Rate of gas phase association of hydroxyl radical and nitrogen dioxide

AK Mollner; L Feng; MK Sprague; M Okumura; DB Milligan; William Bloss; SP Sander; PT Martien; RA Harley; AB McCoy; WP Carter

doi:10.1126/science.1193030

Rate of gas phase association of hydroxyl radical and nitrogen dioxide

AK Mollner, L Feng, MK Sprague, M Okumura, DB Milligan, William Bloss, SP Sander, PT Martien, RA Harley, AB McCoy, WP Carter

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Abstract

The reaction of OH and NO(2) to form gaseous nitric acid (HONO(2)) 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 HONO(2) formation channel, 9.2 (±0.4) × 10(-12) cm(3) 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.

Original language	English
Pages (from-to)	646-649
Number of pages	4
Journal	Science
Volume	330
DOIs	https://doi.org/10.1126/science.1193030
Publication status	Published - 1 Jan 2010

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title = "Rate of gas phase association of hydroxyl radical and nitrogen dioxide",

abstract = "The reaction of OH and NO(2) to form gaseous nitric acid (HONO(2)) 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 HONO(2) formation channel, 9.2 (±0.4) × 10(-12) cm(3) 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.",

author = "AK Mollner and L Feng and MK Sprague and M Okumura and DB Milligan and William Bloss and SP Sander and PT Martien and RA Harley and AB McCoy and WP Carter",

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doi = "10.1126/science.1193030",

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TY - JOUR

T1 - Rate of gas phase association of hydroxyl radical and nitrogen dioxide

AU - Mollner, AK

AU - Feng, L

AU - Sprague, MK

AU - Okumura, M

AU - Milligan, DB

AU - Bloss, William

AU - Sander, SP

AU - Martien, PT

AU - Harley, RA

AU - McCoy, AB

AU - Carter, WP

PY - 2010/1/1

Y1 - 2010/1/1

N2 - The reaction of OH and NO(2) to form gaseous nitric acid (HONO(2)) 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 HONO(2) formation channel, 9.2 (±0.4) × 10(-12) cm(3) 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.

AB - The reaction of OH and NO(2) to form gaseous nitric acid (HONO(2)) 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 HONO(2) formation channel, 9.2 (±0.4) × 10(-12) cm(3) 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.

U2 - 10.1126/science.1193030

DO - 10.1126/science.1193030

M3 - Article

C2 - 21030650

SN - 1095-9203

VL - 330

SP - 646

EP - 649

JO - Science

JF - Science

ER -

Rate of gas phase association of hydroxyl radical and nitrogen dioxide

Abstract

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