Gas phase UV absorption cross-sections for a series of hydroxycarbonyls

Messaadia, L.; Dib, Gisèle El; Ferhati, A.; Roth, E.; Chakir, A.

doi:10.1016/j.cplett.2012.01.044

Cited by 26 publications

(40 citation statements)

References 19 publications

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“…14 days for 3-hydroxy-3-methyl-2-butanone) (Aschmann et al, 2000;Calvert et al, 2011), thus showing large variability in the reactivity that can be attributed to the structure of the molecule. Recently, the determination of the absorption cross-sections for four hydroxycarbonyl (!C4) compounds by Messaadia et al, (2012) showed that all obtained spectra of these compounds were similar in shape with two absorption bands, the first one below 220 nm and the second one between 230 and 340 nm with a maximum in the wavelength range 265e290 nm. The tropospheric lifetime of 3H3M2B due to photolysis was estimated by Messaadia et al (2012) to be at least 0.4 day using an upper limit of the photolysis rate assuming a quantum yield of unity.…”

Section: Introductionmentioning

confidence: 94%

“…Recently, the determination of the absorption cross-sections for four hydroxycarbonyl (!C4) compounds by Messaadia et al, (2012) showed that all obtained spectra of these compounds were similar in shape with two absorption bands, the first one below 220 nm and the second one between 230 and 340 nm with a maximum in the wavelength range 265e290 nm. The tropospheric lifetime of 3H3M2B due to photolysis was estimated by Messaadia et al (2012) to be at least 0.4 day using an upper limit of the photolysis rate assuming a quantum yield of unity. Therefore, atmospheric fate of these compounds may also be significantly affected by photolytic loss processes.…”

Section: Introductionmentioning

confidence: 94%

“…For larger hydroxycarbonyls (!C 4 ), degradation pathways have not been well characterized. The few available studies indicate that saturated hydroxyketones are mainly removed by OH radicals (Aschmann et al, 2000;Magneron et al, 2003;Messaadia et al, 2012;El Dib et al, 2013;Messaadia et al, 2013;Sleiman et al, 2013). Reactivity with O 3 and NO 3 radicals is expected to be not important in the atmosphere (Calvert et al, 2011).…”

Section: Introductionmentioning

confidence: 97%

“…In the atmosphere, OVOCs are supposed to react mainly with OH radicals, although reactions with NO 3 , Cl and ozone cannot be excluded for some of the species in specific environments . The photolysis channel could be significant for carbonyl species (Moortgat, 2001;Bouzidi et al, 2014) and yet, its importance in the case of hydroxycarbonyl VOCs is almost unknown, while recent studies suggest that photolysis could be significant (Henry et al, 2012;Messaadia et al, 2012). Atmospheric chemistry of hydroxyacetone, the smallest hydroxyketone compound, is reasonably well understood (Orlando et al, 1999;Dillon et al, 2006).…”

Section: Introductionmentioning

confidence: 97%

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Reactivity of 3-hydroxy-3-methyl-2-butanone: Photolysis and OH reaction kinetics

Bouzidi

Laversin

Tomás

et al. 2014

Atmospheric Environment

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h i g h l i g h t s 3H3M2B photolysis is the major oxidation channel in the atmosphere. Slight positive temperature dependence in the OH þ 3H3M2B reaction kinetics. Need for a better understanding of the atmospheric chemistry of oxygenated VOC. a b s t r a c t Hydroxycarbonyl compounds are important secondary reaction products in the oxidation of Volatile Organic Compounds (VOCs) in the atmosphere. The atmospheric fate of these oxygenated VOCs is however poorly understood, especially the relevance of the photolytic pathway. In this work, a combined investigation of the photolysis and temperature-dependent OH radical reaction of 3-hydroxy-3-methyl-2-butanone (3H3M2B) is presented. A photolysis lifetime of about 4e5 days was estimated with a global quantum yield of 0.10. The OH reaction rate coefficient follows the Arrhenius trend (298e356 K) and could be modelled through the following expression: k 3H3M2B (T) ¼ (5.12 ± 0.07) Â 10 À12 exp(À563 ± 119/ T) in cm 3 molecule À1 s À1 . A 3H3M2B atmospheric lifetime of 15 days towards the OH radical was evaluated. Our results showed that the photolysis pathway is the major degradation channel for 3H3M2B. Photolysis products were identified and quantified in the present work with a carbon balance of around 80% enabling a reaction mechanism to be proposed. The present work underlines the need for further studies on the atmospheric chemistry of oxygenated VOCs.

