HOx and NOx production in oxidation flow reactors via photolysis of isopropyl nitrite, isopropyl nitrite-d(7), and 1,3-propyl dinitrite at lambda=254, 350, and 369 nm

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Lambe , A T , Krechmer , J E , Peng , Z , Casar , J R , Carrasquillo , A J , Raff , J D , Jimenez , J L & Worsnop , D R 2019 , ' HOx and NOx production in oxidation flow reactors via photolysis of isopropyl nitrite, isopropyl nitrite-d(7), and 1,3-propyl dinitrite at lambda=254, 350, and 369 nm ' , Atmospheric Measurement Techniques , vol. 12 , no. 1 , pp. 299-311 . https://doi.org/10.5194/amt-12-299-2019

Title: HOx and NOx production in oxidation flow reactors via photolysis of isopropyl nitrite, isopropyl nitrite-d(7), and 1,3-propyl dinitrite at lambda=254, 350, and 369 nm
Author: Lambe, Andrew T.; Krechmer, Jordan E.; Peng, Zhe; Casar, Jason R.; Carrasquillo, Anthony J.; Raff, Jonathan D.; Jimenez, Jose L.; Worsnop, Douglas R.
Contributor: University of Helsinki, INAR Physics
Date: 2019-01-17
Language: eng
Number of pages: 13
Belongs to series: Atmospheric Measurement Techniques
ISSN: 1867-1381
URI: http://hdl.handle.net/10138/310953
Abstract: Oxidation flow reactors (OFRs) are an emerging technique for studying the formation and oxidative aging of organic aerosols and other applications. In these flow reactors, hydroxyl radicals (OH), hydroperoxyl radicals (HO2), and nitric oxide (NO) are typically produced in the following ways: photolysis of ozone (O-3) at), = 254 nm, photolysis of H2O at), = 185 nm, and via reactions of O(D-1) with H2O and nitrous oxide (N2O); O(D-1) is formed via photolysis of O-3 at = 254 nm and/or N2O at = 185 nm. Here, we adapt a complementary method that uses alkyl nitrite photolysis as a source of OH via its production of HO2 and NO followed by the reaction NO + HO2 -> NO2 + OH. We present experimental and model characterization of the OH exposure and NO, levels generated via photolysis of C3 alkyl nitrites (isopropyl nitrite, perdeuterated isopropyl nitrite, 1,3-propyl dinitrite) in the Potential Aerosol Mass (PAM) OFR as a function of photolysis wavelength (7, = 254 to 369 nm) and organic nitrite concentration (0.5 to 20 ppm). We also apply this technique in conjunction with chemical ionization mass spectrometer measurements of multifunctional oxidation products generated following the exposure of a-Pinene to HO, and NO, obtained using both isopropyl nitrite and O-3 + H2O + N2O as the radical precursors.
Subject: SECONDARY ORGANIC AEROSOL
RADICAL-INITIATED REACTIONS
GAS-PHASE REACTIONS
RATE CONSTANTS
ATMOSPHERIC CHEMISTRY
PHOTOCHEMICAL DATA
QUANTUM YIELDS
RELATIVE RATE
OH RADICALS
PHOTOOXIDATION
114 Physical sciences
116 Chemical sciences
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