正丁醇的大气化学:在有和没有氮氧化物(NO(x))存在的情况下,氯原子和羟基自由基引发氧化的动力学、机理及产物

Atmospheric chemistry of n-butanol: kinetics, mechanisms, and products of Cl atom and OH radical initiated oxidation in the presence and absence of NO(x).

作者信息

Hurley M D, Wallington T J, Laursen L, Javadi M S, Nielsen O J, Yamanaka T, Kawasaki M

机构信息

Systems Analytics and Environmental Sciences Department, Ford Motor Company, Mail Drop RIC-2122, Dearborn, Michigan 48121-2053, USA.

出版信息

J Phys Chem A. 2009 Jun 25;113(25):7011-20. doi: 10.1021/jp810585c.

Abstract

Smog chamber/FTIR techniques were used to determine rate constants of k(Cl+n-butanol) = (2.21 +/- 0.38) x 10(-10) and k(OH+n-butanol) = (8.86 +/- 0.85) x 10(-12) cm(3) molecule(-1) s(-1) in 700 Torr of N(2)/O(2) diluent at 296 +/- 2K. The sole primary product identified from the Cl atom initiated oxidation of n-butanol in the absence of NO was butyraldehyde (38 +/- 2%, molar yield). The primary products of the Cl atom initiated oxidation of n-butanol in the presence of NO were (molar yield) butyraldehyde (38 +/- 2%), propionaldehyde (23 +/- 3%), acetaldehyde (12 +/- 4%), and formaldehyde (33 +/- 3%). The substantially lower yields of propionaldehyde, acetaldehyde, and formaldehyde as primary products in experiments conducted in the absence of NO suggests that chemical activation is important in the atmospheric chemistry of CH(3)CH(2)CH(O)CH(2)OH and CH(3)CH(O)CH(2)CH(2)OH alkoxy radicals. The primary products of the OH radical initiated oxidation of n-butanol in the presence of NO were (molar yields) butyraldehyde (44 +/- 4%), propionaldehyde (19 +/- 2%), and acetaldehyde (12 +/- 3%). In all cases, the product yields were independent of oxygen concentration over the partial pressure range of 10-600 Torr. The yields of propionaldehyde, acetaldehyde, and formaldehyde quoted above were not corrected for secondary formation via oxidation of higher aldehydes and should be treated as upper limits. The reactions of Cl atoms and OH radicals with n-butanol proceed 38 +/- 2 and 44 +/- 4%, respectively, via attack on the alpha-position to give an alpha-hydroxy alkyl radical which reacts with O(2) to give butyraldehyde. The results are discussed with respect to the atmospheric chemistry of n-butanol.

摘要

利用烟雾箱/傅里叶变换红外光谱技术,在296±2K、700托的氮气/氧气稀释气体中,测定了k(Cl + 正丁醇) = (2.21±0.38)×10⁻¹⁰和k(OH + 正丁醇) = (8.86±0.85)×10⁻¹²厘米³·分子⁻¹·秒⁻¹的速率常数。在不存在一氧化氮的情况下,由氯原子引发的正丁醇氧化反应中唯一确定的主要产物是丁醛(摩尔产率为38±2%)。在存在一氧化氮的情况下,氯原子引发的正丁醇氧化反应的主要产物(摩尔产率)为丁醛(38±2%)、丙醛(23±3%)、乙醛(12±4%)和甲醛(33±3%)。在不存在一氧化氮的实验中,丙醛、乙醛和甲醛作为主要产物的产率显著较低,这表明化学活化在CH₃CH₂CH(O)CH₂OH和CH₃CH(O)CH₂CH₂OH烷氧基自由基的大气化学中很重要。在存在一氧化氮的情况下,羟基自由基引发的正丁醇氧化反应的主要产物(摩尔产率)为丁醛(44±4%)、丙醛(19±2%)和乙醛(12±3%)。在所有情况下,产物产率在10 - 600托的分压范围内与氧气浓度无关。上述丙醛、乙醛和甲醛的产率未针对通过高级醛氧化的二次生成进行校正,应视为上限。氯原子和羟基自由基与正丁醇的反应分别有38±2%和44±4%通过进攻α位生成α - 羟基烷基自由基,该自由基与氧气反应生成丁醛。针对正丁醇的大气化学对结果进行了讨论。

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