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Ion chemistry of Clono{sub 2} involving NO{sub 3}{sup -} core ions: A detection scheme for Clono{sub 2} in the atmosphere

Journal Article · · Journal of Geophysical Research
DOI:https://doi.org/10.1029/94JD00425· OSTI ID:136240
;  [1];  [2]
  1. Hanscom Air Force Base, MA (United States)
  2. College of the Holy Cross, Worcester, MA (United States)

Rate constants and product branching ratios for reactions involving atmospherically interesting ions and ClONO{sub 2} have been measured. H{sub 3}O{sup +} reacts rapidly with ClONO{sub 2}, but hydrates of H{sub 3}O{sup +} do not. This implies that ClONO{sub 2} does not play a central role in the positive ion chemistry of the atmosphere. CO{sub 3}{sup -} reacts with ClONO{sub 2} to form NO{sub 3}{sup -}. Both NO{sub 3}{sup -} (H{sub 2}O) react with ClONO{sub 2} to form NO{sub 3}{sup -} (ClONO{sub 2}). H{sub 2}O does not react with NO{sub 3}{sup -} (ClONO{sub 2}), which is essential to the proposed in situ measurement technique. NO{sub 3}{sup -} (ClONO{sub 2})does react with HNO{sub 3} and HCl, producing NO{sub 3}{sup -} (HNO{sub 3}) in both cases. The reaction of NO{sub 3}{sup -} (HCl) with ClONO{sub 2} also produces NO{sub 3}{sup -} (HNO{sub 3}). 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 ClONO{sub 2} which is important in the chemistry of the Antarctic stratosphere. A detection scheme is presented for atmospheric ClONO{sub 2} based on the reactions studied and utilizing mass spectrometry. A ClONO{sub 2} detection limit of 10{sup 7} molecules cm{sup -3} is estimated based on the operating characteristics of current ion-molecule based mass spectrometric field instruments. 19 refs., 1 tab.

OSTI ID:
136240
Journal Information:
Journal of Geophysical Research, Journal Name: Journal of Geophysical Research Journal Issue: D4 Vol. 99; ISSN JGREA2; ISSN 0148-0227
Country of Publication:
United States
Language:
English

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