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Thermal decomposition of peroxyacetyl nitrate in the presence of O2, NO2 and NO

Die thermische Zersetzung von Peroxyacetylnitrat in Gegenwart von O2, NO2 und NO

  • Organische Chemie Und Biochemie
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Summary

The thermal decomposition of purePAN 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 purePAN in N2 thermal decomposition. In the presence of sufficiently large amounts of O2, no methyl nitrate was formed at 333 K, indicating that the homolyticPAN 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 · 10−4s−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.

Zusammenfassung

Die thermische Zersetzung von reinemPAN in N2 und in Gegenwart von zugemischtem O2, NO2 und No wurde bei 1 atm Druck untersucht. Zusätzlich zu Methylnitrat war NO2 ein signifikantes N-Produkt bei der thermischen Zersetzung von reinemPAN in N2. In Gegenwart genügend großer Mengen von O2 wurde bei 333 K kein Methylnitrat gebildet. Dies zeigt an, daß der homolytische Zerfall vonPAN zu Methylnitrat und Kohlendioxid nicht eintritt. Im Gegensatz zu früheren Untersuchungen wurde in Gegenwart von NO nicht Methylnitrat, sondern Methylnitrit als wichtigste Organo-Stickstoff-Verbindung gefunden. Im SystemPAN-NO-N2 wurde die Geschwindigkeitskonstante, in Übereinstimmung mit früheren Untersuchungen, zu 3.1 · 10−4s−1 bei 298 K für die Reaktion (1):PAN → CH3COO2+NO2 bestimmt. Computersimulierung auf Basis des freien Radikal-Mechanismus beginnend mit Reaktion (1) waren mit den experimentellen Resultaten in sehr guter Übereinstimmung.

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Authors and Affiliations

  1. Department of Chemistry, University of Patras, GR-26110, Patras, Greece

    Nikolaos Roumelis & Sotirios Glavas

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  1. Nikolaos Roumelis
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  2. Sotirios Glavas
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Roumelis, N., Glavas, S. Thermal decomposition of peroxyacetyl nitrate in the presence of O2, NO2 and NO. Monatsh Chem 123, 63–72 (1992). https://doi.org/10.1007/BF01045298

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  • DOI: https://doi.org/10.1007/BF01045298

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