DOI: 10.1002/kin.550100106. Temperature dependence of the reactions of HO<sub>2</sub> with NO and NO<sub>2</sub>

Temperature dependence of the reactions of HO2 with NO and NO2

10.1002/kin.550100106

Crossref journal-article

Wiley

International Journal of Chemical Kinetics (311)

Abstract

AbstractMixtures of N2O, H2, O2, and trace amounts of NO and NO2 were photolyzed at 213.9 nm, at 245°–328°K, and at about 1 atm total pressure (mostly H2). HO2 radicals are produced from the photolysis and they react as follows: equation image Reaction (1b) is unimportant under all of our reaction conditions. Reaction (1a) was studied in competition with reaction (3) from which it was found that k1a/k31/2 = 6.4 × 10−6 exp { z−(1400 ± 500)/RT} cm3/2/sec1/2. If k3 is taken to be 3.3 × 10−12 cm3/sec independent of temperature, k1a = 1.2 × 10−11 exp {−(1400 ± 500)/RT} cm3/sec. Reaction (2a) is negligible compared to reaction (2b) under all of our reaction conditions. The ratio k2b/k1 = 0.61 ± 0.15 at 245°K. Using the Arrhenius expression for k1a given above leads to k2b = 4.2 × 10−13 cm3/sec, which is assumed to be independent of temperature. The intermediate HO2NO2 is unstable and induces the dark oxidation of NO through reaction (−2b), which was found to have a rate coefficient k−2b = 6 × 1017 exp {−26,000/RT} sec−1 based on the value of k1a given above. The intermediate can also decompose via equation image Reaction (10b) is at least partially heterogeneous.

Bibliography

Simonaitis, R., & Heicklen, J. (1978). Temperature dependence of the reactions of HO2 with NO and NO2. International Journal of Chemical Kinetics, 10(1), 67â87. Portico.

Authors 2

R. Simonaitis (first)
Julian Heicklen (additional)

References 11 Referenced 26

10.1021/j100628a003
10.1021/j100600a001
10.1021/j100542a001
10.1016/0047-2670(75)80020-7
10.1126/science.179.4070.280
10.1021/ja00804a013
W.Hack K.Hoyermann andH. G.Wagner Int. J. Chem. Kin. Symposium No. 1 329(1975).
R. F.HampsonJr. andD.Garvin “Chemical Kinetic and Photochemical Data for Modelling Atmospheric Chemistry ” Tech. Note 866 National Bureau of Standards 1975.
10.1063/1.431984
{'key': 'e_1_2_1_10_2', 'first-page': '815', 'volume-title': 'Photochemistry', 'author': 'Calvert J. G.', 'year': '1967'} / Photochemistry by Calvert J. G. (1967)
{'key': 'e_1_2_1_11_2', 'first-page': '665', 'volume-title': 'Foundations of Chemical Kinetics', 'author': 'Benson S. W.', 'year': '1960'} / Foundations of Chemical Kinetics by Benson S. W. (1960)

Dates

Type	When
Created	20 years, 7 months ago (Jan. 1, 2005, 9:19 p.m.)
Deposited	1 year, 10 months ago (Oct. 19, 2023, 4:44 a.m.)
Indexed	1 year, 6 months ago (Feb. 10, 2024, 11:50 a.m.)
Issued	47 years, 7 months ago (Jan. 1, 1978)
Published	47 years, 7 months ago (Jan. 1, 1978)
Published Online	20 years, 10 months ago (Oct. 19, 2004)
Published Print	47 years, 7 months ago (Jan. 1, 1978)

Funders 0

None

BibTeX

@article{Simonaitis_1978, title={Temperature dependence of the reactions of HO2 with NO and NO2}, volume={10}, ISSN={1097-4601}, url={http://dx.doi.org/10.1002/kin.550100106}, DOI={10.1002/kin.550100106}, number={1}, journal={International Journal of Chemical Kinetics}, publisher={Wiley}, author={Simonaitis, R. and Heicklen, Julian}, year={1978}, month=jan, pages={67–87} }

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  "abstract": "<jats:title>Abstract</jats:title><jats:p>Mixtures of N<jats:sub>2</jats:sub>O, H<jats:sub>2</jats:sub>, O<jats:sub>2</jats:sub>, and trace amounts of NO and NO<jats:sub>2</jats:sub> were photolyzed at 213.9 nm, at 245\u00b0\u2013328\u00b0K, and at about 1 atm total pressure (mostly H<jats:sub>2</jats:sub>). HO<jats:sub>2</jats:sub> radicals are produced from the photolysis and they react as follows:<jats:disp-formula>\n<jats:graphic xmlns:xlink=\"http://www.w3.org/1999/xlink\" position=\"anchor\" xlink:href=\"urn:x-wiley:05388066:media:KIN550100106:nueq001\"><jats:alt-text>equation image</jats:alt-text></jats:graphic>\n</jats:disp-formula></jats:p><jats:p>Reaction (1b) is unimportant under all of our reaction conditions. Reaction (1a) was studied in competition with reaction (3) from which it was found that <jats:italic>k</jats:italic><jats:sub>1a</jats:sub>/<jats:italic>k</jats:italic><jats:sub>3</jats:sub><jats:sup>1/2</jats:sup> = 6.4 \u00d7 10<jats:sup>\u22126</jats:sup> exp { z\u2212(1400 \u00b1 500)/<jats:italic>RT</jats:italic>} cm<jats:sup>3/2</jats:sup>/sec<jats:sup>1/2</jats:sup>. If <jats:italic>k</jats:italic><jats:sub>3</jats:sub> is taken to be 3.3 \u00d7 10<jats:sup>\u221212</jats:sup> cm<jats:sup>3</jats:sup>/sec independent of temperature, <jats:italic>k</jats:italic><jats:sub>1a</jats:sub> = 1.2 \u00d7 10<jats:sup>\u221211</jats:sup> exp {\u2212(1400 \u00b1 500)/<jats:italic>RT</jats:italic>} cm<jats:sup>3</jats:sup>/sec. Reaction (2a) is negligible compared to reaction (2b) under all of our reaction conditions. The ratio <jats:italic>k</jats:italic><jats:sub>2b</jats:sub>/<jats:italic>k</jats:italic><jats:sub>1</jats:sub> = 0.61 \u00b1 0.15 at 245\u00b0K. Using the Arrhenius expression for <jats:italic>k</jats:italic><jats:sub>1a</jats:sub> given above leads to <jats:italic>k</jats:italic><jats:sub>2b</jats:sub> = 4.2 \u00d7 10<jats:sup>\u221213</jats:sup> cm<jats:sup>3</jats:sup>/sec, which is assumed to be independent of temperature. The intermediate HO<jats:sub>2</jats:sub>NO<jats:sub>2</jats:sub> is unstable and induces the dark oxidation of NO through reaction (\u22122b), which was found to have a rate coefficient <jats:italic>k</jats:italic><jats:sub>\u22122b</jats:sub> = 6 \u00d7 10<jats:sup>17</jats:sup> exp {\u221226,000/<jats:italic>RT</jats:italic>} sec<jats:sup>\u22121</jats:sup> based on the value of <jats:italic>k</jats:italic><jats:sub>1a</jats:sub> given above. The intermediate can also decompose via <jats:disp-formula>\n<jats:graphic xmlns:xlink=\"http://www.w3.org/1999/xlink\" position=\"anchor\" xlink:href=\"urn:x-wiley:05388066:media:KIN550100106:nueq002\"><jats:alt-text>equation image</jats:alt-text></jats:graphic>\n</jats:disp-formula> Reaction (10b) is at least partially heterogeneous.</jats:p>",
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