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Supercritical Fluids: Their Properties and Applications

  • J. M. H. Levelt Sengers
Chapter
Part of the NATO Science Series book series (NSSE, volume 366)

Abstract

This introductory chapter is intended to acquaint the reader with the unusual properties of supercritical fluids, and with the ways these properties are exploited for a variety of applications in the chemical process industry. The presentation is closely tied to the program of this Advanced Study Institute (ASI), and points to chapters to follow in various subject areas. The behavior of thermodynamic and transport properties near a critical point is described, with water as an example. The structure of the supercritical fluid is discussed. The unusual solvent properties of supercritical fluids are explained within the framework of binary fluid phase diagrams, including a solid solute. Tunable solvent properties and environmental compatibility make supercritical fluids desirable agents in the chemical process industry. This ASI will focus on their role as extractants of food and other products, as carriers in chromatography, and as media for chemical reactions and for materials processing; moreover, virtually all aspects of polymer processing may involve the use of supercritical solvents. In this chapter, the basic knowledge and terminology required for an understanding of the chapters to follow will be introduced at an elementary level. For more advanced treatments, see [1], [2].

Keywords

Supercritical Fluid Supercritical Carbon Dioxide Critical Line Isothermal Compressibility Supercritical Water 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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References

  1. 1.
    Levelt Scngers, J.M.H. (1991), Thermodynamics of solutions near the solvent critical point, in Bruno, Th. J. and Ely, J.F. (eds.), Supercritical Fluid Technology, CRC Press, Boca Raton, FL, pp. 1–56.Google Scholar
  2. 2.
    Levelt Scngers, J.M.I.I. (1994), Critical behavior of fluids: concepts and applications, in Kiran, E. and Levelt Sengers, J.M.H. (eds), Supercritical Fluids, Fundamentals for Application, Klywer Academic Publishers, Dordrecht, pp. 1–38.Google Scholar
  3. 3.
    Setzmann, U. and Wagner, W. (1991), A new equation of stale and tables of thermodynamic properties for methane covering the range from the melling line to 625 K at pressures up to 1000 MPa, J. Phys. Chem. Ref. Data 20, 1061–1155.CrossRefGoogle Scholar
  4. 4.
    Douslin, D.R., and Harrison, R.H. (1973), J. Chem. Thermodynamics 5, 491–512.CrossRefGoogle Scholar
  5. 5.
    Span, R. and Wagner, W. (1996), A new equation of state for carbon dioxide covering the fluid region from the triple-point temperature to 1100 K at pressures up to 800 MPa, J. Phys. Chem. Ref. Data 25, 1509–156.CrossRefGoogle Scholar
  6. 6.
    Levelt Sengers, J.M.H., Straub, J., Watanabe, K. and Hill, P.G. (1985), Assessment of critical parameter values for H2O and D2O, J. Phys. Chem. Ref. Data 14, 193–207. Temperature scale adjusted to ITS-90 in Table 1.Google Scholar
  7. 7.
    Harvey, A.H., Peskin, A.P., and Klein, S.A. (1997), NIST/ASME Steam Properties, NIST Standard Reference Data Base 10, Version 2. 1. Standard Reference Data Program, NIST, Gailhersburg, MD.Google Scholar
  8. 8.
    Sandier, S.I. (1994), Equations of slate for phase equilibria computations, in Kiran E. and Levelt Sengers, J.M.H. (eds). Supercritical Fluids, Fundamentals for Application, Kluwer Academic Publishers, Dordrecht, pp. 147–175.Google Scholar
  9. 9.
    Hirschfelder, J.O., Curtiss, C.F., and Bird, R.B. (1954), Molecular Theory of Gases and Liquids, John Wiley and Sons, Inc. New York, p. 323.Google Scholar
  10. 10.
    Sengers, J.V. and Levelt Sengers, J.M.H. (1986), Thcrmodynamic behavior of fluids near the critical point, Ann. Rev. Phys. Chem. 37, 189–222.CrossRefGoogle Scholar
  11. 11.
    Stell, G and Høye, J.S. (1974) Dielectric constant and mean polarizability in the critical region, Phys. Rev. Lett. 33. 1268–1271.CrossRefGoogle Scholar
