Rate coefficients, k(1)(T), over the temperature range of 210-390 K are reported for the gas-phase reaction OH + HC(O)C(O)H (glyoxal) -> products at pressures between 45 and 300 Torr (He, N-2). Rate coefficients were determined under pseudo-first-order conditions in OH using pulsed laser photolysis production of OH radicals coupled with OH detection by laser-induced fluorescence. The rate coefficients obtained were independent of pressure and bath gas. The room-temperature rate coefficient, k(1)(296 K), was determined to be (9.15 +/- 0.8) x 10(-12) cm(3) molecule(-1) s(-1). k(1)(T) shows a negative temperature dependence with a slight deviation from Arrhenius behavior that is reproduced over the temperature range included in this study by k(1)(T) = (6.6 +/- 0.6) x 10(-18)T-2exp(820 +/- 30/T) cm(3) molecule(-1) s(-1). For atmospheric modeling purposes, a fit to an Arrhenius expression over the temperature range included in this study that is most relevant to the atmosphere, 210-296 K, yields k(1)(T) = (2.8 +/- 0.7) x 10(-12) exp(340 +/- 50)/T cm(3) molecule(-1) s(-1) and reproduces the rate coefficient data very well. The quoted uncertainties in k(1)(T) are at the 95% confidence level (2 sigma) and include estimated systematic errors. Comparison of the present results with the single previous determination of k(1)(296 K) and a discussion of the reaction mechanism and non-Arrhenius temperature dependence are presented.
%0 Journal Article
%1 Feierabend:2008p2263
%A Feierabend, Karl J
%A Zhu, Lei
%A Talukdar, R. K
%A Burkholder, James B
%D 2008
%J Journal of Physical Chemistry A
%K Atmospheric Chemistry, Constants, Gas-Phase, Hydroxyl Initiated Mechanism, Oh Organic-Compounds Oxidation, Photolysis, Product Radical Radicals, Rate Reactions, Yields,
%N 1
%P 73--82
%R 10.1021/jp076857.1
%T Rate Coefficients for the OH+HC(O)C(O)H (glyoxal) Reaction between 210 and 390
%U http://apps.isiknowledge.com/InboundService.do?Func=Frame&product=WOS&action=retrieve&SrcApp=Papers&UT=000252122300010&SID=4FmEEk3OFc8K9DpCib5&Init=Yes&SrcAuth=mekentosj&mode=FullRecord&customersID=mekentosj&DestFail=http%253A%252F%252Faccess.isiproducts.com%252Fcustom_images%252Fwok_failed_auth.html
%V 112
%X Rate coefficients, k(1)(T), over the temperature range of 210-390 K are reported for the gas-phase reaction OH + HC(O)C(O)H (glyoxal) -> products at pressures between 45 and 300 Torr (He, N-2). Rate coefficients were determined under pseudo-first-order conditions in OH using pulsed laser photolysis production of OH radicals coupled with OH detection by laser-induced fluorescence. The rate coefficients obtained were independent of pressure and bath gas. The room-temperature rate coefficient, k(1)(296 K), was determined to be (9.15 +/- 0.8) x 10(-12) cm(3) molecule(-1) s(-1). k(1)(T) shows a negative temperature dependence with a slight deviation from Arrhenius behavior that is reproduced over the temperature range included in this study by k(1)(T) = (6.6 +/- 0.6) x 10(-18)T-2exp(820 +/- 30/T) cm(3) molecule(-1) s(-1). For atmospheric modeling purposes, a fit to an Arrhenius expression over the temperature range included in this study that is most relevant to the atmosphere, 210-296 K, yields k(1)(T) = (2.8 +/- 0.7) x 10(-12) exp(340 +/- 50)/T cm(3) molecule(-1) s(-1) and reproduces the rate coefficient data very well. The quoted uncertainties in k(1)(T) are at the 95% confidence level (2 sigma) and include estimated systematic errors. Comparison of the present results with the single previous determination of k(1)(296 K) and a discussion of the reaction mechanism and non-Arrhenius temperature dependence are presented.
