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Micellar solutions of ionic surfactants and their mixtures with nonionic surfactants: Theoretical modeling vs. Experiment

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Abstract

Here, we review two recent theoretical models in the field of ionic surfactant micelles and discuss the comparison of their predictions with experimental data. The first approach is based on the analysis of the stepwise thinning (stratification) of liquid films formed from micellar solutions. From the experimental step-wise dependence of the film thickness on time, it is possible to determine the micelle aggregation number and charge. The second approach is based on a complete system of equations (a generalized phase separation model), which describes the chemical and mechanical equilibrium of ionic micelles, including the effects of electrostatic and non-electrostatic interactions, and counterion binding. The parameters of this model can be determined by fitting a given set of experimental data, for example, the dependence of the critical micellization concentration on the salt concentration. The model is generalized to mixed solutions of ionic and nonionic surfactants. It quantitatively describes the dependencies of the critical micellization concentration on the composition of the surfactant mixture and on the electrolyte concentration, and predicts the concentrations of the monomers that are in equilibrium with the micelles, as well as the solution’s electrolytic conductivity; the micelle composition, aggregation number, ionization degree and surface electric potential. These predictions are in very good agreement with experimental data, including data from stratifying films. The model can find applications for the analysis and quantitative interpretation of the properties of various micellar solutions of ionic surfactants and mixed solutions of ionic and nonionic surfactants.

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References

  1. McBain, J.W., Trans. Faraday Soc., 1913, vol. 9, p. 99.

    Google Scholar 

  2. McBain, J.W. and Salmon, C.S., J. Am. Chem. Soc., 1920, vol. 42, p. 427.

    Article  Google Scholar 

  3. Hartley, G.S., Aqueous Solutions of Paraffin Chain Salts, Paris: Hermann, 1936.

    Google Scholar 

  4. Vincent, B., Adv. Colloid Interface Sci. 2014, vol. 20, p. 51.

    Article  Google Scholar 

  5. Kroflič, A., Šarac, B., and Bešter-Rogač, M., J. Chem. Thermodynamics, 2011, vol. 43, p. 1557.

    Article  Google Scholar 

  6. Gehlen, M.H. and De Schryver, F.C., J. Phys. Chem., 1993, vol. 97, p. 11242.

    Article  CAS  Google Scholar 

  7. Alargova, R., Petkov, J., Petsev, D., Ivanov, I.B., Broze, G., and Mehreteab A., Langmuir, 1995, vol. 11, p. 1530.

    Article  CAS  Google Scholar 

  8. Lang. P. and Glatter, O., Langmuir, 1996, vol. 12, p. 1193.

    Article  CAS  Google Scholar 

  9. Petkov, J.T., Tucker, I.M., Penfold, J., Thomas, R.K., Petsev, D.N., Dong, C.C., Golding, S., and Grillo, I., Langmuir, 2010, vol. 26, p. 16699.

    Article  CAS  Google Scholar 

  10. Bales, B.L., Messina, L., Vidal, A., Peric, M., and Nascimento, O.R., J. Phys. Chem. B, 1998, vol. 102, p. 10347.

    Article  CAS  Google Scholar 

  11. Törnblom, M., Henriksson, U., and Ginley, M., J. Phys. Chem., 1994, vol. 98, p. 7041.

    Article  Google Scholar 

  12. Zana, R., Dynamics of Surfactant Self-Assemblies, New York: CRC Press, 2005.

    Book  Google Scholar 

  13. Kamrath, R.F. and Frances, E.I., J. Phys. Chem. 1984, vol. 88, p. 1642.

    Article  CAS  Google Scholar 

  14. Tadros, T.F., Applied Surfactants: Principles and Applications, Weinheim: Wiley-VCH Verlag, 2005.

    Book  Google Scholar 

  15. Israelachvili, J.N., Mitchell, D.J., and Ninham, B.W., J. Chem. Soc., Faraday Trans. 2, 1976, vol. 72, p. 1525.

    Article  Google Scholar 

  16. Missel, P.J., Mazer, N.A., Benedek, G.B., Young, C.Y., and Carey, M.C., J. Phys. Chem., 1980, vol. 84, p. 1044.

    Article  CAS  Google Scholar 

  17. Alargova, R.G., Danov, K.D., Kralchevsky, P.A., Broze, G., and Mehreteab, A., Langmuir, 1998, vol. 14, p. 4036.

    Article  CAS  Google Scholar 

  18. Scrinivasan, V. and Blankstein, D., Langmuir, 2003, vol. 19, p. 9932.

    Article  Google Scholar 

  19. Kralchevsky, P.A., Danov, K.D., Anachkov, S.E., Georgieva, G.S., and Ananthapadmanabhan, K.P., Curr. Opin. Colloid Interface Sci., 2013, vol. 18, p. 524.

