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Photochemistry of Methylglyoxal in the Vapor Phase

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Max-Planck-Institut für Chemie, Atmospheric Chemistry Division, Postfach 3060, 55020 Mainz, Germany
Cite this: J. Phys. Chem. A 1998, 102, 46, 9142–9153
Publication Date (Web):October 21, 1998
Copyright © 1998 American Chemical Society

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    The photolysis of methylglyoxal (CH3COCHO) in the presence of synthetic air was studied by laboratory experiments in a static reactor in order to determine its atmospheric lifetime. Quantum yields of the molecular photolysis products CO and HCHO were determined at 298 K as a function of wavelength (260 ≤ λ ≤ 440 nm) and pressure (30 ≤ P ≤ 900 Torr) using an optical resolution of 8.5 nm. The results can be distinguished with respect to both UV/VIS-absorption bands of methylglyoxal. For the short-wavelength band (260 ≤ λ ≤ 320 nm) photolysis quantum yields were found to be unity, independent of wavelength and pressure, consistent with a dissociation mechanism yielding peroxy radicals and CO according to CH3COCHO CH3COO2 + HO2 + CO (P1). For the long-wavelength band (380 ≤ λ ≤ 440 nm) two different processes were distinguished. The major process is photodissociation (P1) with quantum yields (φD) decreasing with increasing wavelength and pressure following the Stern−Volmer relationship:  1/φD(λ) = 1/φ0(λ) + P/kD(λ) with φ0(λ) = (8.15 ± 0.5)(10-9) [exp(7131 ± 267)] nm/λ and kD(λ) = (7.34 ± 0.1)(10-9 Torr) [exp(8793 ± 300)] nm/λ. The minor process could be described by an H-atom transfer between electronically excited MG and ground-state MG, yielding the experimentally observed products [CH3COCHO]* + CH3COCHO CH3COO2 + HCHO + CO + CH3COO2 (R10). The atmospheric lifetime due to photolysis (τphot) was calculated using an atmospheric radiation model and the above expression, where φ0(λ) = 1 for λ < 380 nm, resulting in τphot = (4.1 ± 0.7) h for a solar zenith angle of 50° at ground level. Therefore, photolysis can be identified as the most important degradation process of atmospheric methylglyoxal.

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