@article{Feierabend:2008p2263,
abstract = {Rate coefficients, k(1)(T), over the temperature range of 210-390 K are reported for the gas-phase reaction OH + HC(O)C(O)H (glyoxal) -> products at pressures between 45 and 300 Torr (He, N-2). Rate coefficients were determined under pseudo-first-order conditions in OH using pulsed laser photolysis production of OH radicals coupled with OH detection by laser-induced fluorescence. The rate coefficients obtained were independent of pressure and bath gas. The room-temperature rate coefficient, k(1)(296 K), was determined to be (9.15 +/- 0.8) x 10(-12) cm(3) molecule(-1) s(-1). k(1)(T) shows a negative temperature dependence with a slight deviation from Arrhenius behavior that is reproduced over the temperature range included in this study by k(1)(T) = [(6.6 +/- 0.6) x 10(-18)]T-2[exp([820 +/- 30]/T)] cm(3) molecule(-1) s(-1). For atmospheric modeling purposes, a fit to an Arrhenius expression over the temperature range included in this study that is most relevant to the atmosphere, 210-296 K, yields k(1)(T) = (2.8 +/- 0.7) x 10(-12) exp[(340 +/- 50)/T] cm(3) molecule(-1) s(-1) and reproduces the rate coefficient data very well. The quoted uncertainties in k(1)(T) are at the 95% confidence level (2 sigma) and include estimated systematic errors. Comparison of the present results with the single previous determination of k(1)(296 K) and a discussion of the reaction mechanism and non-Arrhenius temperature dependence are presented.},
added-at = {2010-06-22T19:38:37.000+0200},
affiliation = {NOAA, Div Chem Sci, Earth Syst Res Lab, Boulder, CO 80305 USA},
author = {Feierabend, Karl J and Zhu, Lei and Talukdar, R. K and Burkholder, James B},
biburl = {https://www.bibsonomy.org/bibtex/2b9b3f99ba8da912200ab3ced1c70ca8c/gsmith},
date-added = {2010-03-23 14:06:37 -0400},
date-modified = {2010-03-23 15:12:31 -0400},
doi = {10.1021/jp076857.1},
interhash = {729bfb5253a8ec9cbf9dc36ad66e4667},
intrahash = {b9b3f99ba8da912200ab3ced1c70ca8c},
journal = {Journal of Physical Chemistry A},
keywords = {Atmospheric Chemistry, Constants, Gas-Phase, Hydroxyl Initiated Mechanism, Oh Organic-Compounds Oxidation, Photolysis, Product Radical Radicals, Rate Reactions, Yields,},
language = {English},
local-url = {file://localhost/Users/geoffreysmith/Documents/Papers/Journal%20of%20Physical%20Chemistry%20A/2008/Journal%20of%20Physical%20Chemistry%20A,%20112,%2073-82%202008.pdf},
month = Jan,
number = 1,
pages = {73--82},
pmid = {000252122300010},
rating = {0},
read = {Yes},
timestamp = {2010-06-22T19:38:53.000+0200},
title = {Rate Coefficients for the OH+HC(O)C(O)H (glyoxal) Reaction between 210 and 390},
uri = {papers://E88B624E-D406-46FF-9D95-BB9C1AAE3FDC/Paper/p2263},
url = {http://apps.isiknowledge.com/InboundService.do?Func=Frame&product=WOS&action=retrieve&SrcApp=Papers&UT=000252122300010&SID=4FmEEk3OFc8K9DpCib5&Init=Yes&SrcAuth=mekentosj&mode=FullRecord&customersID=mekentosj&DestFail=http%253A%252F%252Faccess.isiproducts.com%252Fcustom_images%252Fwok_failed_auth.html},
volume = 112,
year = 2008
}