The atmospheric oxidation of dimethyl, diethyl, and diisopropyl ethers. The role of the intramolecular hydrogen shift in peroxy radicals

2016 ◽  
Vol 18 (11) ◽  
pp. 7707-7714 ◽  
Author(s):  
Sainan Wang ◽  
Liming Wang
Keyword(s):  
Atmospheric Oxidation ◽  
Peroxy Radicals ◽  
Hydrogen Shift ◽  
Intramolecular Hydrogen ◽  
Clean Atmosphere

Ethers can be auto-oxidized with no O3 formation in a ‘clean’ atmosphere.

scholarly journals A new model mechanism for atmospheric oxidation of isoprene: global effects on oxidants, nitrogen oxides, organic products, and secondary organic aerosol

2019 ◽  
Author(s):  
Kelvin H. Bates ◽  
Daniel J. Jacob
Keyword(s):  
Secondary Organic Aerosol ◽  
Transport Model ◽  
Oxidation Mechanism ◽  
Organic Aerosol ◽  
Atmospheric Oxidation ◽  
Peroxy Radicals ◽  
Chemical Transport Model ◽  
Total Size ◽  
Hydrogen Shift ◽  
Isomer Distribution

Abstract. Atmospheric oxidation of isoprene, the most abundantly emitted non-methane hydrocarbon, affects the abundances of ozone, the hydroxyl radical (OH), nitrogen oxide radicals (NOx), carbon monoxide (CO), oxygenated and nitrated organic compounds, and secondary organic aerosol (SOA). We analyze these effects in box models and in the global GEOS-Chem chemical transport model using the new Reduced Caltech Isoprene Mechanism (RCIM) condensed from a recently developed explicit isoprene oxidation mechanism. We find many similarities with previous global models of isoprene chemistry along with a number of important differences. Proper accounting of the isomer distribution of peroxy radicals following the addition of OH and O2 to isoprene influences the subsequent distribution of products, decreasing in particular the yield of methacrolein, and increasing the capacity of intramolecular hydrogen shifts to promptly regenerate OH. Hydrogen shift reactions throughout the mechanism lead to increased OH recycling, resulting in less depletion of OH under low-NO conditions than in previous mechanisms. Higher organonitrate yields and faster tertiary nitrate hydrolysis lead to more efficient NOx removal by isoprene and conversion to inorganic nitrate. Only 20 % of isoprene-derived organonitrates (excluding peroxyacyl nitrates) are chemically recycled to NOx. The global yield of formaldehyde from isoprene is 22 % per carbon and less sensitive to NO than in previous mechanisms. The global molar yield of glyoxal is 2 %, much lower than in previous mechanisms because of deposition and aerosol uptake of glyoxal precursors. Global production of isoprene SOA is about one third each from isoprene epoxydiols (IEPOX), organonitrates, and tetrafunctional compounds. We find a SOA yield from isoprene of 13 % per carbon, much higher than commonly assumed in models, and likely offset by SOA chemical loss. We use the results of our simulations to further condense RCIM into a Mini-Caltech Isoprene Mechanism (Mini-CIM) for less expensive implementation in atmospheric models, with a total size (108 species, 345 reactions) comparable to currently used mechanisms.

scholarly journals A new model mechanism for atmospheric oxidation of isoprene: global effects on oxidants, nitrogen oxides, organic products, and secondary organic aerosol

2019 ◽  
Vol 19 (14) ◽  
pp. 9613-9640 ◽  
Author(s):  
Kelvin H. Bates ◽  
Daniel J. Jacob
Keyword(s):  
Secondary Organic Aerosol ◽  
Transport Model ◽  
Oxidation Mechanism ◽  
Organic Aerosol ◽  
Atmospheric Oxidation ◽  
Peroxy Radicals ◽  
Chemical Transport Model ◽  
Total Size ◽  
Hydrogen Shift ◽  
Isomer Distribution

