An Experimental Study
of the Gas-Phase Reactions of
NO<sub>3</sub> Radicals with a Series of Unsaturated Aldehydes: <i>trans</i>-2-Hexenal, <i>trans</i>-2-Heptenal, and <i>trans</i>-2-Octenal
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Abstract
Rate constants for the gas-phase reactions of the NO<sub>3</sub> radical with a series of unsaturated aldehydes, <i>trans</i>-2-hexenal, <i>trans</i>-2-heptenal, and <i>trans</i>-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 <i>trans</i>-2-alkenals. The rate constants were determined
to be (4.7 ± 1.5) × 10<sup>–15</sup>, (5.3 ±
1.6) × 10<sup>–15</sup>, and (5.6 ± 2.3) × 10<sup>–15</sup> cm<sup>3</sup> molecule<sup>–1</sup> s<sup>–1</sup> for <i>trans</i>-2-hexenal, <i>trans</i>-2-heptenal, and <i>trans</i>-2-octenal, respectively.
These results clearly indicate that the carbon chain lengthening of
the <i>trans</i>-2-alkenals does not significantly affect
the rate constant. In addition, the mechanism for the reaction of
NO<sub>3</sub> 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
