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 v
1 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.