Atmospheric Chemistry and Physics Discussions
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10.5194/acpd-8-7111-2008
http://www.atmos-chem-phys-discuss.net/8/7111/2008/
http://www.atmos-chem-phys-discuss.net/8/7111/2008/acpd-8-7111-2008.html
http://www.atmos-chem-phys-discuss.net/8/7111/2008/acpd-8-7111-2008.pdf
7111
7148
2008-04-11
Direct detection of OH formation in the reactions of HO<sub>2</sub> with CH<sub>3</sub> C(O)O<sub>2</sub> and other substituted peroxy radicals
T. J. Dillon
dillon@mpch-mainz.mpg.de
J. N. Crowley
Max-Planck-Institut für Chemie (Otto-Hahn-Institut) Joh.-Joachim-Becher-Weg 27, 55128 Mainz, Germany
This work details the first direct observation of OH as a product from (R1):
HO<sub>2</sub>+CH<sub>3</sub>C(O)O<sub>2</sub>→(products), which has generally been
considered an atmospheric radical termination process. The technique of
pulsed laser photolysis radical generation, coupled to calibrated laser
induced fluorescence detection was used to measure an OH product yield for
(R1) of (α1=0.5±0.2). This study of (R1) included the
measurement of a rate coefficient <i>k</i><sub>1</sub>(298 K)=1.4±0.5)×10<sup>-11</sup>cm<sup>3</sup> molecule<sup>−1</sup> s<sup>−1</sup>, substantially reducing the
uncertainties in modelling this important atmospheric reaction. OH was also
detected as a product from the reactions of HO<sub>2</sub> with three other
carbonyl-containing peroxy radicals, albeit at smaller yield, e.g. (R2):
HO<sub>2</sub>+CH<sub>3</sub>C(O)CH<sub>2</sub>O<sub>2</sub>→(products), α<sub>2</sub>≈0.15.
By contrast, OH was not observed (α<0.06)
as a major product from reactions where carbonyl functionality was absent,
e.g. HO<sub>2</sub>+HOCH<sub>2</sub>CH<sub>2</sub>O<sub>2</sub> (R8), and HO<sub>2</sub>+CH<sub>3</sub>CH(OH)CH<sub>2</sub>O<sub>2</sub> (R9).
Andersen, M. P. S., Hurley, M. D., Wallington, T. J., Ball, J. C., Martin, J. W., Ellis, D. A., and Mabury, S. A.: Atmospheric chemistry of C<sub>2</sub>F$_5$CHO: mechanism of the C<sub>2</sub>F$_5$C(O)O<sub>2</sub>+HO<sub>2</sub> reaction, Chem. Phys. Lett., 381, 14–21, 2003.
Atkinson, R. and Arey, J.: Gas-phase tropospheric chemistry of biogenic volatile organic compounds: a review, Atmos. Environ., 37, S197–S219, 2003.
Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes, R. G., Jenkin, M. E., Kerr, J. A., Rossi, M. J., and Troe, J.: IUPAC Subcommittee for gas kinetic data evaluation. Evaluated kinetic data: http://www.iupac-kinetic.ch.cam.ac.uk/, 2007.
Bailey, A. E., Heard, D. E., Paul, P. H., and Pilling, M. J.: Collisional quenching of OH ($A^2§igma ^+$, ν'=0) by N<sub>2</sub>, O<sub>2</sub> and CO<sub>2</sub> between 204 and 294 K. Implications for atmospheric measurements of OH by laser-induced fluorescence, Journal of the Chemical Society-Faraday Transactions, 93, 2915–2920, 1997.
Bridier, I., Veyret, B., Lesclaux, R., and Jenkin, M. E.: Flash-Photolysis Study of the UV Spectrum and Kinetics of Reactions of the Acetonylperoxy Radical, Journal of the Chemical Society-Faraday Transactions, 89, 2993–2997, 1993.
Carr, S. A., Baeza-Romero, M. T., Blitz, M. A., Pilling, M. J., Heard, D. E., and Seakins, P. W.: OH yields from the CH<sub>3</sub>CO+O<sub>2</sub> reaction using an internal standard, Chem. Phys. Lett., 445, 108–112, 2007.
Crawford, M. A., Wallington, T. J., Szente, J. J., Maricq, M. M., and Francisco, J. S.: Kinetics and mechanism of the acetylperoxy plus HO<sub>2</sub> reaction, J. Phys. Chem. A, 103, 365–378, 1999.
Curtis, A. R. and Sweetenham, W. P.: Facsimile, AERE, Report R-12805, 1987.
Dillon, T. J., Hölscher, D., Sivakumaran, V., Horowitz, A., and Crowley, J. N.: Kinetics of the reactions of HO with methanol (210–351 K) and with ethanol (216–368 K), Phys. Chem. Chem. Phys., 7, 349–355, 2005.
Dillon, T. J., Horowitz, A., and Crowley, J. N.: Absolute rate coefficients for the reactions of O($^1$D) with a series of n-alkanes, Chem. Phys. Lett., 14, 12–16, 2007.
Dillon, T. J., Horowitz, A., Hölscher, D., and Crowley, J. N.: Reaction of HO with hydroxyacetone (HOCH<sub>2</sub>C(O)CH$_3)$: rate coefficients and mechanism., Phys. Chem. Chem. Phys., 8, 236–246, 2006a.
Dillon, T. J., Tucceri, M. E., and Crowley, J. N.: Laser induced fluorescence studies of IO kinetics, part 2: Reaction of IO with CH<sub>3</sub>O<sub>2</sub>, CF<sub>3</sub>O<sub>2</sub> and O$_3 $at 298 K, Phys. Chem. Chem. Phys., 8, 5185–5198, 2006b.
