Model Evaluation of New Techniques for Maintaining High-NO Conditions in Oxidation Flow Reactors for the Study of OH-Initiated Atmospheric Chemistry

Abstract

Oxidation flow reactors (OFRs) efficiently produce OH radicals using low-pressure Hg-lamp emissions at λ = 254 nm (OFR254) or both λ = 185 and 254 nm (OFR185). OFRs under most conditions are limited to studying low-NO chemistry (where RO2 + HO2 dominates RO2 fate), even though substantial amounts of initial NO may be injected. This is due to very fast NO oxidation by high concentrations of OH, HO2, and O3. In this study, we model new techniques for maintaining high-NO conditions in OFRs, that is, continuous NO addition along the length of the reactor in OFR185 (OFR185-cNO), recently proposed injection of N2O at the entrance of the reactor in OFR254 (OFR254-iN2O), and an extension of that idea to OFR185 (OFR185-iN2O). For these techniques, we evaluate (1) fraction of conditions dominated by RO2 + NO while avoiding significant nontropospheric photolysis and (2) fraction of conditions where reactions of precursors with OH dominate over unwanted reactions with NO3. OFR185-iN2O is the most practical for genera...