The Journal of Physical Chemistry A
ARTICLE
also produces OH, it can also explain the environmental chamber
observation of significant OH regeneration.
(10) Nishino, N.; Arey, J.; Atkinson, R. J. Phys. Chem. A 2010,
114, 10140.
(
11) Gomez Alvarez, E.; Viidanoja, J.; Munoz, A.; Wirtz, K.; Hjorth,
J. Environ. Sci. Technol. 2007, 41, 8362.
kinetics/index.jsp, accessed 3/21/11
13) Miller, A. M.; Yeung, L. Y.; Kiep, A. C.; Elrod, M. J. Phys. Chem.
Chem. Phys. 2004, 6, 3402.
14) Seeley, J. V.; Meads, R. F.; Elrod, M. J.; Molina, M. J. J. Phys.
Within the uncertainty limits of our product yield measure-
ments, we determined that the yields of the unsaturated dicar-
bonyl compounds, formed through the bicyclic peroxy radical
ring scission pathway, were in stoichiometric equivalence (i.e.,
obeyed the carbon conservation rule) with the 1,2-dicarbonyl
yields measured in previous photochemical environmental
(
(
(
9,10
chamber techniques.
Because many of these unsaturated
Chem. 1996, 100, 4026.
dicarbonyl compounds were measured in lower yields in the
environmental chamber measurements and our experiments
were photochemically dark and wall-less, it seems likely that
these species are undergoing secondary chemistry under the
conditions of the environmental chamber experiments.
The overall product yields were in reasonable agreement with
the predictions from the MCM. However, we measured a
number of potentially important products not currently included
in the MCM (dienedials and stable bicyclic species for all
aromatic systems). Our results also suggest that the phenolic
yields for the xylenes are too high and the H-abstraction yields for
ethylbenzene are too low in the current version of the MCM.
(15) Baltaretu, C. O.; Lichtman, E. I.; Hadler, A. B.; Elrod, M. J.
J. Phys. Chem. A 2009, 113, 221.
(16) Zhao, J.; Zhang, R.; Misawa, K.; Shibuya, K. J. Photochem.
Photobiol., A 2005, 176, 199.
(17) Wyche, K. P.; Monks, P. S.; Ellis, A. M.; Cordell, R. L.; Parker,
A. E.; Whyte, C.; Metzger, A.; Dommen, J.; Duplissy, J.; Prevot, A. S. H.;
Baltensperger, U.; Rickard, A. R.; Wulfert, F. Atmos. Chem. Phys. 2009,
, 635.
9
(
(
18) Berndt, T.; Boge, O. Phys. Chem. Chem. Phys. 2001, 3, 4946.
19) Seeley, J. V.; Jayne, J. T.; Molina, M. J. Int. J. Chem. Kinet. 1993,
2
5, 571.
(20) Seuwen, R.; Warneck, P. Int. J. Chem. Kinet. 1996, 28, 315.
(21) Berndt, T.; B €o ge, O. Phys. Chem. Chem. Phys. 2006, 8, 1205.
(22) Becker, K. H.; Barnes, I.; Bierbach, A.; Brockmann, K. J.;
Kirchner, F. Chemical Processes in Atmospheric Oxidation; Springer-
Verlag: Berlin, 1997; p 79.
’
ASSOCIATED CONTENT
Supporting Information.
(
23) Jenkin, M. E.; Hayman, G. D. J. Chem. Soc., Faraday Trans.
1995, 91, 1911.
24) Hasson, A. S.; Tyndall, G. S.; Orlando, J. J. J. Phys. Chem. A
2004, 108, 5979.
S
Three tables containing the
b
data graphically depicted in Figures 7ꢀ9. This material is
(
available free of charge via the Internet at http://pubs.acs.org.
(25) Dillon, T. J.; Crowley, J. N. Atmos. Chem. Phys. 2008, 8, 4877.
’
AUTHOR INFORMATION
Corresponding Author
*E-mail: mjelrod@oberlin.edu.
’
ACKNOWLEDGMENT
This material is based upon work supported by the National
Science Foundation under Grant No. 0753103.
’
REFERENCES
(1) Velasco, E.; Lamb, B.; Westberg, H.; Allwine, E.; Sosa, G.;
Arriaga-Colina, J. L.; Jobson, B. T.; Alexander, M. L.; Prazeller, P.;
Knighton, W. B.; Rogers, T. M.; Grutter, M.; Herndon, S. C.; Kolb, C. E.;
Zavala, M.; de Foy, B.; Volkamer, R.; Molina, L. T.; Molina, M. J.
J. Atmos. Chem. Phys. 2007, 7, 329.
(
2) Offenberg, J. H.; Lewis, C. W.; Lewandowski, M.; Jaoui, M.;
Kleindienst, T. E.; Edney, E. O. Environ. Sci. Technol. 2007, 41, 3972.
3) The Mechanisms of Atmospheric Oxidation of Aromatic Hydro-
(
carbons; Calvert, J. G., Atkinson, R., Becker, K. H., Kamens, R. M.,
Seinfeld, J. H., Wallington, T. J., Yarwood, G., Eds.; Oxford University
Press: Oxford, 2002.
(
4) Bloss, C.; Wagner, V.; Jenkin, M. E.; Volkamer, R.; Bloss, W. J.;
Lee, J. D.; Heard, D. E.; Wirtz, K.; Martin-Reviejo, M.; Rea, G.; Wenger,
J. C.; Pilling, M. J. Atmos. Chem. Phys. 2005, 5, 641.
(
5) Wagner, V.; Jenkin, M. E.; Saunders, S. M.; Stanton, J.; Wirtz, K.;
Pilling, M. J. Atmos. Chem. Phys. 2003, 3, 89.
6) Birdsall, A. W.; Andreoni, J. F.; Elrod, M. J. J. Phys. Chem. A 2010,
14, 10655.
7) Noda, J.; Volkamer, R.; Molina, M. J. J. Phys. Chem. A 2009,
13, 9658.
(
1
1
4
(
(8) Aschmann, S. M.; Arey, J.; Atkinson, R. Atmos. Environ. 2010,
4, 3970.
(
9) Arey, J.; Obermeyer, G.; Aschmann, S. M.; Chattopadhyay, S.;
Cusick, R. D.; Atkinson, R. Environ. Sci. Technol. 2009, 43, 683.
5
407
dx.doi.org/10.1021/jp2010327 |J. Phys. Chem. A 2011, 115, 5397–5407