Atmospheric chemistry of benzene oxide/oxepin

Abstract

The atmospheric chemistry of benzene oxide/oxepin, a possible intermediate in the atmospheric oxidation of aromatic hydrocarbons, has been investigated in a large volume photoreactor at 298 K and atmospheric pressure using in situ FTIR spectroscopy for the analysis. Rate coefficients of (10.0±0.4)×10^-11 and (9.2±0.3)×10^-12 cm³ molecule^-1 s^-1 have been determined for the reaction of benzene oxide/oxepin with OH and NO₃ radicals, respectively. Reaction with OH radicals produces almost exclusively the (E,Z)- and (E,E)-isomers of hexa-2,4-dienedial, whereas reaction with NO₃ produces (Z,Z)-hexa-2,4-dienedial and unidentified organic nitrates. Phenol has been observed as a major product of the thermal decomposition, visible and UV photolysis of benzene oxide/oxepin. The results are discussed in conjunction with the oxidation mechanisms of aromatic hydrocarbons. The major atmospheric sinks of benzene oxide/oxepin will be reaction with OH radicals and photolysis and, under smog chamber conditions with high NO₂ concentrations, also reaction with NO₃.

References

1. J. H. Seinfeld, Science, 1989, 243, 745.
2. D. Gao, W. R. Stockwell and J. B. Milford, J. Geophys. Res., 1995, 100, 23153.
3. R. G. Derwent, M. E. Jenkin and S. M. Saunders, Atmos. Environ., 1996, 30, 181.
4. R. Atkinson, J. Phys. Chem. Ref. Data, Monograph No. 2, 1994.
5. R. Knispel, R. Koch, M. Siese and C. Zetzsch, Ber. Bunsen-Ges. Phys. Chem., 1990, 94, 1375.
6. R. Seuwen and P. Warneck, Int. J. Chem. Kinet., 1996, 28, 315.
7. K. H. Becker, in Transport and Transformation of Pollutants in the Troposphere, ed. P. M. Borrell, P. Borrell, T. Cvitas and W. Seiler, SPB Academic Publishing, The Hague, Netherlands, 1994, p. 67.
8. M. Siese, R. Koch, C. Fittschen and C. Zetsch, in ref. 7, p. 115.
9. L. J. Bartolotti and E. O. Edney, Chem. Phys. Lett., 1995, 245, 119.
10. X. M. Pan, M. N. Schuchmann and C. von Sonntag, J. Chem. Soc., Perkin Trans. 2, 1993, 289.
11. A. Bierbach, I. Barnes, K. H. Becker and E. Weisen, Environ. Sci. Technol., 1994, 28, 715.
12. J. M. Andino, J. N. Smith, R. C. Flagan, W. A. Goddard III and J. H. Seinfeld, J. Phys. Chem., 1996, 100, 10967.
13. T. H. Lay, J. W. Bozelli and J. H. Seinfeld, J. Phys. Chem., 1996, 100, 6543.
14. B. E. Dumdei and R. J. O'Brien, Nature (London), 1984, 311, 248.
15. H. Jeffries, in Chemical Mechanisms Describing Oxidation Processes in the Troposphere, ed. K. H. Becker, Wuppertal workshop held at Palacio Pineda, Valencia, Spain, April 25–28, 1995, p. 50.
16. I. Barnes and K. H. Becker, in Regional Photochemical Measurement and Modeling Studies, ed. A. J. Ranzieri and P. A. Solomon. Air & Waste Management Association, San Diego, CA, 1995, vol. I, p. 80.
17. P. B. Shepson, E. O. Edney and E. W. Corse, J. Chem. Phys., 1984, 88, 4122.
18. R. Snyder, G. Witz and B. D. Goldstein, Environ. Health Persp., 1993, 100, 293.
