Photochemistry of acetone under tropospheric conditions

Gierczak, Tomasz; Burkholder, James B.; Bauerle, Stefan; Ravishankara, A. R.

doi:10.1016/s0301-0104(98)00006-8

Cited by 156 publications

(244 citation statements)

References 23 publications

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“…The IBBCEAS measurement is therefore about two orders of magnitude more sensitive than the 320 nm (singlepass) measurement. These species have moderate absorption cross-sections (10 −20 cm 2 molecule −1 ) at 320 nm and literature spectra agree closely (Meyrahn et al, 1986;Hynes et al, 1992;Martinez et al, 1992;Brion et al, 1998;Gierczak et al, 1998;Burrows et al, 1999;Mu and Mellouki, 2000;Wollenhaupt et al, 2000;Voigt et al, 2001;Bogumil et al, 2003). The absorption was determined by measuring a small portion of the light reflected by the Semrock filter, transmitted through an Andover 320 nm band-pass filter, and recorded in another spectrograph (Andor SR-303).…”

Section: Spectrometer Setupsupporting

confidence: 57%

A broadband optical cavity spectrometer for measuring weak near-ultraviolet absorption spectra of gases

Chen

Venables

2011

Atmos. Meas. Tech.

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Abstract. Accurate absorption spectra of gases in the nearultraviolet (300 to 400 nm) are essential in atmospheric observations and laboratory studies. This paper describes a novel incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) instrument for measuring very weak absorption spectra from 335 to 375 nm. The instrument performance was validated against the 3 B 1 -X 1 A 1 transition of SO 2 . The measured absorption varied linearly with SO 2 column density and the resulting spectrum agrees well with published spectra. Using the instrument, we report new absorption cross-sections of O 3 , acetone, 2-butanone, and 2-pentanone in this spectral region, where literature data diverge considerably. In the absorption minimum between the Huggins and Chappuis bands, our absorption spectra fall at the lower range of reported ozone absorption crosssections. The spectra of the ketones agree with prior spectra at moderate absorptions, but differ significantly at the limits of other instruments' sensitivity. The collision-induced absorption of the O 4 dimer at 360.5 nm was also measured and found to have a maximum cross-section of ca. 4.0 × 10 −46 cm 5 molecule −2 . We demonstrate the application of the instrument to quantifying low concentrations of the shortlived radical, BrO, in the presence of stronger absorptions from Br 2 and O 3 .

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Section: Spectrometer Setupsupporting

confidence: 57%

A broadband optical cavity spectrometer for measuring weak near-ultraviolet absorption spectra of gases

Chen

Venables

2011

Atmos. Meas. Tech.

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“…After the transfer of BVOCs from PLUS was completed, 30 ppbv of ozone was injected into SAPHIR. The (Jacob et al, 2002;Gierczak et al, 1998). As can be seen in Fig.…”

Section: Bvoc Ozonolysis Of Real Plant Emissionsmentioning

confidence: 85%

A new plant chamber facility, PLUS, coupled to the atmosphere simulation chamber SAPHIR

Hohaus¹,

Kühn

Andres³

et al. 2016

Atmos. Meas. Tech.

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Abstract. A new PLant chamber Unit for Simulation (PLUS)for use with the atmosphere simulation chamber SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction Chamber) has been built and characterized at the Forschungszentrum Jülich GmbH, Germany. The PLUS chamber is an environmentally controlled flow-through plant chamber. Inside PLUS the natural blend of biogenic emissions of trees is mixed with synthetic air and transferred to the SAPHIR chamber, where the atmospheric chemistry and the impact of biogenic volatile organic compounds (BVOCs) can be studied in detail. In PLUS all important environmental parameters (e.g., temperature, photosynthetically active radiation (PAR), soil relative humidity (RH)) are well controlled. The gas exchange volume of 9.32 m 3 which encloses the stem and the leaves of the plants is constructed such that gases are exposed to only fluorinated ethylene propylene (FEP) Teflon film and other Teflon surfaces to minimize any potential losses of BVOCs in the chamber. Solar radiation is simulated using 15 light-emitting diode (LED) panels, which have an emission strength up to 800 µmol m −2 s −1 . Results of the initial characterization experiments are presented in detail. Background concentrations, mixing inside the gas exchange volume, and transfer rate of volatile organic compounds (VOCs) through PLUS under different humidity conditions are explored. Typical plant characteristics such as light-and temperature-dependent BVOC emissions are studied using six Quercus ilex trees and compared to previous studies. Results of an initial ozonolysis experiment of BVOC emissions from Quercus ilex at typical atmospheric concentrations inside SAPHIR are presented to demonstrate a typical experimental setup and the utility of the newly added plant chamber.

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“…The photolysis laser fluence was varied over the range (7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17)(18)(19) mJ pulse -1 cm -2 . The OH probe laser fluence ranged from 0.2 to 0.4 mJ pulse -1 cm -2 .…”

Section: Methodsmentioning

confidence: 99%

Rate Coefficient and Product Branching Measurements for the Reaction OH + Bromopropane from 230 to 360 K

et al. 2002

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Rate coefficients over the range of 230-360 K were measured for the reaction of OH with the following bromopropane isotopomers: CH 3 CH 2 CH 2 Br (k 1 ), CD 3 CH 2 CH 2 Br (k 2 ), CD 3 CH 2 CD 2 Br (k 3 ), CH 3 CD 2 CD 2 Br (k 4 ), and CD 3 CD 2 CD 2 Br (k 5 ). The hydroxyl radical was produced by pulsed laser photolysis and detected via laser induced fluorescence. Reaction 1 can occur by H atom abstraction from three different carbon sites: OH + CH 3 CH 2 CH 2 Br f CH 3 CH 2 CHBr + H 2 O (1a; R); f CH 3 CHCH 2 Br + H 2 O (1b; ); or f CH 2 CH 2 -CH 2 Br + H 2 O (1c; γ). Branching ratios obtained from an analysis of the kinetic data at 298 K are k 1c /k 1 ) 0.12 ( 0.08, k 1b /k 1 ) 0.56 ( 0.04, and k 1a /k 1 ) 0.32 ( 0.08; uncertainties given are 2 standard deviations and do not include systematic uncertainties. Stable products formed following reaction 1 in a NO x /O 2 environment were measured using long path infrared absorption. Bromoacetone and propanal were observed in the ratio [(CH 3 C(O)CH 2 Br)/(CH 3 CH 2 CHO)] of 1.65 ( 0.50 with an absolute bromoacetone yield of 0.5 ( 0.2 at room temperature. The product yields are consistent with the rate coefficient data. Ab initio calculations show that C-H bond energies at both the R and sites decrease (relative to propane) by the addition of Br at the R site. The calculated transition state energies decrease in the order γ > R > , in qualitative agreement with the experimental observations.

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Photochemistry of acetone under tropospheric conditions

Cited by 156 publications

References 23 publications

A broadband optical cavity spectrometer for measuring weak near-ultraviolet absorption spectra of gases

A broadband optical cavity spectrometer for measuring weak near-ultraviolet absorption spectra of gases

A new plant chamber facility, PLUS, coupled to the atmosphere simulation chamber SAPHIR

Rate Coefficient and Product Branching Measurements for the Reaction OH + Bromopropane from 230 to 360 K

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