Skip to main content
Log in

Measurements of the Henry's Law Coefficients of 2-Methyl-3-buten-2-ol, Methacrolein, and Methylvinyl Ketone

  • Published:
Journal of Atmospheric Chemistry Aims and scope Submit manuscript

Abstract

Using an equilibrium headspace technique, Henry's law coefficients were measured for methacrolein (H = 6.5 ± 0.7 M atm-1) and methylvinyl ketone (41 ± 7.0 M atm-1) in water at 25 °C. In addition, 2-methyl-3-buten-2-ol was studied at 30 °C in water and in an aqueous ionic solution representative of plant tissue. Similar values were found in deionized water (65 ± 3.5 M atm-1) and in a 0.05 mol kg-1 Ca2+, K+, NO3-, SO42- solution (62 ± 0.8 M atm-1). These Henry's Law coefficients are too small to allow for significant partitioning of methacrolein, methylvinyl ketone or methylbutenol into cloud water under equilibrium conditions.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  • Allen, J. M., Balcavage, W. X., Ramachandran, B. R., and Shrout, A. L., 1998: Determination of Henry's law constants by equilibrium partitioning in a closed system using a new in situ optical absorbance method, Environ. Toxicol. Chem. 17, 1216–1221.

    Google Scholar 

  • Atkinson, R., 1994: Gas-phase tropospheric chemistry of organic compounds, J. Phys. Chem. Ref. Data, Monograph 2, American Chemical Society and American Institute of Physics, Woodbury, NY.

    Google Scholar 

  • Bell, R. P., 1966: The reversible hydration of carbonyl compounds, in V. Gold (ed.), Advances in Physical Organic Chemistry, Academic Press, New York, pp. 1–29.

    Google Scholar 

  • Benkelberg, H.-J., Hamm, S., and Warneck, P., 1995: Henry's law coefficients for aqueous solutions of acetone, acetaldehyde and acetonitrile, and equilibrium constants for the addition compounds of acetone and acetaldehyde with bisulfite, J. Atmos. Chem. 20, 17–34.

    Google Scholar 

  • Betterton, E. A., 1991: The partitioning of ketones between the gas and aqueous phases, Atmos. Environ. 25A, 1473–1477.

    Google Scholar 

  • Betterton, E. A., 1992: Henry's law constants of soluble and moderately soluble organic gases: Effects on aqueous phase chemistry, in J. O. Nriagu (ed.), Gaseous Pollutants: Characterization and Cycling, Wiley, New York, pp. 1–50.

    Google Scholar 

  • Betterton, E. A. and Hoffmann, M. R., 1988: Henry's law constants of some environmentally important aldehydes, Environ. Sci. Technol. 22, 1415–1418.

    Google Scholar 

  • Biesenthal, T. A. and Shepson, P. B., 1997: Observations of anthropogenic inputs of the isoprene oxidation products methyl vinyl ketone and methacrolein to the atmosphere, Geophys. Res. Lett. 24, 1375–1378.

    Google Scholar 

  • Burnett, M. G., 1963: Determination of partition coefficients at infinite dilution by the gas chromatographic analysis of the vapor above dilute solutions, Anal. Chem. 35, 1567–1570.

    Google Scholar 

  • Butler, J. A. V., Ramchandani, C. N., and Thomson, D. W., 1935: The solubility of non-electrolytes. Part I. The free energy of hydration of some aliphatic alcohols, J. Chem. Soc., 280–285.

  • Buttery, R. G., Ling, L. C., and Guadagni, D. G., 1969: Volatilities of aldehydes, ketones, and esters in dilute water solution, J. Agr. Food Chem. 17, 385–389.

    Google Scholar 

  • Chameides, W. L., Lindsay, R. W., Richardson, J., and Kiang, C. S., 1988: The role of biogenic hydrocarbons in urban photochemical smog: Atlanta as a case study, Science 241, 1473–1475.

