Formation of hydroxymethyl hydroperoxide and formic acid in alkene ozonolysis in the presence of water vapour

Neeb, Peter; Sauer, Frank; Horie, Osamu; Moortgat, G. K.

doi:10.1016/s1352-2310(96)00322-6

Cited by 262 publications

(303 citation statements)

References 36 publications

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“…A temperature-dependent isomerization of the isoprene RO 2 generates the HPALD (56,92). The O 3 -initated oxidation of isoprene or other exocyclic compounds forms the C 1 stabilized Criegee intermediate (SCI), among other products, which reacts with water to produce HMHP and formic acid (43). NO 3 -initated oxidation of isoprene and monoterpenes, followed by the HO 2 reaction, produces INP and MTNP, respectively (93).…”

Section: Resultsmentioning

confidence: 99%

“…One possible route to secondary formic acid formation may include water-mediated degradation of larger OVOCs that are deposited on canopy surfaces or on aerosol surfaces, e.g., the oxidation of IEPOX (42) and decomposition of HMHP (43). The deposition of HMHP and IEPOX is likely independent of surface chemistry at this site because surface uptake is not a limiting process for these compounds (Fig.…”

Section: Resultsmentioning

confidence: 99%

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Rapid deposition of oxidized biogenic compounds to a temperate forest

Nguyen

Crounse

Teng

et al. 2015

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

246

433

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We report fluxes and dry deposition velocities for 16 atmospheric compounds above a southeastern United States forest, including: hydrogen peroxide (H 2 O 2 ), nitric acid (HNO 3 ), hydrogen cyanide (HCN), hydroxymethyl hydroperoxide, peroxyacetic acid, organic hydroxy nitrates, and other multifunctional species derived from the oxidation of isoprene and monoterpenes. The data suggest that dry deposition is the dominant daytime sink for small, saturated oxygenates. Greater than 6 wt %C emitted as isoprene by the forest was returned by dry deposition of its oxidized products. Peroxides account for a large fraction of the oxidant flux, possibly eclipsing ozone in more pristine regions. The measured organic nitrates comprise a sizable portion (15%) of the oxidized nitrogen input into the canopy, with HNO 3 making up the balance. We observe that water-soluble compounds (e.g., strong acids and hydroperoxides) deposit with low surface resistance whereas compounds with moderate solubility (e.g., organic nitrates and hydroxycarbonyls) or poor solubility (e.g., HCN) exhibited reduced uptake at the surface of plants. To first order, the relative deposition velocities of water-soluble compounds are constrained by their molecular diffusivity. From resistance modeling, we infer a substantial emission flux of formic acid at the canopy level (∼1 nmol m −2 ·s −1 ). GEOS−Chem, a widely used atmospheric chemical transport model, currently underestimates dry deposition for most molecules studied in this work. Reconciling GEOS−Chem deposition velocities with observations resulted in up to a 45% decrease in the simulated surface concentration of trace gases.biosphere−atmosphere exchange | isoprene | dry deposition | OVOCs | fluxes

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Rapid deposition of oxidized biogenic compounds to a temperate forest

Nguyen

Crounse

Teng

et al. 2015

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

246

433

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“…1−11 In particular, the decomposition of α-hydroxyalkyl hydroperoxide (HHP), which is produced in the Criegee intermediate reaction with water, 30,42 serves as the principal mechanism for nonphotochemical H 2 O 2 formation (Scheme 1). [4][5][6]31,32 The decomposition of HHPs to yield carbonyl compounds or carboxylic acids also has significant industrial promise. 43 Further, there have been reports 7,23 suggesting that HHP decomposition can provide an additional source of atmospheric ·OH, although this topic remains controversial.…”