19. D. M. Jerina, J. W. Daly, B. Witkop, P. Zaltzman-Nierenberg and S. Udenfriend, J. Am. Chem. Soc., 1968, 90, 6525.
20. W. Levin, D. R. Thakker, A. W. Wood, R. L. Chang, R. E. Lehr, D. M. Jerina and A. H. Conney, Cancer Res., 1978, 38, 1705.
21. W. Levin, A. Wood, R. Chang, D. Ryan, P. Thomas, H. Yagi, D. Thakker, K. Vyas, C. Boyd and S.-Y. Chu, Drug Metab. Rev., 1982, 13, 555.
22. K. Nojima, T. Ohya, S. Kanno and M. Hirobe, Chem. Pharm. Bull., 1982, 30, 4566.
23. I. Barnes, K. H. Becker and N. Mihalopoulos, J. Atmos. Chem., 1994, 18, 267.
24. B. Klotz, A. Bierbach, I. Barnes and K. H. Becker, Environ. Sci. Technol., 1995, 29, 2332.
25. R. Atkinson, Chem. Rev., 1986, 86, 69.
26. R. Atkinson, S. M. Aschmann and J. N. Pitts Jr., J. Phys. Chem., 1988, 92, 3454.
27. J. R. Gillard, M. J. Newlands, J. N. Bridson and D. J. Burnell, Can. J. Chem., 1991, 69, 1377.
28. E. Vogel and H. Günther, Angew. Chem., 1967, 79, 429; Angew. Chem., Int. Ed. Engl., 6, 385.
29. G. Colot, A. Krief and J.-M. André, Bull. Soc. Chim. Belg., 1975, 84, 897.
30. D. M. Hayes, S. D. Nelson, W. A. Garland and P. A. Kollman, J. Am. Chem. Soc., 1980, 102, 1255.
31. R. Thieme and C. Weiss, Stud. Biophys., 1983, 93, 273.
32. C. W. Bock, P. George, J. J. Stezowski and J. P. Glusker, Struct. Chem., 1990, 1, 33.
33. I. Mani and M. C. Sauer Jr., Adv. Chem. Ser., 1968, 82, 142.
34. D. M. Jerina, B. Witkop, C. L. McIntosh and O. L. Chapman, J. Am. Chem. Soc., 1974, 96, 5578.
35. J. M. Holovka and P. D. Gardner, J. Am. Chem. Soc., 1967, 89, 6390.
36. B. J. Finlayson-Pitts and J. Finlayson Jr., Atmospheric Chemistry, Wiley, New York, 1986.
37. K. L. Demerjian, K. L. Schere and J. T. Peterson, Environ. Sci. Technol., 1980, 10, 369.
38. R. Prinn, D. Cunnold, P. Simmonds, F. Alyea, R. Boldi, A. Crawford, P. Fraser, D. Gutzler, D. Hartley, R. Rosen and R. Rasmussen, J. Geophys. Res., 1992, 97, 2445.
39. P. J. Crutzen and P. H. Zimmermann, Tellus A, 1991, 43, 136.
40. E. C. Tuazon, H. MacLeod, R. Atkinson and W. P. L. Carter, Environ. Sci. Technol., 1986, 20, 383.
41. B. T. Golding, G. Kennedy and W. P. Watson, Tetrahedron Lett., 1988, 29, 5991.
42. R. P. Wayne, I. Barnes, P. Biggs, J. P. Burrows, C. E. Canosa-Mas, J. Hjorth, G. Le Bras, G. K. Moortgat, D. Perner, G. Poulet, G. Restelli and H. Sidebottom, Atmos. Environ. A, 1991, 25, 1.
43. S. G. Davies and G. H. Whitham, J. Chem. Soc., Perkin 1, 1977, 1347.
44. J. M. Roberts, Atmos. Environ. A, 1990, 24, 243.
45. I. Barnes, V. Bastian, K. H. Becker and Z. Tong, J. Phys. Chem., 1990, 94, 2413.
46. I. Barnes, K. J. Brockmann, B. Klotz, I. Patroescu, T. Etzkorn, R. Volkamer, J. Bea, M. Martín-Reviejo and K. Wirtz, in The European Photoreactor EUPHORE, ed. K. H. Becker, Final Report of the EC-Project Contract EV5V-CT92-0059, February 1996, p. 111.
47. W. P. L. Carter, Atmos. Environ. A, 1990, 24, 481.