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 k₁= 2.6 ± 0.3, k₂= 8.7 ± 0.8, k₃= 4.9 ± 0.5, k₄= 4.9 ± 0.4, k₅= 15.1 ± 1.3, k₆= 12.8 ± 1.2 and k₇= 6.2 ± 0.6, respectively, in the units of 10⁻¹⁵ cm³ molec.⁻¹ s⁻¹ at 298 ± 2 K. The rate coefficient k₁₃ for the reaction of the NO₃ radical with deuterated benzaldehyde (benzaldehyde-d₁) was found to be half that of k₁. 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.

中文翻译：

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NO3 与芳香醛的反应：气相动力学和对反应机理的深入了解

在环境温度和压力下，在 7300 L 模拟室中，通过相对和绝对方法测量NO ₃自由基与一系列芳香醛反应的速率系数。苯甲醛 (BA)、邻甲苯醛 (O-TA)、间甲苯醛 (M-TA)、对甲苯醛 (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) 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 和 k ₇ =  6.2  ±  0.6，单位为10 ^-15  cm ³ 摩尔。^-1  s ^-1在298  ±  2 K。发现NO ₃自由基与氘代苯甲醛（苯甲醛-d ₁）反应的速率系数 k ₁₃是k _{1 的}一半。反应的终产物在过量的 NO _{2 中}测量为C ₆ H ₅ C(O)O ₂ NO ₂。醛键能和反应途径的理论计算表明，NO ₃自由基主要通过提取醛氢原子与芳香醛反应。简要讨论了测量速率系数对大气的影响。