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Section: Introductionmentioning

confidence: 94%

Section: Introductionmentioning

confidence: 94%

Section: Introductionmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 97%

See 2 more Smart Citations

Reactivity of 3-hydroxy-3-methyl-2-butanone: Photolysis and OH reaction kinetics

Bouzidi

Laversin

Tomás

et al. 2014

Atmospheric Environment

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“…The experimental setup used to measure the UV cross sections of 2,3-pentanedione and 2,4-pentanedione has been previously described [12,13], therefore, it will only be described The absorption cross-section ( ) values were determined using the Lambert-Beer's law (1), as a function of the pressure P, temperature T, optical path l and intensities described above. R represents the gas constant and N A is Avogadro's number.…”

Section: Uv-visible Spectrummentioning

confidence: 99%

UV–visible spectra and gas-phase rate coefficients for the reaction of 2,3-pentanedione and 2,4-pentanedione with OH radicals

Messaadia

Dib

Ferhati

et al. 2015

Chemical Physics Letters

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The UV absorption cross-sections of 2,3-pentanedione and 2,4-pentanedione were measured and their reactions with OH were investigated in the gas-phase using a relative rate method. A temperature dependence of the rate coefficients was observed for both reactions over the temperature range 298 -338 K. This work provides the first UV cross-section in the gas phase for 2,4-pentanedione and the first kinetic data for the reaction of 2,3-pentanedione with OH radicals as a function of temperature. The tropospheric lifetimes obtained in this work suggest that once emitted into the atmosphere, these species could be quickly degraded close to their emission sources.

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The gas phase aldose‐ketone isomerization mechanism: Direct interconversion of the model hydroxycarbonyls 2‐hydroxypropanal and hydroxyacetone

Sun

Silva

2017

Int J Quantum Chem

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We report a novel mechanism for the interconversion of 2-hydroxypropanal with its more-stable ketone isomer hydroxyacetone. Reaction proceeds via concerted transfer of two H atoms, requires a barrier of only 40 kcal mol 21 , bypasses the enediol intermediate, and is general for a-hydroxy carbonyls. A similar isomerization mechanism is shown to persist for b, g, and d-hydroxy carbonyls; these compounds are skeletal forms of the monosaccharides and this work, therefore, discloses the gas-phase mechanism for aldose-ketose isomerization. As an example, the isomerization of glyceraldehyde to dihydroxyacetone is shown to proceed via this mechanism with a barrier of 31 kcal mol 21 . Rate coefficients and thermochemical properties are reported for the isomerization of 2-hydroxypropanal and hydroxyacetone for use in detailed kinetic models. Additionally, RRKM theory k(E) values for this reaction suggest that it may transpire in the troposphere following solar excitation. K E Y W O R D S computational chemistry, gas-phase reactions, pyrolysis, reaction mechanisms 1 | I N T R O D U C T I O N Hydroxycarbonyls are common oxygenated intermediates formed in the photochemical oxidation of volatile organic compounds and in the thermal processing of lignocellulosic material. Hydroxyacetone (HOCH 2 C(O)CH 3 ), the simplest a-hydroxy ketone, is a widely-detected trace gas in the troposphere, [1] and its photochemical oxidation mechanisms have been studied extensively. [2-5] 2-Hydroxypropanal (CH 3 CHOH-CHO), an isomer of hydroxyacetone, is an intermediate in the pyrolysis and combustion chemistry of glyceral. [6] More broadly, the open-chain forms of the monosaccharides are hydroxycarbonyls, with an aldehyde (aldose) or ketone (ketose) moiety and a hydroxyl group at each remaining carbon. Hydroyxacetone and 2-hydroxypropanal thus serve as model compounds for the a-hydroxy carbonyl functionality in these simple sugars.Recently, we reported on the isomerization mechanism of glycolaldehyde (HOCH 2 CHO), [7] the archetypal a-hydroxy carbonyl and an important tropospheric compound in its own right. [8] This work revealed that glycolaldehyde could undergo keto-enol tautomerization via intramolecular transfer of two H atoms, mediated by the hydroxyl group. This process is reminiscent of a bimolecular mechanism previously shown to catalyze keto-enol tautomerizations. [9] In the course of our investigation into glycolaldehyde it became apparent that this compound could undergo degenerate isomerization reactions in which the unique O atoms (i.e., the alcohol and aldehyde functional groups) were effectively scrambled. The present work extends this analysis to hydroxycarbonyl compounds in which the alcohol and aldehyde/ketone groups are not interchangeable, starting with the hydroxyacetone/2-hydroxypropanal pairing, through the application of ab initio calculations and reaction rate theory modelling. This study expands our understanding of rearrangement reactions available to hydroxycarbonyl compounds in thermal environments and in the troposph...

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Gas phase UV absorption cross-sections for a series of hydroxycarbonyls

Cited by 26 publications

References 19 publications

Reactivity of 3-hydroxy-3-methyl-2-butanone: Photolysis and OH reaction kinetics

Reactivity of 3-hydroxy-3-methyl-2-butanone: Photolysis and OH reaction kinetics

UV–visible spectra and gas-phase rate coefficients for the reaction of 2,3-pentanedione and 2,4-pentanedione with OH radicals

The gas phase aldose‐ketone isomerization mechanism: Direct interconversion of the model hydroxycarbonyls 2‐hydroxypropanal and hydroxyacetone

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