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Ion Chemistry of C10no2 Involving NO3(-) Core Ions: A Detection Scheme for ClONOsub2 in the Atmosphere
PHILLIPS LAB HANSCOM AFB MA
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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.
APPROVED FOR PUBLIC RELEASE