Skip to content
Licensed Unlicensed Requires Authentication Published by De Gruyter May 8, 2013

Monomer Exchange Kinetics, Dynamics of Concentration Fluctuations, and Chain Isomerization of Nonionic Surfactant/Water Systems. Evidence from Broadband Ultrasonic Spectra

Kinetik des Monomeraustauschs, Dynamik von Konzentrationsfluktuationen, sowie Kettenisomerisierungen in Lösungen von nichtionischen Detergentien in Wasser. Ergebnisse breitbandiger Ultraschallspektrometrie
  • Elke Hanke , Thomas Telgmann and Udo Kaatze


Ultrasonic absorption spectra, measured between 0.1 and 2000 MHz, are discussed for a variety of poly(ethylene glycol) monoalkyl ether/water (CiEj=H2O) mixtures. Depending on the temperature, the surfactant concentration, and on the length of the hydrophobic (Ci) as well as the hydrophilic part (Ej) of the surfactant molecules, the spectra reveal a multitude of shapes. The set of spectra, however, can be consistently described considering (i) a relaxation term representing the monomer exchange of the micellar solutions, (ii) another one that reflects the local fluctuations in the surfactant concentration, and, with several systems, (iii) additional terms due to CiEj associations or conformational isomerizations. The parameters of these terms are discussed in the light of relevant models. Evidence is presented for a more general view of a fluctuation controlled monomer exchange mechanism that combines aspects of both theoretical models, the micelle formation/decay kinetics and dynamics of local concentration fluctuations.


In dieser Arbeit werden zwischen 0.1 und 2000 MHz gemessene Ultraschallabsorptionsspektren für eine Vielzahl von Polyethylenglycol Monoalkylether/Wasser-Mischungen (CiEj=H2O) diskutiert. Je nach der Temperatur, der Detergentienkonzentration sowie der Länge des jeweiligen hydrophoben (Ci) und hydrophilen (Ej) Molekülteils weisen die Spektren eine Vielzahl von Formen auf. Der gesamte Satz von Spektren kann jedoch konsistent beschrieben werden, wenn folgende Relaxationsterme berücksichtigt werden: (i) ein Term, der den Monomeraustausch in den Mizelllösungen darstellt, (ii) ein anderer Term, der die lokalen Fluktuationen der Detergentienkonzentration widerspiegelt und bei einigen Systemen (iii) zusätzliche Terme aufgrund von CiEj-Assoziations- oder Konformationisomerisierungsvorgängen. Die Parameter dieser Terme werden auf der Grundlage relevanter Modelle diskutiert. Es werden allgemeinere Aspekte der Spektren dargestellt, wonach sie im Bilde eines fluktuationskontrollierten Monomeraustauschmechanismus betrachtet werden sollten. Eine Theorie, die die Mizellbildungs-/Zerfallskinetik und die Dynamik lokaler Konzentrationsfluktuationen gemeinsam beschreibt, existiert derzeit aber nicht.

1Dr. Udo Kaatze, Drittes Physikalisches Institut, Georg-August-Universität, Bergerstr. 42–44, 37073 Göttingen, Germany, E-mail:

Elke S. Hanke studied mathematics and physics in Madrid and in Göttingen where she graduated in 2001. Her present research interests are molecular motions of polymers, including the critical dynamics of polymer-polymer mixtures.

Thomas Telgmann studied physics in Göttingen and obtained his PhD in 1997. He is now senior manager in the Automotive Electronics Product Development group of the EPCOS AG, where he is mainly concerned with surface acoustic wave components.

Udo Kaatze studied physics in Mainz and in Göttingen where he received his PhD in 1971. He is heading the Complex Liquids group at the Drittes Physikalisches Institute. U. Kaatze is a founder member of the International Dielectric Society, member of the editorial board of “Measurement Science and Technology”, and Fellow of the Institute of Physics, London.


