Rate constant for the reaction Br + O3 → BrO + O2 from 248 to 418 K: Kinetics and mechanism

Darin W. Toohey; Wm H. Brune; J. G. Anderson

doi:10.1002/kin.550200206

Rate constant for the reaction Br + O₃ → BrO + O₂ from 248 to 418 K: Kinetics and mechanism

Darin W. Toohey, Wm H. Brune, J. G. Anderson

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Abstract

The rate constant for the Br + O₃ → BrO + O₂ reaction was measured by the discharge flow technique, employing resonance fluorescence detection of Br. Over the temperature range 248 to 418 K, in 1 to 3 torr of He, decays of Br in excess O₃ yield the value k₁ = (3.28 ± 0.40) × 10⁻¹¹ e^{[−944±30]/T} cm³ molecule⁻¹ s⁻¹. Cited uncertainties are at the 95% confidence level and include an estimate of the systematic errors. The rate constants for the reactions of O₃ with Br, Cl, F, OH, O, and N correlate with the electron affinities of the radicals suggesting that the reactions proceed through early transition states dominated by transfer of electron density from the highest occupied molecular orbital of ozone to the singly occupied radical MO. The implications of this new measurement of k₁ for stratospheric chemistry are discussed.

Original language	English (US)
Pages (from-to)	131-144
Number of pages	14
Journal	International Journal of Chemical Kinetics
Volume	20
Issue number	2
DOIs	https://doi.org/10.1002/kin.550200206
State	Published - Feb 1988

All Science Journal Classification (ASJC) codes

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Rate constant for the reaction Br + O3 → BrO + O2 from 248 to 418 K: Kinetics and mechanism",

abstract = "The rate constant for the Br + O3 → BrO + O2 reaction was measured by the discharge flow technique, employing resonance fluorescence detection of Br. Over the temperature range 248 to 418 K, in 1 to 3 torr of He, decays of Br in excess O3 yield the value k1 = (3.28 ± 0.40) × 10−11 e[−944±30]/T cm3 molecule−1 s−1. Cited uncertainties are at the 95% confidence level and include an estimate of the systematic errors. The rate constants for the reactions of O3 with Br, Cl, F, OH, O, and N correlate with the electron affinities of the radicals suggesting that the reactions proceed through early transition states dominated by transfer of electron density from the highest occupied molecular orbital of ozone to the singly occupied radical MO. The implications of this new measurement of k1 for stratospheric chemistry are discussed.",

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T1 - Rate constant for the reaction Br + O3 → BrO + O2 from 248 to 418 K

T2 - Kinetics and mechanism

AU - Toohey, Darin W.

AU - Brune, Wm H.

AU - Anderson, J. G.

PY - 1988/2

Y1 - 1988/2

N2 - The rate constant for the Br + O3 → BrO + O2 reaction was measured by the discharge flow technique, employing resonance fluorescence detection of Br. Over the temperature range 248 to 418 K, in 1 to 3 torr of He, decays of Br in excess O3 yield the value k1 = (3.28 ± 0.40) × 10−11 e[−944±30]/T cm3 molecule−1 s−1. Cited uncertainties are at the 95% confidence level and include an estimate of the systematic errors. The rate constants for the reactions of O3 with Br, Cl, F, OH, O, and N correlate with the electron affinities of the radicals suggesting that the reactions proceed through early transition states dominated by transfer of electron density from the highest occupied molecular orbital of ozone to the singly occupied radical MO. The implications of this new measurement of k1 for stratospheric chemistry are discussed.

AB - The rate constant for the Br + O3 → BrO + O2 reaction was measured by the discharge flow technique, employing resonance fluorescence detection of Br. Over the temperature range 248 to 418 K, in 1 to 3 torr of He, decays of Br in excess O3 yield the value k1 = (3.28 ± 0.40) × 10−11 e[−944±30]/T cm3 molecule−1 s−1. Cited uncertainties are at the 95% confidence level and include an estimate of the systematic errors. The rate constants for the reactions of O3 with Br, Cl, F, OH, O, and N correlate with the electron affinities of the radicals suggesting that the reactions proceed through early transition states dominated by transfer of electron density from the highest occupied molecular orbital of ozone to the singly occupied radical MO. The implications of this new measurement of k1 for stratospheric chemistry are discussed.

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Rate constant for the reaction Br + O₃ → BrO + O₂ from 248 to 418 K: Kinetics and mechanism

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