Journal article
Solvation and association of 3:1 electrolytes in N, N-dimethylformamide
The Journal of Physical Chemistry B, Vol.117(46), pp.14468-14476
2013
Abstract
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 C using dielectric relaxation spectroscopy over the frequency range of 0.1 ν/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 ∼15 GHz due to the solvent and one or (for AlTf3 solutions) two solute-related processes at lower frequencies (νmax 2 GHz). Effective solvation numbers, Zib, calculated from the solvent relaxation process indicated that all three cations were strongly solvated by DMF with Zib 0 values at infinite dilution in the order (Al3+ ≈ Sc3+ ≈ 10) < (La3+ ≈ 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 AlTf 3 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-Hückel considerations, the KA values decreased rapidly with increasing solute concentration.
Details
- Title
- Solvation and association of 3:1 electrolytes in N, N-dimethylformamide
- Authors/Creators
- A. Fuchs (Author/Creator)R. Buchner (Author/Creator)G. Hefter (Author/Creator)
- Publication Details
- The Journal of Physical Chemistry B, Vol.117(46), pp.14468-14476
- Publisher
- American Chemical Society
- Identifiers
- 991005540389407891
- Copyright
- © 2013 American Chemical Society.
- Murdoch Affiliation
- School of Veterinary and Life Sciences
- Language
- English
- Resource Type
- Journal article
UN Sustainable Development Goals (SDGs)
This output has contributed to the advancement of the following goals:
Source: InCites
Metrics
13 Record Views
InCites Highlights
These are selected metrics from InCites Benchmarking & Analytics tool, related to this output
- Collaboration types
- Domestic collaboration
- International collaboration
- Citation topics
- 2 Chemistry
- 2.89 Ionic, Molecular & Complex Liquids
- 2.89.677 Liquid Water
- Web Of Science research areas
- Chemistry, Physical
- ESI research areas
- Chemistry