1. Tanford, C.: The Hydrophobic Effect: Formation of Micelles and Biological Membranes, Wiley, New New York, 1972.Search in Google Scholar

2. Lindmann, B. and Wennerström, H.: Micelles. Amphiphile Aggregation in Aqueous Solution, Springer, Berlin, 1980.Search in Google Scholar

3. Bellocq, A.-M.: Micelles, Membranes, Microemulsions and Monolayers, Springer, Berlin, 1994.Search in Google Scholar

4. Evans, D. F. and Wennerström, H.: The Colloidal Domain. Where Physics, Chemistry, and Biology Meet, Wiley-VCH, New York, 1999.Search in Google Scholar

5. Corti, M. and Degiorgio, V.: J. Chem. Phys.85 (1981) 1442.Search in Google Scholar

6. Corti, M., Minero, C. and Degiorgio, V.: J. Phys. Chem.88 (1984) 309.Search in Google Scholar

7. Telgmann, T. and Kaatze, U.: J. Phys. Chem. A104 (2000) 1085.Search in Google Scholar

8. Telgmann, T. and Kaatze, U.: J. Phys. Chem. A104 (2000) 4846.Search in Google Scholar

9. Anisimov, M. A.: Critical Phenomena in Liquids and Liquid Crystals, Gordon and Breach, Philadelphia, P.A.1991.Search in Google Scholar

10. Stanley, H. E.: Rev. Mod. Phys.71 (1999) 5358.Search in Google Scholar

11. Onuki, A.: Phase Transition Dynamics, Cambridge Uiversity Press, Cambridge, 2002.10.1017/CBO9780511534874Search in Google Scholar

12. Zielesny, A., Belkoura, L. and Woermann, D.: Ber. Bunsenges. Phys. Chem.98 (1994) 579.Search in Google Scholar

13. Kaatze, U., Menzel, K., Pottel, R. and Schwerdtfeger, S.: Z. Phys. Chem. (Munich)186 (1994) 14.Search in Google Scholar

14. Menzel, K., Rupprecht, A. and Kaatze, U.: J. Phys. Chem. B101 (1997) 1255.Search in Google Scholar

15. Kaatze, U., Pottel, R., and Schumacher, A.: Ber. Bunsenges. Phys. Chem.96 (1992) 6017.Search in Google Scholar

16. Tlusky, T., Safran, S. A., Menes, R. and Strey, R.: Phys. Rev. Lett.78 (1997) 2616.Search in Google Scholar

17. Bernheim-Grosswasser, A., Wachtel, E., and Talmon, Y.: Langmuir6 (2000) 4131.Search in Google Scholar

18. Strehlow, M.: Rapid Reactions in Solution, VCH, Weinheim, 1992.Search in Google Scholar

19. Rupprecht, A. and Kaatze, U.: J. Phys. Chem. A103 (1999) 6485.Search in Google Scholar

20. Kaatze, U., Hushcha, T. O. and Eggers, F.: J. Sol. Chem.29 (2000) 299.Search in Google Scholar

21. Matheson, A. J.: Molecular Acoustics, Wiley-Interscience, London, 1971.10.1039/gr9716800027Search in Google Scholar

22. Herzfeld, G. and Litovitz, T.: Absorption and Dispersion of Ultrasonic Waves, Academic, New York, 1959.10.1149/1.2427245Search in Google Scholar

23. Eggers, F. and Kaatze, U.: Meas. Sci. Technol.7 (1996) 1.Search in Google Scholar

24. Kaatze, U., Behrends, R. and Lautscham, K.: Ultrasonics39 (2001) 393.Search in Google Scholar

25. Menzel, K., Mirzaev, S. Z. and Kaatze, U.: Phys. Rev. E68 (2003) 011501.Search in Google Scholar

26. Zimmer, H. J. and Woermann, D.: Ber. Bunsenges. Phys. Chem.95 (1991) 553.Search in Google Scholar

27. Pakush, A.: Dissertation, Georg-August-Universität, Göttingen, 1983.Search in Google Scholar

28. Degiorgio, V. and Corti, M., (Eds.): Physics of Amphiphiles: Micelles, Vesicles and Microemulsions, North-Holland, Amsterdam, 1985.10.1051/epn/19851606009Search in Google Scholar

