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Ion association and hydration in aqueous solutions of LiCl and Li 2so4 by dielectric spectroscopy

Wachter, W., Fernandez, Š., Buchner, R. and Hefter, G. (2007) Ion association and hydration in aqueous solutions of LiCl and Li 2so4 by dielectric spectroscopy. Journal of Physical Chemistry B, 111 (30). pp. 9010-9017.

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A systematic study of the dielectric relaxation spectra of aqueous solutions of LiCl and Li2SO4 has been made at solute concentrations of 0.05 ≤ c/M ≤ 1.0 and 2.0, respectively, and over a wide range of frequencies (0.2 ≤ v/GHz ≤ 89) at 25°C. The spectra were best described by a superposition of four Debye processes, consisting of the two well-known water relaxations at ca. 8 and 0.5 ps and two ion-pair contributions at ca. 200 and 20 ps, corresponding to the presence of double-solvent-separated (2SIP) and solvent-shared (SIP) ion pairs, respectively. Consistent with spectroscopic studies, no contact ion pairs were detected over the studied concentration range. The overall ion association constants KAo obtained were in good agreement with literature data for both salts. Detailed analysis of the solvent relaxations indicated that Li + has a significant second solvation sheath although there were differences between the effective hydration numbers obtained from LiCl and Li2SO4, which might arise from competition for the solvent from the anions.

Item Type: Journal Article
Murdoch Affiliation(s): School of Chemical and Mathematical Science
Publisher: American Chemical Society
Copyright: © 2007 American Chemical Society.
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