Amanda L. Gomez, Anaïs M.S. Hallett, Kevin D. Easterbrook, Amanda M. Miller, Hans D. Osthoff
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引用次数: 0
摘要
过氧硝酸丙烯酰(APAN;分子式H2C = CHC(O)O2NO2)是一种在对流层中发现的微量气体,在生物质燃烧羽流和石化厂顺风中浓度升高。由于不饱和侧链的反应性,它的合成对实验室研究和现场仪器的校准都提出了挑战。本文描述了在NOx (= NO + NO2)存在下,丙烯醛在285 nm处光解生成APAN的过程。APAN的形成主要是由羟基自由基(OH)提取醛氢引起的。丙酮的加入增加了APAN的产量,丙酮是OH自由基的来源。光化学生成的APAN在去离子水中的室温亨利定律溶解度(\(\:{H}_{\text{S}}^{cp}\))和液相损失率(kl)常数采用夹套式气泡柱装置测定。APAN的\(\:{H}_{\text{S}}^{cp}\)测量值为(2.67±0.10)M atm−1,误差在1σ水平,与过氧硝酸丙酯(PPN)相当。去离子水中APAN的kl值为(2.7±0.4)×10−4 s−1,与其他pan型化合物的kl值相近。
Measurement of Henry’s law solubility and liquid-phase loss rate constants for acryloyl peroxynitrate (APAN) in deionized water at room temperature
Acryloyl peroxynitrate (APAN; molecular formula H2C = CHC(O)O2NO2) is a trace gas found in the troposphere in elevated concentration in biomass burning plumes and downwind from petrochemical plants. Owing to the reactivity of the unsaturated side chain, its synthesis poses a challenge to laboratory studies and the calibration of field instruments alike. Here, the generation of APAN from photolysis at 285 nm of acrolein in air in the presence of NOx (= NO + NO2) is described. Formation of APAN is primarily initiated by the abstraction of the aldehydic hydrogen by the hydroxyl radical (OH). The output of APAN was increased by the addition of acetone, which acts as a source of OH radicals. Photochemically generated APAN was used to measure its room temperature Henry’s law solubility (\(\:{H}_{\text{S}}^{cp}\)) and liquid phase loss rate (kl) constants in deionized water using a jacketed bubble column apparatus. The measured \(\:{H}_{\text{S}}^{cp}\) value for APAN was (2.67 ± 0.10) M atm− 1, where the error is at the 1σ level, and was on par with propionyl peroxynitrate (PPN). The kl value of APAN in deionized water was determined to be (2.7 ± 0.4)×10− 4 s− 1, which is of similar magnitude as other PAN-type compounds.
期刊介绍:
The Journal of Atmospheric Chemistry is devoted to the study of the chemistry of the Earth''s atmosphere, the emphasis being laid on the region below about 100 km. The strongly interdisciplinary nature of atmospheric chemistry means that it embraces a great variety of sciences, but the journal concentrates on the following topics:
Observational, interpretative and modelling studies of the composition of air and precipitation and the physiochemical processes in the Earth''s atmosphere, excluding air pollution problems of local importance only.
The role of the atmosphere in biogeochemical cycles; the chemical interaction of the oceans, land surface and biosphere with the atmosphere.
Laboratory studies of the mechanics in homogeneous and heterogeneous transformation processes in the atmosphere.
Descriptions of major advances in instrumentation developed for the measurement of atmospheric composition and chemical properties.