Atmospheric Chemistry of 2,3-Pentanedione: Photolysis and Reaction with OH Radicals

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2011-08, Vol.115 (33), p.9160-9168
• Main Authors: Szabó, Emese, Djehiche, Mokhtar, Riva, Matthieu, Fittschen, Christa, Coddeville, Patrice, Sarzyński, Dariusz, Tomas, Alexandre, Dóbé, Sándor
• Format: Article
• Language: English
• Subjects: A: Kinetics, Spectroscopy; Absorption; Absorption cross sections; Atmosphere - chemistry; Atmospherics; Chemical Sciences; Coefficients; Hydroxyl Radical - chemistry; Kinetics; Lasers; Molecular Structure; or physical chemistry; Pentanones - chemistry; Photolysis; Photolysis - radiation effects; Polytetrafluoroethylenes; Pressure; Quantum Theory; Radicals; Reaction kinetics; Spectrophotometry, Ultraviolet; Temperature; Theoretical and; Thermodynamics; Ultraviolet Rays
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp205595c

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 cm3 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 cm3 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 cm3 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 Φ2 = 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.