29. Binana-Limbelé, W., Van Os, N. M., Rupert, L. A. M. and Zana, R.: J. Colloid Interface Sci.144 (1991) 458.Search in Google Scholar

30. Schubert, K.-V., Strey, R. and Kahlweit, M.: J. Colloid Interface Sci.141 (1991) 21.Search in Google Scholar

31. Findi, M., Michels, B. and Zana, R.: J. Phys. Chem.96 (1992) 6095.Search in Google Scholar

32. Kato, S., Harada, S. and Sahara, H.: J. Phys. Chem.99 (1995) 12570.Search in Google Scholar

33. Hall, D. G. and Wyn-Jones, E.: J. Mol. Liq.32 (1986) 63.Search in Google Scholar

34. Lara, J. and Desnoyers, J. E.: J. Sol. Chem.10 (1981) 465.Search in Google Scholar

35. Debye, P.: Polare Molekeln, Hirzel, Leipzig, 1929.Search in Google Scholar

36. Frindi, M., Michels, B. and Zana, R.: Langmuir10 (1994) 1140.10.1017/S0022377800026246Search in Google Scholar

37. Telgmann, T. and Kaatze, U.: J. Phys. Chem. B101 (1997) 7758.Search in Google Scholar

38. Hagen, R.: Diploma-Thesis, Georg-August-Universität, Göttingen, 1998.Search in Google Scholar

39. Polacek, R.: Dissertation, Georg-August-Universität, Göttingen, 2003.Search in Google Scholar

40. Hill, R. M.: Nature(London)275 (1978) 96.10.1179/102452909X417042Search in Google Scholar

41. Hill, R. M.: Status Solidi103 (1981) 319.Search in Google Scholar

42. Menzel, K., Rupprecht, A. and Kaatze, U.: J. Acoust. Soc. Am.104 (1998) 2741.Search in Google Scholar

43. Bhattacharjee, J. K. and Ferrell, R. A.: Phys. Rev. A23 (1981) 371.10.1103/PhysRevA.23.371Search in Google Scholar

44. Ferrell, R. A. and Bhattacharjee, J. K.: Phys. Rev. A31 (1985) 1788.10.1103/PhysRevE.73.059901Search in Google Scholar

45. Bhattacharjee, J. K. and Ferrell, R. A.: Physica A250 (1998) 83.10.1016/S0378-4371(97)00204-5Search in Google Scholar

46. Folk, R. and Moser, G.: Phys. Rev. E57 (1998) 705.10.1103/PhysRevB.63.189901Search in Google Scholar

47. Folk, R. and Moser, G.: Phys. E58 (1998) 6246.10.1103/PhysRevB.63.189901Search in Google Scholar

48. Folk, R. and Moser, G.: Inst. of Thermophys.19 (1998) 1003.Search in Google Scholar

49. Onuki, A.: Phys. Rev. E57 (1997) 403.Search in Google Scholar

50. Onuki, A.: J. Phys. Soc. Jpn.66 (1997) 511.Search in Google Scholar

51. Behrends, R., Kaatze, U., and Schach, M.: J. Chem. Phys.119 (2003).10.1063/1.1610448Search in Google Scholar

52. Iwanowski, I.Behrends, R. and Kaatze, U.: J. Chem. Phys.120 (2004) 9192.Search in Google Scholar

53. Behrends, R., Iwanowski, I.; Kosmowska, M., Szala, A. and Kaatze, U.: J. Chem. Phys.121 (2004) 5929.Search in Google Scholar

