Abstract
Pulsed neutron diffraction measurements have been carried out on 8.6, 5.8, and 1.7 molar lithium chloride (LiCl) solutions in deuterated water (D2O), methanol-d4 (MeOD), and N,N-dimethylformamide-d7 (DMF), respectively. A first-order difference method with chlorine isotopes substitution was used to derive the Cl−-dependent partial structure factors and radial distribution functions. The oscillation patterns of all Cl−-related structure factors normalized by the concentration persist up to the high momentum transfer region (∼10 Å−1), suggesting the presence of the short-range ordering around chloride ion in the three solvent systems. The normalized radial distribution functions have revealed that methanol molecules are hydrogen bonded to a chloride ion with almost linear orientation of Cl⋅⋅⋅D–O, as in the case of chloride hydration. The nearest-neighbor Cl–D distance and the solvation number for Cl− in the methanol solutions were determined as 2.21±0.03 Å and 3.6±0.5, respectively, compared with 2.29±0.01 Å and 5.8±0.5 for the aqueous solutions. The smaller solvation number for Cl− in the methanol solutions suggests that an Li+–Cl− ion association takes place in the solutions. In the DMF solutions, the first peak was observed at a much longer distance, ∼2.85 Å, and assigned to the distance between Cl− and the formyl H atoms of the DMF molecule due mostly to the ion-dipole interaction. The number of DMF molecules around the chloride ion was estimated as 6.8±0.5. The most likely conformations of the solvent molecules around the chloride ion are proposed and discussed on the basis of the solvent properties.
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Dates
| Type | When |
|---|---|
| Created | 23 years, 1 month ago (July 26, 2002, 8:14 a.m.) |
| Deposited | 1 year, 6 months ago (Feb. 11, 2024, 2:16 a.m.) |
| Indexed | 2 weeks, 6 days ago (Aug. 7, 2025, 4:51 a.m.) |
| Issued | 29 years, 9 months ago (Nov. 8, 1995) |
| Published | 29 years, 9 months ago (Nov. 8, 1995) |
| Published Print | 29 years, 9 months ago (Nov. 8, 1995) |
@article{Yamagami_1995, title={Neutron diffraction study on chloride ion solvation in water, methanol, and N,N-dimethylformamide}, volume={103}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.470181}, DOI={10.1063/1.470181}, number={18}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Yamagami, Motoyuki and Wakita, Hisanobu and Yamaguchi, Toshio}, year={1995}, month=nov, pages={8174–8178} }