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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

Abstract

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.

Kurzfassung

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.


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

© 2005, Carl Hanser Publisher, Munich

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