    Google Scholar 

  • Ferronato, C., Orlando, J. J., and Tyndall, G. S., 1998: Rate and mechanism of the reactions of OH and Cl with 2-methyl-3-buten-2-ol, J. Geophys. Res. 103, 25,579–25,586.

    Google Scholar 

  • Friant, S. L. and Suffet, I. H., 1979: Interactive effects of temperature, salt concentration, and pH on head space analysis for isolating volatile trace organics in aqueous enviromental samples, Anal. Chem. 51, 2167–2172.

    Google Scholar 

  • Gierczak, T., Burkholder, J. B., Talukdar, R. K., Mellouki, A., Barone, S. B., and Ravishankara, A. R., 1997: Atmospheric fate of methyl vinyl ketone and methacrolein, J. Photochem. Photobiol. A: Chem. 110, 1–10.

    Google Scholar 

  • Goldan, P. D., Kuster, W. C., Fehsenfeld, F. C., and Montzka, S. A., 1993: The observation of a C5 alcohol emission in a North American pine forest, Geophys. Res. Lett. 20, 1039–1042.

    Google Scholar 

  • Gossett, J. M., 1987: Measurement of Henry's law constants for C1 and C2 chlorinated hydrocarbons, Environ. Sci. Technol. 21, 202–208.

    Google Scholar 

  • Guenther, A., 1997: Seasonal and spatial variations in natural volatile organic compound emissions, Ecol. Appl. 7, 34–45.

    Google Scholar 

  • Guenther, A., Hewitt, N. C., Erickson, D., Fall, R., Geron, C., Graedel, T., Harley, P., Klinger, L., Lerdau, M., McKay, W. A., Pierce, T., Scholes, B., Steinbrecher, R., Tallamraju, R., Taylor, J., and Zimmerman, P., 1995: A global model of natural volatile organic compound emissions, J. Geophys. Res. 100, 8873–8892.

    Google Scholar 

  • Guenther, A., Zimmerman, P., Klinger, L., Greenberg, J., Ennis, C., Davis, K., Pollock, W., Westberg, H., Allwine, G., and Geron, C., 1996: Estimates of regional natural volatile organic compound fluxes from enclosure and ambient measurements, J. Geophys. Res. 101, 1345–1359.

    Google Scholar 

  • Hansen, K. C., Zhou, Z., Yaws, C. L., and Aminabhavi, T. M., 1995: A laboratory method for the determination of Henry's law constants of volatile organic chemicals, J. Chem. Education 72, 93–96.

    Google Scholar 

  • Harley, P., Fridd-Stroud, V., Greenberg, J., Guenther, A., and Vasconcellos, P., 1998: Emission of 2-methyl-3-buten-2-ol by pines: A potentially large natural source of reactive carbon to the atmosphere, J. Geophys. Res. 103, 25,479–25,486.

    Google Scholar 

  • Helmig, D., Greenberg, J., Guenther, A., Zimmerman, P., and Geron, C., 1998: Volatile organic compounds and isoprene oxidation products at a temperate deciduous forest site, J. Geophys. Res. 103, 22,397–22,414.

    Google Scholar 

  • Jorgensen, A. D., Picel, K. C., and Stamoudis, V. C., 1990: Prediction of gas chromatography flame ionization detector response factors from molecular structures, Anal. Chem. 62, 683–689.

    Google Scholar 

  • Lamb, B., Guenther, A., Gay, D., and Westberg, H., 1987: A national inventory of biogenic hydrocarbon emissions, Atmos. Environ. 21, 1695–1705.

    Google Scholar 

  • Lurmann, F. W., Nitta, B., Ganesan, K., and Lloyd, A. C., 1984: Modeling potential ozone impacts from natural sources. III. Ozone modeling in Tampa/St. Petersburg, Florida, Atmos. Environ. 18, 1133–1143.

    Google Scholar 

  • Mackay, D. and Shiu, W. Y., 1981: A critical review of Henry's law constants for chemicals of environmental interest, J. Phys. Chem. Ref. Data 10, 1175–1199.

