Atmospheric Chemistry and Physics Discussions
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10.5194/acpd-8-8881-2008
http://www.atmos-chem-phys-discuss.net/8/8881/2008/
http://www.atmos-chem-phys-discuss.net/8/8881/2008/acpd-8-8881-2008.html
http://www.atmos-chem-phys-discuss.net/8/8881/2008/acpd-8-8881-2008.pdf
8881
8912
2008-05-19
Absolute rate constant and O(<sup>3</sup>P) yield for the O(<sup>1</sup>D)+N<sub>2</sub>O reaction in the temperature range 227 K to 719 K
S. Vranckx
J. Peeters
S. A. Carl
shaun.carl@chem.kuleuven.be
University of Leuven, Department of Chemistry, 200F Celestijnenlaan, 3001 Leuven, Belgium
We have determined, in the temperature range 227 K to 719 K, the absolute
rate constant for the reaction O(<sup>1</sup>D)+N<sub>2</sub>O → products and, in
the temperature range 248 K to 600 K, the fraction of the reaction that
yields O(<sup>3</sup>P). Both the rate constants and product yields were
determined using a recently-developed chemiluminescence technique for
monitoring O(<sup>1</sup>D) that allows for higher precision determinations for
both rate constants, and, particularly, O(<sup>3</sup>P) yields, than do other
methods. We found the rate constant, <i>k</i><sub>R1</sub>, to be essentially independent
of temperature between 400 K and 227 K, having a value of
(1.37±0.09)×10<sup>−10</sup> cm<sup>3</sup> s<sup>−1</sup>. For temperatures greater than 450 K a
marked decrease in value was observed, with a rate constant of only
(0.94±0.11)×10<sup>−10</sup> cm<sup>3</sup> s<sup>−1</sup> at 719 K. The rate constants determined
over the 227 K–400 K range show very low scatter and are significantly
greater, by 20% at room temperature and by 15% at 227 K, than the
current recommended values. The fraction of O(<sup>3</sup>P) produced in this
reaction was determined to be 0.002±0.002 at 250 K rising steadily to
0.010±0.004 at 600 K, thus the channel producing O(<sup>3</sup>P) can be
entirely neglected in atmospheric kinetic modeling calculations. A further
result of this study is an expression of the relative quantum yields as a
function of temperature for the chemiluminescence reactions (<i>k</i><sub>CL1</sub>) C<sub>2</sub>H+O(<sup>1</sup>D) → CH(A)+CO and (<i>k</i><sub>CL2</sub>) C<sub>2</sub>H+O(<sup>3</sup>P) → CH(A)+CO,
both followed by CH(A) → CH(X)+hν,
as <i>k</i><sub>CL1</sub>(T)/<i>k</i><sub>CL2</sub>(T)=(32.8<i>T</i>−3050)/(6.29<i>T</i>+398).
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