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Journal of Atmospheric Chemistry

, Volume 13, Issue 3, pp 211–224 | Cite as

Application of physical adsorption thermodynamics to heterogeneous chemistry on polar stratospheric clouds

  • Scott Elliott
  • Richard P. Turco
  • Owen B. Toon
  • Patrick Hamill
Article

Abstract

Laboratory isotherms for the binding of several nonheterogeneously active atmospheric gases and for HCl to water ice are translated into adsorptive equilibrium constants and surface enthalpies. Extrapolation to polar conditions through the Clausius Clapeyron relation yields coverage estimates below the percent level for N2, Ar, CO2, and CO, suggesting that the crystal faces of type II stratospheric cloud particles may be regarded as clean with respect to these species. For HCl, and perhaps HF and HNO3, estimates rise to several percent, and the adsorbed layer may offer acid or proton sources alternate to the bulk solid for heterogeneous reactions with stratospheric nitrates. Measurements are lacking for many key atmospheric molecules on water ice, and almost entirely for nitric acid trihydrate as substrate. Adsorptive equilibria enter into gas to particle mass flux descriptions, and the binding energy determines rates for desorption of, and encounter between, potential surface reactants.

Key words

Isotherm adsorptive equilibrium isostere differential and integral enthalpy Clausius Clapeyron relation stratospheric acids surface coverage desorption rates surface encounter 

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Copyright information

© Kluwer Academic Publishers 1991

Authors and Affiliations

  • Scott Elliott
    • 1
  • Richard P. Turco
    • 1
  • Owen B. Toon
    • 2
  • Patrick Hamill
    • 3
  1. 1.Department of Atmospheric SciencesUniversity of CaliforniaLos AngelesU.S.A.
  2. 2.NASA Ames Research CenterMoffett FieldU.S.A.
  3. 3.Physics DepartmentSan Jose State UniversitySan JoseU.S.A.

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