Kinetics and mechanism of thermal gas-phase oxidation of hexafluoropropene in the presence of trifluoromethylhypofluorite, CF3OF

The oxidation of hexafluoropropene with molecular oxygen in the presence of CF3OF has been studied at 303.0, 313.0 and 323.4 K, using a conventional static system. The initial pressure of CF3OF was varied between 1.7 and 16.6 Torr, that of C3F6 between 10.0 and 120.2 Torr and that of O2 between 82.0...

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Autores principales: Dos Santos Afonso, M., Romano, R.M., Della Védova, C.O., Czarnowski, J.
Formato: JOUR
Materias:
organofluorine derivative
propylene
article
chemical binding
chemical reaction
decomposition
kinetics
oxidation
reaction analysis
thermal analysis
Acceso en línea:http://hdl.handle.net/20.500.12110/paper_14639076_v2_n7_p1393_DosSantosAfonso
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
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spelling todo:paper_14639076_v2_n7_p1393_DosSantosAfonso2023-10-03T16:16:59Z Kinetics and mechanism of thermal gas-phase oxidation of hexafluoropropene in the presence of trifluoromethylhypofluorite, CF3OF Dos Santos Afonso, M. Romano, R.M. Della Védova, C.O. Czarnowski, J. organofluorine derivative propylene article chemical binding chemical reaction decomposition kinetics oxidation reaction analysis thermal analysis The oxidation of hexafluoropropene with molecular oxygen in the presence of CF3OF has been studied at 303.0, 313.0 and 323.4 K, using a conventional static system. The initial pressure of CF3OF was varied between 1.7 and 16.6 Torr, that of C3F6 between 10.0 and 120.2 Torr and that of O2 between 82.0 and 599.8 Torr. Several runs were made in the presence of 325.3-499.2 Torr of N2. Major products were COF2, CF3C(O)F, CF3OC(O)F and a new compound, CF3OCF2OCF2C(O)F. The latter was characterised by the determination of its relative molecular mass and its IR spectrum, which is consistent with the calculated one using theoretical approximations. Small amounts of CF3OCF2C(O)F were also formed. The oxidation is an homogeneous chain reaction, attaining, at the pressure of O2 used, the pseudo-zero-order condition with respect to O2 as a reactant. It is independent of the total pressure. The basic steps are: the thermal generation of CF3O radicals by abstraction of the fluorine atom from CF3OF by C3F6, chain initiation by the addition of CF3O to olefin leading, in the presence of O2, to the formation of haloalkoxy radicals, which decompose via the C-C scission to give products containing C(O)F group and CF3 radicals, reforming CF3O. The full mechanism is postulated. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_14639076_v2_n7_p1393_DosSantosAfonso
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic organofluorine derivative
propylene
article
chemical binding
chemical reaction
decomposition
kinetics
oxidation
reaction analysis
thermal analysis
spellingShingle organofluorine derivative
propylene
article
chemical binding
chemical reaction
decomposition
kinetics
oxidation
reaction analysis
thermal analysis
Dos Santos Afonso, M.
Romano, R.M.
Della Védova, C.O.
Czarnowski, J.
Kinetics and mechanism of thermal gas-phase oxidation of hexafluoropropene in the presence of trifluoromethylhypofluorite, CF3OF
topic_facet organofluorine derivative
propylene
article
chemical binding
chemical reaction
decomposition
kinetics
oxidation
reaction analysis
thermal analysis
description The oxidation of hexafluoropropene with molecular oxygen in the presence of CF3OF has been studied at 303.0, 313.0 and 323.4 K, using a conventional static system. The initial pressure of CF3OF was varied between 1.7 and 16.6 Torr, that of C3F6 between 10.0 and 120.2 Torr and that of O2 between 82.0 and 599.8 Torr. Several runs were made in the presence of 325.3-499.2 Torr of N2. Major products were COF2, CF3C(O)F, CF3OC(O)F and a new compound, CF3OCF2OCF2C(O)F. The latter was characterised by the determination of its relative molecular mass and its IR spectrum, which is consistent with the calculated one using theoretical approximations. Small amounts of CF3OCF2C(O)F were also formed. The oxidation is an homogeneous chain reaction, attaining, at the pressure of O2 used, the pseudo-zero-order condition with respect to O2 as a reactant. It is independent of the total pressure. The basic steps are: the thermal generation of CF3O radicals by abstraction of the fluorine atom from CF3OF by C3F6, chain initiation by the addition of CF3O to olefin leading, in the presence of O2, to the formation of haloalkoxy radicals, which decompose via the C-C scission to give products containing C(O)F group and CF3 radicals, reforming CF3O. The full mechanism is postulated.
format JOUR
author Dos Santos Afonso, M.
Romano, R.M.
Della Védova, C.O.
Czarnowski, J.
author_facet Dos Santos Afonso, M.
Romano, R.M.
Della Védova, C.O.
Czarnowski, J.
author_sort Dos Santos Afonso, M.
title Kinetics and mechanism of thermal gas-phase oxidation of hexafluoropropene in the presence of trifluoromethylhypofluorite, CF3OF
title_short Kinetics and mechanism of thermal gas-phase oxidation of hexafluoropropene in the presence of trifluoromethylhypofluorite, CF3OF
title_full Kinetics and mechanism of thermal gas-phase oxidation of hexafluoropropene in the presence of trifluoromethylhypofluorite, CF3OF
title_fullStr Kinetics and mechanism of thermal gas-phase oxidation of hexafluoropropene in the presence of trifluoromethylhypofluorite, CF3OF
title_full_unstemmed Kinetics and mechanism of thermal gas-phase oxidation of hexafluoropropene in the presence of trifluoromethylhypofluorite, CF3OF
title_sort kinetics and mechanism of thermal gas-phase oxidation of hexafluoropropene in the presence of trifluoromethylhypofluorite, cf3of
url http://hdl.handle.net/20.500.12110/paper_14639076_v2_n7_p1393_DosSantosAfonso
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AT dellavedovaco kineticsandmechanismofthermalgasphaseoxidationofhexafluoropropeneinthepresenceoftrifluoromethylhypofluoritecf3of
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