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- Title
Efficient photochemical generation of peroxycarboxylic nitric anhydrides with ultraviolet light-emitting diodes.
- Authors
Rider, N. D.; Taha, Y. M.; Odame-Ankrah, C. A.; Huo, J. A.; Tokarek, T. W.; Cairns, E.; Moussa, S. G.; Liggio, J.; Osthoff, H. D.
- Abstract
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 phosphorcoated 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 In this manuscript, a photochemical PAN source in which the Hg lamp has been replaced by arrays of ultraviolet light-emitting diodes (UV-LEDs) is described.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 din-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.
- Subjects
PHOTOCHEMISTRY; ANHYDRIDES; ULTRAVIOLET radiation; LIGHT emitting diodes; PHOTODISSOCIATION; GAS chromatography; ACETONE; KETONES
- Publication
Atmospheric Measurement Techniques, 2015, Vol 8, Issue 7, p2737
- ISSN
1867-1381
- Publication type
Article
- DOI
10.5194/amt-8-2737-2015