Structure−Activity Relationship for the Addition of OH to (Poly)alkenes:  Site-Specific and Total Rate Constants

Peeters, Jozef; Boullart, Werner; Pultau, V.; Vandenberk, Sabine; Vereecken, Luc

doi:10.1021/jp066973o

Cited by 118 publications

(186 citation statements)

References 66 publications

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“…Branching ratios have also been measured for reactions of alkenes with OH radicals by using other techniques. Values of α sec ∕α prim ¼ 0.65∕0.35, identical to those measured here, were obtained by gas chromatographic analysis of products of the reaction of 1 propene in the absence of NO x (3), and values of α sec ∕α prim ¼ 0.85∕0.15, α tert ∕α prim ¼ 0.85∕0.15, and α tert ∕α sec ¼ 0.66∕0.34 that agree fairly well with the values 0.65∕0.35, 0.81∕0.19, and 0.69∕0.31 measured here, were obtained from mass spectrometric analysis of β-hydroxyalkyl radicals formed from reactions of 1-butene, 2-methylpropene, and 2-methyl-2-butene in the absence of O 2 (12).…”

Section: Resultssupporting

confidence: 87%

“…The branching ratios for the combined addition of OH radicals and O 2 to form the 1-hydroxy-2-peroxy and 2-hydroxy-1-peroxy radicals are α 1 and α 2 , respectively, with α 1 þ α 2 ¼ α C¼C . It is assumed here that the yields of the two isomers are determined by the OH radical addition step (12), so that α 1 and α 2 are also the branching ratios for forming 1-hydroxy-2-alkyl and 2-hydroxy-1-alkyl radicals. The β-hydroxyperoxy radicals react with NO to form β-hydroxynitrates [P1, P2] with branching ratios α 3 and α 4 or β-hydroxyalkoxy radicals with branching ratios α 5 and α 6 .…”

Section: Resultsmentioning

confidence: 99%

“…This trend is also observed in site-specific OH radical addition rate constants used in a structure-activity relationship developed from rate constants for reactions of alkenes with OH radicals (12) that predict α tert ∕α sec ∕α prim ¼ 12.2∕6.7∕1.0. The chemical basis for this trend is uncertain (12). Branching ratios have also been measured for reactions of alkenes with OH radicals by using other techniques.…”

Section: Resultsmentioning

confidence: 99%

“…These values should be applicable to other systems, although effects of double-bond conjugation and ring strain on OH radical addition should be considered (12). Values can be extrapolated to carbon numbers below C 14 by using the approach presented previously (11).…”

Section: Discussionmentioning

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: 87%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

See 2 more Smart Citations

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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“…We cannot make a quantitative comparison for the other OH reaction channels at this time. It is expected that OH addition should be somewhat slower for the C 6 -HPALD since addition to either site would result in a secondary alkyl radical (as opposed to a secondary and a tertiary radical), 42 while H-abstraction from the C 4 -carbon should be roughly 2 to 3 times faster for C 6 -HPALD compared to C 5 -HPALD because of the secondary carbon. 43 It is not possible to assess the degree of HO x recycling from reactions of OH with C 6 -HPALD from the available data.…”

Section: Methodsmentioning

confidence: 99%

Photolysis, OH reactivity and ozone reactivity of a proxy for isoprene-derived hydroperoxyenals (HPALDs)

Wolfe

Crounse

Parrish

et al. 2012

Phys. Chem. Chem. Phys.

103

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The C 5 -hydroperoxyenals (C 5 -HPALDs) are a newly-recognized class of multi-functional hydrocarbons produced during the hydroxyl radical (OH)-initiated oxidation of isoprene. Recent theoretical calculations suggest that fast photolysis of these compounds may be an important OH source in high-isoprene, low-NO regions. We report experimental constraints for key parameters of photolysis, OH reaction and ozone reaction of these compounds as derived from a closelyrelated, custom-synthesized C 6 -HPALD. The photolysis quantum yield is 1.0 AE 0.4 over the range 300-400 nm, assuming an absorption cross section equal to the average of those measured for several analogous enals. The yield of OH from photolysis was determined as 1.0 AE 0.8. The OH reaction rate constant is (5.1 AE 1.8) Â 10 À11 cm 3 molecule À1 s À1 at 296 K. The ozone reaction rate constant is (1.2 AE 0.2) Â 10 À18 cm 3 molecule À1 s À1 at 296 K. These results are consistent with previous first-principles estimates, though the nature and fate of secondary oxidation products remains uncertain. Incorporation of C 5 -HPALD chemistry with the above parameters in a 0-D box model, along with experimentally-constrained rates for C 5 -HPALD production from isomerization of first-generation isoprene hydroxyperoxy radicals, is found to enhance modeled OH concentrations by 5-16% relative to the traditional isoprene oxidation mechanism for the chemical regimes of recent observational studies in rural and remote regions. This enhancement in OH will increase if C 5 -HPALD photo-oxidation products also photolyze to yield additional OH or if the C 5 -HPALD production rate is faster than has been observed.

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Gas‐Phase Kinetics of Hydroxyl Radical Reactions with Alkenes: Experiment and Theory

et al. 2010

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Reactions of the hydroxyl radical with propene and 1-butene are studied experimentally in the gas phase in a continuous supersonic flow reactor over the range 50≤T/K≤224. OH radicals are produced by pulsed laser photolysis of H(2)O(2) at 266 nm in the supersonic flow and followed by laser-induced fluorescence in the (1, 0) A(2)Σ(+)←X(2)Π(3/2) band at about 282 nm. These reactions are found to exhibit negative temperature dependences over the entire temperature range investigated, varying between (3.1-19.2) and (4.2-28.6)×10(-11) cm(3) molecule(-1) s(-1) for the reactions of OH with propene and 1-butene, respectively. Quantum chemical calculations of the potential energy surfaces are used as the basis for energy- and rotationally resolved Rice-Ramsperger-Kassel-Marcus calculations to determine the rate constants over a range of temperatures and pressures. The negative temperature dependences of the rate constants are explained by competition between complex redissociation and passage to the adducts by using a model with two transition states. The results are compared and contrasted with earlier studies and discussed in terms of their potential relevance to the atmosphere of Saturn.

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Structure−Activity Relationship for the Addition of OH to (Poly)alkenes: Site-Specific and Total Rate Constants

Cited by 118 publications

References 66 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

Photolysis, OH reactivity and ozone reactivity of a proxy for isoprene-derived hydroperoxyenals (HPALDs)

Gas‐Phase Kinetics of Hydroxyl Radical Reactions with Alkenes: Experiment and Theory

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