Mechanisms of atmospheric oxidation of the alkanes

Jack G Calvert, Richard G Derwent, John J Orlando, Geoffrey S Tyndall, Timothy J Wallington019536581X, 9780195365818, 9780199710881

An international team of eminent atmospheric scientists have prepared Mechanisms of Atmospheric Oxidation of the Alkanes as an authoritative source of information on the role of alkanes in the chemistry of the atmosphere. The book includes the properties of the alkanes and haloalkanes, as well as a comprehensive review and evaluation of the existing literature on the atmospheric chemistry of the alkanes and their major atmospheric oxidation products, and the various approaches now used to model the alkane atmospheric chemistry. Comprehensive coverage is given of both the unsubstituted alkanes and the many haloalkanes. All the existing quality measurements of the rate coefficients for the reactions of OH, Cl, O(3P), NO3, and O3 with the alkanes, the haloalkanes, and their major oxidation products have been reviewed and evaluated. The expert authors then give recommendations of the most reliable kinetic data. They also review the extensive literature on the mechanisms and rates and modes of photodecomposition of the haloalkanes and the products of atmospheric oxidation of the alkanes and the haloalkanes, and make recommendations for future use by atmospheric scientists. The evaluations presented allow an extrapolation of the existing kinetic and photochemical data to those alkanes and haloalkanes that are as yet unstudied. The current book should be of special interest and value to the modelers of atmospheric chemistry as a useful input for development of realistic modules designed to simulate the atmospheric chemistry of the alkanes, their major oxidation products, and their influence on ozone and other trace gases within the troposphere.

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Table of contents :
Contents……Page 8
Acknowledgments……Page 6
About the Authors……Page 10
I-A: Introduction to the Alkanes……Page 16
I-B: Structure and Properties of the Alkanes……Page 17
I-C: General Survey of the Atmospheric Chemistry of the Alkanes……Page 21
I-D: The Role of Alkanes in Urban Photochemical Ozone Formation……Page 26
I-E: The Role of Alkanes in Regional-Scale Photochemical Ozone Formation……Page 32
I-F: The Role of Alkanes in Global Tropospheric Chemistry……Page 40
I-G: Alkanes and the Greenhouse Effect……Page 52
I-H: The Role of Alkanes in Stratospheric Chemistry and Ozone Layer Depletion……Page 55
II: REACTIONS OF ALKANES WITH THE HYDROXYL RADICAL (OH)……Page 58
II-A: Introduction……Page 59
II-B: Rate Coefficients for the Reactions of OH with the Alkanes……Page 63
II-C: Reactions of OH with Cycloalkanes……Page 97
II-D: Reactions of OH with Isotopically Substituted Alkanes at Natural Abundance……Page 110
II-E: Estimation and Prediction of Rate Coefficients of OH with Alkanes……Page 112
II-F: Estimation of Rate Coefficients for Substituted Molecules……Page 115
III-A: Introduction……Page 117
III-B: Reactions of Cl-Atoms with Alkanes……Page 118
III-C: Reactions of O([sup(3)]P) with Alkanes……Page 158
III-D: Reactions of NO[sub(3)] Radicals with Alkanes……Page 168
III-E: Reactions of Ozone with Alkanes……Page 182
III-F: Correlations between Rate Coefficients for Reactions of OH, Cl, O([sup(3)]P), and NO[sub(3)] with the Alkanes……Page 185
IV: MECHANISMS AND END-PRODUCTS OF THE ATMOSPHERIC OXIDATION OF ALKANES……Page 187
IV-A: Peroxy Radical Chemistry……Page 189
IV-B: Alkoxy Radical Chemistry……Page 217
IV-C: Major Products of the Atmospheric Oxidation of the Alkanes……Page 253
V-A: Introduction……Page 302
V-B: Reactions of Ozone with Oxygenated Products from Alkane Oxidation……Page 303
V-C: Reactions of Hydroxy Radicals with Products of Alkane Reactions……Page 304
V-D: Reactions of Nitrate Radicals (NO[sub(3)]) with Products of Alkane Oxidation……Page 375
VI-A: Rate Coefficients for OH-Radical Reactions with the Haloalkanes……Page 392
VI-B: Cl, O([sup(3)]P), NO[sub(3)], and O[sub(3)] Reactions with the Haloalkanes……Page 523
VI-C: Rules for Empirical Estimation of Rate Coefficients for OH–Haloalkane Reactions……Page 525
VI-D: Atmospheric Chemistry of Haloalkylperoxy Radicals……Page 530
VI-E: Atmospheric Chemistry of the Haloalkoxy Radicals……Page 558
VI-F: Major Products of Atmospheric Oxidation of the Haloalkanes……Page 599
VII-A: Introduction……Page 617
VII-B: Photodecomposition of Aldehydes……Page 622
VII-C: Photodecomposition of Acylic Ketones……Page 685
VII-D: Photodecomposition of Cyclic Ketones……Page 738
VII-E: Photodecomposition of Alkyl Halides……Page 758
VII-F: Photodecomposition of Halogen-Atom- and HO-Substituted Aldehydes……Page 775
VII-G: Photodecomposition of Halogen-Atom- and HO-Substituted Ketones……Page 791
VII-H: Photodecomposition of Acyl Halides and Carbonyl Halides……Page 811
VII-I: Photodecomposition of Alkyl Nitrates (RONO[sub(2)])……Page 822
VII-J: Photodecomposition of Peroxyacyl Nitrates [RC(O)OONO[sub(2)]]……Page 829
VII-K: Photodecomposition of Alkyl Hydroperoxides (ROOH)……Page 837
VII-L: Summary of Photochemical Processes……Page 839
VIII-A: Policy Applications of Atmospheric Chemistry Models……Page 844
VIII-B: Representation of the Atmospheric Chemistry of the Alkanes in Urban and Regional Photochemical Ozone Models……Page 850
VIII-C: Determination of VOC Reactivity Scales……Page 868
References……Page 878
APPENDIX A: STRUCTURES OF SOME COMMON ALKANES……Page 940
APPENDIX B: STRUCTURES OF SOME COMMON HALOALKANES……Page 945
APPENDIX C: STRUCTURES OF SOME COMMON ATMOSPHERIC OXIDATION PRODUCTS OF THE ALKANES……Page 955
A……Page 968
B……Page 969
C……Page 971
D……Page 973
F……Page 975
G……Page 976
H……Page 977
J……Page 979
K……Page 980
L……Page 981
M……Page 983
N……Page 985
P……Page 986
R……Page 988
S……Page 989
T……Page 991
U……Page 992
W……Page 993
Z……Page 995
A……Page 996
C……Page 997
D……Page 998
H……Page 999
M……Page 1002
N……Page 1003
R……Page 1004
T……Page 1005