Articles | Volume 8, issue 5
https://doi.org/10.5194/amt-8-2225-2015
https://doi.org/10.5194/amt-8-2225-2015
Research article
 | 
29 May 2015
Research article |  | 29 May 2015

Development of a photochemical source for the production and calibration of acyl peroxynitrate compounds

P. R. Veres and J. M. Roberts

Abstract. A dynamic system for the calibration of acyl peroxynitrate compounds (APNs) has been developed in the laboratory to reduce the difficulty, required time, and instability of laboratory-produced standards for difficult-to-synthesize APN species. In this work we present a photochemical source for the generation of APN standards: acetyl peroxynitrate (PAN), propionyl peroxynitrate (PPN), acryloyl peroxynitrate (APAN), methacryloyl peroxynitrate (MPAN), and crotonyl peroxynitrate (CPAN). APNs are generated via photolysis of a mixture of acyl chloride (RC(O)Cl) and ketone (RC(=O)R) precursor compounds in the presence of O2 and NO2. Subsequent separation by a prep-scale gas chromatograph and detection with a total NOy instrument serve to quantify the output of the APN source. Validation of the APN products was performed using iodide ion chemical ionization mass spectroscopy (I- CIMS). This method of standard production is an efficient and accurate technique for the calibration of instrumentation used to measure PAN, PPN, APAN, MPAN, and CPAN.

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Short summary
A dynamic system for the calibration of acyl peroxynitrate compounds has been developed to reduce the difficulty, required time, and stability of laboratory standards. We present a photochemical source for the generation of acetyl peroxynitrate (PAN), propionyl peroxynitrate (PPN), acryloyl peroxynitrate (APAN), methacryloyl peroxynitrate (MPAN), and crotonyl peroxynitrate (CPAN). Validation of the APN products was performed using iodide ion chemical ionization mass spectroscopy (I- CIMS).