Ion Chemistry of C10no2 Involving NO3(-) Core Ions: A Detection Scheme for ClONOsub2 in the Atmosphere

• Main Authors: Viggiano, A. A., Morris, Robert A., Van Doren, Jane M.
• Other Authors: PHILLIPS LAB HANSCOM AFB MA
• Format: Text
• Language: English
• Published: 1994
• Subjects: Atmospheric Physics; Physical Chemistry; *ATMOSPHERIC DISTURBANCES; *CHEMICAL REACTIONS; *CHLORINE COMPOUNDS; IONS; CHLORINE; NITRATES; ION MOLECULE INTERACTIONS; HYDROGEN CHLORIDE; MASS SPECTROMETRY; STRATOSPHERE; EARTH ATMOSPHERE; HYDRATES; REPRINTS; CHLORINE NITRATE; ION CHEMISTRY; SERDP COLLECTION; SERDP(STRATEGIC ENVIRONMENTAL RESEARCH AND DEVELOPMENT PROGRAM); PE61102F; WUPL2303GJ01; Antarctic; The Antarctic; Antarc*
• Online Access: http://www.dtic.mil/docs/citations/ADA280954; http://oai.dtic.mil/oai/oai?&verb=getRecord&metadataPrefix=html&identifier=ADA280954

Rate constants and product branching ratios for reactions involving atmospherically interesting ions and ClONO2 have been measured. H3O(+) reacts rapidly with ClONO2, but the hydrates of H3O(+) do not. This implies that ClONO2 does not play a central role in the positive ion chemistry of the atmosphere. CO3(-) reacts with ClONO2 to form NO3(-). Both NO3(-) and NO3(-)(H2O) react with ClONO2 to form NO3(-)(ClONO2). H2O does not react with NO3(-)(ClONO2), which is essential to the proposed in situ measurement technique. NO3(-)(ClONO2), does react with HNO3 and HCl, producing NO3(-)(HNO3) in both cases. The reaction of NO3(-)(HCl) with ClONO2 also produces NO3(-)(HNO3). These latter two efficient reactions, which are discussed in detail in a separate publication, are analogous to the efficient neutral heterogeneous reaction of HCl with ClONO2 which is important in the chemistry of the Antarctic stratosphere. A detection scheme is presented for atmospheric ClONO2 based on the reactions studied and utilizing mass spectrometry. A ClONO2 detection limit of 10 to the 7th power molecules cm to the minus 3rd power is estimated based on the operating characteristics of current ion-molecule based mass spectrometric field instruments. Pub. in Journal of Geophysical Research, v99 nD4 p8221-8224, 20 Apr 1994.