Kinetics of dimethyl sulfide (DMS) reactions with isoprene-derived Criegee intermediates studied with direct UV absorption

Abstract. Criegee intermediates (CIs) are formed in the ozonolysis of unsaturated hydrocarbons and play a role in atmospheric chemistry as a non-photolytic OH source or a strong oxidant. Using a relative rate method in an ozonolysis experiment, Newland et al. (2015) reported high reactivity of isoprene-derived Criegee intermediates towards dimethyl sulfide (DMS) relative to that towards SO2 with the ratio of the rate coefficients kDMS+CI/kSO2+CI = 3.5 ± 1.8. Here we reinvestigated the kinetics of DMS reactions with two major Criegee intermediates formed in isoprene ozonolysis, CH2OO, and methyl vinyl ketone oxide (MVKO). The individual CI was prepared following the reported photolytic method with suitable (diiodo) precursors in the presence of O2. The concentration of CH2OO or MVKO was monitored directly in real time through their intense UV–visible absorption. Our results indicate the reactions of DMS with CH2OO and MVKO are both very slow; the upper limits of the rate coefficients are 4 orders of magnitude smaller than the rate coefficient reported by Newland et al. (2015) These results suggest that the ozonolysis experiment could be complicated such that interpretation should be careful and these CIs would not oxidize atmospheric DMS at any substantial level.

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Kinetics of dimethyl sulfide (DMS) reactions with isoprene-derived Criegee intermediates studied with direct UV absorption

10.5194/acp-2020-484 ◽

2020 ◽

Author(s):

Mei-Tsan Kuo ◽

Isabelle Weber ◽

Christa Fittschen ◽

Luc Vereecken ◽

Jim Jr-Min Lin

Keyword(s):

Atmospheric Chemistry ◽

Dimethyl Sulfide ◽

Relative Rate ◽

High Reactivity ◽

Rate Coefficients ◽

Visible Absorption ◽

Criegee Intermediates ◽

Upper Limits ◽

The Individual ◽

Kinetics Of

Abstract. Criegee intermediates (CIs) are formed in the ozonolysis of unsaturated hydrocarbons and play a role in atmospheric chemistry as a non-photolytic OH source or a strong oxidant. Using a relative rate method in an ozonolysis experiment, Newland et al. (2015) reported high reactivity of isoprene-derived Criegee intermediates towards dimethyl sulfide (DMS) relative to that towards SO2 with the ratio of the rate coefficients kDMS+CI/kSO2+CI = 3.5 ± 1.8. Here we reinvestigated the kinetics of DMS reactions with two major Criegee intermediates formed in isoprene ozonolysis, CH2OO and methyl vinyl ketone oxide (MVKO). The individual CI was prepared following reported photolytic method with suitable (diiodo) precursors in the presence of O2. The concentration of CH2OO or MVKO was monitored directly in real time through their intense UV-visible absorption. Our results indicate the reactions of DMS with CH2OO and MVKO are both very slow; the upper limits of the rate coefficients are 4 orders of magnitude smaller than that reported by Newland et al. These results suggest that the ozonolysis experiment could be complicated such that interpretation should be careful and these CIs would not oxidize atmospheric DMS at any substantial level.

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Kinetics of dimethyl sulfide (DMS) reactions with isoprene-derived Criegee intermediates studied with direct UV absorption

10.5194/acp-2020-326 ◽

2020 ◽

Author(s):

Mei-Tsan Kuo ◽

Isabelle Weber ◽

Christa Fittschen ◽

Jim Jr-Min Lin

Keyword(s):

Atmospheric Chemistry ◽

Dimethyl Sulfide ◽

Relative Rate ◽

Chem Phys ◽

High Reactivity ◽

Rate Coefficients ◽

Visible Absorption ◽

Criegee Intermediates ◽

The Individual ◽

Kinetics Of

Abstract. Criegee intermediates (CIs) are formed in the ozonolysis of unsaturated hydrocarbons and play a role in atmospheric chemistry as a non-photolytic OH source or a strong oxidant. Using a relative rate method in an ozonolysis experiment, Newland et al. [Atmos. Chem. Phys., 15, 9521–9536, 2015] reported high reactivity of isoprene-derived Criegee intermediates towards dimethyl sulfide (DMS) relative to that towards SO2 with the ratio of the rate coefficients kDMS+CI / kSO2+CI = 3.5 ± 1.8. Here we reinvestigated the kinetics of DMS reactions with two major Criegee intermediates formed in isoprene ozonolysis, CH2OO and methyl vinyl ketone oxide (MVKO). The individual CI was prepared following reported photolytic method with suitable (diiodo) precursors in the presence of O2. The concentration of CH2OO or MVKO was monitored directly in real time through their intense UV-visible absorption. Our results indicate the reactions of DMS with CH2OO and MVKO are both very slow; the upper limits of the rate coefficients are 4 orders of magnitude smaller than that reported by Newland et al. These results suggest that the ozonolysis experiment could be complicated such that interpretation should be careful and these CIs would not oxidize atmospheric DMS at any substantial level.

