Startseite Kinetics and Mechanism of the Thermal Gas-Phase Reaction between NO2 and Trifluorochloroethene
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Kinetics and Mechanism of the Thermal Gas-Phase Reaction between NO2 and Trifluorochloroethene

  • Rosana M. Romano , C. O. della Védova und J. Czarnowski
Veröffentlicht/Copyright: 25. September 2009
Zeitschrift für Physikalische Chemie
Aus der Zeitschrift Band 216 Heft 10

The reaction of NO2 with CF2CFCl has been studied at 322.8, 332.2 and 342.2 K, using a conventional static system. The initial pressure of CF2CFCl was varied between 13.0 and 90.2 Torr and that of NO2 between 9.3 and 89.5 Torr. Several experiments were carried out in presence of CF4, varying its pressure from 277.6 to 458.5 Torr. Three products were formed: O2NCF2CFClNO2 and equimolecular amounts of ClNO and O2NCF2C(O)F. The product distribution was independent of the initial pressures of the reactants and the total pressure, but the ratio of O2NCF2C(O)F to that of O2NCF2CFClNO2 increased with temperature. The reaction is homogeneous and independent of the total pressure. The following mechanism was postulated to explain the experimental results:

1. NO2 + CF2CFCl → O2NCF2CFCl·

2. O2NCF2CFCl· + NO2 + M → O2NCF2CFClNO2 + M

3. O2NCF2CFCl· + NO2 → O2NCF2C(O)F + ClNO

k1 = (1.7±0.4)×106 exp(−(10.8±1) kcal mol−1/RT) dm3 mol−1 s−1

k3 = (9.8±3)×1010 exp(−(1.1±0.2) kcal mol−1/RT) dm3mol−1 s−1.

Published Online: 2009-09-25
Published in Print: 2002-10
Heruntergeladen am 29.9.2025 von https://www.degruyterbrill.com/document/doi/10.1524/zpch.2002.216.10.1203/html
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