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Thermal stability of Peroxynitrates
Author(s) -
Kirchner F.,
Mayer–Figge A.,
Zabel F.,
Becker K. H.
Publication year - 1999
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/(sici)1097-4601(1999)31:2<127::aid-kin6>3.0.co;2-l
Subject(s) - chemistry , atmospheric pressure , thermal stability , thermal decomposition , reaction rate constant , kinetic energy , decomposition , thermal , analytical chemistry (journal) , work (physics) , absorption (acoustics) , fourier transform infrared spectroscopy , infrared , fourier transform , kinetics , thermodynamics , organic chemistry , meteorology , chemical engineering , physics , quantum mechanics , acoustics , engineering , mathematical analysis , mathematics , optics
Peroxynitrates are thermally unstable intermediates (at ambient temperatures) in the atmospheric degradation of hydrocarbons. In this work, thermal lifetimes of nine peroxynitrates have been measured as a function of temperature and, for two of them, also, as a function of total pressure. In the presence of excess NO, relative concentrations of the peroxynitrates were followed in a 420 I reaction chamber as a function of time by means of longpath IR absorption using a Fourier transform spectrometer. Original data on the unimolecular decomposition rate constants are presented for the peroxynitrates RO 2 NO 2 with R = C 6 H 11 , CH 3 C(O)CH 2 , C 6 H 5 CH 2 , CH 2 I, CH 3 C(O)OC(H)CH 3 , C 6 H 5 OCH 2 , (CH 3 ) 2 NC(O), C 6 H 5 OC(O), and C 2 H 5 C(O). Thermal lifetimes at room temperature and atmospheric pressure are very short (in the order of seconds) for substituted methyl peroxynitrates (i.e., R'CH 2 O 2 NO 2 ) but rather long for substituted formyl peroxynitrates (i.e., R″C(O)O 2 NO 2 ). Kinetic data from this and previous work from our laboratory are used to derive structure‐stability relationships which allow an estimate of the thermal lifetimes of peroxynitrates from readily available 13 C n.m.r. shift data. ©1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 127–144, 1999