Skip to main content
SpringerLink
Log in

Statistical-Thermodynamic Theory of Surfactant Organization in Micelles and Bilayers

  • Chapter
Surfactants in Solution

  • 370 Accesses

Abstract

The probability distribution of chain conformations in micellar aggregates of arbitrary geometry is derived using two alternative approaches: (i) By minimizing the free energy functional of a single chain, subject to the packing constraints imposed by the presence of neighboring chains in the hydrophobic core; (ii) By expanding the many-chain configurational integral in terms of the excluded volumes characterizing one (‘central’) chain in a given conformation. The central assumption in both derivations is that chain organization and conformational statistics in amphiphilic aggregates are governed by the shortrange, repulsive, inter-molecular interactions. Bond order parameter profiles and other single chain properties which can be calculated using the conformational probability distribution are in good agreement with experimental and computer simulation studies. Yet, our main concern in this paper is the theoretical (statistical thermodynamic) description of chain organization within the hydrophobic core, with particular emphasis on the role of micellar geometry. In this spirit a considerable part of the discussion is devoted to comparisions with other theoretical approaches.

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

Access this chapter

Log in via an institution
Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 84.99
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 109.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. C. Tanford, “The Hydrophobic Effect” 2nd edition, Wiley, New York, 1980.

    Google Scholar 

  2. J. N. Israelachvili, D. J. Mitchell and B. W. Ninham, J. Chem. Soc. Faraday Trans. 2, 72, 1525 (1976).

    Article  Google Scholar 

  3. J. N. Israelachvili, S. Marcelja and R. G. Horn, Quart. Rev. Biophys. 13, 121 (1980).

    Article  CAS  Google Scholar 

  4. J. N. Israelachvili, these proceeding, and in “Physics of Amphiphiles: Micelles, Vesicles and Microemulsions” P. P. V. Degiorgio and M. Corti, Editors, North Holland, 1984.

    Google Scholar 

  5. See, e.g., E. Vikingstad and H. Høiland, J. Colloid Interface Sci. 64, 510 (1978).

    Article  Google Scholar 

  6. See, e.g., (a) E. T. Samulski, Ferroelectrics 30, 83 (1980)

    Article  CAS  Google Scholar 

  7. A. Ben-Shaul, Y. Rabin and W. M. Gelbart, J. Chem. Phys. 78, 4303 (1983).

    Article  CAS  Google Scholar 

  8. B. Mely, J. Charvolin and P. Keller, Chem. Phys. Lipids 15 ,161 (1975).

    Article  CAS  Google Scholar 

  9. J. Charvolin, J. Chem. Phys. 80, 15 (1983).

    CAS  Google Scholar 

  10. J. Charvolin and Y. Hendrikx, in “NMR in Liquid Crystals” J.W. Emsley and G. Luckhurst, Editors, Reidel Publishing Co., in press.

    Google Scholar 

  11. H. Walderhaug, O. Soderman and P. Stilbs, J. Phys. Chem. 88, 1655 (1984).

    Article  CAS  Google Scholar 

  12. B. Lindman, T. Ahlnas, O. Soderman and H. Walderhaug, Faraday Disc. Chem. Soc. 76, 317 (1983).

    Article  Google Scholar 

  13. T. Ahlnäs , O. Soderman, H. Walderhaug and B. Lindman, In “Surfactants in Solution” Vol. 1, K.L. Mittal and B. Lindman, Editors, p. 107, Plenum Press, New York, 1984.

    Google Scholar 

  14. For a review see, J. F. Nagle, Ann. Rev. Phys. Chem. 31, 157 (1980).

    Article  CAS  Google Scholar 

  15. F. M. Menger, Acc. Chem. Res. 12 ,111 (1979).

    Article  CAS  Google Scholar 

  16. P. Fromherz, Chem. Phys. Lett. 77, 460 (1981).

    Article  CAS  Google Scholar 

  17. B. Cabane, J. Phys. Paris, 42, 847 (1981).

    CAS  Google Scholar 

  18. T. Zemb and C. Chachaty, in “Surfactants in Solution” K.L. Mittal and B. Lindman, Editors, Vol. 1, Plenum Press, New York, 1984.

    Google Scholar 

  19. B. Lemaire and P. Bothorel, Macromolecules 13, 311 (1980).

    Article  CAS  Google Scholar 

  20. B. Lemaire and P. Bothorel, J. Polym. Sci., Phys. Ed. 20, 867 (1982).

    Article  CAS  Google Scholar 

  21. D. W. R. Gruen and E. H. B. de Lacey, in “Surfactants in Solution” K. L. Mittal and B. Lindraan, Editors, Vol. 1, p. 279, Plenum Press, New York, 1984.

