Rate and mechanism of the reactions of OH and Cl with 2‐methyl‐3‐buten‐2‐ol

Ferronato, Corinne; Orlando, John J.; Tyndall, Geoffrey S.

doi:10.1029/98jd00528

Cited by 89 publications

(129 citation statements)

References 27 publications

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“…Pronounced minima observed in each case between 9 am and 3 pm, indicated strong losses due to vertical mixing and/or reactions with OH radicals. Short lifetimes of wound VOCs are predicted from their fast reactions with OH, estimated to be 6 +3 x 10 -• cm 3 s '• based on OH reaction with 2-methyl-3-buten-2-ol [Ferronato et al, 1998] and hexenyl compounds [Atkinson et al, 1995]. In contrast to the high concentrations of wound VOCs observed from 11 to 17 Nov., considerably lower concentrations were measured during 26 to 30 Nov.…”

Section: Resultsmentioning

confidence: 77%

High concentrations of reactive biogenic VOCs at a high altitude site in late autumn

Karl

Fall

Crutzen

et al. 2001

Geophysical Research Letters

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Abstract. Volatile organic compounds (VOCs) at the Sonnblick Observatory, Austria (3106 m a.s.1.) were measured in autumn 1999 using proton-transfer-reaction mass spectrometry (PTR-MS). Anthropogenic V OCs at this remote site, such as benzene and toluene (50 pptv to 2 ppbv), were primarily traced to air from urban areas. In mid-November, following a hard freeze in the central Alps, a different pattern of VOCs developed similar to that seen with C5 and C6 leaf wound compounds (0.5 to 5 ppbv range). The common origins of these compounds are proposed to be freeze-damaged leaves, inferred from laboratory investigations that identified hexenals, hexanal, methylbutanals, pentenol and pentenone formation in such leaves. We suggest that deciduous forests can release large amounts of reactive VOCs during the autumn, and that these releases may be important for regional tropospheric chemistry.

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Section: Resultsmentioning

confidence: 77%

High concentrations of reactive biogenic VOCs at a high altitude site in late autumn

Karl

Fall

Crutzen

et al. 2001

Geophysical Research Letters

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“…Previous research conducted in chambers establishes that hydroxyl radical oxidation of MBO yields acetone, glycolaldehyde, formaldehyde, and a C 4 -hydroxycarbonyl, tentatively identified as 2-hydroxy-2-methylpropanal [11,13,14]. Due to the lack of an authentic standard, the yield was not calculated and the identity of 2-hydroxy-2-methylpropanal (i.e., the structure of the C 4 -hydroxycarbonyl) was not confirmed.…”

Section: Identification Of Products Arising From Oh Radical Oxidationmentioning

confidence: 99%

“…Laboratory (chamber) studies establish that ⅐OH oxidation of MBO yields acetone and glycolaldehyde (50 -60% yield), and formaldehyde (30 -35% yield) [11,13,14]. A fourth product, 2-hydroxy-2-methylpropanal was also proposed.…”

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confidence: 99%

“…The identification of this product was based on: (1) The proposed reaction mechanism of MBO with ⅐OH ( Figure 1) and a gas chromatographic (GC) retention index for the 2,4-dinitrophenylhydrazine (DNPH) derivative [13]; (2) identification of an ion in the chemical ionization mass spectra that corresponds to the (M Ϫ H 2 O) ϩ ion of a C 4 -hydroxycarbonyl or a C 3 -oxo-acid DNPH derivative [13]; and (3) identification of absorption bands corresponding to C™H, C¢O, and (CH 3 ) 3 Si-OR stretches in the GC-infrared spectrum and an ion corresponding to (M Ϫ CH 3 ) ϩ in the electron ionization MS of a trimethylsilyl derivatized sample extract [14]. The yield is assumed to be equal to that of formaldehyde [11]. However, Alvarado et al [14] estimated a yield of 19 Ϯ 7%, compared to the formaldehyde yield of 29 Ϯ 3%.…”

mentioning

confidence: 99%

“…Although MBO comprises only 5% of the biogenic VOCs in North America, MBO concentrations were measured at 2 to 7 times the concentrations of isoprene in the Blodgett Forest, CA, and at Niwot Ridge, CO [2,9], because of emission from ponderosa and lodgepole pines, trees that are endemic to western North America [10]. Hy-droxyl radical oxidation is the dominant loss mechanism for MBO during daytime [11,12]. Therefore, in order to reduce tropospheric ozone in atmospheres that are affected by MBO emissions, it is essential that we gain insight into atmospheric processes affecting ⅐OH oxidation of MBO, and the generation and fate of the reaction products.…”

