A structure‐activity relationship for the estimation of rate constants for the gas‐phase reactions of OH radicals with organic compounds

International Journal of Chemical Kinetics - Tập 19 Số 9 - Trang 799-828 - 1987
Roger Atkinson1
1Statewide Air Pollution Research Center, University of California, Riverside, California 92521

Tóm tắt

AbstractA previous technique for the calculation of rate constants for the gas‐phase reactions of the OH radical with organic compounds has been updated and extended to include sulfur‐ and nitrogen‐containing compounds. The overall OH radical reaction rate constants are separated into individual processes involving (a) H‐atom abstraction from CH and OH bonds in saturated organics, (b) OH radical addition to >CC< and CC unsaturated bonds, (c) OH radical addition to aromatic rings, and (d) OH radical interaction with NH2, >NH, >N, SH, and S groups. During its development, this estimation technique has been tested against the available database, and only for 18 out of a total of ca. 300 organic compounds do the calculated and experimental room temperature rate constants disagree by more than a factor of 2. This suggests that this technique has utility in estimating OH radical reaction rate constants at room temperature and atmospheric pressure of air, and hence atmospheric lifetimes due to OH radical reaction, for organic compounds for which experimental data are not available. In addition, OH radical reaction rate constants can be estimated over the temperature range ca. 250–1000 K for those organic compounds which react via H‐atom abstraction from CH and OH bonds, and over the temperature range ca. 250–500 K for compounds containing >CC< bond systems.

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Tài liệu tham khảo

Finlayson‐Pitts B. J., 1986, Atmospheric Chemistry: Fundamentals and Experimental Techniques

10.1021/cr00063a002

10.1021/cr00071a004

10.1021/es00120a012

10.1063/1.1674099

10.1021/j100503a001

D. G.HendryandR. A.Kenley “Atmospheric Reaction Products of Organic Compounds” EPA‐560/12‐79‐001 June1979.

10.1002/kin.550130706

10.1002/kin.550141206

10.1002/kin.550111106

10.1002/kin.550121009

10.1016/0047-2670(81)85273-2

10.1007/BF00127264

10.1007/BF00367401

10.1002/kin.550170102

10.1021/j100285a037

10.1016/0004-6981(81)90166-9

Klopffer W., 1985, Z. Naturforsch, 40, 686, 10.1515/zna-1985-0706

W. L.Dilling G. U.Boggs andC. G.Mendoza Presented at the 192nd National Meeting of the American Chemical Society Anaheim CA September 7–12 1986.

J. E.Davenport D. G.Hendry L.Gu andT.Mill Presented at the 192nd National Meeting of the American Chemical Society Anaheim CA September 7–12 1986.

10.1002/kin.550180506

L.Nelson J. J.Treacy andH. W.Sidebottom Proceedings of the 3rd European Symposium on the Physico‐Chemical Behavior of Atmospheric Pollutants D. Riedel Dordrecht 1984 pp.258–263.

J. A.McCaulley N.Mendoza J. L.Durant S. M.Anderson andF.Kaufmann Presented at the 17th Informal Conference on Photochemistry University of Colorado Boulder CO June 22–26 .

10.1146/annurev.pc.33.100182.002425

10.1007/BF00052004

D.Hartmann A.Gedra D.Rhäsa andR.Zellner Proceedings of the 4th European Symposium on the Physico‐Chemical Behavior of Atmospheric Pollutants D. Riedel Dordrecht in press (1987).

10.1016/0009-2614(77)80388-6

10.1002/9780470133415.ch5

10.1016/0009-2614(78)85422-0

S. S.Zabarnick J. W.Fleming A. P.Baronavski andM. C.Lin Proceedings of the 17th International Symposium on Free Radicals Snow Mountain Ranch CO August 18-23 1985

NBS Special Publication 716 1986 pp. 731-756.

Benson S. W., 1976, Thermochemical Kinetics

10.1002/kin.550180311

10.1002/kin.550140810

10.1002/kin.550160904

10.1002/kin.550190308

10.1002/kin.550160308

10.1021/j100273a039

10.1002/kin.550180509

10.1002/kin.550181207

E. C.Tuazon R.Atkinson S. M.Aschmann M. A.Goodman andA. M.Winer Int. J. Chem. Kinet. to be submitted for publication (1987).

10.1246/bcsj.58.2157

10.1021/j100408a062

10.1002/kin.550161215

10.1007/BF00053845

C.Zetzsch Presented at 15th Informal Conference on Photochemistry Stanford CA June 27–July 1 1982.

10.1007/BF01055527

10.1021/ja01551a055

10.1021/j100405a040

10.1002/bbpc.19840880114

10.1021/es00155a007

R.AtkinsonandS. M.Aschmann unpublished data (1987).

10.1021/es00157a013

E. C.Tuazon S. M.Aschmann R.Atkinson andA. M.Winer unpublished data (1987).

R.AtkinsonandS. M.Aschmann Atmos. Environ. in press (1987).

10.1021/es00133a004

Rosenstock H. M., 1977, J. Phys. Chem. Ref. Data, 6

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International Journal of Chemical Kinetics

Tập 19 Số 9

799-828

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