A Simple Interpretation of Hydrophobic Interactions and Critical Concentrations in Micellar Solutions

  • E. Ruckenstein
Part of the Ettore Majorana International Science Series book series (EMISS, volume 41)


Surfactant molecules possess a hydrophobic tail and a hydrophilic head group. Because of this dual property, they form in water (or other polar liquids) a large number of relatively large aggregates, as soon as their concentration becomes greater than the critical micelle concentration[1,2]. In the aggregates, the hydrocarbon tails are shielded from water by the polar head groups. Two factors are mainly responsible for the formation of micelles. One of them, the hydrophobic bonding, is primarily due to the incompatibility of the hydrocarbon tails of the surfactant with the polar solvent. Indeed, the tails interfere with the strong polar interactions between the water molecules and, therefore, the free energy of the system is decreased by diminishing their contact with water. Should this factor act alone, the surfactant molecules will form “infinite size” aggregates, thus leading to a separate surfactant phase. The repulsion that arises between the head groups competes with the hydrophobic bonding and ensures the formation of a large number of finite (but relatively large) size aggregates. The present paper is concerned with the mechanistic interpretation of the hydrophobic bonding, as well as with the critical micelle concentration in both polar and nonpolar solvents. The latter quantity provides information about the conditions under which a large number of aggregates can form.


Critical Micelle Concentration Surfactant Concentration Nonionic Surfactant Surfactant Molecule Free Energy Change 
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.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    C. Tanford, “The Hydrophobic Effect: Formation of Micelles and Biological Membranes,” 2nd ed. Wiley-Interscience, New York (1980).Google Scholar
  2. 2.
    K. Shinoda, “Principles of Solution and Solubility,” M. Decker, New York (1977).Google Scholar
  3. 3.
    H. S. Frank and M. W. Evans, J.Chem.Phys. 13: 507 (1945).ADSCrossRefGoogle Scholar
  4. 4.
    K. Shinoda, J.Phys.Chem. 81: 1300 (1977).CrossRefGoogle Scholar
  5. 5.
    J. W. McBain, “Colloid Science,” D. C. Heath and Co., Boston (1950).Google Scholar
  6. 6.
    P. Debye, Ann.N.Y.Acad.Sci. 51: 575 (1949).ADSCrossRefGoogle Scholar
  7. 7.
    R. Pierotti, J.Phys.Chem. 67: 1840 (1963)CrossRefGoogle Scholar
  8. R. Pierotti, J.Phys.Chem. 69: 281 (1965).CrossRefGoogle Scholar
  9. (b).
    L. R. Pratt and D. Chandler, J.Chem.Phys. 67: 3683 (1977).ADSCrossRefGoogle Scholar
  10. (c).
    R. Fernandez-Prim, R. Czovetto, M. L. Japas, and D. Larsa, Acc.Chem.Res. 18: 207 (1985).CrossRefGoogle Scholar
  11. 8.
    C. Tanford, J.Phys.Chem. 78: 2469 (1974).CrossRefGoogle Scholar
  12. 9.
    E. Ruckenstein and R. Nagarajan, J.Phys.Chem. 79: 2622 (1975).CrossRefGoogle Scholar
  13. 10.
    R. Nagarajan and E. Ruckenstein, J.Colloid Interface Sci., 91: 500 (1983).CrossRefGoogle Scholar
  14. 11.
    A. S. Kertes and H. Gutmann, In: “Surface and Colloid Science,” Vol. 8, E. Matijevic, ed., Interscience, New York (1975).Google Scholar
  15. 12.
    A. S. Kertes, In: “Micellization, Solubilization and Microemulsions,” K. L. Mittal, ed., Plenum Press, New York (1977).Google Scholar
  16. 13.
    A. S. Kertes, H. Gutmann, O. Levy, and G. Y. Markovits, Isr.J.Chem., 6: 421 (1968).CrossRefGoogle Scholar
  17. 14.
    N. Muller, J.Phys.Chem. 79: 287 (1975).CrossRefGoogle Scholar
  18. 15.
    N. Muller, J.Colloid Interface Sci. 63: 383 (1978).CrossRefGoogle Scholar
  19. 16.
    R. Debye and H. Coll, J.Colloid Sci. 17: 220 (1962).CrossRefGoogle Scholar
  20. 17.
    K. Kon-No, A. Kitahara, and O. A. El Seoud, in: “Nonionic Surfactants: Physical Chemistry,” M. J. Schick, ed., (in press).Google Scholar
  21. 18.
    E. Ruckenstein and R. Nagarajan, J.Phys.Chem. 84: 1349 (1980).CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 1989

Authors and Affiliations

  • E. Ruckenstein
    • 1
  1. 1.Institut für Physikalische Chemie IUniversität BayreuthBayreuthWest Germany

Personalised recommendations