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confidence: 99%

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Ion trap mass spectrometry affords advances in the analytical and atmospheric chemistry of 2-hydroxy-2-methylpropanal, a proposed photooxidation product of 2-methyl-3-buten-2-ol

Spaulding

Charles

Tuazon

et al. 2002

J. Am. Soc. Mass Spectrom.

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In the western United States, in areas where emissions of the biogenic hydrocarbon, 2-methyl-3-buten-2-ol (MBO) are high, MBO contributes significantly to the oxidative capacity of the atmosphere. Hydroxyl radical oxidation of MBO can play an important role in forming tropospheric ozone, and MBO reaction products may contribute to the formation of secondary organic aerosols [1][2][3]. Although 2-hdyroxy-2-methylpropanal was tentatively identified as a product from the reaction of MBO with ⅐OH in indoor chamber studies, the identity of the compound was not confirmed due to the lack of an authentic standard. Further, no data exists on the atmospheric generation and fate of 2-hydroxy-2-methylpropanal in the ambient environment. Herein, we provide further evidence that 2-hydroxy-2-methylpropanal is generated by ⅐OH reaction with MBO by identifying 2-hydroxy-2-methylpropanal in an indoor chamber experiment and in ambient air sampled in the Blodgett Forest, where MBO emissions are high. We analyzed 2-hydroxy-2-methylpropanal by using a method that relies on O- (2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) and bis-(trimethylsilyl) trifluoroacetamide (BSTFA) derivatization along with ion-trap mass spectrometry. Tentative identification of 2-hydroxy-2-methylpropanal was possible by using knowledge gained in this study regarding the mass spectrometry of PFBHA-BSTFA derivatives of carbonyls with primary, secondary, and tertiary ϪOH groups, and ado-and keto-acids. The identification was confirmed by comparing the methane CI mass spectra and relative gas chromatographic retention time obtained by analyzing 2-hydroxy-2-methylpropanal in a sample extract and a synthesized authentic standard. Since the standard became available at the end of this study (after all samples were analyzed), we also developed a method for semi-quantification of 2-hydroxy-2-methylpropanal, with a detection limit of 27 pptv in air. We used the method to provide the first ambient air measurements of 2-hydroxy-2-methylpropanal. The analyte is not commercially available, and hence other researchers who have not synthesized an authentic standard can employ the method. (J Am Soc Mass Spectrom 2002, 13, 530 -542)

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Rate constants for the gas-phase reactions of OH radicals with a series of unsaturated alcohols

Papagni

Arey

Atkinson

2001

Int. J. Chem. Kinet.

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Using a relative rate method, rate constants for the gas‐phase reactions of OH radicals with allyl alcohol, 3‐buten‐1‐ol, 3‐buten‐2‐ol, and 2‐methyl‐3‐buten‐2‐ol have been measured at 296 ± 2 K and atmospheric pressure of air. Using 1,3,5‐trimethylbenzene as the reference compound, the rate constants (in units of 10−11 cm3 molecule−1 s−1) were: allyl alcohol, 5.46 ± 0.35; 3‐buten‐1‐ol, 5.50 ± 0.20; 3‐buten‐2‐ol, 5.93 ± 0.23; and 2‐methyl‐3‐buten‐2‐ol, 5.67 ± 0.13; where the indicated errors are two least‐squares standard deviations and do not include the uncertainty in the rate constant for 1,3,5‐trimethylbenzene. The H‐atom abstraction products acrolein and methyl vinyl ketone were observed from the allyl alcohol and 3‐buten‐2‐ol reactions, respectively, with respective yields of 5.5 ± 0.7 and 4.9 ± 1.4%. No evidence for formation of acrolein from 3‐buten‐1‐ol or 3‐buten‐2‐ol was obtained, with upper limits to the acrolein yields of ≤1.2 and ≤0.5%, respectively, being determined. Reaction mechanisms are discussed. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 142–147, 2001

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Rate and mechanism of the reactions of OH and Cl with 2‐methyl‐3‐buten‐2‐ol

Abstract: Abstract. An environmental chamber/Fourier transform infrared system was used to determine the rate coefficient k• for the gas-phase reaction of OH with 2-methyl-3-buten-2-ol (MBO, (CH3)2C(OH)CH=CH2), relative to the rate of its reaction with ethylene (k2) and propylene (k3).

Cited by 89 publications

References 27 publications

High concentrations of reactive biogenic VOCs at a high altitude site in late autumn

High concentrations of reactive biogenic VOCs at a high altitude site in late autumn

Ion trap mass spectrometry affords advances in the analytical and atmospheric chemistry of 2-hydroxy-2-methylpropanal, a proposed photooxidation product of 2-methyl-3-buten-2-ol

Rate constants for the gas-phase reactions of OH radicals with a series of unsaturated alcohols

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