    Google Scholar 

  • Miyoshi, A., Hatakeyama, S., and Washida, N., 1994: OH radical-initiated photooxidation of isoprene: An estimate of global CO production, J. Geophys. Res. 99, 18,779–18,787.

    Google Scholar 

  • Montzka, S. A., Trainer, M., Goldan, P. D., Kuster, W. C., and Fehsenfeld, F. C., 1993: Isoprene and its oxidation products, methyl vinyl ketone and methacrolein, in the rural troposphere, J. Geophys. Res. 98, 1101–1111.

    Google Scholar 

  • Paulson, S. E., Flagan, R. C., and Seinfeld, J. H., 1992: Atmospheric photooxidation of isoprene part I: The hydroxyl radical and ground state atomic oxygen reactions, Int. J. Chem. Kinet. 24, 79–101.

    Google Scholar 

  • Pruppacher, H. R. and Klett, J. D., 1997: Microphysics of Clouds and Precipitation, 2nd edn, Kluwer Academic Publishers, Dordrecht, The Netherlands, p. 23.

    Google Scholar 

  • Raven, P. H. and Curtis, H., 1970: Biology of Plants, Worth Publishers, New York, p. 263.

    Google Scholar 

  • Ryabova, R. S., Osipova, G. F., and Vinnik, M. I., 1992: Kinetics and mechanism of the hydration of the equilibrium mixture of 3-methyl-1-buten-3-ol and 3-methyl-2-buten-1-ol with isoprene in aqueous solutions of sulfuric acid, Bulletin of the Russian Academy of Sciences, Division of Chemical Science 41, 1021–1024.

    Google Scholar 

  • Sander, R., 1998: Compilation of Henry's law constants for inorganic and organic species of potential importance in environmental chemistry, WWW page, http://www.mpchmainz.mpg.de/~sander/res/henry.html.

  • Snider, J. R. and Dawson, G. A., 1985: Tropospheric light alcohols, carbonyls and acetonitrile: Concentrations in the southwestern United States and Henry's law data, J. Geophys. Res. 90, 3797–3805.

    Google Scholar 

  • Trainer, M., Williams, E. J., Parrish, D. D., Buhr, M. P., Allwine, E. J., Westberg, H. H., Fehsenfeld, F. C., and Liu, S. C., 1987: Models and observations of the impact of natural hydrocarbons on rural ozone, Nature 329, 705–707.

    Google Scholar 

  • Tuazon, E. C. and Atkinson, R., 1989: A product study of the gas-phase reaction of methyl vinyl ketone with the OH radical in the presence of NOx, Int. J. Chem. Kinet. 21, 1141–1152.

    Google Scholar 

  • Tuazon, E. C. and Atkinson, R., 1990a: A product study of the gas-phase reaction of isoprene with the OH radical in the presence of NOx, Int. J. Chem. Kinet. 22, 1221–1236.

    Google Scholar 

  • Tuazon, E. C. and Atkinson, R., 1990b: A product study of the gas-phase reaction of methacrolein with the OH radical in the presence of NOx, Int. J. Chem. Kinet. 22, 591–602.

    Google Scholar 

  • Zhou, X. and Mopper, K., 1990: Apparent partition coefficients of 15 carbonyl compounds between air and seawater and between air and freshwater; Implications for air-sea exchange, Environ. Sci. Technol. 24, 1864–1869.

    Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Rights and permissions

Reprints and permissions

About this article

Cite this article

Iraci, L.T., Baker, B.M., Tyndall, G.S. et al. Measurements of the Henry's Law Coefficients of 2-Methyl-3-buten-2-ol, Methacrolein, and Methylvinyl Ketone. Journal of Atmospheric Chemistry 33, 321–330 (1999). https://doi.org/10.1023/A:1006169029230

Download citation

  • Issue Date:

  • DOI: https://doi.org/10.1023/A:1006169029230

Navigation