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Journal of Atmospheric Chemistry

, Volume 29, Issue 1, pp 17–43 | Cite as

On the Exchange of NO3 Radicals with Aqueous Solutions: Solubility and Sticking Coefficient

  • Karin Thomas
  • Andreas Volz-Thomas
  • Djuro Mihelcic
  • Herman G. J. Smit
  • Dieter Kley
Article

Abstract

The exchange of NO3 radicals with the aqueous-phase was investigated at room temperature (293 K) in a series of wetted denuders. From these experiments, the uptake coefficient of NO3 was determined on 0.1 M NaCl solutions and was found to be γ(NO3) ≥ 2 × 10-3 in good agreement with recent studies. The Henry coefficient of NO3 was estimated to be KH(NO3) = 1.8 M · atm-1, with a (2σ) uncertainty of ±3 M · atm-1. From the upper limit for the Henry coefficient (KH = 5 M · atm-1) and available thermodynamic data, the redox potential of dissolved NO3/NO 3 is estimated to be in the range of 2.3 to 2.5 V. This range is at the lower boundary of earlier estimates. The results are discussed in the light of a recent publication. Based on our data and a model of the transport and chemistry in the liquid film, an upper limit is derived for the product of the Henry coefficient KH and the rate coefficient k10 of the potential reaction NO3 + H2O → HNO3 + OH. For KH = 0.6 M · atm-1, we find k10 < 0.05 s-1 · atm-1, i.e., about 100 times smaller than what was suggested by Rudich and co-workers. Because of its small solubility, heterogeneous removal of NO3 is only important under conditions where the dissolved NO3 is removed quickly from equilibrium, for example by reactions with Cl or HSO 3 ions in the liquid-phase. Otherwise, heterogenous removal should mainly proceed via N2O5.

nitrate radical solubility sticking coefficient redox potential heterogeneous removal 

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Copyright information

© Kluwer Academic Publishers 1998

Authors and Affiliations

  • Karin Thomas
    • 1
  • Andreas Volz-Thomas
    • 1
  • Djuro Mihelcic
    • 1
  • Herman G. J. Smit
    • 1
  • Dieter Kley
    • 1
  1. 1.Institut für Chemie und Dynamik der Geosphäre 2Chemie der Belasteten Atmosphäre Forschungszentrum JülichJülichGermany

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