2009年4月
Anion-Catalyzed Dissolution of NO2 on Aqueous Microdroplets
JOURNAL OF PHYSICAL CHEMISTRY A
- ,
- ,
- ,
- ,
- ,
- 巻
- 113
- 号
- 17
- 開始ページ
- 4844
- 終了ページ
- 4848
- 記述言語
- 英語
- 掲載種別
- DOI
- 10.1021/jp900685f
- 出版者・発行元
- AMER CHEMICAL SOC
Fifty-seven years after NOx (NO + NO2) were identified as essential components of photochemical smog, atmospheric chemical models fail to correctly predict center dot OH/HO2 center dot concentrations under NOx-rich conditions. This deficiency is due, in part, to the uncertain rates and mechanism for the reactive dissolution of NO2(g) (2NO(2) + H2O = NO3- + H+ + HONO) in fog and aerosol droplets. Thus, state-of-the-art models parametrize the uptake of NO2 by atmospheric aerosol from data obtained on "deactivated tunnel wall residue". Here, we report experiments in which NO3- production on the surface of microdroplets exposed to NO,(g) for similar to 1 ms is monitored by online thermospray mass spectrometry. NO2 does not dissolve in deionized water (NO3- signals below the detection limit) but readily produces NO3- on aqueous NaX (X = Cl, Br, I) microdroplets with NO2 uptake coefficients gamma that vary nonmonotonically with electrolyte concentration and peak at gamma(max) similar to 10(-4) for [NAX] similar to 1 mM, which is > 10(3) larger than that in neat water. Since I- is partially oxidized to I-2(center dot-) in this process, anions seem to capture NO2(g) into X-NO2 center dot- radical anions for further reaction at the air/water interface. By showing that gamma is strongly enhanced by electrolytes, these results resolve outstanding discrepancies between previous measurements in neat water versus NaCl-seeded clouds. They also provide a general mechanism for the heterogeneous conversion of NO2(g) to (NO3- + HONO) on the surface of aqueous media.
- リンク情報
-
- DOI
- https://doi.org/10.1021/jp900685f
- Web of Science
- https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000265529800004&DestApp=WOS_CPL
- URL
- http://www.scopus.com/inward/record.url?eid=2-s2.0-65649098384&partnerID=MN8TOARS
- URL
- http://orcid.org/0000-0002-9863-4241
- ID情報
-
- DOI : 10.1021/jp900685f
- ISSN : 1089-5639
- ORCIDのPut Code : 34079376
- SCOPUS ID : 65649098384
- Web of Science ID : WOS:000265529800004