Kinetics and Mechanism of the Thermal Gas-Phase Reaction between NO2 and Trifluorochloroethene
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Rosana M. Romano
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.
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Artikel in diesem Heft
- Empirical Interatomic Potential from Polarized and Depolarized Interaction-Induced Light Scattering Spectra for Gaseous Helium
- Preferential Solvation in 2-Propanol/Water Mixtures: Relationship between Solvatochromic Parameters and Ionization and Transfer Thermodynamics of Nalidixic Acid Antibiotic
- Electrodeposition of Copper on Pt(111) Pretreated with Organic Adsorbates
- Kinetics and Mechanism of the Thermal Gas-Phase Reaction between NO2 and Trifluorochloroethene
- Anomalous X-Ray Scattering Studies on Glassy GexSe1−x across the Stiffness Threshold Composition x = 0.20
- Thermodynamics of Dissolution of some Dicarboxylic Acids in Water/Ethane-1,2-Diol Mixtures
- Effects of Pressure on Two Types of Complexations of 4-Dimethylaminoazobenzene with β-Cyclodextrin
- Book Reviews