Section: Introductionmentioning

confidence: 99%

Role of Tunable Acid Catalysis in Decomposition of α-Hydroxyalkyl Hydroperoxides and Mechanistic Implications for Tropospheric Chemistry

et al. 2014

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Electronic structure calculations have been used to investigate possible gasphase decomposition pathways of α-hydroxyalkyl hydroperoxides (HHPs), an important source of tropospheric hydrogen peroxide and carbonyl compounds. The uncatalyzed as well as waterand acid-catalyzed decomposition of multiple HHPs have been examined at the M06-2X/augcc-pVTZ level of theory. The calculations indicate that, compared to an uncatalyzed or watercatalyzed reaction, the free-energy barrier of an acid-catalyzed decomposition leading to an aldehyde or ketone and hydrogen peroxide is dramatically lowered. The calculations also find a direct correlation between the catalytic effect of an acid and the distance separating its hydrogen acceptor and donor sites. Interestingly, the catalytic effect of an acid on the HHP decomposition resulting in the formation of carboxylic acid and water is relatively much smaller. Moreover, since the free-energy barrier of the acid-catalyzed aldehyde-or ketoneforming decomposition is ∼25% lower than that required to break the O−OH linkage of the HHP leading to the formation of hydroxyl radical, these results suggest that HHP decomposition is likely not an important source of tropospheric hydroxyl radical. Finally, transition state theory estimates indicate that the effective rate constants for the acid-catalyzed aldehyde-or ketone-forming HHP decomposition pathways are 2− 3 orders of magnitude faster than those for the water-catalyzed reaction, indicating that an acid-catalyzed HHP decomposition is kinetically favored as well.

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“…[1][2][3][4][5]8 The hydroxymethoxy radical (H 2 C(OH)O • ) is an oxygenated alkoxy radical, proposed to be formed from the UV photofragmentation of hydroxymethyl hydroperoxide (H 2 C(OH)OOH), a product from the tropospheric oxidation of alkenes. [9][10][11][12][13] In addition to the potential atmospheric importance of the H 2 C(OH)O • radical, its corresponding anion, hydroxymethoxide (H 2 C(OH)O -), is the conjugate base of methanediol (H 2 C(OH) 2 ), considered to be a molecule of astrochemical and possible prebiotic relevance [14][15][16][17][18] as a building block of simple amino acids. 19,20 Despite the relevance of the hydroxymethoxy radical to combustion and planetary chemistry, very little is known about its spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

Photoelectron spectroscopy of the hydroxymethoxide anion, H2C(OH)O−

Oliveira

Lehman

McCoy

et al. 2016

The Journal of Chemical Physics

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We report the negative ion photoelectron spectroscopy of the hydroxymethoxide anion, H2C(OH)O−. The photoelectron spectra show that 3.49 eV photodetachment produces two distinct electronic states of the neutral hydroxymethoxy radical (H2C(OH)O⋅). The H2C(OH)O⋅ ground state (X̃ 2A) photoelectron spectrum exhibits a vibrational progression consisting primarily of the OCO symmetric and asymmetric stretches, the OCO bend, as well as combination bands involving these modes with other, lower frequency modes. A high-resolution photoelectron spectrum aids in the assignment of several vibrational frequencies of the neutral H2C(OH)O⋅ radical, including an experimental determination of the H2C(OH)O⋅ 2ν12 overtone of the H–OCO torsional vibration as 220(10) cm−1. The electron affinity of H2C(OH)O⋅ is determined to be 2.220(2) eV. The low-lying Ã 2A excited state is also observed, with a spectrum that peaks ∼0.8 eV above the X̃ 2A state origin. The Ã 2A state photoelectron spectrum is a broad, partially resolved band. Quantum chemical calculations and photoelectron simulations aid in the interpretation of the photoelectron spectra. In addition, the gas phase acidity of methanediol is calculated to be 366(2) kcal mol−1, which results in an OH bond dissociation energy, D0(H2C(OH)O–H), of 104(2) kcal mol−1, using the experimentally determined electron affinity of the hydroxymethoxy radical.

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Formation of hydroxymethyl hydroperoxide and formic acid in alkene ozonolysis in the presence of water vapour

Cited by 262 publications

References 36 publications

Rapid deposition of oxidized biogenic compounds to a temperate forest

Rapid deposition of oxidized biogenic compounds to a temperate forest

Role of Tunable Acid Catalysis in Decomposition of α-Hydroxyalkyl Hydroperoxides and Mechanistic Implications for Tropospheric Chemistry

Photoelectron spectroscopy of the hydroxymethoxide anion, H2C(OH)O−

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