The production of organic nitrates from various anthropogenic volatile organic compounds

Abstract

Production of organic nitrates from OH reaction with cyclohexane, cyclohexene, n-butane, 1-bromopropane, and p-xylene in the presence of NO was studied. The total organic nitrate yields for cyclohexane and n-butane were determined to be 17 ± 4 and 7 ± 2% respectively, which is in good agreement with previous determinations. Total yields for cyclohexene, 1-bromopropane, and p-xylene were 2.5 ± 0.5, 1.2 ± 0.3, and 3.2 ± 0.7 respectively. The yield for cyclohexene was five times smaller than that for cyclohexane. The 1-bromopropane yield is three times smaller that that for n-propane, but similar to that for propene, indicating that the effect of Br substitution in the reactant may be similar to that for OH substitution. The only nitrooxy product detected for p-xylene was 4-methylbenzylnitrate, which was formed following H abstraction from either methyl group. No organic nitrate was detected for peroxy radicals produced from OH addition to the ring, which accounts for 90% of the OH oxidation of p-xylene. The calculated k 3b /k 3 value for p-methyl benzyl peroxy radicals (0.32) was slightly smaller than for n-octyl peroxy radicals (0.39). These data imply that substituent inductive effects impact the k 3b /k 3 ratios. We found no significant difference in the k 3b /k 3 ratios for primary vs. secondary peroxy radicals of the same carbon chain. C 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: [675][676][677][678][679][680][681][682][683][684][685] 2005

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

“…The PFBHA reaction product observed from the via hydrogen abstraction was benzaldehyde. Elucidation of the proposed reaction products for 2-butoxyethanol (listed in Table II) was facilitated by mass spectrometry of the derivatized reaction product coupled with plausible reaction mechanisms based on the previously published gas-phase reaction as described below [7,[23][24][25][26][27].…”

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

“…1) was determined to be 1.8 (±0.4)%. This value is 26% of the value 7.0% obtained for the total organic nitrate yield for n-butane [14,16] (i.e. the alkane with the same number of carbons).…”

“…From a plot of [2NPME] vs. − [MP], we obtain a value for the branching ratio (k 3b /k 3 ) for the CH 3 CH(OO · )CH 2 OCH 3 radical of 0.0101 (±0.002)/ [16]. We believe this represents an oxygen substituent stabilization effect, i.e.…”

“…O'Brien et al [15] have determined that yields of organic nitrates from precursor peroxy radicals that contain an OH ␤-to the peroxy group are significantly smaller than from those with no OH group ␤-to the peroxy group. It is also known that certain electron-withdrawing substituents (like Br) can affect the value of k 3b /k 3 of different peroxy radicals [16].…”

β‐Ionone reactions with the nitrate radical: Rate constant and gas‐phase products

“…Structures and ions (expected CI vs. observed CI) used to identify these compounds are listed in Table I. Elucidation of the other major proposed reaction products (also listed in Table I) were facilitated by mass spectrometry of the derivatized reaction product coupled with plausible β-ionone/NO 3 • reaction mechanisms on the basis of previously published VOC/NO 3 • gas-phase reaction as described in the following text [5,12,[24][25][26][27].…”