Kinetics of SH with NO2, O3, O2, and H2O2

Randall R. Friedl, William H. Brune, James G. Anderson

Research output: Contribution to journalArticle

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Abstract

A low pressure (1-8 torr of He) discharge flow reactor with (a) LIF detection of SH using a high repetition rate (20 kHz) metal atom laser to circumvent severe predissociation of the A2Σ+ state and (b) resonance fluorescence detection of OH has been used to examine the kinetics of the title reactions at 298 K: SH + NO2 → HSO + NO, k1 = (3.0 ± 0.8) × 10-11 cm3 s-1; SH + O3 → HSO + O2, k2 = (3.2 ± 1.0) × 10-12 cm3 s-1; SH + O2 → SO + OH, k3 < 1 × 10-17 cm3 s-1; SH + H2O2 → H2S + HO2, k4a; SH + H2O2 → HSOH + OH, k4b; SH + H2O2 → HSO + H2O, k4c. k4 = k4a + k4b + k4c < 5 × 10-15 cm3 s-1. Regeneration of SH in reaction 2 by HSO + O3 is observed and is used to infer a rate constant for HSO + O3 → products of (1.0 ± 0.4) × 10-13 cm3 s-1. Absence of OH production in that reaction implies that the primary products are SH + 2O2. Isotope experiments with H2S replaced by D2S substantiate that conclusion and yield a reaction rate constant for DSO + O3 → SD + 2O2 of 9 × 10-14 cm3 s-1. Brief discussions of SH reactivity compared with OH and Br are offered, as well as a summary of the atmospheric chemistry of SH.

Original languageEnglish (US)
Pages (from-to)5505-5510
Number of pages6
JournalJournal of physical chemistry
Volume89
Issue number25
StatePublished - Dec 1 1985

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Atom lasers
Rate constants
Atmospheric chemistry
Kinetics
kinetics
Isotopes
Reaction rates
atmospheric chemistry
Metals
Fluorescence
resonance fluorescence
products
regeneration
laser induced fluorescence
repetition
reaction kinetics
low pressure
reactivity
isotopes
reactors

All Science Journal Classification (ASJC) codes

  • Engineering(all)
  • Physical and Theoretical Chemistry

Cite this

Friedl, R. R., Brune, W. H., & Anderson, J. G. (1985). Kinetics of SH with NO2, O3, O2, and H2O2. Journal of physical chemistry, 89(25), 5505-5510.
Friedl, Randall R. ; Brune, William H. ; Anderson, James G. / Kinetics of SH with NO2, O3, O2, and H2O2. In: Journal of physical chemistry. 1985 ; Vol. 89, No. 25. pp. 5505-5510.
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abstract = "A low pressure (1-8 torr of He) discharge flow reactor with (a) LIF detection of SH using a high repetition rate (20 kHz) metal atom laser to circumvent severe predissociation of the A2Σ+ state and (b) resonance fluorescence detection of OH has been used to examine the kinetics of the title reactions at 298 K: SH + NO2 → HSO + NO, k1 = (3.0 ± 0.8) × 10-11 cm3 s-1; SH + O3 → HSO + O2, k2 = (3.2 ± 1.0) × 10-12 cm3 s-1; SH + O2 → SO + OH, k3 < 1 × 10-17 cm3 s-1; SH + H2O2 → H2S + HO2, k4a; SH + H2O2 → HSOH + OH, k4b; SH + H2O2 → HSO + H2O, k4c. k4 = k4a + k4b + k4c < 5 × 10-15 cm3 s-1. Regeneration of SH in reaction 2 by HSO + O3 is observed and is used to infer a rate constant for HSO + O3 → products of (1.0 ± 0.4) × 10-13 cm3 s-1. Absence of OH production in that reaction implies that the primary products are SH + 2O2. Isotope experiments with H2S replaced by D2S substantiate that conclusion and yield a reaction rate constant for DSO + O3 → SD + 2O2 of 9 × 10-14 cm3 s-1. Brief discussions of SH reactivity compared with OH and Br are offered, as well as a summary of the atmospheric chemistry of SH.",
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Friedl, RR, Brune, WH & Anderson, JG 1985, 'Kinetics of SH with NO2, O3, O2, and H2O2', Journal of physical chemistry, vol. 89, no. 25, pp. 5505-5510.

