Formation of Nitric Acid in the Gas-Phase HO2 + NO Reaction: Effects of Temperature and Water Vapor

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Abstract
A high-pressure turbulent flow reactor coupled with a chemical ionization mass spectrometer was used to investigate the minor channel (1b) producing nitric acid, HNO3, in the HO2 + NO reaction for which only one channel (1a) is known so far: HO2 + NO → OH + NO2 (1a), HO2 + NO → HNO3 (1b). The reaction has been investigated in the temperature range 223−298 K at a pressure of 200 Torr of N2 carrier gas. The influence of water vapor has been studied at 298 K. The branching ratio, k1b/k1a, was found to increase from (0.1 )% at 298 K to (0.8 )% at 223 K, corresponding to k1b = (1.6 ± 0.5) × 10-14 and (10.4 ± 1.7) × 10-14 cm3 molecule-1 s-1, respectively at 298 and 223 K. The data could be fitted by the Arrhenius expression k1b = 6.4 × 10-17 exp((1644 ± 76)/T) cm3 molecule-1 s-1 at T = 223−298 K. The yield of HNO3 was found to increase in the presence of water vapor (by 90% at about 3 Torr of H2O). Implications of the obtained results for atmospheric radicals chemistry and chemical amplifiers used to measure peroxy radicals are discussed. The results show in particular that reaction 1b can be a significant loss process for the HOx (OH, HO2) radicals in the upper troposphere.

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