Adsorption of europium(III) and americium(III) on kaolinite and montmorillonite in the presence of humic acid

Distribution of trace amount of Eu(III), or Am(III), in the aqueous/solid system containing humic acid and kaolinite, or montmorillonite, was studied by batch experiments. Humic acid was also adsorbed on the clay minerals and its adsorption isotherm can be regarded as a Langmuir type. It is shown that Eu(III), or Am(III), exists as humate complex either in the aqueous or on solid phase in the system including kaolinite, or montmorillonite. These results suggest that the organic-inorganic complex like clay minerals coated with humic substances is important as metal reservoir in the environment.     

Interaction of humic acid with plutonium/III/

The stability constants of the complex of Pu/III/ with a humic acid at pH 2.9 and 5.0 were measured using solvent-extraction technique. The organic extractant was dinonyl naphthalene sulphonic acid in sodium form /NaD/ in benzene while the humate aqueous phase had a constant ionic strength of 0.5M /NaClO₄/. The total carboxylate capacity of the humic acid was determined by direct potentiometric titration to be 6.201 Meq g^–1. The apparent pKa increased as the degree of ionization // increased. The 1g ₁ values of the complex of Pu/III/ with humic acid have been determined to be 2.8 and 3.11 at pH 2.9 and 5.0, respectively.     

Spectrophotometric determination of plutonium III, IV, and VI concentrations in nitric acid solution

The determination of the concentration of various valency states of plutonium is desirable in various stages of the Plutonium/Uranium Recovery by EXtraction (PUREX) process for the effective separation and purification of plutonium. A method is optimized for the quantitative spectrophotometric determination of Pu(III), Pu(IV) and Pu(VI) existing separately or in mixed oxidation states in 1.5?M nitric acid medium. Molar absorption co-efficient (??) for the major absorption peaks with baseline correction are evaluated. With these ?? data a method is proposed for determining the molar concentration of each oxidation state.     

Influence ofpH and concentration of complexing agents on fluorescence of europium (III) ethylenediaminetetraacetic acid and europium (III) nitrilotriacetic acid complexes in aqueous solutions

The fluorescence of aqueous solutions of Eu(III) complexes withEDTA andNTA has been investigated. Intensities of the fluorescence bands have been measured as a function of complexone concentrations in the solutions and thepH. The results are interpreted in terms of the different forms of Eu(III) complexes and their relative stabilities.

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Einfluß vonpH und Konzentration der Komplexbildner auf die Fluoreszenz der Komplexe des Europium (III) mit Ethylendiamintetraessigsäure und Nitrilotriessigsäure in wäßrigen Lösungen

Zusammenfassung Die Fluoreszenz von wäßrigen Lösungen der Komplexe des Europium(III) mit Ethylendiamintetraessigsäure und Nitrilotriessigsäure wurde untersucht. Die Intensitäten der Fluoreszenzbanden in Abhängigkeit vonpH und Konzentration der Komplexbildner wurden auf der Basis vorkommender Komplexgeometrien und deren Stabilitäten interpretiert.

     

Fluorescent properties of europium(III) complexes with polyacrylic acid containing graftedo-phenanthroline groups

Fluorescent properties of Eu^III complexes with polyacrylic acid containing graftedo-phenanthroline groups were studied. The presence ofo-phenanthroline groups (2%) in the macromolecular ligand provides a 2- to 3-fold increase in the fluorescence intensity as compared to that for Eu^III polyacrylates. The effect of concentration quenching of fluorescence, which is observed as the temperature decreases from 300 to 77 K, is explained by the shortening of the average Eu-Eu distances and by the increase in the efficiency of energy redistribution in the complex. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2253–2255, December, 1997.     

Selective extraction of plutonium(IV) over uranium(VI), americium(III), europium(III) and zirconium(IV) with bidentate O-phenoxydiamide ligands: experimental and theoretical study

To rapidly assess the contamination of actinides in emergency water, a method was developed to simultaneously analyze U, Th, Pu and Am. The method consists of two steps: extraction chromatographic separation using UTEVA and DGA resins and isotopic determination of actinides by inductively coupled plasma mass spectrometry (ICPMS). The whole analytical procedure takes only 8 h and high chemical recoveries of actinides were obtained. The cross spectral interferences between actinides in ICPMS measurement were sufficiently removed. The accuracy was validated by analyzing IAEA-443 seawater sample. The low limits of detection of actinides allow this method to distinguish low level contamination.     

Syntheses and structures of strontium, barium, and europium bis(diphosphanylamido) complexes

Bis(diphosphanylamido) complexes of strontium and europium, [{(Ph(2)P)(2)N}(2)M(THF)(3)] (M = Sr (1), Eu (2)), have been prepared by reaction of [K(THF)(n)()][N(PPh(2))(2)] (n = 1.25, 1.5) and MI(2). The single-crystal X-ray structures of compounds 1 and 2 always show a eta(2) coordination of the ligand via the nitrogen and one phosphorus atom. In solution, a dynamic behavior of the ligand is observed, which is caused by the rapid exchange of the two different phosphorus atoms. As a result of the radius of the larger ion, treatment of [K(THF)(n)()][N(PPh(2))(2)] with BaI(2) gives the coordination polymer [{(Ph(2)P)(2)N}(2)Ba(THF){(Ph(2)P)(2)N}K](n)() (3). Two of the three {(Ph(2)P)(2)N}(-) ligands of compound 3 bind to the metal in eta(2) (N, P) while the third shows a heteroallylic (P, P) coordination mode. In the solid state, the infinite chain is formally held together by pi coordination of the phenyl rings to the potassium atoms.     

