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Titel Efficient photochemical generation of peroxycarboxylic nitric anhydrides with ultraviolet light-emitting diodes
VerfasserIn N. D. Rider, Y. M. Taha, C. A. Odame-Ankrah, J. A. Huo, T. W. Tokarek, E. Cairns, S. G. Moussa, J. Liggio, H. D. Osthoff
Medientyp Artikel
Sprache Englisch
ISSN 1867-1381
Digitales Dokument URL
Erschienen In: Atmospheric Measurement Techniques ; 8, no. 7 ; Nr. 8, no. 7 (2015-07-08), S.2737-2748
Datensatznummer 250116476
Publikation (Nr.) Volltext-Dokument vorhandencopernicus.org/amt-8-2737-2015.pdf
 
Zusammenfassung
Photochemical sources of peroxycarboxylic nitric anhydrides (PANs) are utilized in many atmospheric measurement techniques for calibration or to deliver an internal standard. Conventionally, such sources rely on phosphor-coated low-pressure mercury (Hg) lamps to generate the UV light necessary to photo-dissociate a dialkyl ketone (usually acetone) in the presence of a calibrated amount of nitric oxide (NO) and oxygen (O2). In this manuscript, a photochemical PAN source in which the Hg lamp has been replaced by arrays of ultraviolet light-emitting diodes (UV-LEDs) is described. The output of the UV-LED source was analyzed by gas chromatography (PAN-GC) and thermal dissociation cavity ring-down spectroscopy (TD-CRDS). Using acetone, diethyl ketone (DIEK), diisopropyl ketone (DIPK), or di-n-propyl ketone (DNPK), respectively, the source produces peroxyacetic (PAN), peroxypropionic (PPN), peroxyisobutanoic (PiBN), or peroxy-n-butanoic nitric anhydride (PnBN) from NO in high yield (> 90 %). Box model simulations with a subset of the Master Chemical Mechanism (MCM) were carried out to rationalize product yields and to identify side products. The present work demonstrates that UV-LED arrays are a viable alternative to current Hg lamp setups.
 
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