The Mechanisms of Atmospheric Oxidation of the Alkenes

by Calvert, J. G.; Atkinson, R.; Kerr, J. A.; Madronich, Sasha; Moortgat, G. K.; Wallington, Timothy J.; Yarwood, G.

• ISBN13: 9780195131772
• ISBN10: 0195131770
• Format: Hardcover
• Copyright: 2000-04-06
• Publisher: Oxford University Press

Summary

The formation of smog in urban atmospheres involves the interaction of sunlight with an air mixture containing nitrogen oxides and reactive hydrocarbons -- the most reactive class of these hydrocarbons being alkenes. This important new book, by a team of leading atmospheric chemists, reviews and evaluates the existing literature on the atmospheric chemistry of these compounds, focusing on the search for a more quantitative understanding of the phenomenon which can then be applied to control methods. It includes detailed examinations of the reactions of alkenes and even suggests areas for further laboratory studies. This book is ideal for climatologists, meteorologists, and scientists studying the chemistry of the atmosphere and can also serve as a valuable text for graduate courses in atmospheric chemistry and atmospheric science.

Table of Contents

Acknowledgments	vii
Importance of Alkenes in the Chemistry of Ozone Generation in the Urban Atmosphere	3	(20)
Typical Composition of the Hydrocarbons Present in Urban Air	4	(8)
Relative Importance of OH, NO3, O3, and O(3P) as Reactants for Alkenes	12	(4)
Importance of Alkenes Relative to Other Volatile Organic Compounds as Reactants for OH, NO3, and O3	16	(1)
Relative Importance of Individual Alkenes	17	(6)
Reaction of Alkenes with the OH Radical	23	(104)
Mechanisms of the OH-Alkene Reactions	23	(10)
Measured Rate Coefficients for OH--Alkene Reactions	33	(57)
Estimation of Rate Coefficients for OH--Alkene Reactions	90	(3)
Major Products of the Reactions of OH with Alkenes	93	(13)
Reactions of HOCxHyO2 Radicals Formed Following OH Addition to the Alkene Double Bond	106	(7)
Reactions of HOCxHyO Radicals Formed from HOCxHyO2 Radicals	113	(14)
Reactions of Alkene with the NO3 Radical	127	(45)
Mechanisms of the NO3--Alkene Reactions	127	(5)
Measured Rate Coefficients for NO3--Alkene Reactions	132	(30)
Estimation of Rate Coefficients for NO3--Alkene Reactions	162	(2)
Major Products of the Reaction of NO3 Radicals with Alkenes	164	(8)
Reactions of Alkenes with O3	172	(64)
Mechanisms of the Ozone--Alkene Reactions	174	(1)
Measured Rate Coefficients for O3--Alkene Reactions	174	(57)
Estimation of Rate Coefficients for O3--Alkene Reactions	231	(4)
Products and Mechanism of the Reaction of Ozone with Alkenes	235	(1)
Reactions of Alkenes with O(3P)--Atoms and NO2	236	(111)
Measured Rate Coefficients for O(3P)--Alkene Reactions	338	(4)
Products and Mechanism of Alkene--O(3P) Reactions	342	(2)
Thermal Reactions of Alkenes with NO2	344	(3)
Rate Coefficients of OH, NO3, and O3 Reactions with the First-Generation Atmospheric Oxidation Products of Alkenes	347	(21)
Reactions of OH Radicals with Oxygen-Containing Organic Compounds	348	(14)
Reactions of NO3 Radical with Oxygen-Containing Organic Compounds	362	(4)
Reactions of O3 with Oxygen-Containing Organic Compounds	366	(2)
Primary Photochemical Processes in Some Important Light-Absorbing Products of Atmospheric Oxidation of the Alkenes	368	(39)
Photolysis Model Description	369	(2)
Formaldehyde	371	(8)
Ethanal (Acetaldehyde)	379	(7)
Propanal (Propionaldehyde)	386	(3)
Glyoxal	389	(3)
Methylglyoxal	392	(3)
Acetone	395	(6)
Methyl Hydroperoxide	401	(1)
Methyl Nitrate	402	(5)
Application of Findings to the Modeling of Alkene Atmospheric Chemistry	407	(6)
Atmospheric Chemistry Modeling Methods	407	(3)
Some Special Considerations of Chemical Mechanisms that Simulate Alkene Atmospheric Oxidation	410	(3)
Important Areas for Further Laboratory Studies	413	(9)
Areas of Greatest Uncertainty in the Mechanisms of the Atmospheric Oxidation of Alkenes	414	(6)
A Qualitative Prioritization of the Research Efforts in Areas Suggested for Further Studies	420	(2)
Summary	422	(8)
Importance of Alkenes in the Chemistry of Ozone Generation in the Urban Atmosphere	422	(1)
Reactions of Alkenes with the OH Radical	423	(1)
Reactions of Alkenes with the NO3 Radical	424	(1)
Reactions of Alkenes with O3	425	(2)
Reactions of Alkenes with O(3P)-Atoms and NO2	427	(1)
Rate Coefficients of OH, NO3, and O3 Reactions with the First-Generation Atmospheric Oxidation Products of Alkenes	427	(1)
Primary Photochemical Processes in Some Important Light-Absorbing Products of the Atmospheric Oxidation of the Alkenes	428	(1)
Application of Findings to the Modeling of Alkene Atmospheric Chemistry	428	(1)
Important Areas for Further Laboratory Studies	429	(1)
References	430	(27)
Appendix A Nomenclature and Molecular Structure of the Alkenes	457	(32)
Appendix B Nomenclature and Structure of Some Major Products of Alkene Atmospheric Oxidation Processes	489	(32)
Author Index	521	(14)
Subject Index	535