Abstract
The interest of ultrasonic absorption methods for the study of problems specific to poly- electrolyte solutions is pointed out. It is shown that the conjunction of ultrasonic absorption and density measurements should provide quantitative informations (1) on the distribution of site bound counter-ions between those bound without and with dehydration and (2) on the exchange rates between the various types of ions. On the basis of previous ultrasonic absorption measurements a model for counter-ion site binding is presented. Ultrasonic relaxation spectra (absorption vs frequency curves) of a series of polyphosphate solutions are then given. They indicate that two relaxation processes are present. The low frequency relaxation process seems to be essentially dependent on the counter-ion while the high frequency relaxation process seems to be associated with the polyion. In view of these results a model is presented for the kinetics of counter-ion site binding. This model rests primarily (1) on the similarity between counter-ion site binding by polyions and ion-pair formation in simple electrolytic solutions and (2) on Manning’s theory for counter-ion condensation in polyelec- trolyte solutions. It assigns the ultrasonic absorption found in polysalt solutions to the perturbation by the ultrasonic waves of the equilibria between various states of hydration of the complex formed by the bound ion and that part of the polyion involved in the binding. From this model are derived equations relating the relaxation times and relaxation amplitudes to the rate constants of the equilibria between site bound counter-ions, to the volume changes associated with these equilibria and to the concentrations of the different types of counter-ions. These equations can be shown to account qualitatively for all of the experimental results. However, their use for the determination of the various parameters characterizing site binding equilibria in cobalt polyphosphate solutions appears to be limited by the large number of these parameters and the limited ultrasonic frequency range investigated in this work. To overcome the first limitation extensive density measurements have been performed on polyelectrolyte solutions. Such measurements yield the total volume change associated with site Wading which is used in the analysis of the ultrasonic results.
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© 1974 D. Reidel Publishing Company, Dordrecht-Holland
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Tondre, C., Zana, R. (1974). Ultrasonic Absorption and Density Studies of Counter-Ion Site Binding in Aqueous Solutions of Polyelectrolytes. In: Sélégny, E., Mandel, M., Strauss, U.P. (eds) Polyelectrolytes. Charged and Reactive Polymers, vol 1. Springer, Dordrecht. https://doi.org/10.1007/978-94-010-2185-2_19
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DOI: https://doi.org/10.1007/978-94-010-2185-2_19
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