Temperature dependence of pentyl nitrate formation from the reaction of pentyl peroxy radicals with NO

Cassanelli, Paola; Fox, David J.; Cox, R. A.

doi:10.1039/b700285h

Cited by 30 publications

(41 citation statements)

References 39 publications

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“…The values α sec ∕α prim ¼ 0.15∕0.12 ¼ 1.3 and α tert ∕α prim ¼ 0.25∕0.12 ¼ 2.1 bracket the ratios of 1.5 and 1.5 measured for the corresponding alkylperoxy radicals (18), with our values indicating an enhancement in branching ratios for tertiary compared to secondary β-hydroxyperoxy radicals.…”

Section: Resultssupporting

confidence: 77%

“…For the β-HN isomers, 1H2NC are OH addition-normalized yields as reported above. In our study of reactions of linear 1-alkenes (11), these equations were solved for values of the four branching ratios by assuming α 3 ∕α 4 , the ratio of branching ratios for forming β-HN from reactions of NO with secondary and primary β-hydroxyperoxy radicals, is 1 or 1.5 (18). We combined measured product yields for reactions of linear internal alkenes, linear 1-alkenes, and 2-methyl-1-alkenes to estimate branching ratios for forming primary, secondary, and tertiary β-hydroxyalkyl radicals by OH radical addition to a C ¼ C double bond, and branching ratios for forming β-HN from reactions of the corresponding β-hydroxyperoxy radicals with NO.…”

Section: Resultsmentioning

confidence: 99%

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Yields ofβ-hydroxynitrates, dihydroxynitrates, and trihydroxynitrates formed from OH radical-initiated reactions of 2-methyl-1-alkenes

Matsunaga

Ziemann

2009

Proc. Natl. Acad. Sci. U.S.A.

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Yields of β-hydroxynitrates, dihydroxynitrates, and trihydroxynitrates, in particles formed from OH radical-initiated reactions of C 9 -C 15 2-methyl-1-alkenes in the presence of NO x were measured by using a thermal desorption particle beam mass spectrometer coupled to a high-performance liquid chromatograph with a UVvisible (UV-vis) detector. Yields of β-hydroxynitrates and dihydroxynitrates increased with carbon number primarily due to enhanced gas-to-particle partitioning before reaching plateaus at ≈C 14 -C 15 , where the compounds were essentially entirely in the particle phase. Plateau yields of β-hydroxynitrates, dihydroxynitrates, and trihydroxynitrates were 0.183 AE 0.005, 0.045 AE 0.005, and 0.034AE 0.005, and, after normalization for OH radical addition to the C ¼ C double bond, were 0.225 AE 0.007, 0.055 AE 0.006, and 0.042 AE 0.006. The fractions of 1-hydroxy and 2-hydroxy β-hydroxynitrate isomers were 0.90∕0.10. Yields measured here and in our previous study of reactions of linear internal alkenes and linear 1-alkenes indicate that, for these alkene classes, the relative branching ratios for forming tertiary, secondary, and primary β-hydroxyalkyl radicals by OH radical addition to the C ¼ C double bond are 4.3∕1.9∕1.0, and the branching ratios for forming β-hydroxynitrates from reactions of tertiary, secondary, and primary β-hydroxyperoxy radicals with NO are 0.25, 0.15, and 0.12. The effects of H 2 O vapor and NH 3 on yields were also explored.aerosol | atmospheric chemistry | organice nitrate | particles H ydrocarbons are emitted to the atmosphere from anthropogenic and biogenic sources. Globally, more than half are biogenic alkenes including isoprene (C 5 ), monoterpenes (C 10 ), and sesquiterpenes (C 15 ) (1). These compounds have a variety of linear, branched, and cyclic structures containing one or more C ¼ C double bonds and in the atmosphere react with OH radicals, O 3 , and NO 3 radicals to form oxidized products (2, 3). In urban and polluted rural areas where peroxy radical intermediates react primarily with NO (4), one important class of products is organic nitrates (2, 3). For example, hydroxynitrates formed from OH radical-initiated reactions of isoprene have been identified in urban air (5) and impact O 3 formation and NO x removal (6) as well as secondary organic aerosol (SOA) formation (7). It has been estimated that, globally, about two-thirds of hydroxyperoxy radicals formed from isoprene oxidation react with NO (8), a value that probably applies to other terpenes.In spite of their atmospheric importance, little is known about the chemistry of hydroxynitrates. This is primarily because of a lack of analytical methods and reference compounds (5, 9). In a recent study, Paulot et al. (10) employed chemical ionization mass spectrometry to monitor hydroxynitrates formed during isoprene photooxidation, and then used this information to help constrain a detailed chemical mechanism. Even here, however, significant uncertainties exist because many hydroxynitrate isomers could not be disti...

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Section: Resultssupporting

confidence: 77%

Section: Resultsmentioning

confidence: 99%

Yields ofβ-hydroxynitrates, dihydroxynitrates, and trihydroxynitrates formed from OH radical-initiated reactions of 2-methyl-1-alkenes

Matsunaga

Ziemann

2009

Proc. Natl. Acad. Sci. U.S.A.