    Article  CAS  Google Scholar 

  20. Rubingh, D.N., in Solution Chemistry of Surfactants, Vol. 1, Mittal, K.L., Ed., New York: Plenum Press; 1979.

  21. Kamrath, R.F. and Frances, E.I., Ind. Eng. Chem. Fundam., 1983, vol. 22, p. 230.

    Article  CAS  Google Scholar 

  22. Rusanov, A.I., Shchekin, A.K., and Kuni, F.M., Colloid J., 2009, vol. 71, p. 816.

    Article  CAS  Google Scholar 

  23. Rusanov, A.I., Micellization in Surfactant Solutions, Reading: Harwood Academic, 1997.

    Google Scholar 

  24. Nagarajan, R., Langmuir, 1985, vol. 1, p. 331.

    Article  CAS  Google Scholar 

  25. Rusanov, A.I., Shchekin, A.K., and Kuni, F.M., Colloid J., 2009, vol. 71, p. 826.

    Article  CAS  Google Scholar 

  26. Szleifer, I., Ben-Shaul, A., and Gelbart, W.M., J. Chem. Phys., 1986, vol. 85, p. 5345.

    Article  CAS  Google Scholar 

  27. Reif, I., Mulqueen, M., and Blankschtein, D., Langmuir, 2001, vol. 17, p. 5801.

    Article  CAS  Google Scholar 

  28. Huibers, P.D.T., Langmuir, 1999, vol. 15, p. 7546.

    Article  CAS  Google Scholar 

  29. Hu, J., Zhang, X., and Wang, Z., Int. J. Mol. Sci., 2010, vol. 11, p. 1020.

    Article  CAS  Google Scholar 

  30. Kresheck, G.C., Hamory, E., Davenport, G., and Scheraga, H.A., J. Am. Chem. Soc., 1966, vol. 88, p. 246.

    Article  CAS  Google Scholar 

  31. Aniansson, E.A.G. and Wall, S.N., J. Phys. Chem., 1974, vol. 78, p. 1024.

    Article  CAS  Google Scholar 

  32. Danov, K.D., Kralchevsky, P.A., Denkov, N.D., Ananthapadmanabhan, K.P., and Lips, A., Adv. Colloid Interface Sci., 2006, vol. 119, p. 1.

    Article  CAS  Google Scholar 

  33. Noskov, B.A., Adv. Colloid. Interface Sci., 2002, vol. 95, p. 237.

    Article  CAS  Google Scholar 

  34. Danov, K.D., Kralchevsky, P.A., Denkov, N.D., Ananthapadmanabhan, K.P., and Lips, A., Adv. Colloid Interface Sci., 2006, vol. 119, p. 17.

    Article  CAS  Google Scholar 

  35. Christov, N.C., Danov, K.D., Kralchevsky, P.A., Ananthapadmanabhan, K.P., and Lips, A., Langmuir, 2006, vol. 22, p. 7528.

    Article  CAS  Google Scholar 

  36. Shchekin, A.K., Rusanov, A.I., and Kuni, F.M., Chem. Lett., 2012, vol. 41, p. 1081.

    Article  CAS  Google Scholar 

  37. Danov, K.D., Basheva, E.S., Kralchevsky, P.A., Ananthapadmanabhan, K.P. and Lips, A., Adv. Colloid Interface Sci., 2011, vol. 168, p. 50.

    Article  CAS  Google Scholar 

  38. Anachkov, S.E., Danov, K.D., Basheva, E.S., Kralchevsky, P.A., and Ananthapadmanabhan, K.P., Adv. Colloid Interface Sci., 2012, vol. 183–184, p. 55.

    Article  Google Scholar 

  39. Danov, K.D., Kralchevsky, P.A., and Ananthapad-manabhan, K.P., Adv. Colloid Interface Sci., 2013, DOI: 10.1016/j.cis.2013.02.001.

    Google Scholar 

  40. Horn, R.G. and Israelachvili, J.N., J. Chem. Phys., 1981, vol. 75, p. 1400.

    Article  CAS  Google Scholar 

  41. Nikolov, A.D., Wasan, D.T., Kralchevsky, P.A., and Ivanov, I.B., in Ordering and Organisation in Ionic Solutions, Ise, N. and Sogami, I., Eds., Singapore: World Scientific, 1988.

