The production of organic nitrates from atmospheric oxidation of ethers and glycol ethers

✍ Scribed by Cyntia Espada; Paul B. Shepson

• Publisher: John Wiley and Sons
• Year: 2005
• Tongue: English
• Weight: 265 KB
• Volume: 37
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.20121

✦ Synopsis

Abstract

The production of organic nitrates from OH reaction (in the presence of NO) with methoxy propane, 1‐methoxy‐2‐propanol, ethoxy butane, and 2‐butoxyethanol was studied. The measured total organic nitrate yields were 1.8 (±0.4)%, 0.98 (±0.2)%, 7.7 (±2)%, and 9.6 (±1)%, respectively. The total organic nitrate yield for methoxypropane is 26% of that (7.0%) for n‐butane. The organic nitrate yield for ethoxy butane is 55% of that (14%) for n‐hexane. The peroxy radicals produced from OH reaction with the methylene groups α to the ether linkage have an organic nitrate branching ratio (k~3b~/k~3~) value ∼50% of those in analogous n‐alkanes. On the other hand, k~3b~/k~3~ values for peroxy radical functional groups not adjacent to the ether linkage (in γ and δ positions) are on average 1.7 times greater than for the analogous n‐alkyl peroxy radicals. The organic nitrate formation yield for 1‐methoxy‐2‐propanol is almost half that of methoxy propane, while for 2‐butoxyethanol it is 21% greater than that of butoxyethane. Our data lead us to the conclusion that the ether linkage imparts an inductive effect that decreases the value of k~3b~/k~3~ for peroxy radicals adjacent to it, yet has a stabilizing effect, from the additional vibrational modes for those peroxy radicals not adjacent to it, increasing their k~3b~/k~3~ values. The effect of both the O and OH groups in these molecules and the importance of their position relative to the peroxy group are discussed in this paper. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 686–699, 2005