Thermische Zerfallsreaktionen von Nitroverbindungen I: Dissoziation von Nitromethan

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Abstract
The thermal decomposition of CH3NO2 highly diluted in Ar has been studied in shock waves at 900 < T < 1500 K and 1.5 · 10−5 < [Ar] < 3.5 · 10−4 mol/cm3. Concentration profiles of CH3NO2 and NO2 were recorded. The unimolecular reaction was found to be in its fall‐off range. Limiting low pressure rate constants of k0 = [Ar] · 1017.1 exp(−42(kcal/mol)/RT) cm3/ mol sec in the range 900 < T < 1400 K and limiting high pressure rate constants of k∞ = 1016.25 exp (−(58.5 ± 0.5 kcal/mol)/RT) sec−1 have been derived. A rate constant of 1.3 · 1013 cm3/mol sec was found for the first subsequent reaction CH3+NO2 → CH3O+NO.