References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-8-6261-2008

Absolute rate constant and O(3P) yield for the O(1D)+N2O reaction in the temperature range 227 K to 719 K

Vranckx

¹ Peeters

¹ Carl

S. A.

University of Leuven, Department of Chemistry, 200F Celestijnenlaan, 3001 Leuven, Belgium

28 10 2008

8 20 6261 6272

This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

This article is available from http://www.atmos-chem-phys.net/8/6261/2008/acp-8-6261-2008.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/8/6261/2008/acp-8-6261-2008.pdf

The absolute rate constant for the reaction that is the major source of stratospheric NOx, O(1D)+N2O → products, has been determined in the temperature range 227 K to 719 K, and, in the temperature range 248 K to 600 K, the fraction of the reaction that yields O(3P). Both the rate constants and product yields were determined using a recently-developed chemiluminescence technique for monitoring O(1D) that allows for higher precision determinations for both rate constants, and, particularly, O(3P) yields, than do other methods. We found the rate constant, kR1, to be essentially independent of temperature between 400 K and 227 K, having a value of (1.37±0.11)×10−10 cm3 s−1, and for temperatures greater than 450 K a marked decrease in rate constant was observed, with a rate constant of only (0.94±0.11)×10−10 cm3 s−1 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 15% at 227 K, than the current recommended values. The fraction of O(3P) 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(3P) 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 (kCL1)C2H + O(1D) → CH(A) + CO and (kCL2)C2H + O(3P) → CH(A) + CO, both followed by CH(A) → CH(X) + hν, as kCL1(T)/kCL2(T)=(32.8T−3050)/(6.29T+398).

References 1

Amimoto, S. T., Force, A. P., Gulotty Jr., R. G., and Wiesenfeld, J. R.: Collisional deactivation of O($^1$D$_2)$ by the atmospheric gases, J. Chem. Phys., 71, 3640–3647, 1979.

Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes, R. G., Jenkin, M. E., Rossi, M. J., and Troe, J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume I – gas phase reactions of Ox, HOx, NOx and SOx species, Atmos. Chem. Phys., 4, 1461–1738, 2004.

Bhardwaj, A. and Haider, S. A.: Chemistry of O$^1$D atoms in the coma: implications for cometary missions, Adv. Space Res., 29, 745–750, 2002.

Blitz, M. A., Dillon, T. J., Heard, D. E., Pilling, M. J., and Trought, I. D.: Laser induced fluorescence studies of the reactions of O($^1$D$_2)$ with N2, O2, N2O, CH4, H2, CO2, Ar, Kr and n-C4H$_10$, Phys. Chem. Chem. Phys., 6, 2162–2171, 2004.

Cantrell, C. A., Shetter R. E., and Calvert, J. G.: Branching ratios for the O($^1$D)+N2O reaction, J. Geophys. Res., 99, 3739–3743, 1994.

Carl, S. A.: A highly sensitive method for time-resolved detection of O($^1$D) applied to precise determination of absolute O($^1$D) reaction rate constants and O(3P) yields, Phys. Chem. Chem. Phys., 7, 4051–4053, 2005.

Crutzen, P. J.: Ozone production rates in an oxygen-hydrogen-nitrogen oxide atmosphere, J. Geophys. Res., 76, 7311–7327, 1971.

Crutzen, P. J. and Brühl, C.: Catalysis by NOx as the Main Cause of the Spring to Fall Stratospheric Ozone Decline in the Northern Hemisphere, J. Phys. Chem. A, 105, 1579–1582, 2001.

Davidson, J. A., Howard, C. J., Schiff, H. I., and Fehsenfeld, F. C.: Measurement of the branching ratios for the reactionof O($^1$D$_2)$ with N2O, J. Chem. Phys., 70, 1697–1704, 1979.

Devriendt, K., Van Look, H., Ceursters, B., and Peeters, J.: Kinetics of formation of chemiluminescent CH(A$^2\Delta )$ by the elementary reactions of C2H(X$^2§igma ^+)$ with O(3P) and O2(X$^3§igma _g^-)$: A pulse laser photolysis study, Chem. Phys. Lett., 261, 450–456, 1996.

Dillon, T. J., Horowitz, A., and Crowley, J. N.: The atmospheric chemistry of sulphuryl fluoride, SO2F2, Atmos. Chem. Phys., 8, 1547–1557, 2008.

Dils, B., Kulkarni, R. M., Peeters, J., and Carl S. A.: Absolute rate coefficients of the reactions of CF2(aB$^3_1)$ with C3H$_8$, C3H$_6$, iso-C4H$_8$ andC3H4 between 295 and 550 K, Phys. Chem. Chem. Phys., 6, 2211–2215 , 2004.

