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

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

doi:10.1021/j100271a038

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

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

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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, k_4a; SH + H₂O₂ → HSOH + OH, k_4b; SH + H₂O₂ → HSO + H₂O, k_4c. k₄ = k_4a + k_4b + k_4c < 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 language	English (US)
Pages (from-to)	5505-5510
Number of pages	6
Journal	Journal of physical chemistry
Volume	89
Issue number	25
DOIs	https://doi.org/10.1021/j100271a038
State	Published - 1985

All Science Journal Classification (ASJC) codes

General Engineering
Physical and Theoretical Chemistry

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10.1021/j100271a038

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@article{62625c95ed434774a01565addc392339,

title = "Kinetics of SH with NO2, O3, O2, and H2O2",

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.",

author = "Friedl, {Randall R.} and Brune, {William H.} and Anderson, {James G.}",

year = "1985",

doi = "10.1021/j100271a038",

language = "English (US)",

volume = "89",

pages = "5505--5510",

journal = "Journal of physical chemistry",

issn = "0022-3654",

publisher = "American Chemical Society",

number = "25",

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TY - JOUR

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

AU - Friedl, Randall R.

AU - Brune, William H.

AU - Anderson, James G.

PY - 1985

Y1 - 1985

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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JO - Journal of physical chemistry

JF - Journal of physical chemistry

IS - 25

ER -

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

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