A theoretical study of the thermal stability of the FS(O<SUB>2</SUB>)OSO<SUB>2</SUB> radical and the recombination kinetics with the FSO<SUB>3</SUB> radical

The kinetics of the thermal reaction of FS(O2)OO(O2)SF with SO2 have been theoretically studied. Experimental investigations performed at 293–323 K indicate that the FSO3 radical, in equilibrium with the peroxide FS(O2)OO(O2)SF ¢ 2 FSO3 (1, -1), initially attacks the SO2 forming the FS(O2)OSO2 radic...

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Detalles Bibliográficos
Autores principales: Badenes, María Paula, Cobos, Carlos Jorge, Croce, Adela Ester
Formato: Articulo
Lenguaje:Inglés
Publicado: 2018
Materias:
Química
FSO<SUB>3</SUB>, FS(O<SUB>2</SUB>)OSO<SUB>2</SUB>, (FS(O<SUB>2</SUB>)O)<SUB>2</SUB>SO<SUB>2</SUB>, quantum-chemical calculations, transition state theory, statistical adiabatic channel model
Acceso en línea:http://sedici.unlp.edu.ar/handle/10915/73218
Aporte de:
SEDICI (UNLP) de Universidad Nacional de La Plata
id I19-R120-10915-73218
record_format dspace
institution Universidad Nacional de La Plata
institution_str I-19
repository_str R-120
collection SEDICI (UNLP)
language Inglés
topic Química
FSO<SUB>3</SUB>, FS(O<SUB>2</SUB>)OSO<SUB>2</SUB>, (FS(O<SUB>2</SUB>)O)<SUB>2</SUB>SO<SUB>2</SUB>, quantum-chemical calculations, transition state theory, statistical adiabatic channel model
spellingShingle Química
FSO<SUB>3</SUB>, FS(O<SUB>2</SUB>)OSO<SUB>2</SUB>, (FS(O<SUB>2</SUB>)O)<SUB>2</SUB>SO<SUB>2</SUB>, quantum-chemical calculations, transition state theory, statistical adiabatic channel model
Badenes, María Paula
Cobos, Carlos Jorge
Croce, Adela Ester
A theoretical study of the thermal stability of the FS(O<SUB>2</SUB>)OSO<SUB>2</SUB> radical and the recombination kinetics with the FSO<SUB>3</SUB> radical
topic_facet Química
FSO<SUB>3</SUB>, FS(O<SUB>2</SUB>)OSO<SUB>2</SUB>, (FS(O<SUB>2</SUB>)O)<SUB>2</SUB>SO<SUB>2</SUB>, quantum-chemical calculations, transition state theory, statistical adiabatic channel model
description The kinetics of the thermal reaction of FS(O2)OO(O2)SF with SO2 have been theoretically studied. Experimental investigations performed at 293–323 K indicate that the FSO3 radical, in equilibrium with the peroxide FS(O2)OO(O2)SF ¢ 2 FSO3 (1, -1), initially attacks the SO2 forming the FS(O2)OSO2 radical which afterwards may dissociate back, FSO3 + SO2 ¢FS(O2)OSO2 (2, -2), or recombinewith FSO3 generating the final product, FSO3 + FS(O2)OSO2? (FS(O2)O)2SO2 (3). Several DFT formulations and composite ab initio models were employed to characterize FS(O2)OSO2 molecular properties and to determine relevant potential energy surfaces features of reactions (2), (-2) and (3). Transition state theory calculations lead to the high pressure rate coefficients k1;2 ¼ 9:1 10 14 expð 5:2 kcal mol 1 = RTÞ cm3 molecule 1 s 1 and k1; 2 ¼ 4:9 1015 expð 13:9 kcal mol 1 =RTÞ s 1 while statistical adiabatic channel model (SACM/CT) calculations predict for the barrierless reaction (3) the expression k1;3 ¼ 2:9 10 11ðT=300Þ0:4 cm3 molecule 1 s 1. The experimental phenomenological rate coefficients are very well reproduced by these rate coefficients.
format Articulo
Articulo
author Badenes, María Paula
Cobos, Carlos Jorge
Croce, Adela Ester
author_facet Badenes, María Paula
Cobos, Carlos Jorge
Croce, Adela Ester
author_sort Badenes, María Paula
title A theoretical study of the thermal stability of the FS(O<SUB>2</SUB>)OSO<SUB>2</SUB> radical and the recombination kinetics with the FSO<SUB>3</SUB> radical
title_short A theoretical study of the thermal stability of the FS(O<SUB>2</SUB>)OSO<SUB>2</SUB> radical and the recombination kinetics with the FSO<SUB>3</SUB> radical
title_full A theoretical study of the thermal stability of the FS(O<SUB>2</SUB>)OSO<SUB>2</SUB> radical and the recombination kinetics with the FSO<SUB>3</SUB> radical
title_fullStr A theoretical study of the thermal stability of the FS(O<SUB>2</SUB>)OSO<SUB>2</SUB> radical and the recombination kinetics with the FSO<SUB>3</SUB> radical
title_full_unstemmed A theoretical study of the thermal stability of the FS(O<SUB>2</SUB>)OSO<SUB>2</SUB> radical and the recombination kinetics with the FSO<SUB>3</SUB> radical
title_sort theoretical study of the thermal stability of the fs(o<sub>2</sub>)oso<sub>2</sub> radical and the recombination kinetics with the fso<sub>3</sub> radical
publishDate 2018
url http://sedici.unlp.edu.ar/handle/10915/73218
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