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Nitromethane dissociation: Implications for the CH 3 + NO 2 reaction
Author(s) -
Glarborg P.,
Bendtsen A. B.,
Miller J. A.
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)31:9<591::aid-kin1>3.0.co;2-e
Subject(s) - nitromethane , chemistry , shock tube , reaction rate constant , thermodynamics , atmospheric temperature range , reaction rate , thermal decomposition , atmospheric pressure , dissociation (chemistry) , analytical chemistry (journal) , shock wave , kinetics , catalysis , organic chemistry , meteorology , physics , quantum mechanics
The thermal decomposition of nitromethane under highly diluted conditions in shock tubes has been analyzed in terms of a detailed chemical kinetic model. The experimental data were adopted from Glänzer and Troe, Hsu and Lin, and Zhang and Bauer, respectively; they cover the temperature range 1000–1400 K and pressures from 0.5 to 6.0 bar. Based on these results, rate constants for the reactions CH 3 NO 2 (+M) ⇌ CH 3 + NO 2 (+M) (R1) and CH 3 + NO 2 ⇌ CH 3 O + NO (R14) have been re‐examined. The high and low pressure limits for reaction (R1) determined by Glänzer and Troe have been shown to be consistent with more recent shock tube data, provided a center broadening parameter is introduced to describe the fall‐off behavior. Our reinterpretation of the shock tube results of Glänzer and Troe together with room temperature measurements indicate that the rate constant for (R14) decreases slightly with temperature, as k 14 = 4.0 · 10 13 T −0.2 cm 3 mol −1 s −1 . At high temperatures and atmospheric pressure this reaction is more than an order of magnitude faster than recombination of CH 3 and NO 2 to form nitromethane. Based on the available data for the forward and reverse rate of reaction (R1) a value of 66.7 ± 2.0 cal/(mol K) for the entropy S 0,298 of CH 3 NO 2 is estimated. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 591–602, 1999