Kinetics of SH with NO2, O3, O2, and H2O2. / Friedl, Randall R.; Brune, William H.; Anderson, James G.

In: Journal of physical chemistry, Vol. 89, No. 25, 01.12.1985, p. 5505-5510.

Research output: Contribution to journalArticle

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T1 - Kinetics of SH with NO2, O3, O2, and H2O2

AU - Friedl, Randall R.

AU - Brune, William H.

AU - Anderson, James G.

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N2 - A low pressure (1-8 torr of He) discharge flow reactor with (a) LIF detection of SH using a high repetition rate (20 kHz) metal atom laser to circumvent severe predissociation of the A2Σ+ state and (b) resonance fluorescence detection of OH has been used to examine the kinetics of the title reactions at 298 K: SH + NO2 → HSO + NO, k1 = (3.0 ± 0.8) × 10-11 cm3 s-1; SH + O3 → HSO + O2, k2 = (3.2 ± 1.0) × 10-12 cm3 s-1; SH + O2 → SO + OH, k3 < 1 × 10-17 cm3 s-1; SH + H2O2 → H2S + HO2, k4a; SH + H2O2 → HSOH + OH, k4b; SH + H2O2 → HSO + H2O, k4c. k4 = k4a + k4b + k4c < 5 × 10-15 cm3 s-1. Regeneration of SH in reaction 2 by HSO + O3 is observed and is used to infer a rate constant for HSO + O3 → products of (1.0 ± 0.4) × 10-13 cm3 s-1. Absence of OH production in that reaction implies that the primary products are SH + 2O2. Isotope experiments with H2S replaced by D2S substantiate that conclusion and yield a reaction rate constant for DSO + O3 → SD + 2O2 of 9 × 10-14 cm3 s-1. Brief discussions of SH reactivity compared with OH and Br are offered, as well as a summary of the atmospheric chemistry of SH.

AB - A low pressure (1-8 torr of He) discharge flow reactor with (a) LIF detection of SH using a high repetition rate (20 kHz) metal atom laser to circumvent severe predissociation of the A2Σ+ state and (b) resonance fluorescence detection of OH has been used to examine the kinetics of the title reactions at 298 K: SH + NO2 → HSO + NO, k1 = (3.0 ± 0.8) × 10-11 cm3 s-1; SH + O3 → HSO + O2, k2 = (3.2 ± 1.0) × 10-12 cm3 s-1; SH + O2 → SO + OH, k3 < 1 × 10-17 cm3 s-1; SH + H2O2 → H2S + HO2, k4a; SH + H2O2 → HSOH + OH, k4b; SH + H2O2 → HSO + H2O, k4c. k4 = k4a + k4b + k4c < 5 × 10-15 cm3 s-1. Regeneration of SH in reaction 2 by HSO + O3 is observed and is used to infer a rate constant for HSO + O3 → products of (1.0 ± 0.4) × 10-13 cm3 s-1. Absence of OH production in that reaction implies that the primary products are SH + 2O2. Isotope experiments with H2S replaced by D2S substantiate that conclusion and yield a reaction rate constant for DSO + O3 → SD + 2O2 of 9 × 10-14 cm3 s-1. Brief discussions of SH reactivity compared with OH and Br are offered, as well as a summary of the atmospheric chemistry of SH.

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Friedl RR, Brune WH, Anderson JG. Kinetics of SH with NO2, O3, O2, and H2O2. Journal of physical chemistry. 1985 Dec 1;89(25):5505-5510.