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Measurement of the reactivity of OH with methyl nitrate: Implications for prediction of alkyl nitrate-OH reaction rates

✍ Scribed by J. S. Gaffney; R. Fajer; G. I. Senum; J. H. Lee

Publisher: John Wiley and Sons
Year: 1986
Tongue: English
Weight: 474 KB
Volume: 18
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550180311

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✦ Synopsis

The rate of the gas phase reaction of hydroxyl radical with methyl nitrate has been measured to be (3.4 * 0.4) x cm3 molecule-' s-' at 298 K using flow discharge/ resonance fluorescence techniques. By means of correlation methods, this rate determination is used to predict a vertical ionization potential of 12.6 eV, a bond dissociation energy for H-CH20N02 of 101 kcal mol-', and a rate for O?P) reaction with methyl nitrate of ca. 9 x cm3 molecule-' s-'. In conjunction with previously derived relative data for reaction of alkyl nitrates with OH radical in the gas phase, a priori estimated reactivities for 1-, 2-, and 3-positionally substituted straight chain alkyl nitrates have been reexamined. Revised reactivities for OH abstraction of specific hydrogens substituted on straight chain alkyl nitrates are presented and discussed, and an atmospheric lifetime of ca. 2 yrs is estimated for methyl nitrate removal due to OH.

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