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The atmospheric chemistry of sulphuryl fluoride, SO2F2

Atmospheric Chemistry and Physics ◽

10.5194/acp-8-1547-2008 ◽

2008 ◽

Vol 8 (6) ◽

pp. 1547-1557 ◽

Cited By ~ 19

Author(s):

T. J. Dillon ◽

A. Horowitz ◽

J. N. Crowley

Keyword(s):

Atmospheric Chemistry ◽

Rate Coefficient ◽

Relative Rate ◽

Significant Loss ◽

Rate Coefficients ◽

Atmospheric Species ◽

Upper Limits ◽

Wall Flow ◽

Temperature Rate ◽

Good Agreement

Abstract. The atmospheric chemistry of sulphuryl fluoride, SO2F2, was investigated in a series of laboratory studies. A competitive rate method, using pulsed laser photolysis (PLP) to generate O(1D) coupled to detection of OH by laser induced fluorescence (LIF), was used to determine the overall rate coefficient for the reaction O(1D) + SO2F2 → products (R1) of k1 (220–300 K) = (1.3 ± 0.2) × 10−10 cm3 molecule−1 s−1. Monitoring the O(3P) product (R1a) enabled the contribution (α) of the physical quenching process (in which SO2F2 is not consumed) to be determined as α (225–296 K)=(0.55 ± 0.04). Separate, relative rate measurements at 298 K provided a rate coefficient for reactive loss of O(1D), k1b, of (5.8 ± 0.8) × 10−11 cm3 molecule−1 s−1 in good agreement with the value calculated from (1−α) × k1=(5.9 ± 1.0) × 10−11 cm3 molecule−1 s−1. Upper limits for the rate coefficients for reaction of SO2F2 with OH (R2, using PLP-LIF), and with O3 (R3, static reactor) were determined as k2 (294 K)<1 × 10−15 cm3 molecule−1 s−1 and k3 (294 K)<1 × 10−23 cm3 molecule−1 s−1. In experiments using the wetted-wall flow tube technique, no loss of SO2F2 onto aqueous surfaces was observed, allowing an upper limit for the uptake coefficient of γ(pH 2–12)<1 × 10−7 to be determined. These results indicate that SO2F2 has no significant loss processes in the troposphere, and a very long stratospheric lifetime. Integrated band intensities for SO2F2 infrared absorption features between 6 and 19 μm were obtained, and indicate a significant global warming potential for this molecule. In the course of this work, ambient temperature rate coefficients for the reactions O(1D) with several important atmospheric species were determined. The results (in units of 10−10 cm3 molecule−1 s−1, k(O1D + N2)=(0.33 ± 0.06); k(O1D + N2O)=(1.47 ± 0.2) and k(O1D + H2O)=(1.94 ± 0.5) were in good agreement with other recent determinations.

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The atmospheric chemistry of sulphuryl fluoride, SO2F2

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acpd-7-15213-2007 ◽

2007 ◽

Vol 7 (5) ◽

pp. 15213-15249

Author(s):

T. J. Dillon ◽

A. Horowitz ◽

J. N. Crowley

Keyword(s):

Atmospheric Chemistry ◽

Rate Coefficient ◽

Relative Rate ◽

Significant Loss ◽

Rate Coefficients ◽

Atmospheric Species ◽

Upper Limits ◽

Wall Flow ◽

Temperature Rate ◽

Good Agreement

Abstract. The atmospheric chemistry of sulphuryl fluoride, SO2F2, was investigated in a series of laboratory studies. A competitive rate method, using pulsed laser photolysis (PLP) to generate O(1D) coupled to detection of OH by laser induced fluorescence (LIF), was used to determine the overall rate coefficient for the reaction O(1D)+SO2F2 → products (R1) of k1 (220–300 K)=(1.3±0.2)×10−10 cm³ molecule−1 s−1. Monitoring the O(³P) product (R1a) enabled the contribution (α) of the physical quenching process (in which SO2F2 is not consumed) to be determined as α1 (225–296 K)=(0.55±0.04). Separate, relative rate measurements at 298 K provided a rate coefficient for reactive loss of O(1D), k1b, of (5.8±0.8)×10−11 cm³ molecule−1 s−1 in good agreement with the value calculated from (1−α)×k1=(5.9±1.0)×10−11 cm³ molecule−1 s−1. Upper limits for the rate coefficients for reaction of SO2F2 with OH (R2, using PLP-LIF), and with O3 (R3, static reactor) were determined as k2 (294 K)<1×10−15 cm³ molecule−1 s−1 and k3 (294 K)<1×10−23 cm³ molecule−1 s−1. In experiments using the wetted-wall flow tube technique, no loss of SO2F2 onto aqueous surfaces was observed, allowing an upper limit for the uptake coefficient of γ(pH 2–12)<1×10−7 to be determined. These results indicate that SO2F2 has no significant loss processes in the troposphere, and a very long stratospheric lifetime. Integrated band intensities for SO2F2 infrared absorption features between 6 and 19 μm were obtained, and indicate a significant global warming potential for this molecule. In the course of this work, ambient temperature rate coefficients for the reactions O(1D) with several important atmospheric species were determined. The results (in units of 10−10 cm³ molecule−1 s−1), k(O1D+N2)=(0.33±0.06); k(O1D+N2O)=(1.47±0.2) and k(O1D+H2O)=(1.94±0.5) were in good agreement with other recent determinations.