Dunlea, E. J. and Ravishankara, A. R.: Kinetic studies of the reactions of O(1D) with several atmospheric molecules, Phys. Chem. Chem. Phys. 6, 2152–2161, 2004.

Elsamra, R. M. I., Vranckx, S., and Carl, S. A.: CH(A$^2\Delta )$ formation in hydrocarbon combustion: The temperature dependence of the rate constant of the reaction C2H+O$_2\to$CH(A$^2\Delta)$+CO2, J. Phys. Chem. A. 109, 10 287–10 293, 2005.

Forst, W.: Unimolecular reactions: a concise introduction, Chap. 7, Cambridge University Press, 2003.

Heidner, R. F., Wiesen Jr., F. E., and Husain, D.: Kinetic study of electronically excited oxygen atoms, O(2$^1$D$_2)$, by time-resolved atomic absorption spectroscopy in the vacuum ultra-violet ($\lambda $=115.2 nm, O(3$^1$D$^0_2\leftarrow $2$^1$D$_2))$, Chem. Phys. Lett., 16, 530–533, 1972.

Kaspar, T., Tuan, A., Tonkyn, R., Hess, W. P., Rogers, J. W., and Ono, Y. J.: Role of O$^1$D in the oxidation of Si(100), Vac. Sci. Technol., B, 21b, 895–899, 2003, and references therein.

Khamaganov, V. G., Bui, V. X., Carl, S. A., and Peeters, J.: Absolute rate coefficient of the OH + CH3C(O)OH reaction at $T$=287-802 K. The two faces of pre-reactive H-bonding, J. Phys. Chem A, 110, 12 852–12 859, 2006.

Kharchenko, V. and Dalgarno, A.: Thermalization of fast O($^1$D) atoms in the stratosphere and mesosphere, J. Geophys. Res.-Atoms., 109, D18311, doi:10.1029/2004JD004597, 2004.

Luque, J. and Crosley, D. R.: Electronic transition moment and rotational transition probabilities in CH .1. A$^2\Delta $-X$^2\Pi $ system, J. Chem. Phys., 104, 2146–2155, 1996.

Nair, H., Summers, M. E., Miller, C. E., and Yung, Y. L.: Isotopic fractionation of methane in the martian atmosphere, Icarus, 175, 32–35, 2005.

Nishida, S., Takahashi, K., Matsumi, Y., Taniguchi, N., and Hayashida, S. J.: Formation of O(3P) atoms in the photolysis of N2O at 193 nm and O(3P) + N2O product channel in the reaction of O($^1$D) + N2O, Phys. Chem. A, 108, 2451–2456, 2004.

Sander, S. P., Friedl, R. R., Ravishankara, A. R., Golden, D. M., Kolb, C. E., Kurylo, M. J., Molina, M. J., Moortgat, G. K., Keller-Rudek, H., Finlayson-Pitts, B. J., Wine, P. H., Huie, R. E., and Orkin, V. L.: Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Evaluation Number 15, JPL Publication 06-2, National Aeronautics and Space Administration, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, California July 10, 2006.

Selwyn, G., Podolske, J., and Johnston, H. S.: Nitrous-oxide ultraviolet-absorption spectrum at stratospheric temeratures, Geophys. Res. Lett., 4, 427–430, 1977.

Takahashi, K., Takeuchi, Y., and Matsumi,Y.: Rate constants of the O($^1$D) reactions with N2, O2, N2O, and H2O at 295 K, Chem. Phys. Lett., 410, 196–200, 2005.

Tamura, M., Berg, P. A., Harrington, J. E., Luque, J., Jeffries, B., Smith, G. P., and Crosley, D. R.: Collisional quenching of CH(A), OH(A), and NO(A) in low pressure hydrocarbon flames, Combust. Flame, 114, 502–514, 1998.

Vakhtin, A. B., Heard, D. E., Smith, I. W. M., and Leone, S. R.: Kinetics of reactions of C2H radical with acetylene, O2, methylacetylene, and allene in a pulsed Laval nozzle apparatus at T=103 K, Chem. Phys. Lett., 344, 317–324, 2001.

Van Look, H. and Peeters, J.: Rate coefficients of the reactions of C2H with O2, C2H2, and H2O between 295 and 450 K, J. Phys. Chem., 99, 16 284–16 289, 1995.

Wine, P. H. and Ravishankara, A. R.: Kinetics of the O($^1$D) interactions with the atmopsheric gases N2, N2O, H2O, H2, CO2, and O3, Chem. Phys. Lett., 77, 103–109, 1981.

Wine, P. H. and Ravishankara, A. R.: O3 Photolysis at 248 nm and O($^1$D$_2)$ quenching by H2O, CH4, H2, and N2O - O(3P$_J)$ yields, Chem. Phys., 69, 365–373, 1982.