    Google Scholar 

  22. D. W. R. Gruen, J. Colloid Interface Sci. 84, 281 (1981)

    Article  CAS  Google Scholar 

  23. D. W. R. Gruen, Biochem. Biophys. Acta 595, 161 (1980).

    Article  CAS  Google Scholar 

  24. D. W. R. Gruen, J. Phys. Chem. 89, 146, 153 (1985).

    Article  CAS  Google Scholar 

  25. D. W. R. Gruen, Prog. Colloid Polymer Sci. 70, 6 (1985).

    Article  CAS  Google Scholar 

  26. K. A. Dill and P. J. Flory, Proc. Natl. Acad. Sci., USA, 77, 3115, (1980).

    Article  CAS  Google Scholar 

  27. K. A. Dill and P. J. Flory, ibid. 78, 676 (1981).

    CAS  Google Scholar 

  28. K. A. Dill and R. S. Cantor, Macromolecules VT, 380 (1984).

    Google Scholar 

  29. R. S. Cantor and K. A. Dill, Macromolecules 17, 384 (1984).

    Article  CAS  Google Scholar 

  30. K. A. Dill, D. E. Koppel, R. S. Cantor, J. D. Dill, D. Bendedouch and S.-H. Chen, Nature, 309, 42 (1984).

    Article  CAS  Google Scholar 

  31. A. Ben-Shaul, I. Szleifer and W. M. Gelbart, Proc. Natl. Acad. Sci. USA 81, 4601 (1984).

    Article  CAS  Google Scholar 

  32. A. Ben-Shaul, I. Szleifer and W. M. Gelbart, in “Physics of Amphiphiles: Micelles, Vesicles and Microemulsions” V. Degiorgio and M. Corti, Editors, North Holland, 1984.

    Google Scholar 

  33. A. Ben-Shaul, I. Szleifer and W. M. Gelbart, J. Chem. Phys. 83, 3597 (1985).

    Article  CAS  Google Scholar 

  34. I. Szleifer, A. Ben-Shaul and W. M. Gelbart, J. Chem. Phys. 83, 3612 (1985).

    Article  CAS  Google Scholar 

  35. P. van der Ploeg and H. J. C. Berendsen, (a) Mol. Phys. 49, 233 (1983).

    Article  Google Scholar 

  36. P. van der Ploeg and H. J. C. J. Chem. Phys. 76, 3271 (1982).

    Article  Google Scholar 

  37. B. Owenson and L. R. Pratt, to be published.

    Google Scholar 

  38. B. Owenson and L. R. Pratt, J. Phys. Chem. 88, 2905 (1984).

    Article  CAS  Google Scholar 

  39. S. W. Haan and L. R. Pratt, Chem. Phys. Lett. 79, 436 (1981).

    Article  CAS  Google Scholar 

  40. J. M. Haile and J. P. O’Connell, J. Phys. Chem. 88, 6363 (1984).

    Article  CAS  Google Scholar 

  41. J. D. Weeks, D. Chandler and H. C. Andersen, 54, 5237 (1971).

    Google Scholar 

  42. J. A. Barker and D. Henderson, Ann. Rev. Phys. Chem. 23, 439 (1972).

    Article  CAS  Google Scholar 

  43. A. Wulf, J. Chem. Phys. 64, 104 (1975).

    Article  Google Scholar 

  44. W. M. Gelbart and B. Barboy, Accts. Chem. Res. 13., 290 (1980).

    Article  CAS  Google Scholar 

  45. E. T. Jaynes, in “Statistical Physics” Brandeis Lectures, K. W. Ford, Editor, Vol. 3, p. 182, Benjamin, New York, 1963.

    Google Scholar 

  46. R. D. Levine and M. Tribus, Editors. “The Maximum Entropy Formalism,” MIT Press, Cambridge, 1979.

    Google Scholar 

  47. S. Marcelja, a) Biochem. Biophys. Acta 367, 165 (1974).

    Article  CAS  Google Scholar 

  48. S. Marcelja, J. Chem. Phys. 60, 3599 (1974).

    Article  CAS  Google Scholar 

  49. P. J. Flory, “Statistical Mechanics of Chain Molecules,” Wiley, New York, 1969.

    Google Scholar 

  50. M. A. Winnik, D. Rigby, R. F. T. Stepto and B. Lemaire, Macromolecules, 13, 699 (1980).

    Article  CAS  Google Scholar 

  51. P. J. Missel, N. A. Mazer, G. B. Benedek, C.Y. Young and M. C. Carey, J. Phys. Chem. 84, 1044 (1980).

    Article  CAS  Google Scholar 

  52. J. Seelig and W. Niederberger, Biochemistry j 3, 1585 (1974).

    Article  Google Scholar 

  53. See, e.g., S. Chandrasekhar, “Liquid Crystals,” Cambridge University Press, Cambridge, U.K., 1977.

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Physical Chemistry and The Fritz Haber Center for Molecular Dynamics, The Hebrew University, Jerusalem, 91904, Israel

    A. Ben-Shaul & I. Szleifer

  2. Department of Chemistry, University of California, Los Angeles, CA, 90024, USA

    W. M. Gelbart

Authors
  1. A. Ben-Shaul
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. I. Szleifer
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. W. M. Gelbart
    View author publications

    You can also search for this author in PubMed Google Scholar

Editor information

Editors and Affiliations

  1. IBM Corporate Technical Institutes, 500 Columbus Ave., Thornwood, New York, 10594, USA

    Kashmiri Lal Mittal

  2. Centre de Recherches Paul Pascal, Domaine Universitaire, F-33405, Talence Cedex, France

    P. Bothorel

Rights and permissions

Reprints and permissions

Copyright information

© 1986 Plenum Press, New York

About this chapter

Cite this chapter

Ben-Shaul, A., Szleifer, I., Gelbart, W.M. (1986). Statistical-Thermodynamic Theory of Surfactant Organization in Micelles and Bilayers. In: Mittal, K.L., Bothorel, P. (eds) Surfactants in Solution. Springer, Boston, MA. https://doi.org/10.1007/978-1-4613-1831-6_2

Download citation

  • DOI: https://doi.org/10.1007/978-1-4613-1831-6_2

  • Publisher Name: Springer, Boston, MA

  • Print ISBN: 978-1-4612-9023-0

  • Online ISBN: 978-1-4613-1831-6

  • eBook Packages: Springer Book Archive

Publish with us

Policies and ethics

Search

Navigation