Rate coefficients for the reaction of chlorine atoms with Fs(O<SUB>2</SUB>)O and Fs(O<SUB>2</SUB>)OCl at 298 k

The kinetics of the recombination reaction Cl + FS(O2)O → FS(O2)OCl (1) has been studied by using an ArF excimer laser flash photolysis technique over the 25-950 mbar total pressure range of the bath gases He, N2 and CF4 at 298 K. The reaction was found to be essentially in the second-order regime....

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Autores principales: Tucceri, María Eugenia, Castellano, Enrique, Croce, Adela Ester, Cobos, Carlos Jorge
Formato: Articulo
Lenguaje:Inglés
Publicado: 2005
Materias:
Química
Acceso en línea:http://sedici.unlp.edu.ar/handle/10915/175803
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SEDICI (UNLP) de Universidad Nacional de La Plata
id I19-R120-10915-175803
record_format dspace
spelling I19-R120-10915-1758032025-01-29T20:15:27Z http://sedici.unlp.edu.ar/handle/10915/175803 Rate coefficients for the reaction of chlorine atoms with Fs(O<SUB>2</SUB>)O and Fs(O<SUB>2</SUB>)OCl at 298 k Tucceri, María Eugenia Castellano, Enrique Croce, Adela Ester Cobos, Carlos Jorge 2005 2025-01-29T14:30:53Z en Química The kinetics of the recombination reaction Cl + FS(O2)O → FS(O2)OCl (1) has been studied by using an ArF excimer laser flash photolysis technique over the 25-950 mbar total pressure range of the bath gases He, N2 and CF4 at 298 K. The reaction was found to be essentially in the second-order regime. The derived limiting high-pressure rate coefficient is k1,∞=(1.3±0.3)x10-10 cm3 molecule-1 s-1. For the reaction Cl + FS(O2)OCl → FS(O2)O + Cl2 (2) a rate coefficient of k2 = (2.1±0.9)x10-11 cm3 molecule-1 s-1 was measured. The ratio between both rate coefficients of 0.16 agrees very well with data determined by Vasini and Schumacher. Quantum chemical calculations carried out at the G3MP2//B3LYP/6- 311+G(3df) level of theory allow to determine an standard heat of formation of -136.5 kcal mol-1 for FS(O2)OCl. Rate coefficient calculations in the framework of the phase space theory, performed on a G3MP2B3 electronic potential, indicate that central forces mainly dominate the present recombination reaction. La técnica de fotólisis flash con láser del excímero ArF se empleó para estudiar la cinética de la reacción de recombinación Cl + FS(O2)O → FS(O2)OCl (1) a presiones totales comprendidas entre 25 y 950 mbar de los gases He, N2 y CF4 y a 298 K. La reacción se encuentra esencialmente en la región de segundo orden. El coeficiente de velocidad determinado en el límite de alta presión es k1,∞=(1,3±0,3)x10-10 cm3 molécula-1 s-1. Se midió el coeficiente de velocidad k2=(2,1±0,9)x10-11 cm3 molécula-1 s-1 para la reacción Cl + FS(O2)OCl → FS(O2)O + Cl2 (2). El cociente entre ambos coeficientes de velocidad es 0,16 y se encuentra en muy buen acuerdo con el valor determinado por Vasini y Schumacher. Se calculó el valor -136,5 kcal mol-1 para el calor de formación estándar de FS(O2)OCl mediante el modelo G3MP2//B3LYP/6-311+G(3df). A partir de cálculos realizados mediante la teoría del espacio de las fases se encontró que la reacción de recombinación estudiada se encuentra dominada principalmente por fuerzas centrales. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas Articulo Articulo http://creativecommons.org/licenses/by-nc-sa/4.0/ Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0) application/pdf 29-41
institution Universidad Nacional de La Plata
institution_str I-19
repository_str R-120
collection SEDICI (UNLP)
language Inglés
topic Química
spellingShingle Química
Tucceri, María Eugenia
Castellano, Enrique
Croce, Adela Ester
Cobos, Carlos Jorge
Rate coefficients for the reaction of chlorine atoms with Fs(O<SUB>2</SUB>)O and Fs(O<SUB>2</SUB>)OCl at 298 k
topic_facet Química
description The kinetics of the recombination reaction Cl + FS(O2)O → FS(O2)OCl (1) has been studied by using an ArF excimer laser flash photolysis technique over the 25-950 mbar total pressure range of the bath gases He, N2 and CF4 at 298 K. The reaction was found to be essentially in the second-order regime. The derived limiting high-pressure rate coefficient is k1,∞=(1.3±0.3)x10-10 cm3 molecule-1 s-1. For the reaction Cl + FS(O2)OCl → FS(O2)O + Cl2 (2) a rate coefficient of k2 = (2.1±0.9)x10-11 cm3 molecule-1 s-1 was measured. The ratio between both rate coefficients of 0.16 agrees very well with data determined by Vasini and Schumacher. Quantum chemical calculations carried out at the G3MP2//B3LYP/6- 311+G(3df) level of theory allow to determine an standard heat of formation of -136.5 kcal mol-1 for FS(O2)OCl. Rate coefficient calculations in the framework of the phase space theory, performed on a G3MP2B3 electronic potential, indicate that central forces mainly dominate the present recombination reaction.
format Articulo
Articulo
author Tucceri, María Eugenia
Castellano, Enrique
Croce, Adela Ester
Cobos, Carlos Jorge
author_facet Tucceri, María Eugenia
Castellano, Enrique
Croce, Adela Ester
Cobos, Carlos Jorge
author_sort Tucceri, María Eugenia
title Rate coefficients for the reaction of chlorine atoms with Fs(O<SUB>2</SUB>)O and Fs(O<SUB>2</SUB>)OCl at 298 k
title_short Rate coefficients for the reaction of chlorine atoms with Fs(O<SUB>2</SUB>)O and Fs(O<SUB>2</SUB>)OCl at 298 k
title_full Rate coefficients for the reaction of chlorine atoms with Fs(O<SUB>2</SUB>)O and Fs(O<SUB>2</SUB>)OCl at 298 k
title_fullStr Rate coefficients for the reaction of chlorine atoms with Fs(O<SUB>2</SUB>)O and Fs(O<SUB>2</SUB>)OCl at 298 k
title_full_unstemmed Rate coefficients for the reaction of chlorine atoms with Fs(O<SUB>2</SUB>)O and Fs(O<SUB>2</SUB>)OCl at 298 k
title_sort rate coefficients for the reaction of chlorine atoms with fs(o<sub>2</sub>)o and fs(o<sub>2</sub>)ocl at 298 k
publishDate 2005
url http://sedici.unlp.edu.ar/handle/10915/175803
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