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Dielectric relaxation of concentrated alkaline aluminate solutions
Journal article   Peer reviewed

Dielectric relaxation of concentrated alkaline aluminate solutions

R. Buchner, P. Sipos, G. Hefter and P.M. May
Journal of Physical Chemistry A, Vol.106(28), pp.6527-6532
2002
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Abstract

The complex dielectric permittivity of concentrated aqueous alkaline aluminate solutions at total concentrations 1 ≲ [Al]T/mol dm-3 ≲ 6 with either [Na]T = 8.33 mol dm-3 or [Al]T/[Na]T = 0.750 has been determined at 25 °C in the frequency range 0.5 ≲ ν/GHz ≤ 20. All solution spectra could be represented as a superposition of a Cole-Cole relaxation-time distribution for the solvent relaxation with an additional low-frequency Debye dispersion assigned to the solute. The variation of the effective hydration number, deduced from the water dispersion amplitude, shows that the aluminate ion, Al(OH)4-, is less strongly solvated than the hydroxide ion, OH-. Additionally, a "melting" of the hydration shells is observed at high concentration, probably due to co-sphere overlap and/or packing effects. The features of the solute relaxation are consistent with solvent-shared ion pairs of Na+ with a previously proposed dimeric anion, [(HO)3Al-O-Al(OH)3]2-. However, the data are not sufficient for an unequivocal assignment.

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