Fuchs, Anna and Buchner, Richard and Hefter, Glenn (2013) Solvation and Association of 3:1 Electrolytes in N,N-Dimethylformamide. JOURNAL OF PHYSICAL CHEMISTRY B, 117 (46). pp. 14468-14476. ISSN 1520-6106,
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A detailed study has been made of the solvation and ion association of the trifluoromethanesulfonate (Tf-) salts of aluminum(III), scandium(III), and lanthanum(III) in N,N-dimethylformamide (DMF) at 25 degrees C using dielectric relaxation spectroscopy over the frequency range of 0.1 less than or similar to v/GHz <= 89. The spectra of all solutions exhibited either two (for ScTf3 and LaTf3) or three (for AlTf3) relaxation processes, a dominant mode centered at similar to 45 GHz due to the solvent and one or (for AlTf3 solutions) two solute-related processes at lower frequencies (v(max) less than or similar to 2 GHz). Effective solvation numbers, 4b, calculated from the solvent relaxation process indicated that all three cations were strongly solvated by DMF with Z(ib) values at infinite dilution in the order (Al3+ approximate to Sc3+ approximate to 10) < (La3+ approximate to 13), consistent with at least partial formation of a second solvation shell around each cation. One solute-related mode for each set of salt solutions was assigned to the rotational diffusion of solvent-shared ion pairs (SIPs) of 1:1 stoicheometry; the additional slower process for AlTf3 solutions in DMF was attributed to the presence of double-solvent-separated IPs. The overall association constants at infinite dilution for the 1:1 IPs, KA (MTf2+), were significant, but as expected from Debye Huckel considerations, the KA values decreased rapidly with increasing solute concentration.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | DIELECTRIC-RELAXATION; AQUEOUS-SOLUTION; ION ASSOCIATION; MOLAR VOLUMES; EARTH-METAL; FRICTION; N,N-DIMETHYLACETAMIDE; SPECTROSCOPY; COEFFICIENTS; DISPERSION; |
| 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: | 26 Mar 2020 07:41 |
| Last Modified: | 26 Mar 2020 07:41 |
| URI: | https://pred.uni-regensburg.de/id/eprint/15660 |
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