54. Aniansson, E. A. G. and Wall, S. N.: J. Phys. Chem.78 (1974) 1024.Search in Google Scholar

55. Aniansson, E. A. G.: J. Phys. Chem.82 (1978) 2805.Search in Google Scholar

56. Aniansson, E. A. G.: Ber. Bunsenges. Phys. Chem.82 (1978) 981.Search in Google Scholar

57. Aniansson, E. A. G.: Progr. Colloid Polym. Sci.70 (1985) 2.Search in Google Scholar

58. Teubner, M.: J. Phys. Chem.83 (1979) 2917.Search in Google Scholar

59. Kahlweit, M. and Teubner, M.: Adv. Colloid Interface Sci.13 (1980) 1.Search in Google Scholar

60. Telgmann, T. and Kaatze, U.: J. Phys. Chem. B101 (1997) 7766.Search in Google Scholar

61. Giese, K.: Adv. Mol. Relax. Processes5 (1973) 363.Search in Google Scholar

62. Kaatze, U.: J. Solution Chem.26 (1997) 1049.Search in Google Scholar

63. Sanches, G. and Garland, C. W.: J. Chem. Phys.79 (1983) 3100.Search in Google Scholar

64. Berg, R. F. and Moldover, M. R.: Phys. Rev. E60 (1999) 4079.Search in Google Scholar

65. Limberg, S., Belkoura, L. and Woermann, D.: J. Mol. Liquids73,74 (1997) 223.Search in Google Scholar

66. Rebillot, P. F. and Jacobs, D. T.: J. Chem. Phys.109 (1998) 4009.Search in Google Scholar

67. Bervillier, C. and Godréche, C.: Phys. Rev. B.21 (1980) 5427.Search in Google Scholar

68. Fast, S. J. and Yun, S. S.: J. Acoust. Soc. Am.83 (1988) 1384.Search in Google Scholar

69. Belkoura, L., Harnisch, F. P., Kölchens, S., Müller-Kirschbaum, T., and Woermann, D.: Ber. Bunsenges. Phys. Chem.91 (1987) 1036.Search in Google Scholar

70. Zalczer, G. and Beyens, D.: J. Chem. Phys.92 (1990) 6747.Search in Google Scholar

71. Würz, U.Grubic, M. and Woermann, D.: Ber. Bunsenges. Phys. Chem.96 (1992) 1460.Search in Google Scholar

72. Mirzaev, S. Z., Telgmann, T. and Kaatze, U.: Phys. Rev. E61 (2000) 542.Search in Google Scholar

73. Mirzaev, S. Z. and Kaatze, U.: Phys. Rev. E65 (2002) 021509.Search in Google Scholar

74. Kaatze, U., Berger, W. and Lautscham, K.: Ber. Bunsenges. Phys. Chem.92 (1988) 872.Search in Google Scholar

75. Kaatze, U., Lautscham, K. and Berger, W.: Z. Phys. Chem. (Munich)159 (1988) 161.Search in Google Scholar

76. Kaatze, U., Lautscham, K. and Berger, W.: Chem. Phys. Lett.144 (1988) 273.Search in Google Scholar

77. Behrends, R. and Kaatze, U.: J. Phys. Chem. A104 (2000) 3269.Search in Google Scholar

78. Tobolsky, A. V.: J. Polym. Sci.A-26 (1968) 1177.Search in Google Scholar

79. Tobolsky, A. V. and DuPré, D. B.: Adv. Polym. Sci.6 (1969) 103.Search in Google Scholar

80. Cochran, M. A., Jones, P. B., North, A. M., and Pethrick, R. A.: J. Chem. Soc., Faraday Trans.268 (1972) 1719.Search in Google Scholar

81. Madigosky, W. M. and Warfield, R. W.: J. Chem. Phys.78 (1983) 1912.Search in Google Scholar

82. Madigosky, W. M. and Warfield, R. W.: Acustica55 (1984) 123.Search in Google Scholar

83. Behrends, R. and Kaatze, U.: Meas. Sci. Technol.12 (2001) 519.Search in Google Scholar

84. Rouse, P. E.: J. Chem. Phys.21 (1953) 1272.10.1063/1.462909Search in Google Scholar

Received: 2004-11-4
Published Online: 2013-05-08
Published in Print: 2005-03-01

© 2005, Carl Hanser Publisher, Munich

Downloaded on 27.2.2024 from
Scroll to top button