Temperature dependence of the rate constant and the branching ratio for the reaction Cl+HO2

Yuan-Pern Lee; Carleton J. Howard

doi:10.1063/1.443892

Temperature dependence of the rate constant and the branching ratio for the reaction Cl+HO₂

Yuan-Pern Lee^*, Carleton J. Howard

^*Corresponding author for this work

Department of Applied Chemistry

Research output: Contribution to journal › Article › peer-review

44 Scopus citations

Abstract

The rate constant and branching ratio for the reaction Cl+HO ₂-HCl+O₂ (1a) -OH+ClO, (1b) have been measured in a discharge-flow system with far infrared laser magnetic resonance detection of HO₂, OH and ClO. Chlorine atom concentrations were determined by titration with O₃ and detected as ClO. Measurements were made at low pressure (0.9-1.5 Torr) and at temperatures between 250 and 420 K under pseudo-first-order conditions. The total rate constant showed no significant temperature dependence k₁ = (4.2±0.7)±10^-11 cm^-3 molecule^-1 s^-1. k_1a = (1.8 ±0.5)×10^-11 exp[(170±80)/T]cm³ molecule^-1 s^-1, and k_1b = (4.1±0.8) ×10^-11exp[(-450±60)/T] cm³ molecule ^-1 s^-1, the latter corresponds to about 20% of k ₁ at 298 K. The errors are 95% confidence limits and include a factor for possible systematic errors.

Original language	English
Pages (from-to)	756-763
Number of pages	8
Journal	The Journal of chemical physics
Volume	77
Issue number	2
DOIs	https://doi.org/10.1063/1.443892
State	Published - Jul 1982

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@article{431e1393385c4f8cbf3429cac28f3db9,

title = "Temperature dependence of the rate constant and the branching ratio for the reaction Cl+HO2",

abstract = "The rate constant and branching ratio for the reaction Cl+HO 2-HCl+O2 (1a) -OH+ClO, (1b) have been measured in a discharge-flow system with far infrared laser magnetic resonance detection of HO2, OH and ClO. Chlorine atom concentrations were determined by titration with O3 and detected as ClO. Measurements were made at low pressure (0.9-1.5 Torr) and at temperatures between 250 and 420 K under pseudo-first-order conditions. The total rate constant showed no significant temperature dependence k1 = (4.2±0.7)±10-11 cm-3 molecule-1 s-1. k1a = (1.8 ±0.5)×10-11 exp[(170±80)/T]cm3 molecule-1 s-1, and k1b = (4.1±0.8) ×10-11exp[(-450±60)/T] cm3 molecule -1 s-1, the latter corresponds to about 20% of k 1 at 298 K. The errors are 95% confidence limits and include a factor for possible systematic errors.",

author = "Yuan-Pern Lee and Howard, {Carleton J.}",

year = "1982",

month = jul,

doi = "10.1063/1.443892",

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pages = "756--763",

journal = "The Journal of chemical physics",

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T1 - Temperature dependence of the rate constant and the branching ratio for the reaction Cl+HO2

AU - Lee, Yuan-Pern

AU - Howard, Carleton J.

PY - 1982/7

Y1 - 1982/7

N2 - The rate constant and branching ratio for the reaction Cl+HO 2-HCl+O2 (1a) -OH+ClO, (1b) have been measured in a discharge-flow system with far infrared laser magnetic resonance detection of HO2, OH and ClO. Chlorine atom concentrations were determined by titration with O3 and detected as ClO. Measurements were made at low pressure (0.9-1.5 Torr) and at temperatures between 250 and 420 K under pseudo-first-order conditions. The total rate constant showed no significant temperature dependence k1 = (4.2±0.7)±10-11 cm-3 molecule-1 s-1. k1a = (1.8 ±0.5)×10-11 exp[(170±80)/T]cm3 molecule-1 s-1, and k1b = (4.1±0.8) ×10-11exp[(-450±60)/T] cm3 molecule -1 s-1, the latter corresponds to about 20% of k 1 at 298 K. The errors are 95% confidence limits and include a factor for possible systematic errors.

AB - The rate constant and branching ratio for the reaction Cl+HO 2-HCl+O2 (1a) -OH+ClO, (1b) have been measured in a discharge-flow system with far infrared laser magnetic resonance detection of HO2, OH and ClO. Chlorine atom concentrations were determined by titration with O3 and detected as ClO. Measurements were made at low pressure (0.9-1.5 Torr) and at temperatures between 250 and 420 K under pseudo-first-order conditions. The total rate constant showed no significant temperature dependence k1 = (4.2±0.7)±10-11 cm-3 molecule-1 s-1. k1a = (1.8 ±0.5)×10-11 exp[(170±80)/T]cm3 molecule-1 s-1, and k1b = (4.1±0.8) ×10-11exp[(-450±60)/T] cm3 molecule -1 s-1, the latter corresponds to about 20% of k 1 at 298 K. The errors are 95% confidence limits and include a factor for possible systematic errors.

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ER -

Temperature dependence of the rate constant and the branching ratio for the reaction Cl+HO₂

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