fundamental chemical interest, and is a key technological process for emerging clean and efficient combustion strategies. Carbon-centered radicals containing an –OOH group, commonly denoted ˙QOOH radicals, are produced by isomerization of the alkylperoxy radicals that are formed in the first stages of oxidation. These ˙QOOH radicals are among the most critical species for modeling autoignition, as their reactions with O2 are responsible for chain branching below 1000 K. Despite their importance, no ˙QOOH radicals have ever been observed by any means, and only computational and indirect experimental evidence has been available on their reactivity. Here, we directly produce a ˙QOOH radical, 2-hydroperoxy-2-methylprop-1-yl, and experimentally determine rate coefficients for its unimolecular decomposition and its association reaction with O2. The results are supported by high-level theoretical kinetics calculations. Our experimental strategy opens up a new avenue to study the chemistry of ˙QOOH radicals in isolation.

Graphical abstract: Directly measuring reaction kinetics of ˙QOOH – a crucial but elusive intermediate in hydrocarbon autoignition

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Publication details

The article was received on 18 Mar 2013, accepted on 19 Apr 2013 and first published on 23 Apr 2013


Article type: Paper
DOI: 10.1039/C3CP51185E
Citation: Phys. Chem. Chem. Phys., 2013,15, 10753-10760
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    Directly measuring reaction kinetics of ˙QOOH – a crucial but elusive intermediate in hydrocarbon autoignition

    J. Zádor, H. Huang, O. Welz, J. Zetterberg, D. L. Osborn and C. A. Taatjes, Phys. Chem. Chem. Phys., 2013, 15, 10753
    DOI: 10.1039/C3CP51185E

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