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“…f a = 1 for secondary peroxy radicals by definition. The equivalent value for tertiary peroxy radicals, and the lower value for primary peroxy radicals, is based on a consensus of information from Cassanelli et al (2007), Orlando and Tyndall (2012) and Teng et al (2015) and on previous consideration of the OH + isoprene system ; b Inhibition of nitrate formation has been reported for complex hydroxy-dioxa-bicyclo peroxy radicals derived from aromatics, relative to comparably sized alkyl peroxy radicals by Rickard et al (2010) and Elrod (2011), with a particular impact from the presence of alkyl substituents reported by Elrod (2011). The reduced values of f a for tertiary peroxy radicals, and the general reduction in f a for peroxy radicals with a neighbouring alkyl substituent (as shown), is inferred from the trend in nitrate yields reported for benzene, toluene, p-xylene and 1,3,5-trimethylbenzene by Elrod (2011). presence of oxygenated substituents (e.g.…”

Section: Product Branching Ratiosmentioning

confidence: 99%

Estimation of rate coefficients and branching ratios for reactions of organic peroxy radicals for use in automated mechanism construction

et al. 2019

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Organic peroxy radicals (RO 2 ), formed from the degradation of hydrocarbons and other volatile organic compounds (VOCs), play a key role in tropospheric oxidation mechanisms. Several competing reactions may be available for a given RO 2 radical, the relative rates of which depend on both the structure of RO 2 and the ambient conditions. Published kinetics and branching ratio data are reviewed for the bimolecular reactions of RO 2 with NO, NO 2 , NO 3 , OH and HO 2 ; and for their self-reactions and cross-reactions with other RO 2 radicals. This information is used to define generic rate coefficients and structure-activity relationship (SAR) methods that can be applied to the bimolecular reactions of a series of important classes of hydrocarbon and oxygenated RO 2 radicals. Information for selected unimolecular isomerization reactions (i.e. H-atom shift and ring-closure reactions) is also summarized and discussed. The methods presented here are intended to guide the representation of RO 2 radical chemistry in the next generation of explicit detailed chemical mechanisms.Under tropospheric conditions, a given RO 2 radical may have several competing reactions available, the relative rates of which are dependent both on the prevailing ambient conditions and on the structure of RO 2 . These include a series of bimolecular reactions (i.e. with NO, NO 2 , NO 3 , OH and HO 2 ; and the self-reaction and cross-reactions with the multitude of other RO 2 radicals present in the atmosphere), which are generally available for all RO 2 radicals; and specific unimolecular isomerization reactions (i.e. H-atom shiftPublished by Copernicus Publications on behalf of the European Geosciences Union.

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“…fa = 1 for secondary peroxy radicals, by definition. The equivalent value for tertiary peroxy radicals, and the lower value for primary peroxy radicals, are based on a consensus of information from Cassanelli et al (2007), Orlando and Tyndall (2012) and Teng et al (2015) and on previous consideration of the OH + isoprene system (Jenkin et al, 2015); b Inhibition of nitrate formation has been reported for complex hydroxy-dioxa-bicyclo peroxy radicals derived from aromatics, relative to comparably sized alkyl peroxy radicals, by Rickard et al (2010) and Elrod (2011), with a particular impact from the presence of alkyl substituents reported by Elrod (2011). The reduced values of fa for tertiary peroxy radicals, and the general reduction in fa for peroxy radicals with a neighbouring alkyl substituent (as shown), is inferred from the trend in nitrate yields reported for benzene, toluene, p-xylene and 1,3,5-trimethylbenzene by Elrod (2011).…”

Section: -Hydroxyalkylmentioning

confidence: 99%

Estimation of rate coefficients and branching ratios for reactions of organic peroxy radicals for use in automated mechanism construction

Jenkin¹,

Valorso²,

Aumont³

et al. 2019

Preprint

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Abstract. Organic peroxy radicals (RO2), formed from the degradation of hydrocarbons and other volatile organic compounds (VOCs), play a key role in tropospheric oxidation mechanisms. Several competing reactions may be available for a given RO2 radical, the relative rates of which depend on both the structure of RO2 and the ambient conditions. Published kinetics and branching ratio data are reviewed for the bimolecular reactions of RO2 with NO, NO2, NO3, OH and HO2; and for their self-reactions and cross-reactions with other RO2 radicals. This information is used to define generic rate coefficients and structure-activity relationship (SAR) methods that can be applied to the bimolecular reactions of a series of important classes of hydrocarbon and oxygenated RO2 radical. Information for selected unimolecular isomerization reactions (i.e. H-atom shift and ring-closure reactions) is also summarised and discussed. The methods presented here are intended to guide the representation of RO2 radical chemistry in the next generation of explicit detailed chemical mechanisms.

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Temperature dependence of pentyl nitrate formation from the reaction of pentyl peroxy radicals with NO

Cited by 30 publications

References 39 publications

Yields ofβ-hydroxynitrates, dihydroxynitrates, and trihydroxynitrates formed from OH radical-initiated reactions of 2-methyl-1-alkenes

Yields ofβ-hydroxynitrates, dihydroxynitrates, and trihydroxynitrates formed from OH radical-initiated reactions of 2-methyl-1-alkenes

Estimation of rate coefficients and branching ratios for reactions of organic peroxy radicals for use in automated mechanism construction

Estimation of rate coefficients and branching ratios for reactions of organic peroxy radicals for use in automated mechanism construction

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