2–Butoxyethanol and benzyl alcohol reactions with the nitrate radical: Rate coefficients and gas‐phase products

The bimolecular rate coefficients k   NO   3  •+ 2‐butoxyethanoland k   NO   3  •+ benzyl alcoholwere measured using the relative rate technique at (297 ± 3) K and 1 atmosphere total pressure. Values of (2.7 ± 0.7) and (4.0 ± 1.0) × 10 −15 cm 3 molecule −1 s −1 were observed for k   NO   3  •+ 2‐butoxyethanoland k   NO   3  •+ benzyl alcohol , respectively. In addition, the products of 2‐butoxyethanol + NO 3 • and benzyl alcohol + NO 3 • gas‐phase reactions were investigated. Derivatizing agents O ‐(2,3,4,5,6‐pentafluorobenzyl)hydroxylamine and N , O ‐bis (trimethylsilyl)trifluoroacetamide and gas chromatography mass spectrometry (GC/MS) were used to identify the reaction products. For 2‐butoxyethanol + NO 3 • reaction: hydroxyacetaldehyde, 3‐hydroxypropanal, 4‐hydroxybutanal, butoxyacetaldehyde, and 4‐(2‐oxoethoxy)butan‐2‐yl nitrate were the derivatized products observed. For the benzyl alcohol + NO 3 • reaction: benzaldehyde ((C 6 H 5 )C(O)H) was the only derivatized product observed. Negative chemical ionization was used to identify the following nitrate products: [(2‐butoxyethoxy)(oxido)amino]oxidanide and benzyl nitrate, for 2‐butoxyethanol + NO 3 • and benzyl alcohol + NO 3 • , respectively. The elucidation of these products was facilitated by mass spectrometry of the derivatized reaction products coupled with a plausible 2‐butoxyethanol or benzyl alcohol + NO 3 • reaction mechanisms based on previously published volatile organic compound + NO 3 • gas‐phase mechanisms. © 2012 Wiley Periodicals, Inc. * This article is a U.S. Government work and, as such, is in the public domain of the United States of America. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 778–788, 2012