  12. 12.
    Mountain, R.D. (1997), Molecular dynamics and hydrogen bonds in water, NISTIR 6028. Mountain, R.D. (1998) Molecular dynamics and hydrogen bonds in water, in Rev. High Press. Sci. Technol. 7, 1106–1111.Google Scholar
  13. 13.
    Tucker, S.C., and Maddox, M.W. (1998), The effect of solvent density inhomogeneities on solute dynamics in supercritical fluids: a theoretical perspective. J. Chem. Phys. B102, 2437–2453.CrossRefGoogle Scholar
  14. 14.
    De Loo S, Th.W. (1994), Understanding phase diagrams, in Kiran, K. and ixveli Sengers, J.M.H. (eds), Supercritical Fluids, Fundamentals for Application, Kluwer Academic Publishers, Dordrecht, pp. 65–89.Google Scholar
  15. 15.
    Van Wasen, U., Swaid, I., and Schneider, G.M. (1980), Physicochemical principles and applications of supercritical fluid chromatography, Angew. Chemie, 19, 575–658.CrossRefGoogle Scholar
  16. 16.
    Peters, C.J. (1994), Multiphase equilibria in near-critical solvents, in Kiran, E. and Levelt Sengers, J.M.H. (eds), Supercritical Fluids, Fundamentals for Application, Kluwer Academic Publishers, Dordrecht, pp. 117–145.Google Scholar
  17. 17.
    Ixveli Sengers, J.M.H. (1991), Solubility near the solvent s critical point, J. Supercrit. Fluids 4, 215–222.CrossRefGoogle Scholar
  18. 18.
    Levelt Sengers, J.M.H., Harvey, A.H., Crovetio, R., and Gallagher, J.S. (1992), Standard stales, reference states and finite-concentration effects in near-critical mixtures with application to aqueous solutions, Fluid Phase Equil. 81, 85–107.CrossRefGoogle Scholar
  19. 18.
    Levelt Sengers, J.M.H., Harvey, A.H., Crovetio, R., and Gallagher, J.S. (1992), Standard stales, reference states and finite-concentration effects in near-critical mixtures with application to aqueous solutions, Fluid Phase Equil. 81, 85–107.CrossRefGoogle Scholar
  20. 20.
    Reverchon, E. (1997), Supercritical fluid extraction and fractionation of essential oils aod related products, J. Supercrit. Fluids 10, 1.CrossRefGoogle Scholar
  21. 21.
    Brunncr, G.H.: Upnmoor, D. (1994), Scale-up of supercritical fluid chromatography (SPC), in Supercritical Fluids, Fundamentals for Application, Kiran, E. and Levelt Sengers, J.M.H., eds. Kluwer Academic Publishers, Dordrecht, pp. 653–668.Google Scholar
  22. 22.
    Petitet, J.P. (1995), Elaboration des matériaux en milieu hydrothermal, in Fluides Supercritiques et Matériaux, P. Cansell, F. and J.P. Petitet, J.P., Eds., Presence Graphique, Paris, France, (in French) pp. 251–300.Google Scholar
  23. 23.
    Franck, E.U. (1987), Fluids at high temperatures and pressures, J. Chem. Thermodynamics 19, 225–242.CrossRefGoogle Scholar
  24. 24.
    Tester, J.W., Holgate, U.R., Armellini, F.J., Webley, P.A., Killilea, W.R. Hong, G.T., and Barner, H.E. (1993), Supercritical water oxidation technology: a review of process development and fundamental research, in Emerging Technologies for Hazardous Waste Management III, Tedder D.W. aod Pohland, F.G. (eds.) ACS Symposium Series 518, Chapter 3, American Chemical Society, Washington D.C.Google Scholar
  25. 25.
    Hodes, M.S., Smith, K.A., Hurst, W.S., Bowers, Jr., W.J. and Griffith, P. (1997), Measurements and modeling of deposition rates from a near supercritical aqueous sodium sulfate solution to a heated cylinder, Proc. 32nd Natl. Heat Transfer Conf. 12, HTD-350, ASME, New York.Google Scholar
  26. 26.
    Gallagher, J.S. (1998), private communications.Google Scholar
  27. 27.
    Abdulagatov, I.M., Dvoryanchikov, V.I., Mursalov, B.A., and Kamalov, A.N. (1998), Measurements of the heat capacity at constant volume of H2O and Na2SO4 in near-critical and supercritical water, Proc. 13th Symposium on Thermophys. Prop., Haynes, W.M., ed., Fluid Phase Equilibria 150–151, 525–535.Google Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2000

Authors and Affiliations

  • J. M. H. Levelt Sengers
    • 1
  1. 1.Physical and Chemical Properties DivisionNational Institute of Standards and TechnologyGaithersburgUSA

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