Sonnleitner, Thomas and Nikitina, Viktoriya and Nazet, Andreas and Buchner, Richard (2013) Do H-bonds explain strong ion aggregation in ethylammonium nitrate plus acetonitrile mixtures? PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 15 (42). pp. 18445-18452. ISSN 1463-9076, 1463-9084
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Binary mixtures of the protic ionic liquid ethylammonium nitrate (EAN) and acetonitrile (AN) were studied at 25 degrees C over the entire composition range by means of broadband dielectric spectroscopy covering 0.2 <= n/GHz <= 89. The dielectric spectra could be decomposed into two relaxation processes, both of which proved to be composite modes. For dilute solutions the higher-frequency Debye relaxation centered at similar to 60 GHz is associated with the rotational diffusion of AN molecules, whereas at higher salt concentrations ultra-fast intermolecular vibrations and librations of EAN dominate the process. For EAN-rich solutions the lower-frequency relaxation is mainly due to jump reorientation of the ethylammonium cation, whereas contact ion pairs (CIPs) dominate this mode for dilute solutions. From the relaxation amplitudes effective solvation numbers and ion-pair concentrations were determined. For vanishing EAN mole fraction, x(EAN) -> 0, an effective cation solvation number of similar to 7 was found which steeply drops until x(EAN) approximate to 0.2 but shows only moderate decrease later on. The obtained association constant for EAN, K-A(0) = 970 L mol(-1), exceeds that of other 1 : 1 electrolytes in AN by a factor of similar to 30-50. This observation, as well as the fact that CIPs are formed despite strong cation solvation, indicates that ion pairing is mainly driven by the formation of strong hydrogen bonds between anions and cations.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | DIELECTRIC-RELAXATION SPECTROSCOPY; AQUEOUS-ELECTROLYTE-SOLUTIONS; WATER MIXTURES; SOLVATION DYNAMICS; POLAR SOLVATION; BINARY-MIXTURES; LIQUIDS; SYSTEM; ASSOCIATION; SOLVENTS; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie > Chair of Chemistry VI - Physical Chemistry (Solution Chemistry) 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: | 28 Apr 2020 11:47 |
| Last Modified: | 28 Apr 2020 11:47 |
| URI: | https://pred.uni-regensburg.de/id/eprint/17358 |
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