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Atmospheric Chemistry, Sources, and Sinks of Carbon Suboxide, C3O2

10.5194/acp-2017-49 ◽

2017 ◽

Author(s):

Stephan Keßel ◽

David Cabrera-Perez ◽

Abraham Horowitz ◽

Patrick R. Veres ◽

Rolf Sander ◽

...

Keyword(s):

Atmospheric Chemistry ◽

Relative Rate ◽

Ambient Air ◽

Rate Coefficients ◽

Oh Radicals ◽

Carbon Suboxide ◽

Air Samples ◽

Sources And Sinks

Abstract. Carbon suboxide, O = C = C = C = O, has been detected in ambient air samples and has the potential to be a noxious pollutant and oxidant precursor; however, its lifetime and fate in the atmosphere is largely unknown. In this work, we collect an extensive set of studies on the atmospheric chemistry of C3O2. Rate coefficients for the reactions of C3O2 with OH radicals and ozone were determined using relative rate techniques as k4 = (2.6 ± 0.5) × 10−12 cm3 molecule−1 s1 at 295 K (independent of pressure between ~ 25 and 1000 mbar) and k6

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Photo degradation kinetics of insensitive munitions constituents nitroguanidine, nitrotriazolone, and dinitroanisole in natural waters

10.21079/11681/41900 ◽

2021 ◽

Author(s):

Lee Moores ◽

Stacy Jones ◽

Garrett George ◽

David Henderson ◽

Timothy Schutt

Keyword(s):

Laboratory Experiments ◽

Natural Waters ◽

Matrix Effects ◽

Degradation Kinetics ◽

Relative Rate ◽

Ph Dependence ◽

Degradation Pathway ◽

Quantum Yields ◽

The Individual ◽

Kinetics Of

Herein the matrix effects on the kinetics of aqueous photolysis for the individual munitions constituents of IMX-101: nitroguanidine (NQ), dinitroanisole (DNAN), and nitrotriazolone (NTO) are reported along with the environmentally relevant kinetics and quantum yields. Photolysis potentially represents a major degradation pathway for these munitions in the environment and further understanding the complex matrices effects on photolytic kinetics was needed. Aqueous systems are of particular interest due to the high solubility of NQ (3,800 ppm) and NTO (16,642 ppm) compared to the traditional munitions trinitrotoluene (TNT, 100.5 ppm) and 1,3,5-trinitro-1,3,5-triazine (RDX, 59.9 ppm). Environmental half-lives (and quantum yields) were found to be 0.44 days, 0.83 days, and 4.4 days for NQ, DNAN, and NTO, respectively, under natural sunlight. In laboratory experiments using nominally 300 nm bulbs in a merry-go-round style reactor in DI water the relative rate of photolysis for the three munitions constituents followed the same order NQ > DNAN > NTO, where DNAN and NTO reacted 57 and 115 times more slowly, respectively, than NQ. In the various environmentally relevant matrices tested in the laboratory experiments NQ was not significantly affected, DNAN showed a faster degradation with increasing ionic strength, and NTO showed a modest salinity and pH dependence on its rate of photolysis.

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Evaluated kinetic and photochemical data for atmospheric chemistry: Volume VII – Criegee intermediates

Atmospheric Chemistry and Physics ◽

10.5194/acp-20-13497-2020 ◽

2020 ◽

Vol 20 (21) ◽

pp. 13497-13519

Author(s):

R. Anthony Cox ◽

Markus Ammann ◽

John N. Crowley ◽

Hartmut Herrmann ◽

Michael E. Jenkin ◽

...

Keyword(s):

Gas Phase ◽

Atmospheric Chemistry ◽

Kinetic Data ◽

Chemical Kinetic ◽

Photochemical Reactions ◽

Task Group ◽

Rate Coefficients ◽

Laboratory Measurements ◽

Bimolecular Reactions ◽

Criegee Intermediates

Abstract. This article, the seventh in the series, presents kinetic and photochemical data sheets evaluated by the IUPAC Task Group on Atmospheric Chemical Kinetic Data Evaluation. It covers an extension of the gas-phase and photochemical reactions related to Criegee intermediates previously published in Atmospheric Chemistry and Physics (ACP) in 2006 and implemented on the IUPAC website up to 2020. The article consists of an introduction, description of laboratory measurements, a discussion of rate coefficients for reactions of O3 with alkenes producing Criegee intermediates, rate coefficients of unimolecular and bimolecular reactions and photochemical data for reactions of Criegee intermediates, and an overview of the atmospheric chemistry of Criegee intermediates. Summary tables of the recommended kinetic and mechanistic parameters for the evaluated reactions are provided. Data sheets summarizing information upon which the recommendations are based are given in two files, provided as a Supplement to this article.

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