The temperature and wavelength dependence of the photo-oxidation of propionaldehyde

Heicklen, Julian; Desai, Jayant; Bahta, Abraha; Harper, Charles A.; Simonaitis, R.

doi:10.1016/0047-2670(86)85014-6

Cited by 23 publications

(27 citation statements)

References 49 publications

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“…(1) C 4 H 9 + C 4 H 9 f C 8 H 18 (9) C 4 H 9 + O 2 f C 4 H 9 O 2 (10) k rad ) ∫ σ(λ)Φ(rad,λ)J(λ) dλ (11) …”

Section: Resultsmentioning

confidence: 99%

“…Aldehydes play an important role in the formation of photochemical smog, peroxyacetyl nitrate (PAN), and regional ozone. Photodissociation of aldehydes represents a significant source of free radicals in the lower atmosphere. − There have been a relatively large number of studies devoted to the photodissociation of shorter chain aldehydes, such as CH 2 O, CH 3 CHO, and C 2 H 5 CHO. − However, the photolysis of longer chain aldehydes is not well-understood. Such an investigation is important in order to determine the fates of longer chain aldehydes in the atmosphere and to understand their contribution to radical formation.…”

Section: Introductionmentioning

confidence: 99%

“…[1][2][3] There have been a relatively large number of studies devoted to the photodissociation of shorter chain aldehydes, such as CH 2 O, CH 3 CHO, and C 2 H 5 CHO. [4][5][6][7][8][9][10][11][12] However, the photolysis of longer chain aldehydes is not well-understood. Such an investigation is important in order to determine the fates of longer chain aldehydes in the atmosphere and to understand their contribution to radical formation.…”

Section: Introductionmentioning

confidence: 99%

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Dye Laser Photolysis of n-Pentanal from 280 to 330 nm

Cronin

Zhu

1998

J. Phys. Chem. A

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The UV photolysis of n-pentanal in the 280-330-nm region has been studied in 5-nm intervals by using dye laser photolysis in combination with cavity ring-down spectroscopy. Absorption cross sections of n-pentanal were measured at each wavelength studied. n-Pentanal exhibited a broad, structureless absorption band similar, in appearance, to that of previously studied short-chain aldehydes. The absorption spectrum peaked at 295 nm with a cross section of (6.56 ( 0.17) × 10 -20 cm 2 molecule -1 . The formation of the HCO radical, which is a photodissociation product, was monitored in these experiments. The HCO yield was found to be independent of n-pentanal pressure (2-18 Torr) and total pressure (8-480 Torr) except for 325-and 330-nm photolysis where the size of the HCO signal was small and the dissociation was near the threshold. The dependence of the HCO radical yield on the photolysis wavelength was determined. The HCO yields were 0.058 ( 0.006, 0.095 ( 0.009, 0.10 ( 0.02, 0.14 ( 0.01, 0.10 ( 0.02, 0.15 ( 0.02, 0.14 ( 0.02, 0.20 ( 0.06, 0.14 ( 0. 02, 0.085 ( 0.034, 0.087 ( 0.015 at 280, 285, 290, 295, 300, 305, 310, 315, 320, 325, and 330 nm, respectively, where uncertainty reflects experimental scatter only. End products from closed-cell photolysis of n-pentanal with and without O 2 were investigated at 290, 310, and 330 nm by using GC/MS and HPLC. Acetaldehyde was found to be a significant product from the photodissociation of n-pentanal/N 2 mixtures. Photolysis rates of n-pentanal to form HCO were calculated for two representative atmospheric conditions (noontime at sea level and 40°N latitude on January 1 and on July 1). The estimated radical formation rate constants from n-pentanal photolysis were about twice as fast as those obtained from acetaldehyde photolysis.

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“…(1) C 4 H 9 + C 4 H 9 f C 8 H 18 (9) C 4 H 9 + O 2 f C 4 H 9 O 2 (10) k rad ) ∫ σ(λ)Φ(rad,λ)J(λ) dλ (11) …”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Dye Laser Photolysis of n-Pentanal from 280 to 330 nm

Cronin

Zhu

1998

J. Phys. Chem. A

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“…Photodissociation of aldehydes produces free radicals, which are subsequently involved in other atmospheric reactions and reaction cycles. There have been a number of studies devoted to the photodissociation of the simplest alkyl aldehydes, such as HCHO, CH 3 CHO, C 2 H 5 CHO [ 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 ], but a relatively small number devoted to longer chain aldehydes, such as C 3 H 7 CHO, C 4 H 9 CHO [ 17 , 18 ] and iso -pentanal and tert -pentanal [ 32 ].…”

Section: Introductionmentioning

confidence: 99%

Photooxidation of n-Hexanal in Air

2001

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Dilute mixtures of hexanal in synthetic air (up to 100 ppm) were photolyzed with fluorescent UV lamps (275-380 nm) in air at 298 K. The main photooxidation products, identified and quantitatively analyzed by FTIR spectroscopy, were butene, CO, vinylalcohol and ethanal. The photolysis rates and the absolute quantum yield Φ were found to be slightly dependent on the total pressure. At 100 Torr, Φ100 = 0.43 ± 0.02, whereas at 700 Torr the total quantum yield was Φ700 = 0.38 ± 0.02. These results may be explained by the collisional deactivations of photoexcited molecules. Two decomposition channels were identified: the radical channel C5H11CHO → C5H11 + HCO, and the molecular channel C5H11CHO → C4H8 + CH2=CHOH, having the relative yields of 27 and 73 % at 700 Torr. The product CH2=CHOH tautomerizes to ethanal.

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“…Photodecomposition rates in air for a number of aldehydes and ketones are calculated from the actinic fluxes within the planetary boundary layer (Dimerjian et al, 1980), along with absorption cross-sections and quantum yields, ~z (F6rgeteg et al, 1979;Horowitz and Calvert, 1982;Gardner et aL, 1984;Desai et aL, 1989;Heicklen et al, 1986;Meyrahn et al;Atkinson et al, 1986), or from photolysis rates relative to NO 2 (Plum et aL, 1983). For CH3COC2Hs, a 9~a of 0.1 is assumed (Carter et al, 1986), and for C2HsCOC2H 5 and (CH3)2CHCOCH 3, a #z of 0.2 is assumed within the range of 295 um to 340 nm.…”

Section: Calculation Of Co Yields From Oxygenated Productsmentioning

confidence: 99%

The production of carbon monoxide by the homogeneous NO x -induced photooxidation of volatile organic compounds in the troposphere

Altshuller

1991

J Atmos Chem

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The reaction mechanisms of products, along with their rates of reaction with hydroxyl radicals and their rates of photolysis, have been used to obtain carbon monoxide, CO, yields from the products of the homogenous atmospheric photooxidation from emissions of hydrocarbons and other volatile organic compounds, VOCs. Seasonally averaged CO yields are estimated for a number of types of VOCs. The annual production of CO is estimated for the contiguous United States from combustion sources of CO and from the atmospheric photooxidation of anthropogenic and biogenic emissions of volatile organic compounds. Limitations on estimates of CO yields and of CO production from various heterogeneous processes are discussed.

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The temperature and wavelength dependence of the photo-oxidation of propionaldehyde

Cited by 23 publications

References 49 publications

Dye Laser Photolysis of n-Pentanal from 280 to 330 nm

Dye Laser Photolysis of n-Pentanal from 280 to 330 nm

Photooxidation of n-Hexanal in Air

The production of carbon monoxide by the homogeneous NO x -induced photooxidation of volatile organic compounds in the troposphere

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