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Thermal Decomposition of C3-Substituted Peroxyacyl Nitrates

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The gas phase thermal decomposition rates of C3-substituted peroxyacyl nitrates, RC(O)OONO2 have been measured at ambient temperature (287-298 K) and 1 atm. of air. Two saturated compounds (PnBN, R = n-C3H7- and PiBN, R = i-C3H7-) and two unsaturated compounds (MPAN, R = CH2=C(CH3)-and CPAN, R = CH3CH=CH-) have been studied. In the narrow temperature range studied, thermal decomposition rates for PiBN, PnBN and MPAN exhibited linear Arrhenius behavior with, in units of 10-4 s-1, and at 298 K, k = 2.2 for PiBN, 2.3 for MPAN, and 2.7 for PnBN. The thermal decomposition rate of CPAN was 1.6 x 10-4 s-1 at 291.6 K and 1.73 x 10-4 s-1 at 293.2 K. These thermal decomposition rates are of the same magnitude as that for PAN, R = CH3. Implications for the atmospheric persistence of C3substituted peroxyacyl nitrates are briefly discussed.

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