The thermal decomposition of peroxyacetic nitric anhydride (PAN) and peroxymethacrylic nitric anhydride (MPAN)

Roberts, J. M.; Bertman, S. B.

doi:10.1002/kin.550240307

Cited by 109 publications

(94 citation statements)

References 29 publications

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“…The reported values from , , Roberts and Bertman, (1992) and Roumelis and Glavas (1992) as well as the selected more recent measurements from are all in very good agreement at 298 K and are preferred here. The direct PAN decompositions to methyl nitrate and CO 2 (Roumelis and Glavas, 1992; or to CH 3 C(O)O and NO 3 …”

Section: Comments On Preferred Valuesmentioning

confidence: 55%

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Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – gas phase reactions of organic species

et al. 2006

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Abstract. This article, the second in the series, presents kinetic and photochemical data evaluated by the IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry. It covers the gas phase and photochemical reactions of Organic species, which were last published in 1999, and were updated on the IUPAC website in late 2002, and subsequently during the preparation of this article. The article consists of a summary table of the recommended rate coefficients, containing the recommended kinetic parameters for the evaluated reactions, and eight appendices containing the data sheets, which provide information upon which the recommendations are made.

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Section: Comments On Preferred Valuesmentioning

confidence: 55%

“…The preferred values are based on the sole study of this reaction by Roberts and Bertman (1992). The preferred values for the decomposition of MPAN are very similar to those for the thermal decomposition of CH 3 C(O)OONO 2 (PAN) (Roberts and Bertman, 1992; IUPAC, see also this evaluation).…”

Section: Comments On Preferred Valuesmentioning

confidence: 57%

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – gas phase reactions of organic species

et al. 2006

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“…This NO 2 formation is likely due to thermal decomposition of MPAN (t 288 K B 35 h at the NO x conditions in Exp. 2-3) 23,44 because a 10 AE 5% yield of PAN was also observed. The MPAN decomposition produces NO 2 and acylperoxyl radical, which is subsequently converted to the acyloxyl radical from reaction with either NO or HO 2 .…”

Section: Resultsmentioning

confidence: 88%

Mechanism of the hydroxyl radical oxidation of methacryloyl peroxynitrate (MPAN) and its pathway toward secondary organic aerosol formation in the atmosphere

Nguyen

Bates

Crounse

et al. 2015

Phys. Chem. Chem. Phys.

120

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Methacryloyl peroxynitrate (MPAN), the acyl peroxynitrate of methacrolein, has been suggested to be an important secondary organic aerosol (SOA) precursor from isoprene oxidation. Yet, the mechanism by which MPAN produces SOA through reaction with the hydroxyl radical (OH) is unclear. We systematically evaluate three proposed mechanisms in controlled chamber experiments and provide the first experimental support for the theoretically-predicted lactone formation pathway from the MPAN + OH reaction, producing hydroxymethyl-methyl-a-lactone (HMML). The decomposition of the MPAN-OH adduct yields HMML + NO 3 (B75%) and hydroxyacetone + CO + NO 3 (B25%), out-competing its reaction with atmospheric oxygen. The production of other proposed SOA precursors, e.g., methacrylic acid epoxide (MAE), from MPAN and methacrolein are negligible (o2%). Furthermore, we show that the beta-alkenyl moiety of MPAN is critical for lactone formation. Alkyl radicals formed cold via H-abstraction by OH do not decompose to HMML, even if they are structurally identical to the MPAN-OH adduct. The SOA formation from HMML, from polyaddition of the lactone to organic compounds at the particle interface or in the condensed phase, is close to unity under dry conditions. However, the SOA yield is sensitive to particle liquid water and solvated ions. In hydrated inorganic particles, HMML reacts primarily with H 2 O to produce the monomeric 2-methylglyceric acid (2MGA) or with aqueous sulfate and nitrate to produce the associated organosulfate and organonitrate, respectively. 2MGA, a tracer for isoprene SOA, is semivolatile and its accommodation in aerosol water decreases with decreasing pH. Conditions that enhance the production of neutral 2MGA suppress SOA mass from the HMML channel. Considering the liquid water content and pH ranges of ambient particles, 2MGA will exist largely as a gaseous compound in some parts of the atmosphere.

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“…The latter explanation seems less likely, as we expect depositional and chemical losses (i.e. thermal decomposition) of APNs to be similar since their physical and chemical properties are comparable (Roberts and Bertman, 1992;Grosjean et al, 1994a, b;Kames and Schurath, 1995), excepting the relatively fast MPAN+OH reaction (Orlando et al, 2002). The net flux of a reactive species above a forest can be represented as the sum of fluxes from a number of processes that vary with height, including deposition, chemical production and chemical loss (Eq.…”

Section: Differences In Pan Mpan and Ppn Exchange Velocitiesmentioning

confidence: 90%

Eddy covariance fluxes of acyl peroxy nitrates (PAN, PPN and MPAN) above a Ponderosa pine forest

et al. 2009

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Abstract. During the Biosphere Effects on AeRosols and Photochemistry EXperiment 2007 (BEARPEX-2007), we observed eddy covariance (EC) fluxes of speciated acyl peroxy nitrates (APNs), including peroxyacetyl nitrate (PAN), peroxypropionyl nitrate (PPN) and peroxymethacryloyl nitrate (MPAN), above a Ponderosa pine forest in the western Sierra Nevada. All APN fluxes are net downward during the day, with a median midday PAN exchange velocity of −0.3 cm s −1 ; nighttime storage-corrected APN EC fluxes are smaller than daytime fluxes but still downward. Analysis with a standard resistance model shows that loss of PAN to the canopy is not controlled by turbulent or molecular diffusion. Stomatal uptake can account for 25 to 50% of the observed downward PAN flux. Vertical gradients in the PAN thermal decomposition (TD) rate explain a similar fraction of the flux, suggesting that a significant portion of the PAN flux into the forest results from chemical processes in the canopy. The remaining "unidentified" portion of the net PAN flux (∼15%) is ascribed to deposition or reactive uptake on nonstomatal surfaces (e.g. leaf cuticles or soil). Shifts in temperature, moisture and ecosystem activity during the summerfall transition alter the relative contribution of stomatal uptake, non-stomatal uptake and thermochemical gradients to the net PAN flux. Daytime PAN and MPAN exchange velocities are a factor of 3 smaller than those of PPN during the first two weeks of the measurement period, consistent with strong intra-canopy chemical production of PAN and MPAN Correspondence to: J. A. Thornton (thornton@atmos.washington.edu) during this period. Depositional loss of APNs can be 3-21% of the gross gas-phase TD loss depending on temperature. As a source of nitrogen to the biosphere, PAN deposition represents approximately 4-19% of that due to dry deposition of nitric acid at this site.

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The thermal decomposition of peroxyacetic nitric anhydride (PAN) and peroxymethacrylic nitric anhydride (MPAN)

Cited by 109 publications

References 29 publications

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – gas phase reactions of organic species

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – gas phase reactions of organic species

Mechanism of the hydroxyl radical oxidation of methacryloyl peroxynitrate (MPAN) and its pathway toward secondary organic aerosol formation in the atmosphere

Eddy covariance fluxes of acyl peroxy nitrates (PAN, PPN and MPAN) above a Ponderosa pine forest

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