Mechanisms of Atmospheric Oxidation of the AlkanesAn 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. |
Contents
IMPORTANCE OF ALKANES IN ATMOSPHERIC CHEMISTRY OF THE URBAN REGIONAL AND GLOBAL SCALES | 3 |
REACTIONS OF ALKANES WITH THE HYDROXYL RADICAL OH | 45 |
KINETICS AND MECHANISMS OF REACTIONS OF Cl Osup3P NOsub3 AND Osub3 WITH ALKANES | 104 |
MECHANISMS AND ENDPRODUCTS OF THE ATMOSPHERIC OXIDATION OF ALKANES | 174 |
REACTIONS OF PRODUCTS OF ALKANE REACTIONS | 289 |
ATMOSPHERIC CHEMISTRY OF THE HALOALKANES | 379 |
THE PRIMARY PHOTOCHEMICAL PROCESSES IN THE ALKANES THE HALOALKANES AND SOME OF THEIR OXIDATION PRODUCTS | 604 |
REPRESENTATION OF THE ATMOSPHERIC CHEMISTRY OF ALKANES IN MODELS | 831 |
References | 865 |
STRUCTURES OF SOME COMMON ALKANES | 927 |
STRUCTURES OF SOME COMMON HALOALKANES | 932 |
STRUCTURES OF SOME COMMON ATMOSPHERIC OXIDATION PRODUCTS OF THE ALKANES | 942 |
| 955 | |
| 983 | |
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Common terms and phrases
2-butanone 2-methylpentane 2-methylpropane 2-pentanone 2,3-dimethylbutane Abbreviations absolute basis acetaldehyde acetone aldehydes alkanes alkoxy radicals alkyl Arrhenius expression Arrhenius fit Arrhenius plot atmospheric chemistry atmospheric oxidation atoms butane Calvert carbon carbonyl CH2O CH3CHO Chem Cl-atom-initiated oxidation Cl-atoms cm3 molecule cm3 molecule−1 s−1 coefficient for reaction compounds cycloalkanes cyclohexane cyclopentane cyclopropane D’Anna decomposition defined in table employed are defined estimated uncertainty ethane experimental techniques employed expression gives formation given in table H-atom haloalkanes heptane hexane hydrogen isomerization j-values k(OH+ ketone kinetic kJ mol−1 measured mechanism methyl nitrate observed OH radicals ozone column pentanal peroxy radicals photochemical photodecomposition photodissociation photolysis frequencies Phys pressure primary processes propanal quantum yields quenching rate coefficient reaction of OH reaction with O2 reactivity recommended Reference Range reported solar zenith angle table II-A-1 Talukdar techniques are defined Temperature 1012 temperature dependence Torr of air values Wallington wavelength