  42. Israelachvili, J.N., Intermolecular and Surface Forces, 3rd Ed., London: Academic Press, 2011.

    Google Scholar 

  43. Johonnott, E.S., Phil. Mag. 1906, vol. 11, p. 746.

    Article  Google Scholar 

  44. Perrin, J., Ann. Phys. (Paris), 1918, vol. 10, p. 160.

    CAS  Google Scholar 

  45. Nikolov, A.D. and Wasan, D.T., J. Colloid Interface Sci., 1989, vol. 133, p. 1.

    Article  CAS  Google Scholar 

  46. Nikolov A.D., Kralchevsky, P.A., Ivanov, I.B., and Wasan, D.T., J. Colloid Interface Sci., 1989, vol. 133, p. 13.

    Article  CAS  Google Scholar 

  47. Mitchell, D.J., Ninham, B.W., and Pailthorpe, B.A., J. Chem. Soc., Faraday Trans. 2, 1978, vol. 74, p. 1116.

    Article  CAS  Google Scholar 

  48. Kjellander, R. and Sarman, S., Chem. Phys. Lett., 1988, vol. 149, p. 102.

    Article  CAS  Google Scholar 

  49. Henderson, D., J. Colloid Interface Sci., 1988, vol. 121, p. 486.

    Article  CAS  Google Scholar 

  50. Kralchevsky, P.A. and Denkov, N.D. Chem. Phys. Lett. 1995, vol. 240, p. 385.

    Article  CAS  Google Scholar 

  51. Trokhymchuk, A., Henderson, D., Nikolov, A., and Wasan, D.T., Langmuir, 2001, vol. 17, p. 4940.

    Article  CAS  Google Scholar 

  52. Christov, N.C., Danov, K.D., Zeng, Y., Kralchevsky, P.A., and von Klitzing, R., Langmuir, 2010, vol. 26, p. 915.

    Article  CAS  Google Scholar 

  53. Denkov, N.D., Yoshimura, H., Nagayama, K., and Kouyama, T., Phys. Rev. Lett., 1996, vol. 76, p. 2354.

    Article  CAS  Google Scholar 

  54. Basheva, E.S., Danov, K.D., and Kralchevsky, P.A., Langmuir, 1997, vol. 13, p. 4342.

    Article  CAS  Google Scholar 

  55. Basheva, E.S., Kralchevsky, P.A., Danov, K.D., Ananthapadmanabhan, K.P., and Lips, A., Phys. Chem. Chem. Phys., 2007, vol. 9, p. 5183.

    Article  CAS  Google Scholar 

  56. Scheludko, A. and Exerowa, D., Comm. Dept. Chem. Bulg. Acad. Sci., 1959, vol. 7, p. 123.

    Google Scholar 

  57. Scheludko, A., Adv. Colloid Interface Sci., 1967, vol. 1, p. 391.

    Article  Google Scholar 

  58. Scheludko, A. and Platikanov, D., Kolloid Z., 1961, vol. 175, p. 150.

    Google Scholar 

  59. Trokhymchuk, A., Henderson, D., Nikolov, A.D., and Wasan, D.T., J. Phys. Chem. B, 2003, vol. 107, p. 3927.

    Article  CAS  Google Scholar 

  60. Jönsson, B., Broukhno, A., Forsman, J., and Åkesson, T., Langmuir, 2003, vol. 19, p. 9914

    Article  Google Scholar 

  61. Piech, M. and Walz, J.Y., J. Phys. Chem. B, 2004, vol. 108, p. 9177.

    Article  CAS  Google Scholar 

  62. Tulpar, A., Van Tassel, P.R., and Walz, J.Y., Langmuir, 2006, vol. 22, p. 2876.

    Article  CAS  Google Scholar 

  63. Klapp, S.H.L., Zeng, Y., Qu, D., and von Klitzing, R., Phys. Rev. Lett., 2008, vol. 100, art. no. 118303.

  64. Klapp, S.H.L., Qu, D., and von Klitzing, R., J. Phys. Chem. B, 2007, vol. 111, p. 1296.

    Article  CAS  Google Scholar 

  65. Klapp, S.H.L., Grandner, S., Zeng, Y., and von Klitzing, R., J. Phys.-Condensed Matter, 2008, vol. 20, art. no. 494232.

  66. Zeng, Y., Grandner, S., Oliveira, C.L.P., Thünemann, A.F., Paris, O., Pedersen, J.S., Klapp, S.H.L., and von Klitzing, R., Soft Matter, 2011, vol. 7, p. 10899.