Dillon, T. J., Tucceri, M. E., Sander, R., and Crowley, J. N.: LIF studies of iodine oxide chemistry, Part 3. Reactions IO + NO$_3->$ OIO + NO<sub>2</sub>, I + NO$_3->$ IO + NO<sub>2</sub>, and CH<sub>2</sub>I + O$_2->$ (products): implications for the chemistry of the marine atmosphere at night, Phys. Chem. Chem. Phys., 10, 1540–1554, 2008.
Gierczak, T., Gilles, M. K., Bauerle, S., and Ravishankara, A. R.: Reaction of hydroxyl radical with acetone, 1. Kinetics of the reactions of OH, OD, and $^18$OH with acetone and acetone-D$_6$, J. Phys. Chem. A, 107, 5014–5020, 2003.
Hasson, A. S., Kuwata, K. T., Arroyo, M. C., and Petersen, E. B.: Theoretical studies of the reaction of hydroperoxy radicals (HO$_2)$ with ethyl peroxy (CH<sub>3</sub>CH<sub>2</sub>O$_2)$, acetyl peroxy (CH<sub>3</sub>C(O)O$_2)$ and acetonyl peroxy (CH<sub>3</sub>C(O)CH<sub>2</sub>O$_2)$ radicals, J. Phtochem. Photobiol, A Chemistry, 176, 218–230, 2005.
Hasson, A. S., Tyndall, G. S., and Orlando, J. J.: A product yield study of the reaction of HO<sub>2</sub> radicals with ethyl peroxy (C<sub>2</sub>H$_5$O$_2)$, acetyl peroxy (CH<sub>3</sub>C(O)O$_2)$, and acetonyl peroxy (CH<sub>3</sub>C(O)CH<sub>2</sub>O$_2)$ radicals, J. Phys. Chem. A, 108, 5979–5989, 2004.
Horie, O. and Moortgat, G. K.: Reactions of CH<sub>3</sub>C(O)O<sub>2</sub> Radicals with CH<sub>3</sub>O<sub>2</sub> and HO<sub>2</sub> between 263 and 333 K – a Product Study, Journal of the Chemical Society-Faraday Transactions, 88, 3305–3312, 1992.
Jenkin, M. E., Hurley, M. D., and Wallington, T. J.: Investigation of the radical product channel of the CH<sub>3</sub>C(O)O<sub>2</sub>+HO<sub>2</sub> reaction in the gas phase, Phys. Chem. Chem. Phys., 9, 3149–3162, 2007.
Karunanandan, R., Hölscher, D., Dillon, T. J., Horowitz, A., and Crowley, J.: Reaction of HO with glycolaldehyde, HOCH<sub>2</sub>CHO: Rate coefficients (240–362 K) and mechanism, J. Phys. Chem. A, 111, 897–908, 2007.
Le Crane, J. P., Rayez, M. T., Rayez, J. C., and Villenave, E.: A reinvestigation of the kinetics and the mechanism of the CH<sub>3</sub>C(O)O<sub>2</sub>+HO<sub>2</sub> reaction using both experimental and theoretical approaches, Phys. Chem. Chem. Phys., 8, 2163–2171, 2006.
Lightfoot, P. D., Cox, R. A., Crowley, J. N., Destriau, M., Hayman, G. D., Jenkin, M. E., Moortgat, G. K., and Zabel, F.: Organic peroxy radicals: kinetics, spectroscopy and tropospheric chemistry, Atmos. Environ., 264, 1805–1964, 1993.
Moortgat, G. K., Veyret, B., and Lesclaux, R.: Kinetics of the Reaction of HO<sub>2</sub> with CH<sub>3</sub>C(O)O<sub>2</sub> in the Temperature-Range 253–368 K, Chem. Phys. Lett., 160, 443–447, 1989.
Niki, H., Maker, P. D., Savage, C. M., and Breitenbach, L. P.: Ftir Study of the Kinetics and Mechanism For Cl-Atom-Initiated Reactions of Acetaldehyde, J. Phys. Chem., 89, 588–591, 1985.
Salahub, D. R. and Sandorfy, C.: Far-Ultraviolet Spectra of Some Simple Alcohols and Fluoroalcohols, Chem. Phys. Lett., 8, 71–74, 1971.
Tomas, A., Villenave, E., and Lesclaux, R.: Reactions of the HO<sub>2</sub> radical with CH<sub>3</sub>CHO and CH<sub>3</sub>C(O)O<sub>2</sub> in the gas phase, J. Phys. Chem. A, 105, 3505–3514, 2001.
Tyndall, G. S., Cox, R. A., Granier, C., Lesclaux, R., Moortgat, G. K., Pilling, M. J., Ravishankara, A. R., and Wallington, T. J.: Atmospheric chemistry of small organic peroxy radicals, J. Geophys. Res., 106, 12 157–12 182, 2001.
Tyndall, G. S., Orlando, J. J., Kegley-Owen, C. S., Wallington, T. J., and Hurley, M. D.: Rate coefficients for the reactions of chlorine atoms with methanol and acetaldehyde, Int. J. Chem. Kin., 31, 776–784, 1999.
Wollenhaupt, M., Carl, S. A., Horowitz, A., and Crowley, J. N.: Rate coefficients for reaction of OH with acetone between 202 and 395 K, J. Phys. Chem. A, 104, 2695–2705, 2000.