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Stability, Phase Equilibria, and Interfacial Free Energy in Microemulsions

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Micellization, Solubilization, and Microemulsions

Abstract

The stability of emulsions is examined from the points of view of thermodynamics as well as dynamics. First a statistical thermodynamical treatment is developed, which demonstrates that, in contrast to usual emulsions, microemulsions can be stable from a thermodynamic point of view. The expression established for the free energy of formation of microemulsions predicts phase inversion from one type of microemulsion to the other one as well as phase separation. Several basic types of multiphase systems are found theoretically:

  1. (1)

    microemulsion in equilibrium with another (in particular dilute) microemulsion of oil-in-water;

  2. (2)

    microemulsion in equilibrium with another (in particular dilute) microemulsion of water-in-oil, and

  3. (3)

    a dilute microemulsion of water-in-oil in equilibrium with a dilute microemulsion of oil-in-water. Similar multiphase systems have been previously identified experimentally by Winsor and by Healy et al. The present expressions also explain the low values of the interfacial free energy between two microemulsion phases in equilibrium. Second, a transport equation is established for a concentrated colloidal system. Based on this equation conditions are identified when the system is stable or unstable to small perturbations and information about its time evolution obtained. This dynamic approach provides a time scale for significant changes to occur in an unstable system.

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References

  1. B. V. Derjaguin and L.D. Landau, Acta Physico-chimica 14, 633 (1941).

    Google Scholar 

  2. E. W. J. Verwey and J.Th.G. Overbeek, “Theory of the Stability of Lyophobic Colloids,” Elsevier, New York, Amsterdam, 1948.

    Google Scholar 

  3. W. Albers and J. Th. G. Overbeek, J. Colloid Sci. 14, 501 (1959).

    Article  CAS  Google Scholar 

  4. W. Albers and J. Th. G. Overbeek, J. Colloid Sci. 14, 510 (1959).

    Article  CAS  Google Scholar 

  5. T. P. Hoar and J. H. Schulman, Nature 152, 103 (1943).

    Article  Google Scholar 

  6. J. H. Schulman and T. S. McRoberts, Trans. Faraday Soc. 42B, 165 (1946).

    Article  CAS  Google Scholar 

  7. J. H. Schulman and D. P. Riley, J. Colloid Sci. 3, 383 (1948).

    Article  CAS  Google Scholar 

  8. J. H. Schulman, W. Stocckenius, and L. M. Prince, J. Phys. Chem. 63, 1677 (1959).

    Article  CAS  Google Scholar 

  9. W. Stocckenius, J. H. Schulman, and L. M. Prince, Kolloid Z. 169 170 (1960).

    Article  Google Scholar 

  10. J. H. Schulman and J. A. Friend, J. Colloid Interface Sci. 4, 1988 (1971).

    Google Scholar 

  11. L. M. Prince, J. Colloid Interface Sci. 23, 165 (1967).

    Article  CAS  Google Scholar 

  12. D. O. Shah, A. Tamjeedi, J. W. Falco, and R. D. Walker, Jr., AIChE J. 18, 1116 (1972).

    Article  CAS  Google Scholar 

  13. G. Gillberg, H. Lehtinen, and S. Friberg, J. Colloid Interface Sci. 33, 215 (1970).

    Article  Google Scholar 

  14. S. I. Ahmed, K. Shinoda, and S. Friberg, J. Colloid Interface Sci. 47, 32 (1974).

    Article  Google Scholar 

  15. J. W. Falco, R. D. Walker, Jr., and D. O. Shah, AIChE J. 20, 510 (1974).

    Article  CAS  Google Scholar 

  16. P.A. Winsor, “Solvent Properties of Amphiphilic Compounds,” Butterworth’s Scientific Publications, London, 1954.

    Google Scholar 

  17. R. N. Healy, R. L. Reed, and D. G. Stenmark, Soc. Pet. Eng. J. 147 (June 1976).

    Google Scholar 

  18. K. Shinoda and S. Friberg, Adv. Colloid Interface Sci. 4, 281 (1975).

    Article  CAS  Google Scholar 

  19. E. Ruckenstein and J. C. Chi, J. Chem. Soc. Faraday Trans. II 71, 1690 (1975).

    Google Scholar 

  20. J. W. Cahn and J. E. Hilliard, J. Chem. Phys. 28, 258 (1958).

    Article  CAS  Google Scholar 

  21. H. Metiu and E. Ruckenstein, J. Colloid Interface Sci. 46, 394 (1974).

    Article  CAS  Google Scholar 

  22. A. Silberberg and W. Kuhn, Nature 170, 450 (1952).

    Article  CAS  Google Scholar 

  23. W. Kuhn, H. Majer, and F. Burckhart, Heim. Chim. Acta. 43, 1208 (1960).

    Article  CAS  Google Scholar 

  24. G. Langhammer and L. Nestler, Makromoleculare Chemie 88, 179 (1965).

    Article  CAS  Google Scholar 

  25. A. Vrij, J. Polym. Sci. A-2, 6, 1919 (1968).

    CAS  Google Scholar 

  26. T. Nose, Polymer Journal (Japan) 8, 96 (1976).

    CAS  Google Scholar 

  27. S. Agarwal and H. Herman, Scripta Met. 7, 503 (1973).

    Article  CAS  Google Scholar 

  28. J. W. Cahn, J. Chem. Phys. 42, 93 (1965).

    Article  CAS  Google Scholar 

  29. E. Ruckenstein, Stability of Concentrated Colloidal Systems (unpublished 1972).

    Google Scholar 

  30. R. B. Bird, W. E. Stewart and E. N. Lightfoot, Transport Phenomena, John Wiley & Sons, New York (1960).

    Google Scholar 

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© 1977 Plenum Press, New York

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Ruckenstein, E. (1977). Stability, Phase Equilibria, and Interfacial Free Energy in Microemulsions. In: Mittal, K.L. (eds) Micellization, Solubilization, and Microemulsions. Springer, Boston, MA. https://doi.org/10.1007/978-1-4613-4157-4_15

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  • DOI: https://doi.org/10.1007/978-1-4613-4157-4_15

  • Publisher Name: Springer, Boston, MA

  • Print ISBN: 978-1-4613-4159-8

  • Online ISBN: 978-1-4613-4157-4

  • eBook Packages: Springer Book Archive

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