caa a22 4500 378903799 CHVBK 20180305123524.0 cr unu---uuuuu 161128e20040501xx s 000 0 eng 10.1524/zpch.218.5.575.30504 doi (NATIONALLICENCE)gruyter-10.1524/zpch.218.5.575.30504 Kinetics and Mechanism of the Thermal Gas-Phase Reaction between NO2 and Perfluoropropene [Elektronische Daten] [R. M. Romano, Joanna Czarnowski] The reaction of NO2 with perfluoropropene (C3F6) has been studied at 413.1, 421.0 and 432.8K, using a conventional static system. The initial pressure of NO2 was varied between 43.6 and 204.0Torr and that of C3F6 between 10.2 and 108.5Torr. Several experiments were made adding CF4, varying its pressure from 338.8 to 433.6Torr. Four products were observed: NO and perfluoropropene oxide (PFPO), formed in equivalent amounts, CF3CF(NO2)CF2NO2 and CF3C(O)CF2NO2. The relation R=[PFPO]/([CF3CF(NO2)CF2NO2] + [CF3C(O)CF2NO2]) increases with temperature and decreases as the concentration of NO2 and the total pressure M increase. The yields of PFPO, based on the amount of C3F6 consumed, varied between 63 and 89% and those of CF3CF(NO2)CF2NO2 between 0.33 and 0.08%. Increasing the temperature, the yields of CF3C(O)CF2NO2 decreased from 0.04 to 0.01%. The reaction is homogenous and the consumption rate of perfluoropropene, −d[C3F6]/dt= k1[C3F6][NO2], is independent of the total pressure. The following mechanism is postulated to explain the experimental results: 1) C3F6 + NO2 → CF3C•FCF2NO2, 2) CF3C•FCF2NO2 → PFPO+NO, 3) CF3C•FCF2NO2 + NO2+M → CF3CF(NO2)CF2NO2+M, 4) CF3C•FCF2NO2 + NO2 → CF3C(O)CF2NO2+FNO. k1=(4.57±1.4)×106exp(−(15.44±1.2) kcal mol−1/RT) dm3mol−1s−1. The value of k2, the rate constant for the unimolecular dissociation of the radical CF3C•FCF2NO2, was found to be of order of 1014s−1. © 2004 Oldenbourg Wissenschaftsverlag GmbH Thermodynamics & statistical physics nationallicence Laboratory techniques, experiments nationallicence Physical chemistry nationallicence Romano R. M. aut Czarnowski Joanna aut Zeitschrift für Physikalische Chemie/International journal of research in physical chemistry and chemical physics Oldenbourg Wissenschaftsverlag GmbH 218/5/2004(2004-05-01), 575-598 0942-9352 218:5/2004<575 2004 218 zpch https://doi.org/10.1524/zpch.218.5.575.30504 text/html Onlinezugriff via DOI 1 research article jats NATIONALLICENCE 856 40 https://doi.org/10.1524/zpch.218.5.575.30504 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Romano R. M. aut NATIONALLICENCE 700 1- Czarnowski Joanna aut NATIONALLICENCE 773 0- Zeitschrift für Physikalische Chemie/International journal of research in physical chemistry and chemical physics Oldenbourg Wissenschaftsverlag GmbH 218/5/2004(2004-05-01), 575-598 0942-9352 218:5/2004<575 2004 218 zpch CC0 http://creativecommons.org/publicdomain/zero/1.0 nationallicence SWISSBIB 378761439 BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-gruyter