Thermal Decomposition of Peroxyacetyl Nitrate in the Presence of O2, NO2 and NO

Article abstract of DOI:10.1007/BF01045298

The thermal decomposition of pure PAN in N2 as well as in the presence of added O2, NO2 and NO was studied at 1 atm pressure.In addition to methyl nitrate, NO2 was a significant N-product of pure PAN in N2 thermal decomposition.In the presence of sufficiently large amounts of O2, no methyl nitrate was formed at 333 K, indicating that the homolytic PAN decay to methyl nitrate and carbon dioxide is not occurring.In the presence of NO (in contrast to former studies) methyl nitrite was found to be the major organo-nitrogen compound instead of methyl nitrate.The systemPAN-NO-N2 allowed the determination of the rate constant 3.1*10^-4 s^-1 at 298 K for reaction (1): PAN --> CH3COO2 + NO2, in agreement with prior studies.Computer simulations based on the free radical mechanism starting with reaction (1) fitted very well the experimental results.Keywords: PAN; Thermal decomposition; O2; NO2; NO.