Report

Rate of Gas Phase Association of Hydroxyl Radical and Nitrogen Dioxide

Science  29 Oct 2010:
Vol. 330, Issue 6004, pp. 646-649
DOI: 10.1126/science.1193030

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Honing in on HONO2

Modeling air pollution requires knowledge of all the interrelated reactions occurring in the atmosphere. Among the most significant is the formation of nitric acid (HONO2) from OH and NO2 radicals. One sticking point in the study of this reaction has been the uncertainty in how often radicals link through an O-O rather than an O-N bond. Mollner et al. (p. 646) measured the partitioning coefficient, as well as the overall consumption rate of the radicals, with an array of highly sensitive spectroscopic techniques in the laboratory. The measurements yielded a well-defined rate constant for nitric acid formation, which was applied to the prediction of ozone levels in atmospheric simulations of the Los Angeles basin.

Abstract

The reaction of OH and NO2 to form gaseous nitric acid (HONO2) is among the most influential in atmospheric chemistry. Despite its importance, the rate coefficient remains poorly determined under tropospheric conditions because of difficulties in making laboratory rate measurements in air at 760 torr and uncertainties about a secondary channel producing peroxynitrous acid (HOONO). We combined two sensitive laser spectroscopy techniques to measure the overall rate of both channels and the partitioning between them at 25°C and 760 torr. The result is a significantly more precise value of the rate constant for the HONO2 formation channel, 9.2 (±0.4) × 10−12 cm3 molecule−1 s−1 (1 SD) at 760 torr of air, which lies toward the lower end of the previously established range. We demonstrate the impact of the revised value on photochemical model predictions of ozone concentrations in the Los Angeles airshed.

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