Harrison Joel C, Wells J R
Exposure Assessment Branch, Health Effects Laboratory Division, National Institute for Occupational Safety and Health, Morgantown, WV 26505.
Int J Chem Kinet. 2012 Dec;44(12):778-788. doi: 10.1002/kin.20726. Epub 2012 Jun 14.
The bimolecular rate coefficients [Formula: see text] and [Formula: see text] were 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 cm molecule s were observed for [Formula: see text] and [Formula: see text], respectively. In addition, the products of [Formula: see text] and [Formula: see text] gas-phase reactions were investigated. Derivatizing agents -(2,3,4,5,6-pentafluorobenzyl)hydroxylamine and -bis (trimethylsilyl)trifluoroacetamide and gas chromatography mass spectrometry (GC/MS) were used to identify the reaction products. For [Formula: see text] reaction: hydroxyacetaldehyde, 3-hydroxypropanal, 4-hydroxybutanal, butoxyacetaldehyde, and 4-(2-oxoethoxy)butan-2-yl nitrate were the derivatized products observed. For the [Formula: see text] reaction: benzaldehyde ((CH)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 [Formula: see text] and [Formula: see text], respectively. The elucidation of these products was facilitated by mass spectrometry of the derivatized reaction products coupled with a plausible 2-butoxyethanol or [Formula: see text] reaction mechanisms based on previously published [Formula: see text] gas-phase mechanisms.
在(297±3)K和1个大气压的总压力下,使用相对速率技术测量了双分子速率系数[公式:见原文]和[公式:见原文]。对于[公式:见原文]和[公式:见原文],分别观察到(2.7±0.7)和(4.0±1.0)×10⁻¹² cm³ molecule⁻¹ s⁻¹的值。此外,还研究了[公式:见原文]和[公式:见原文]气相反应的产物。使用衍生剂 -(2,3,4,5,6 - 五氟苄基)羟胺和 - 双(三甲基硅基)三氟乙酰胺以及气相色谱 - 质谱联用仪(GC/MS)来鉴定反应产物。对于[公式:见原文]反应:观察到的衍生化产物有羟基乙醛、3 - 羟基丙醛、4 - 羟基丁醛、丁氧基乙醛和4 -(2 - 氧代乙氧基)丁 - 2 - 基硝酸盐。对于[公式:见原文]反应:观察到的唯一衍生化产物是苯甲醛((CH)C(=O)H)。分别使用负化学电离来鉴定[公式:见原文]和[公式:见原文]反应的以下硝酸盐产物:[(2 - 丁氧基乙氧基)(氧化)氨基]氧化酰胺和苄基硝酸盐。通过对衍生化反应产物进行质谱分析,并结合基于先前发表的[公式:见原文]气相机制的合理的2 - 丁氧基乙醇或[公式:见原文]反应机制,有助于阐明这些产物。