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

Abstract

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.