    Article  CAS  Google Scholar 

  67. Beresford-Smith, B. and Chan, D.Y.C., Faraday Discuss. Chem. Soc., 1983, vol. 76, p. 65.

    Article  Google Scholar 

  68. Beresford-Smith, B., Chan, D.Y.C., and Mitchell, D.J., J. Colloid Interface Sci., 1985, vol. 105, p. 216.

    Article  CAS  Google Scholar 

  69. Pashley, R.M. and Ninham, B.W., J. Phys. Chem., 1987, vol. 91, p. 2902.

    Article  CAS  Google Scholar 

  70. Richetti, P. and Kékicheff, P., Phys. Rev. Lett., 1992, vol. 68, p. 1951.

    Article  CAS  Google Scholar 

  71. Toshev, B.V. and Ivanov, I.B., Colloid. Polym. Sci., 1975, vol. 253, p. 558.

    Article  CAS  Google Scholar 

  72. Bourrel, M. and Schechter, R.S., Microemulsions and Related Systems. Formulation, Solvency, and Physical Properties, New York: Marcel Dekker, 1988.

    Google Scholar 

  73. Robinson, R.A. and Stokes, R.H., Electrolyte Solutions, London: Butterworths, 1959.

    Google Scholar 

  74. Prigogine, I. and Defay, R., Chemical Thermodynamics, London: Longmans, Green and Co., 1954.

    Google Scholar 

  75. Winstein, S., Clippinger, E., Fainberg, A.H., Heck, R., and Robinson, G.C., J. Am. Chem. Soc., 1956, vol. 78, p. 328.

    Article  CAS  Google Scholar 

  76. Mitchell, D.J. and Ninham, B.W., J. Phys. Chem., 1983, vol. 87, p. 2996.

    Article  CAS  Google Scholar 

  77. Evans, E.A. and Skalak, R., CRC Crit. Rev. Bioeng., 1979, vol. 3, 181.

    CAS  Google Scholar 

  78. Ohshima, H., Healy, T.W., and White, L.R., J. Colloid Interface Sci., 1982, vol. 90, p. 17.

    Article  CAS  Google Scholar 

  79. Corrin, M.L. and Harkins, W.D., J. Am. Chem. Soc., 1947, vol. 69, p. 683.

    Article  CAS  Google Scholar 

  80. Mukhim, T. and Ismail, K., J. Surf. Sci. Technol., 2005, 21, 113.

    CAS  Google Scholar 

  81. Corrin, M.L., J. Colloid Sci., 1948; vol. 3, p. 333.

    Article  CAS  Google Scholar 

  82. Harned, H.S. and Owen, B.B., The Physical Chemistry of Electrolytic Solutions, 2nd Ed. New York: Reinhold Publishing Corp., 1950.

    Google Scholar 

  83. Kralchevsky, P.A., Boneva, M.P., Danov, K.D., Ananthapadmanabhan, K.P., and Lips, A., J. Colloid Interface Sci., 2008, vol. 327, p. 169.

    Article  CAS  Google Scholar 

  84. Ravdel, A.A. and Ponomareva, A.M., Concise Handbook of Physicochemical Quantities, 8th Ed. Leningrad: Khimiya, 1983 [in Russian].

    Google Scholar 

  85. Lide, D.R., Ed., CRC Handbook of Chemistry and Physics, 89th Ed. New York: CRC Press, 2008.

    Google Scholar 

  86. Moroi, Y. and Yoshida, N., Langmuir, 1997, vol. 13, p. 3909.

    Article  CAS  Google Scholar 

  87. Hill, T.L., An Introduction to Statistical Thermodynamics. New York: Dover, 1987.

    Google Scholar 

  88. Tzocheva, S.S., Kralchevsky, P.A., Danov, K.D., Georgieva, G.S., Post, A.J., and Ananthapadmanabhan, K.P., J. Colloid Interface Sci., 2012, Vol. 369, p. 274.

    Article  CAS  Google Scholar 

  89. Bergström, M., Jonsson, P., Persson, M., and Eriksson, J.C., Langmuir, 2003, vol. 19, p. 10719.

    Article  Google Scholar 

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  1. Department of Chemical Engineering, Faculty of Chemistry and Pharmacy, Sofia University, 1 James Bourchier Blvd., Sofia, 1164, Bulgaria

    P. A. Kralchevsky, K. D. Danov & S. E. Anachkov

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  1. P. A. Kralchevsky
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  3. S. E. Anachkov
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Kralchevsky, P.A., Danov, K.D. & Anachkov, S.E. Micellar solutions of ionic surfactants and their mixtures with nonionic surfactants: Theoretical modeling vs. Experiment. Colloid J 76, 255–270 (2014). https://doi.org/10.1134/S1061933X14030065

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