The kinetics of the overall reaction between OH radicals and 2,3-pentanedione (1) were studied using both direct and relative kinetic methods at laboratory temperature. The low pressure fast discharge flow experiments coupled with resonance fluorescence detection of OH provided the direct rate coefficient of (2.25 ± 0.44) × 10(-12) cm(3) molecule(-1) s(-1). The relative-rate experiments were carried out both in a collapsible Teflon chamber and a Pyrex reactor in two laboratories using different reference reactions to provide the rate coefficients of 1.95 ± 0.27, 1.95 ± 0.34, and 2.06 ± 0.34, all given in 10(-12) cm(3) molecule(-1) s(-1). The recommended value is the nonweighted average of the four determinations: k(1) (300 K) = (2.09 ± 0.38) × 10(-12) cm(3) molecule(-1) s(-1), given with 2σ accuracy. Absorption cross sections for 2,3-pentanedione were determined: the spectrum is characterized by two wide absorption bands between 220 and 450 nm. Pulsed laser photolysis at 351 nm was used and the depletion of 2,3-pentanedione (2) was measured by GC to determine the photolysis quantum yield of Φ(2) = 0.11 ± 0.02(2σ) at 300 K and 1000 mbar synthetic air. An upper limit was estimated for the effective quantum yield of 2,3-pentanedione applying fluorescent lamps with peak wavelength of 312 nm. Relationships between molecular structure and OH reactivity, as well as the atmospheric fate of 2,3-pentanedione, have been discussed.
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Environ Sci Pollut Res Int
December 2024
Departamento de Química Física, Facultad de Ciencias y Tecnologías Químicas, Universidad de Castilla-La Mancha, Avda. Camilo José Cela, 1B, 13071, Ciudad Real, Spain.
In this work, the rate coefficients for OH radical, k(T), and Cl atom, k(T), reaction with allyl 1,1,2,2-tetrafluoroethyl ether, CH=CHCHOCFCHF, were studied as a function of temperature and pressure in a collaborative effort made between UCLM, Spain, and LAPKIN, Greece. OH rate coefficients were determined in UCLM, between 263 and 353 K and 50-600 Torr, using the absolute rate method of pulsed laser photolysis-laser-induced fluorescence technique, while Cl kinetics were studied in temperature (260-363 K) and pressure (34-721 Torr) ranges, using the relative rate method of the thermostated photochemical reactor equipped with Fourier transform infrared spectroscopy as the detection technique. In both OH and Cl reactions, a negative temperature dependence of the measured rate coefficients was observed, which is consistent with complex association reactions.
View Article and Find Full Text PDFJ Phys Chem A
November 2024
Copenhagen Center for Atmospheric Research, Department of Chemistry, University of Copenhagen, Universitetsparken 5, Frederiksberg, Copenhagen Ø DK-2100, Denmark.
Smog chamber experiments were conducted to establish the atmospheric chemistry of ()- and ()-CFCFCH═CHCFCF. Kinetics of the reactions of the two compounds with Cl atoms and OH radicals were measured using relative rate techniques, giving (Cl + ()-CFCFCH═CHCFCF) = (5.63 ± 0.
View Article and Find Full Text PDFJ Am Chem Soc
November 2024
Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States.
Environ Sci Process Impacts
December 2024
Department of Chemistry, University of California Irvine, CA 92697, USA.
ACS Earth Space Chem
October 2024
Departamento de Química Física, Facultad de Ciencias y Tecnologías Químicas, Universidad de Castilla-La Mancha, Avda. Camilo José Cela 1B, 13071 Ciudad Real, Spain.
Formamide (NHC(O)H) has been observed both in the interstellar medium (ISM), being identified as a potential precursor of prebiotic molecules in space, and in the Earth's atmosphere. In these environments where temperature is very distinct, hydroxyl (OH) radicals may play an important role in the degradation of NHC(O)H. Thus, in this work, we report for the first time the experimental study of the temperature dependence of the gas-phase removal of OH in the presence of NHC(O)H over the 11.
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