Journal of Atmospheric Chemistry

, Volume 24, Issue 2, pp 113–119 | Cite as

Henry's law coefficients of formic and acetic acids

  • Bryan J. Johnson
  • Eric A. Betterton
  • David Craig


The Henry's law constants, KH, of dilute aqueous formic and acetic acids were determined experimentally as a function of concentration and temperature using a new counterflow packed-column technique. KH was found to be (8.9±1.3)×103 and (4.1±0.4)×103 M atm-1 at 25°C for HCOOH and CH3COOH, respectively. The reaction enthalpies, ΔH, were found to be −51±2 kJ mol-1 and −52±1 kJ mol-1 for formic and acetic acid, respectively. These are in good agreement with calculated thermochemical values.

Whereas the KH values are in reasonably good agreement with certain other experimentally determined values, KH (HCOOH) is two to three times higher than calculated thermochemical values while KH (CH3COOH) is lower than the two calculated values.

The ‘best’ experimental values appear to be (11±2)×103 M atm-1 and (7±3)×103 M atm-1 for HCOOH and CH3COOH, respectively.

Key words

Henry's law formic acid acetic acid carboxylic acids 


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  1. BettertonE.A., 1992: Henry's law constants of soluble and moderately soluble organic gases: effects on aqueous phase chemistry, Adv. Env. Sci. Technol. 24, 1–50.Google Scholar
  2. BettertonE.A. and HoffmannM.R., 1988. Henry's law constants of some environmentally important aldehydes, Environ. Sci. Technol. 22, 1415–1418.Google Scholar
  3. ChameidesW. L. and DavisD. D., 1983: Aqueous-phase source of formic acid in clouds, Nature 304, 427–429.Google Scholar
  4. ChaoJ. and ZwolinskiB.J., 1978: Ideal gas thermodynamic properties of methanoic and ethanoic acids, J. Phys. Chem. Ref. Data 7, 363–377.Google Scholar
  5. CleggS. L. and BrimblecombeP., 1990: Solubility of volatile electrolytes in multicomponent solutions with atmospheric applications, in D. C.Melchior and R. L.Brossett (eds), Chemical Modeling in Aqueous Systems II, Amer. Chemical Society, Washington, pp. 58–73.Google Scholar
  6. DawsonG. A., FarmerJ. C., and MoyersJ. L., 1980: Formic and acetic acids in the atmosphere of the southwest U.S.A., Geophys. Res. Lett. 7, 725–728.Google Scholar
  7. HelasG., AndreaeM. O., and HartmannW. R., 1992: Behavior of atmospheric formic and acetic acid in the presence of hydrometeors, J. Atmos. Chem. 15, 101–115.Google Scholar
  8. JacobD. J., 1986: The chemistry of OH in remote clouds and its role in the production of formic acid and peroxymonosulfate, J. Geophys. Res. 91, 9807–9826.Google Scholar
  9. KeeneW. C. and GallowayJ. N., 1986: Considerations regarding sources for formic and acetic acids in the troposphere, J. Geophys. Res. 91, 14466–14474.Google Scholar
  10. KeeneW. C., MosherB. W., JacobD. J., MungerJ. W., TalbotR.W., ArtzR. S., MabenJ. M., DaubeB.'R., GallowayJ. N., 1995: Carboxylic acids in clouds at a high-elevation forested site in central Virginia, USA, J. Geophys. Res. 100, 9345–9357.Google Scholar
  11. MadronichS., ChatfieldR. B., CalvertJ. G., MoortgatG. K., VeyretB., and LesclauxR., 1990: A photochemical origin of acetic acid in the troposphere, Geophys. Res. Lett. 12, 2361–2364.Google Scholar
  12. McCabe, W. L. and Smith, J. C., 1976: Unit Operations of Chemical Engineering, 3rd edn., Tokyo.Google Scholar
  13. MungerJ. W., CollettJ.Jr., DaubeB. C.Jr., and HoffmannM. R., 1989: Carboxylic acids and carbonyl compounds in California clouds and fogs, Tellus 41B, 230–242.Google Scholar
  14. PandisS. N. and SeinfeldJ. H., 1991: Should bulk cloudwater and fogwater samples obey Henry's law?, J. Geophys. Res. 96, 10791–10798.Google Scholar
  15. SeinfeldJ. H., 1986: Atmospheric Physics and Chemistry of Air Pollution, Wiley-Interscience, New York.Google Scholar
  16. ServantJ., KouadioG., CrosB., and DelmasR., 1991: Carboxylic monoacids in the air of Mayombe forest (Congo): role of the forest as a source or sink, J. Atmos. Chem. 12, 367–380.Google Scholar
  17. SmithR. M. and MartellA. E., 1977: Critical Stability Constants, Vol. 3, Plenum, New York.Google Scholar
  18. TalbotR. W., BeecherK. M., HarrissR. C., and CoferW. R.III, 1988: Atmospheric geochemistry of formic and acetic acids at mid-latitude temperate site, J. Geophys. Res. 93, 1638–1652.Google Scholar
  19. Wagman, D. D., Evans, W. H., Parker, V. B., Halow, I., Bailey, S. M., and Schumm, R. H., 1968: Selected values of chemical thermodynamic properties, NBS Technical Note, No.270-3, 107–109.Google Scholar

Copyright information

© Kluwer Academic Publishers 1996

Authors and Affiliations

  • Bryan J. Johnson
    • 1
  • Eric A. Betterton
    • 2
  • David Craig
    • 2
  1. 1.Department of Atmospheric SciencesUniversity StationU.S.A.
  2. 2.Department of Atmospheric SciencesUniversity of ArizonaTucsonU.S.A.

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