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Henry's law and the behavior of weak acids and bases in fog and cloud

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Abstract

Experimental data from two field experiments on ground based clouds were used to study the distribution of formic acid, acetic acid, ammonia and S(IV) species between liquid and gas phase. The ratio of the concentrations of these compounds between the phases during concurrent measurements was compared to ratios expected according to Henry's law (considering the pH influence). Large discrepancies of several orders of magnitude were seen. Three hypotheses have been investigated to explain the observed discrepancies: The existence of a microscale equilibrium which does not persist in a bulk sample, a thermodynamic shift of the equilibrium due to competing reactions, and nonequilibrium conditions due to mass transfer limitations. Approximate quantitative calculations show that none of these hypotheses is sufficient to explain all of the discrepancies, so a combination of different effects seems to be responsible for this observation. The same theoretical considerations also suggest that mass transfer limitation may be an important factor for highly soluble compounds. The data presented here indicates that it is not possible to simply extrapolate interstitial gas phase composition from measured bulk liquid phase concentrations of a fog or cloud.

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Abbreviations

[r max]:

liquid phase molar uptake rate (mol l−1 s−1)

[A g ]:

concentration ofA in gas phase (atm)

[A l ]:

concentration ofA in liquid phase (mol l−1)

[A g , 0]:

concentration ofA in gas phase (atm) at time 0

LWC:

liquid water content (g m−3)

R :

universal gas constant (0.082 l atm mol−1 K−1

D g :

diffusivity (for all gases 0.1 cm2 s−1 was used)

K * H :

effective Henry's law coefficient (mol l−1 atm−1)

t f :

lifetime of fog droplet (s)

a :

droplet radius (cm)

α :

accommodation coefficient

R :

factor of discrepancy

T :

temperature (K)

v :

mean molecular speed (cm s−1) formic acid: 35 000 acetic acid: 31 000 ammonia: 58 000

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Author notes

  1. W. Winiwarter

    Present address: Austrian Research Centre, A-2444, Seibersdorf, Austria

  2. H. Fierlinger

    Present address: Amt für Umweltschutz, Magistrat Linz, A-4041, Linz, Austria

  3. M. C. Facchini

    Present address: Presidio Multizonale di Prevenzione, Settore Chimico, Via Tracehini 17, 40138, Bologna, Italy

Authors and Affiliations

  1. Institut für Analytische Chemie, Technische Universität Wien, Getreidemarkt 9/151, A-1060, Vienna, Austria

    W. Winiwarter, H. Fierlinger & H. Puxbaum

  2. Istituto FISBAT-C.N.R., Via Gobetti 101, 40129, Bologna, Italy

    M. C. Facchini & S. Fuzzi

  3. Netherland Energy Research Foundation, PO Box 1, 1755 ZG, Petten, The Netherlands

    B. G. Arends

  4. Zentrum für Umweltforschung und Institut für Meteorologie und Geophysik, J. W.-Goethe Universität, Postfach 111932, D-60054, Frankfurt a.M., Germany

    D. Schell

  5. Deutscher Wetterdienst, Meteorologisches Observatorium Hamburg, Frahmredder 95, D-22361, Hamburg, Germany

    U. Kaminski, S. Pahl & T. Schneider

  6. Institut für Experimentalphysik, Universität Wien, Strudlhofgasse 4, A-1090, Vienna, Austria

    A. Berner, I. Solly & C. Kruisz

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  1. W. Winiwarter
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  2. H. Fierlinger
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  7. D. Schell
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  8. U. Kaminski
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Winiwarter, W., Fierlinger, H., Puxbaum, H. et al. Henry's law and the behavior of weak acids and bases in fog and cloud. J Atmos Chem 19, 173–188 (1994). https://doi.org/10.1007/BF00696588

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  • DOI: https://doi.org/10.1007/BF00696588

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