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Measurement of the reactivity of OH with methyl nitrate: Implications for prediction of alkyl nitrate‐OH reaction rates
Author(s) -
Gaffney J. S.,
Fajer R.,
Senum G. I.,
Lee J. H.
Publication year - 1986
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550180311
Subject(s) - chemistry , alkyl , nitrate , dissociation (chemistry) , bond dissociation energy , reactivity (psychology) , molecule , reaction rate constant , reaction rate , medicinal chemistry , photochemistry , organic chemistry , kinetics , catalysis , medicine , physics , alternative medicine , pathology , quantum mechanics
The rate of the gas phase reaction of hydroxyl radical with methyl nitrate has been measured to be (3.4 ± 0.4) × 10 −14 cm 3 molecule −1 s −1 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 HCH 2 ONO 2 of 101 kcal mol −1 , and a rate for O( 3 P) reaction with methyl nitrate of ca. 9 × 10 −17 cm 3 molecule −1 s −1 . 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.