Formation, thermal decomposition and atmospheric implications of the CF<sub>2</sub>(OH)CF<sub>2</sub>OONO<sub>2</sub> and CF<sub>3</sub>CF<sub>2</sub>OONO<sub>2</sub> peroxynitrates: a theoretical study

A SACM/CT study of the CF<sub>2</sub>(OH)CF<sub>2</sub>OO + NO<sub>2</sub>→CF<sub>2</sub>(OH)CF<sub>2</sub>OONO<sub>2</sub> and CF<sub>3</sub>CF<sub>2</sub>OO + NO<sub>2</sub>→CF<sub>3&l...

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Autor principal: Badenes, María Paula
Formato: Articulo
Lenguaje:Inglés
Publicado: 2017
Materias:
Química
Peroxynitrates
Quantum-chemical calculations
SACM/CT calculations
Acceso en línea:http://sedici.unlp.edu.ar/handle/10915/103538
Aporte de:
SEDICI (UNLP) de Universidad Nacional de La Plata
id I19-R120-10915-103538
record_format dspace
institution Universidad Nacional de La Plata
institution_str I-19
repository_str R-120
collection SEDICI (UNLP)
language Inglés
topic Química
Peroxynitrates
Quantum-chemical calculations
SACM/CT calculations
spellingShingle Química
Peroxynitrates
Quantum-chemical calculations
SACM/CT calculations
Badenes, María Paula
Formation, thermal decomposition and atmospheric implications of the CF<sub>2</sub>(OH)CF<sub>2</sub>OONO<sub>2</sub> and CF<sub>3</sub>CF<sub>2</sub>OONO<sub>2</sub> peroxynitrates: a theoretical study
topic_facet Química
Peroxynitrates
Quantum-chemical calculations
SACM/CT calculations
description A SACM/CT study of the CF<sub>2</sub>(OH)CF<sub>2</sub>OO + NO<sub>2</sub>→CF<sub>2</sub>(OH)CF<sub>2</sub>OONO<sub>2</sub> and CF<sub>3</sub>CF<sub>2</sub>OO + NO<sub>2</sub>→CF<sub>3</sub>CF<sub>2</sub>OONO<sub>2</sub> recombination reactions and their reverse unimolecular decomposition process was performed. The electronic energy along the reaction pathways was calculated at the G4(MP2) level. High-pressure rate coefficients of 1.53 x 10<sup>-12</sup> (T/300<sup>)0.37</sup> cm<sup>3</sup> molecule<sup>-1</sup> s<sup>-1</sup> and 1.79 x 10<sup>16</sup> (T/300)<sup>0.40</sup> exp (-24.4 kcal mol<sup>-1</sup>/RT) s<sup>-1</sup> were derived at 200–300 K for the direct and backward reactions of CF<sub>2</sub>(OH) CF<sub>2</sub>OONO<sub>2</sub>, while for CF<sub>3</sub>CF<sub>2</sub>OONO<sub>2</sub>, the expressions 1.01 x 10<sup>-12</sup> (T/300)<sup>0.39</sup> cm<sup>3</sup> molecule<sup>-1</sup> s<sup>-1</sup> and 1.05 x 1016 (T/300)<subp>0.44</sup> exp(-23.0 kcal mol<sup>-1</sup>/RT) s<sup>-1</sup> were obtained. A decomposition lifetime profile was derived for CF<sub>2</sub>(OH)CF<sub>2</sub>OONO<sub>2</sub>, indicating that it could act as transport and reservoir of CF<sub>2</sub>(OH) CF<sub>2</sub>OO and NO<sub>2</sub> in the stratosphere.
format Articulo
Articulo
author Badenes, María Paula
author_facet Badenes, María Paula
author_sort Badenes, María Paula
title Formation, thermal decomposition and atmospheric implications of the CF<sub>2</sub>(OH)CF<sub>2</sub>OONO<sub>2</sub> and CF<sub>3</sub>CF<sub>2</sub>OONO<sub>2</sub> peroxynitrates: a theoretical study
title_short Formation, thermal decomposition and atmospheric implications of the CF<sub>2</sub>(OH)CF<sub>2</sub>OONO<sub>2</sub> and CF<sub>3</sub>CF<sub>2</sub>OONO<sub>2</sub> peroxynitrates: a theoretical study
title_full Formation, thermal decomposition and atmospheric implications of the CF<sub>2</sub>(OH)CF<sub>2</sub>OONO<sub>2</sub> and CF<sub>3</sub>CF<sub>2</sub>OONO<sub>2</sub> peroxynitrates: a theoretical study
title_fullStr Formation, thermal decomposition and atmospheric implications of the CF<sub>2</sub>(OH)CF<sub>2</sub>OONO<sub>2</sub> and CF<sub>3</sub>CF<sub>2</sub>OONO<sub>2</sub> peroxynitrates: a theoretical study
title_full_unstemmed Formation, thermal decomposition and atmospheric implications of the CF<sub>2</sub>(OH)CF<sub>2</sub>OONO<sub>2</sub> and CF<sub>3</sub>CF<sub>2</sub>OONO<sub>2</sub> peroxynitrates: a theoretical study
title_sort formation, thermal decomposition and atmospheric implications of the cf<sub>2</sub>(oh)cf<sub>2</sub>oono<sub>2</sub> and cf<sub>3</sub>cf<sub>2</sub>oono<sub>2</sub> peroxynitrates: a theoretical study
publishDate 2017
url http://sedici.unlp.edu.ar/handle/10915/103538
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bdutipo_str Repositorios
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