Hydration and ion pairing in aqueous sodium oxalate solutions

R. Buchner; F. Samani; P.M. May; P. Sturm; G. Hefter

doi:10.1002/cphc.200390064

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Hydration and ion pairing in aqueous sodium oxalate solutions

Journal article

Peer reviewed

Hydration and ion pairing in aqueous sodium oxalate solutions

R. Buchner, F. Samani, P.M. May, P. Sturm and G. Hefter

ChemPhysChem, Vol.4(4), pp.373-378

2003

DOI: https://doi.org/10.1002/cphc.200390064

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Abstract

Dielectric spectra have been measured for aqueous sodium oxalate solutions up to the saturation concentration (0.04≤ c[mmol L-1] ≤0.25) at 25°C over the approximate frequency range 0.2 ≤ ν [GHz] ≤20. The spectra exhibit a process at about 1 GHz associated with the presence of ion pairs, in addition to the dominant solvent relaxation process at about 18 GHz. Detailed analysis of the solvent dispersion amplitude indicates that the oxalate ion is highly hydrated but that its solvation sheath is "fragile", decreasing quickly with increasing solute concentration. The NaOx(aq)- ion pair is shown to be of the double-solvent-separated (251P) type, with an infinite dilution association constant KA = 1.04 ± 0.02. Analysis of the ion-pair relaxation time as a function of solute concentration gave rate constants for the formation (k12 = (.7.3 ± 0.4)109 L mol-1 s-1) and dissociation (k21 = (6.7 ± 0.5)108 s-1) of the ion pair. These values are reasonably close to the diffusion-controlled values predicted by the Eigen theory, consistent with a2SIP structure for the ion pair.

Details

Title: Hydration and ion pairing in aqueous sodium oxalate solutions
Authors/Creators: R. Buchner (Author/Creator) - Murdoch University
F. Samani (Author/Creator) - Murdoch University
P.M. May (Author/Creator) - Murdoch University
P. Sturm (Author/Creator) - University of Regensburg
G. Hefter (Author/Creator) - Murdoch University
Publication Details: ChemPhysChem, Vol.4(4), pp.373-378
Publisher: John Wiley & Sons Ltd.
Identifiers: 991005544817607891
Murdoch Affiliation: School of Chemical and Mathematical Science
Language: English
Resource Type: Journal article

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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; Physics, Atomic, Molecular & Chemical
ESI research areas: Chemistry