Raman spectroscopy of neptunyl and plutonyl ions in aqueous solution: hydrolysis of Np(VI) and Pu(VI) and disproportionation of Pu(V). [Vibrational spectra of neptunyl ions and plutonyl ions]

Journal Article · Wed Jun 20 04:00:00 EDT 1984 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00181a025· OSTI ID:6138479

Madic, C; Begun, G M; Hobart, D E; Hahn, R L

Raman spectra of plutonyl(VI) and neptunyl(VI) ions have been measured as a function of pH in complexing aqueous solutions (ClO/sub 4//sup -/ and Cl/sup -/ (..mu.. = 1.0 for Pu(VI)) and NO/sub 3//sup -/ (..mu.. = 1.0 for Np(VI)). The symmetrical stretching vibration, nu/sub 1/, was found, for Pu(VI), to consist of four bands at 833, 817, 826, and 805 cm/sup -1/ and, for Np(VI), of two bands at 854 and 834 cm/sup -1/. These bands have been identified as vibrational transitions for PuO/sub 2//sup 2 +/ (833 cm/sup -1/), (PuO/sub 2/)/sub 2/(OH)/sub 2//sup 2 +/ (817 cm/sup -1/), (PuO/sub 2/)/sub 4/(OH)/sub 7//sup +/ (826, 805 cm/sup -1/), NpO/sub 2//sup 2 +/ (854 cm/sup -1/), and (NpO/sub 2/)/sub 2/(OH/sub 2/)/sup 2 +/ (834 cm/sup -1/). For high values of pH (13-14), a new Pu(VI) band was found at 794 cm/sup -1/, which exhibited a moderate resonance Raman effect. A plutonyl(V) solution, PuO/sub 2//sup +/, was prepared by electrochemical reduction of PuO/sub 2//sup 2 +/. The Raman spectrum of Pu(V) showed a band at 748 cm/sup -1/, assigned to the symmetrical stretching vibration, nu/sub 1/, of PuO/sub 2//sup +/. Evidence for the disproportionation of PuO/sub 2//sup +/ as a function of time was obtained from Raman spectrometry by observing the decrease of the intensity of the 748-cm/sup -1/ PuO/sub 2//sup +/ band and the increase of bands located at 833 and 817 cm/sup -1/ belonging to PuO/sub 2//sup 2 +/ and (PuO/sub 2/)/sub 2/(OH)/sub 2//sup 2 +/, respectively. 41 references, 13 figures, 3 tables.

• Research Organization: Oak Ridge National Lab., TN
• DOE Contract Number: W-7405-ENG-26
• OSTI ID: 6138479
• Journal Information: Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 23:13; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400702* -- Radiochemistry & Nuclear Chemistry-- Properties of Radioactive Materials
ACTINIDE COMPLEXES
AQUEOUS SOLUTIONS
CATIONS
CHARGED PARTICLES
CHEMICAL REACTIONS
CHEMISTRY
CHLORIDES
CHLORINE COMPOUNDS
COMPLEXES
DATA
DATA ANALYSIS
DECOMPOSITION
DISPERSIONS
ELECTROCHEMISTRY
ELECTROMAGNETIC RADIATION
ENERGY LEVELS
ENERGY-LEVEL TRANSITIONS
EXCITATION
EXCITED STATES
EXPERIMENTAL DATA
HALIDES
HALOGEN COMPOUNDS
HYDROLYSIS
INFORMATION
IONS
LASER RADIATION
LASER SPECTROSCOPY
LYSIS
MIXTURES
NEPTUNIUM COMPLEXES
NEPTUNYL COMPLEXES
NITRATES
NITROGEN COMPOUNDS
NUMERICAL DATA
OXYGEN COMPOUNDS
PERCHLORATES
PH VALUE
PLUTONIUM COMPLEXES
PLUTONYL COMPLEXES
POTENTIOMETRY
RADIATIONS
RAMAN EFFECT
RAMAN SPECTROSCOPY
REDUCTION
SOLUTIONS
SOLVOLYSIS
SPECTROSCOPY
STRUCTURAL CHEMICAL ANALYSIS
TIME DEPENDENCE
TITRATION
TRANSURANIUM COMPLEXES
VIBRATIONAL STATES