Thermal Decomposition of PAN, PPN and Vinyl-PAN

The gas phase thermal decomposition rates of the C1 and C2-substituted peroxyacyl nitrates (RC(O)OONO2), PAN (R = CH3), PPN (R = C2H5) and vinyl-PAN (R = CH2 = CH-) have been measured at ambient temperature (288 - 299 K) and 1 atm. of air. Our results for PAN (k = A exp (-Ea/RT), log10 (A, s-1) = 16.2 ± 1.6, Ea = 26.9 ± 2.1 kcal / mol, k298 = 3.0 × 10−4S−1) are consistent with literature data. Thermal decomposition rates for PPN and vinyl-PAN are similar to that for PAN, with k298 = 3.0 × 10−4S−1 for PAN, 3.4 × 10−4S−1 for PPN and 3.0 × 10−4S−1 for vinyl-PAN. Implications for the atmospheric persistence of PPN and vinyl-PAN as compared to that of PAN are briefly discussed.