Directly measuring reaction kinetics of (center dot)QOOH - a crucial but elusive intermediate in hydrocarbon autoignition
Zador, Judit ; Huang, Haifeng ; Welz, Oliver ; Zetterberg, Johan LU
; Osborn, David L.
and Taatjes, Craig A.
(2013)
In Physical Chemistry Chemical Physics
15(26).
p.10753-10760
- 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 (center dot)QOOH radicals, are produced by isomerization of the alkylperoxy radicals that are formed in the first stages of oxidation. These (center dot)QOOH radicals are among the most critical species for modeling autoignition, as their reactions with O-2 are responsible for chain branching below 1000 K. Despite their importance, no (center dot)QOOH radicals have ever been observed by any means, and only computational and indirect experimental evidence has been available on their reactivity.... (More)
- 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 (center dot)QOOH radicals, are produced by isomerization of the alkylperoxy radicals that are formed in the first stages of oxidation. These (center dot)QOOH radicals are among the most critical species for modeling autoignition, as their reactions with O-2 are responsible for chain branching below 1000 K. Despite their importance, no (center dot)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 (center dot)QOOH radical, 2-hydroperoxy-2-methylprop-1-yl, and experimentally determine rate coefficients for its unimolecular decomposition and its association reaction with O-2. The results are supported by high-level theoretical kinetics calculations. Our experimental strategy opens up a new avenue to study the chemistry of (center dot)QOOH radicals in isolation. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/3990539
- author
- Zador, Judit
; Huang, Haifeng
; Welz, Oliver
; Zetterberg, Johan
LU
; Osborn, David L.
and Taatjes, Craig A.
- organization
- publishing date
- 2013
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Physical Chemistry Chemical Physics
- volume
- 15
- issue
- 26
- pages
- 10753 - 10760
- publisher
- Royal Society of Chemistry
- external identifiers
-
- wos:000320321600021
- scopus:84881111096
- pmid:23689671
- ISSN
- 1463-9084
- DOI
- 10.1039/c3cp51185e
- language
- English
- LU publication?
- yes
- id
- 140caaff-fffb-44a3-8f81-a1eb6bbca02e (old id 3990539)
- date added to LUP
- 2016-04-01 13:49:50
- date last changed
- 2022-09-26 10:52:07
@article{140caaff-fffb-44a3-8f81-a1eb6bbca02e,
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 (center dot)QOOH radicals, are produced by isomerization of the alkylperoxy radicals that are formed in the first stages of oxidation. These (center dot)QOOH radicals are among the most critical species for modeling autoignition, as their reactions with O-2 are responsible for chain branching below 1000 K. Despite their importance, no (center dot)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 (center dot)QOOH radical, 2-hydroperoxy-2-methylprop-1-yl, and experimentally determine rate coefficients for its unimolecular decomposition and its association reaction with O-2. The results are supported by high-level theoretical kinetics calculations. Our experimental strategy opens up a new avenue to study the chemistry of (center dot)QOOH radicals in isolation.}},
author = {{Zador, Judit and Huang, Haifeng and Welz, Oliver and Zetterberg, Johan and Osborn, David L. and Taatjes, Craig A.}},
issn = {{1463-9084}},
language = {{eng}},
number = {{26}},
pages = {{10753--10760}},
publisher = {{Royal Society of Chemistry}},
series = {{Physical Chemistry Chemical Physics}},
title = {{Directly measuring reaction kinetics of (center dot)QOOH - a crucial but elusive intermediate in hydrocarbon autoignition}},
url = {{http://dx.doi.org/10.1039/c3cp51185e}},
doi = {{10.1039/c3cp51185e}},
volume = {{15}},
year = {{2013}},
}