Laboratoire Interuniversitaire des Systèmes Atmosphériques, UMR CNRS 7583, Université Paris Est Créteil (UPEC) et Université Paris Diderot (UPD), Institut Pierre Simon Laplace, 61 Avenue du Général de Gaulle, 94010 cedex Créteil, France.
J Phys Chem A. 2012 Oct 18;116(41):10135-42. doi: 10.1021/jp3071234. Epub 2012 Oct 10.
Rate constants for the gas-phase reactions of the NO(3) radical with a series of unsaturated aldehydes, trans-2-hexenal, trans-2-heptenal, and trans-2-octenal, have been measured using absolute rate method at 294 ± 3 K and atmospheric pressure. This work was performed to clarify discrepancies found in the literature and thus led to a clearer view of the effect of the increasing carbon chain length on the reactivity of trans-2-alkenals. The rate constants were determined to be (4.7 ± 1.5) × 10(-15), (5.3 ± 1.6) × 10(-15), and (5.6 ± 2.3) × 10(-15) cm(3) molecule(-1) s(-1) for trans-2-hexenal, trans-2-heptenal, and trans-2-octenal, respectively. These results clearly indicate that the carbon chain lengthening of the trans-2-alkenals does not significantly affect the rate constant. In addition, the mechanism for the reaction of NO(3) with these unsaturated aldehydes was also investigated. Unsaturated peroxynitrate-type compounds that are exclusively formed through the abstraction channel were observed as the main products.
使用绝对速率法在 294 ± 3 K 和大气压下测量了 NO(3)自由基与一系列不饱和醛（反式-2-己烯醛、反式-2-庚烯醛和反式-2-辛烯醛）在气相中的反应速率常数。这项工作旨在澄清文献中的差异，从而更清楚地了解碳链长度增加对反式-2-链烯醛反应性的影响。反式-2-己烯醛、反式-2-庚烯醛和反式-2-辛烯醛的速率常数分别为 (4.7 ± 1.5) × 10(-15)、(5.3 ± 1.6) × 10(-15) 和 (5.6 ± 2.3) × 10(-15) cm(3) molecule(-1) s(-1)。这些结果清楚地表明，反式-2-链烯醛的碳链延长不会显著影响速率常数。此外，还研究了 NO(3)与这些不饱和醛反应的机理。通过抽氢通道专门形成的不饱和过氧硝酸盐型化合物被观察为主要产物。
