Luksic, Miha and Hribar-Lee, Barbara and Buchner, Richard and Vlachy, Vojko (2009) Modelling fast mode dielectric relaxation of counterions in aqueous solutions of ionene bromides and fluorides. PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 11 (43). pp. 10053-10058. ISSN 1463-9076, 1463-9084
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The parameters derived from previously published (M. Luksic. et al., Macromolecules, 2009, 42, 4337-4342) dielectric spectra of aqueous solutions of aliphatic 3,3-, 4,5-, 6,6-, and 6,9-ionene bromides and fluorides were analyzed within the existing models for the fast counterion-relaxation process. By fitting the Poisson-Boltzmann results to the experimental data for the osmotic coefficients of the ionenes in question, we were able to estimate the self diffusion coefficients of counterions. The coefficients were then used to calculate the correlation lengths as proposed by the Ito model. The corresponding correlation lengths obtained by the Mandel-Manning model were of similar magnitude. The observed trends in correlation lengths were consistent with the model-independent values derived from the experimental relaxation times. Combination of the dielectric data and Poisson-Boltzmann model analysis yields the conclusion that the fluoride counterions prefer longitudinal, whereas the bromide counterions favour transverse, fluctuation with respect to the polyelectrolyte backbone.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | POLYELECTROLYTE SOLUTIONS; LIMITING LAWS; DIFFUSION-COEFFICIENTS; SELF-DIFFUSION; CHARGE-DENSITY; SPECTROSCOPY; CONDENSATION; DYNAMICS; DILUTE; WATER; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie > Chair of Chemistry VI - Physical Chemistry (Solution Chemistry) > PD Dr. Richard Buchner |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 13 Oct 2020 15:11 |
| Last Modified: | 13 Oct 2020 15:11 |
| URI: | https://pred.uni-regensburg.de/id/eprint/29861 |
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