Reactions of NO3 with aromatic aldehydes: gas-phase kinetics and insights into the mechanism of the reaction
Reactions of NO3 with aromatic aldehydes: gas-phase kinetics and insights into the mechanism of the reaction
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DOI：
10.5194/acp-21-13537-2021
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发表时间：
2021-09-10
影响因子：
6.3
通讯作者：
Ravishankara, A. R.
中科院分区：
文献类型：
--
作者：
Ren, Yangang;Zhou, Li;Ravishankara, A. R.
在7300型L模拟室中，用相对法和绝对法测定了常温常压下硝酸根与一系列芳香醛反应的速率系数。苯甲醛(BA)、邻甲苯甲醛(O-TA)、间甲苯甲醛(M-TA)、对甲苯甲醛(P-TA)、2，4-二甲基苯甲醛(2，4-DMBA)、2，5-二甲基苯甲醛(2，5-DMBA)和3，5-二甲基苯甲醛(3，5-DMBA)的反应速率系数分别为k(1)=2.6+/-0.3，k(2)=8.7+/-0.8，k(3)=4.9+/-0.5，k(4)=4.9+/-0.4。K(5)=15.1+/-1.3，k(6)=12.8+/-1.2，k(7)=6.2+/-0.6，单位为10(-15)cm(3)。1 S(-1)在298+/-2K下，测得硝酸根与苯甲醛(苯甲醛-d(1))反应的速率系数k(13)是k(1)的一半。在过量的NO2条件下，反应的最终产物为C6H5C(O)O2NO2。对醛的键能和反应路径的理论计算表明，NO3自由基主要通过醛氢原子的抽提与芳醛反应。简要讨论了测量的速率系数对大气的影响。
Rate coefficients for the reaction of NO3 radicals with a series of aromatic aldehydes were measured in a 7300 L simulation chamber at ambient temperature and pressure by relative and absolute methods. The rate coefficients for benzaldehyde (BA), ortho-tolualdehyde (O-TA), meta-tolualdehyde (M-TA), para-tolualdehyde (P-TA), 2,4-dimethyl benzaldehyde (2,4-DMBA), 2,5-dimethyl benzaldehyde (2,5-DMBA) and 3,5-dimethyl benzaldehyde (3,5-DMBA) were k(1) = 2.6 +/- 0.3, k(2) = 8.7 +/- 0.8, k(3) = 4.9 +/- 0.5, k(4) = 4.9 +/- 0.4, k(5) = 15.1 +/- 1.3, k(6) = 12.8 +/- 1.2 and k(7) = 6.2 +/- 0.6, respectively, in the units of 10(-15) cm(3) molec. 1 s(-1) at 298 +/- 2 K. The rate coefficient k(13) for the reaction of the NO3 radical with deuterated benzaldehyde (benzaldehyde-d(1)) was found to be half that of k(1). The end product of the reaction in an excess of NO2 was measured to be C6H5C(O)O2NO2. Theoretical calculations of aldehydic bond energies and reaction pathways indicate that the NO3 radical reacts primarily with aromatic aldehydes through the abstraction of an aldehydic hydrogen atom. The atmospheric implications of the measured rate coefficients are briefly discussed.