RATE OF WATER EXCHANGE BETWEEN AL(C2O4) (H2O)+4 (AQ) COMPLEXES AND AQUEOUS SOLUTIONS DETERMINED BY 17O-NMR SPECTROSCOPY
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dc.contributor.author | Phillips B.L. | |
dc.contributor.author | Neugebauer Crawford S. | |
dc.contributor.author | Casey W.H. | |
dc.date.accessioned | 2020-12-17T04:15:19Z | |
dc.date.available | 2020-12-17T04:15:19Z | |
dc.date.issued | 1997 | |
dc.identifier | https://elibrary.ru/item.asp?id=275057 | |
dc.identifier.citation | Geochimica et Cosmochimica Acta, 1997, , 23, 4965-4973 | |
dc.identifier.issn | 0016-7037 | |
dc.identifier.uri | https://repository.geologyscience.ru/handle/123456789/20984 | |
dc.description.abstract | Substitution of an oxalate molecule for two inner-coordination-sphere waters of Al(H2O)3+6 (aq) enhances, by a factor of ~ 102, the rate of exchange of water molecules from the inner-coordination sphere to the bulk solution. The rate parameters for chemical exchange are: k298ex = 109 s-1, ΔH\PG = 68.9 +/- 2.4 kJ/mol, and ΔS\PG = 25.3 +/- 6.7 J/mol/K, measured via dynamic 17O-NMR. This reactivity enhancement of coordinated waters by oxalate results from a change in bonding between Al(III) and oxygens throughout the complex upon ligation by oxalate. A similar process has been proposed to explain ligand-enhanced dissolution of oxide minerals (e.g., Stumm, 1991; Casey and Ludwig, 1995; Phillips et al., 1997) where a stable adsorbate increases the flux of metals from a surface. These new rate coefficients for aluminum-oxalate complexes, along with previous work on aluminum-fluoride complexes, show a correlation with the respective equilibrium constants similar to that obtained by Ludwig et al. (1995, 1996). | |
dc.title | RATE OF WATER EXCHANGE BETWEEN AL(C2O4) (H2O)+4 (AQ) COMPLEXES AND AQUEOUS SOLUTIONS DETERMINED BY 17O-NMR SPECTROSCOPY | |
dc.type | Статья |
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