Evidence for formation of a PAN analogue of pinonic structure and investigation of its thermal stability

The first evidence and laboratory study of a peroxyacetyl nitrate (PAN) analogue produced by the photooxidation of a terpene, α-pinene, is presented. This PAN analogue, assigned to 3-acetyl-2,2-dimethyl-cyclobutane-acetyl peroxynitrate and referred to as “α-pinonyl peroxynitrate” (αP-PAN) was synthesized in the gas phase from the radical (OH, Cl, Br, or NO3) initiated oxidation of pinonaldehyde (3-acetyl-2,2-dimethyl-cyclobutyl-ethanal) in the presence of excess NO2 and evidenced by Fourier transform-infrared (FT-IR) spectroscopy. Another reaction channel producing PAN was also observed for some of the radical initiators. Of particular atmospheric interest, the experiments with OH radicals demonstrated that αP-PAN is the main product of pinonaldehyde under NOx-rich conditions with a yield of (81.3±16)%, while an upper limit of the PAN yield for this reaction is around 8%. The further photooxidation of αP-PAN was also observed to produce PAN directly. The thermal stability of αP-PAN was studied between 303 and 281 K. The rate constant of thermal dissociation was found to be k−1 = 10(9.25±0.33) × exp [−(72.0±1.9)/RT] where the activation energy is in kJ mol−1. Distortions of the kinetic profiles attributed to aerosol formation were observed and led to large errors in the above estimation of k−1. Within the uncertainties, the observed thermal stability of αP-PAN is comparable to that of PAN. The tropospheric importance of pinonaldehyde and of αP-PAN are discussed.

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