HO x and NO x production in oxidation flow reactors via photolysis of isopropyl nitrite, isopropyl nitrite-d 7, and 1,3-propyl dinitrite at λ = 254, 350, and 369 nm

Lambe, Andrew T.; Krechmer, Jordan E.; Peng, Zhe; Casar, Jason R.; Carrasquillo, Anthony J.; Raff, Jonathan D.; Jimenez, Jose L.; Worsnop, Douglas R.

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 (inline-formulaHO2), and nitric oxide (NO) are typically produced in the following ways: photolysis of ozone (inline-formulaO3) at inline-formulaλ=254 nm, photolysis of inline-formulaH2O at inline-formulaλ=185 nm, and via reactions of inline-formulaO(1D) with inline-formulaH2O and nitrous oxide inline-formula(N2O); inline-formulaO(1D) is formed via photolysis of inline-formulaO3 at inline-formulaλ=254 nm and/or inline-formulaN2O at inline-formulaλ=185 nm. Here, we adapt a complementary method that uses alkyl nitrite photolysis as a source of OH via its production of inline-formulaHO2 and NO followed by the reaction NO inline-formula+inline-formulaHO2inline-formula→inline-formulaNO2inline-formula+ OH. We present experimental and model characterization of the OH exposure and inline-formulaNOx levels generated via photolysis of inline-formulaC3 alkyl nitrites (isopropyl nitrite, perdeuterated isopropyl nitrite, 1,3-propyl dinitrite) in the Potential Aerosol Mass (PAM) OFR as a function of photolysis wavelength (inline-formulaλ=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 inline-formulaα-Pinene to inline-formulaHOx and inline-formulaNOx obtained using both isopropyl nitrite and inline-formulaO3inline-formula+inline-formulaH2Oinline-formula+inline-formulaN2O as the radical precursors.

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Lambe, Andrew T. / Krechmer, Jordan E. / Peng, Zhe / et al: HOx and NOx production in oxidation flow reactors via photolysis of isopropyl nitrite, isopropyl nitrite-d7, and 1,3-propyl dinitrite at λ = 254, 350, and 369 nm. 2019. Copernicus Publications.

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