Aqueous uranium complexes. 2. Raman spectroscopic study of the complex formation of the dioxouranium(VI) ion with a variety of inorganic and organic ligands

Journal Article · Wed Dec 09 04:00:00 EST 1992 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00051a021· OSTI ID:6837031

Nguyen-Trung, C; Begun, G M; Palmer, D A ^[1]

---

1. 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), Journal Name: Inorganic Chemistry; (United States) Vol. 31:25; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102* -- Chemical & Spectral Procedures
400201 -- Chemical & Physicochemical Properties
ACETATES
ACID SULFATES
ACTINIDE COMPLEXES
ACTINIDE COMPOUNDS
ANIONS
AQUEOUS SOLUTIONS
BROMIDES
BROMINE COMPOUNDS
CARBOXYLIC ACID SALTS
CHARGED PARTICLES
CHLORIDES
CHLORINE COMPOUNDS
COMPLEXES
DISPERSIONS
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
IONS
LASER SPECTROSCOPY
LIGANDS
MIXTURES
NITRATES
NITROGEN COMPOUNDS
OXALATES
OXYGEN COMPOUNDS
PERCHLORATES
PH VALUE
QUANTITY RATIO
RAMAN SPECTROSCOPY
SOLUTIONS
SPECTROSCOPY
STABILITY
STOICHIOMETRY
SULFATES
SULFUR COMPOUNDS
URANIUM COMPLEXES
URANIUM COMPOUNDS
URANYL CHLORIDES
URANYL COMPLEXES
URANYL COMPOUNDS
URANYL FLUORIDES
URANYL NITRATES
URANYL PERCHLORATES
URANYL SULFATES