Aqueous uranium complexes. 2. Raman spectroscopic study of the complex formation of the dioxouranium(VI) ion with a variety of inorganic and organic ligands
- Oak Ridge National Lab., TN (United States)
The Raman spectra of the aqueous dioxouranium(VI) ion have been measured as a function of ligand and uranyl concentrations at various constant pH values. The ligands investigated were F[sup [minus]], Cl[sup [minus]], Br[sup [minus]], SO[sub 4][sup 2[minus]], HSO[sub 4][sup [minus]], NO[sub 3][sup [minus]], ClO[sub 4][sup [minus]], CH[sub 3]CO[sub 2][sup [minus]], and C[sub 2]O[sub 4][sup 2[minus]]. A linear correlation between the frequency of the O=U=O symmetrical stretching vibration ([nu][sub 1], cm[sup [minus]1]) and the average number [bar n] of ligand coordinated equatorially to the central uranium atom in the given species has been established for the above-mentioned ligands according to the following equation: [nu][sub 1] (cm[sup [minus]1]) = -A[bar n] + 870, where A is a characteristic coefficient (cm[sup [minus]1]) representing the shift in the [nu][sub 1] band for the addition of each ligand to the uranyl(VI) center relative to 870 cm[sup [minus]1] for UO[sub 2][sup 2+](aq). Except for the case of ClO[sub 4][sup [minus]] (A = -15 cm[sup [minus]1]), the values of A are positive and vary in the range 0-15. The preceding equation was derived earlier for OH[sup [minus]] anions with A = 21.5 [+-] 1.0 cm[sup [minus]1]. Results obtained elsewhere for CO[sub 3][sup 2[minus]] also fit this equation with A = 19.0 [+-] 1.0 cm[sup [minus]1]. This linear correlation provides a convenient, nondestructive method of identifying the possible stoichiometry of uranyl(VI) complexes in solution and a means for estimating their stability fields with respect to ligand concentration and pH.
- DOE Contract Number:
- AC05-84OR21400
- OSTI ID:
- 6837031
- Journal Information:
- Inorganic Chemistry; (United States), Vol. 31:25; ISSN 0020-1669
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
URANYL COMPLEXES
RAMAN SPECTROSCOPY
STOICHIOMETRY
ACETATES
ACID SULFATES
ANIONS
AQUEOUS SOLUTIONS
BROMIDES
LIGANDS
OXALATES
PH VALUE
QUANTITY RATIO
STABILITY
URANYL CHLORIDES
URANYL FLUORIDES
URANYL NITRATES
URANYL PERCHLORATES
URANYL SULFATES
ACTINIDE COMPLEXES
ACTINIDE COMPOUNDS
BROMINE COMPOUNDS
CARBOXYLIC ACID SALTS
CHARGED PARTICLES
CHLORIDES
CHLORINE COMPOUNDS
COMPLEXES
DISPERSIONS
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
IONS
LASER SPECTROSCOPY
MIXTURES
NITRATES
NITROGEN COMPOUNDS
OXYGEN COMPOUNDS
PERCHLORATES
SOLUTIONS
SPECTROSCOPY
SULFATES
SULFUR COMPOUNDS
URANIUM COMPLEXES
URANIUM COMPOUNDS
URANYL COMPOUNDS
400102* - Chemical & Spectral Procedures
400201 - Chemical & Physicochemical Properties