Yields of HONO₂ and HOONO Products from the Reaction of HO₂ and NO Using Pulsed Laser Photolysis and Mid-Infrared Cavity-Ringdown Spectroscopy

Abstract

The reaction of HO₂ with NO is one of the most important steps in radical cycling throughout the stratosphere and troposphere. Previous literature experimental work revealed a small yield of nitric acid (HONO₂) directly from HO₂ + NO. Atmospheric models previously treated HO₂ + NO as radical recycling, but inclusion of this terminating step had large effects on atmospheric oxidative capacity and the concentrations of HONO₂ and ozone (O₃), among others. Here, the yield of HONO₂, φHONO₂, from the reaction of HO₂ + NO was investigated in a flow tube reactor using mid-IR pulsed-cavity ringdown spectroscopy. HO₂, produced by pulsed laser photolysis of Cl₂ in the presence of methanol, reacted with NO in a buffer gas mixture of N₂ and CO between 300 and 700 Torr at 278 and 300 K. HONO₂ and its weakly bound isomer HOONO were directly detected by their v1 absorption bands in the mid-IR region. CO was used to suppress HONO₂ produced from OH + NO₂ and exploit a chemical amplification scheme, converting OH back to HO₂. Under the experimental conditions described here, no evidence for the formation of either HONO₂ or HOONO was observed from HO₂ + NO. Using a comprehensive chemical model, constrained by observed secondary reaction products, all HONO₂ detected in the system could be accounted for by OH + NO₂. At 700 ± 14 Torr and 300 ± 3 K, φHONO₂ = 0.00 ± 0.11% (2σ) with an upper limit of 0.11%. If all of the observed HONO₂ was attributed to the HO₂ + NO reaction, φHONO₂ = 0.13 ± 0.07% with an upper limit of 0.20%. At 278 ± 2 K and 718 ± 14 Torr, we determine an upper limit, φHONO₂ ≤ 0.37%. Our measurements are significantly lower than those previously reported, lying outside of the uncertainty of the current experimental and recommended literature values.