Abstract. Atmospheric oxidation of isoprene, the most abundantly emitted non-methane hydrocarbon, affects the abundances of ozone (O3), the hydroxyl radical (OH), nitrogen oxide radicals (NOx), carbon monoxide (CO), oxygenated and nitrated organic compounds, and secondary organic aerosol (SOA). We analyze these effects in box models and in the global GEOS-Chem chemical transport model using the new reduced Caltech isoprene mechanism (RCIM) condensed from a recently developed explicit isoprene oxidation mechanism. We find many similarities with previous global models of isoprene chemistry along with a number of important differences. Proper accounting of the isomer distribution of peroxy radicals following the addition of OH and O2 to isoprene influences the subsequent distribution of products, decreasing in particular the yield of methacrolein and increasing the capacity of intramolecular hydrogen shifts to promptly regenerate OH. Hydrogen shift reactions throughout the mechanism lead to increased OH recycling, resulting in less depletion of OH under low-NO conditions than in previous mechanisms. Higher organonitrate yields and faster tertiary nitrate hydrolysis lead to more efficient NOx removal by isoprene and conversion to inorganic nitrate. Only 20 % of isoprene-derived organonitrates (excluding peroxyacyl nitrates) are chemically recycled to NOx. The global yield of formaldehyde from isoprene is 22 % per carbon and less sensitive to NO than in previous mechanisms. The global molar yield of glyoxal is 2 %, much lower than in previous mechanisms because of deposition and aerosol uptake of glyoxal precursors. Global production of isoprene SOA is about one-third from each of the following: isoprene epoxydiols (IEPOX), organonitrates, and tetrafunctional compounds. We find a SOA yield from isoprene of 13 % per carbon, much higher than commonly assumed in models and likely offset by SOA chemical loss. We use the results of our simulations to further condense RCIM into a mini Caltech isoprene mechanism (Mini-CIM) for less expensive implementation in atmospheric models, with a total size (108 species, 345 reactions) comparable to currently used mechanisms.

scholarly journals Intramolecular Hydrogen Shift Chemistry of Hydroperoxy-Substituted Peroxy Radicals

2018 ◽  
Vol 123 (2) ◽  
pp. 590-600 ◽  
Author(s):  
Eric Praske ◽  
Rasmus V. Otkjær ◽  
John D. Crounse ◽  
J. Caleb Hethcox ◽  
Brian M. Stoltz ◽  
...  
Keyword(s):  
Peroxy Radicals ◽  
Hydrogen Shift ◽  
Intramolecular Hydrogen

scholarly journals Aging of atmospheric aerosols and the role of iron in catalyzing brown carbon formation

2021 ◽  
Author(s):  
Hind A. A. Al-Abadleh
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Atmospheric Aerosols ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Atmospheric Oxidation ◽  
Carbon Formation ◽  
Brown Carbon ◽  
Volatile Organic

Extensive research has been done on the processes that lead to the formation of secondary organic aerosol (SOA) including atmospheric oxidation of volatile organic compounds (VOCs) from biogenic and anthropogenic...

scholarly journals Thermodynamics of primary antioxidant action of flavonols in polar solvents

2019 ◽  
Vol 12 (1) ◽  
pp. 108-118 ◽  
Author(s):  
Martin Michalík ◽  
Ján Rimarčík ◽  
Vladimír Lukeš ◽  
Erik Klein
Keyword(s):  
Reaction Pathway ◽  
Hydrogen Atom Transfer ◽  
Antioxidant Effect ◽  
Antioxidant Action ◽  
Polar Solvents ◽  
Polar Media ◽  
Primary Antioxidant ◽  
Intramolecular Hydrogen

Abstract Very recently, a report on the antioxidant activity of flavonoids has appeared, where authors concluded that Hydrogen Atom Transfer mechanism represents the thermodynamically preferred mechanism in polar media (https://doi.org/10.1016/j.foodres.2018.11.018). Unfortunately, serious errors in the theoretical part of the paper led to incorrect conclusions. For six flavonols (galangin, kaempferol, quercetin, morin, myricetin, and fisetin), reaction enthalpies related to three mechanisms of the primary antioxidant action were computed. Based on the obtained results, the role of intramolecular hydrogen bonds (IHB) in the thermodynamics of the antioxidant effect is presented. Calculations and the role of solvation enthalpies of proton and electron in the determination of thermodynamically preferred mechanism is also briefly explained and discussed. The obtained results are in accordance with published works considering the Sequential Proton-Loss Electron-Transfer thermodynamically preferred reaction pathway.

Role of hydrogen migrations in carbonyl peroxy radicals in the atmosphere

2019 ◽  
Vol 32 (4) ◽  
pp. 457-466
Author(s):  
Sai-nan Wang ◽  
Run-run Wu ◽  
Li-ming Wang
Keyword(s):  
Peroxy Radicals
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