Synthesis and luminescent properties of europium(III) and Terbium(III) complexes with acylated derivatives of 2-aminobenzoic acid

The optimal conditions for complex formation in solutions and synthesis of solid Eu(III) and Tb(III) complexes with acylated derivatives of aminobenzoic acid have been determined. The character and degree of effect of organic solvents, additional ligands, and surfactants on the complex photoluminescence intensity have been established.     

pH-sensitive fluorescent sensors based on europium(III) complexes

New europium(III) complexes Eu(TTA)(2)-DSQ and Eu(TTA)(3)-DR1 were designed and synthesized as new fluorescent pH probes (where HDSQ = 5-(dimethylamino)-N-(4-(2-((8-hydroxyquinolin-2-yl)methylene)hydrazinecarbonyl)phenyl)naphthalene-1-sulfonamide, DR1 = N(1)-(4-(dimethylamino)benzylidene)-N(2)-(rhodamine-6G) lactamethylene-diamine and TTA = thiophentrifluoroacetone). Eu(TTA)(2)-DSQ exhibited high sensitivity in monitoring pH changes in neutral aqueous solution with negligible background fluorescence. Eu(TTA)(3)-DR1 comprised a green light emitting Rhodamine 6G fluorophore and a Eu(III) moiety as the origin of red light. These pH-sensitive emitter components have pK(a) values of 5.0 and 7.2 respectively, and exhibit isolated protonated steps within one molecule. Luminescence titrations demonstrate that Eu(TTA)(3)-DR1 was able to detect pH values at both near neutral pH and acidic pH ranges, and was also able to detect pH in both cultured cells and in vivo.     

Studies on the adsorption of plutonium (IV) on alumina from phosphoric acid-nitric acid solution

Results of experiments on the adsorption of plutonium (IV) on alumina and their application to the recovery of plutonium from analytical waste solutions containing phosphoric-nitric acid are reported. Distribution ratios of plutonium (IV) between alumina and solutions containing varying concentrations of phosphoric acid and nitric acid are determined. The influence of various ions like UO₂ ²⁺, Fe³⁺, MoO₄ ^2–, VO²⁺ and SO₄ ^2– on the distribution ratio is evaluated. Saturation values of adsorption of plutonium (IV) on alumina and optimum conditions for loading and elution of plutonium on a column packed with alumina are described.     

Luminescent properties of europium(III) and terbium(III) complexes with para- and ortho-ethoxybenzoic acids

The luminescent properties of europium(III) and terbium(III) complexes with para- and ortho-ethoxybenzoic acids are studied. The excitation energies of the triplet states of ligands are determined, a hypothesis is made about the efficient luminescence of europium(III) and terbium(III) complexes, the geometry of the coordination polyhedron of a europium complex is established, and the luminescence quantum yields of the complexes in solution are determined.     

Solvent extraction studies on the recovery of plutonium(IV) from phosphoric acid solution using monooctylphenylphosphoric acid

Extraction of plutonium from analytical waste solutions containing phosphoric acid using a solution of monooctylphenylphosphoric acid (MOPPA) is described. Effect of reagent concentration, presence of uranium, plutonium loading and back extraction of plutonium from the organic phase are described. Using a solution of 0.05 F MOPPA in xylene, more than 90% plutonium could be extracted in one cycle.     

Aqueous complexation of thorium(IV), uranium(IV), neptunium(IV), plutonium(III/IV), and cerium(III/IV) with DTPA

Aqueous complexation of Th(IV), U(IV), Np(IV), Pu(III/IV), and Ce(III/IV) with DTPA was studied by potentiometry, absorption spectrophotometry, and cyclic voltammetry at 1 M ionic strength and 25 °C. The stability constants for the 1:1 complex of each trivalent and tetravalent metal were calculated. From the potentiometric data, we report stability constant values for Ce(III)DTPA, Ce(III)HDTPA, and Th(IV)DTPA of log β(101) = 20.01 ± 0.02, log β(111) = 22.0 ± 0.2, and log β(101) = 29.6 ± 1, respectively. From the absorption spectrophotometry data, we report stability constant values for U(IV)DTPA, Np(IV)DTPA, and Pu(IV)DTPA of log β(101) = 31.8 ± 0.1, 32.3 ± 0.1, and 33.67 ± 0.02, respectively. From the cyclic voltammetry data, we report stability constant values for Ce(IV) and Pu(III) of log β(101) = 34.04 ± 0.04 and 20.58 ± 0.04, respectively. The values obtained in this work are compared and discussed with respect to the ionic radius of each cationic metal.     

Studies on synthesis, infrared and fluorescence spectra of new europium (III) and terbium (III) complexes with an beta-diketonate-type ligand

A new beta-diketonate-type ligand, N-(2-amino-6-methyl-pyridinyl)ketoacetamide (L) and its complexes with europium (III) and terbium (III) were synthesized. The complexes were characterized by elemental analysis, infrared spectra and conductivity. The europium (III) and terbium (III)-ions were found to coordinate to the CO oxygen atoms and pyridine nitrogen atoms. The fluorescence properties of these complexes in solid, DMF and CH3OH were studied. The solvent factors influencing the fluorescent intensity are discussed.     

Comparative spectroscopic and electrochemical properties of bis(octakis(dodecylthio)naphthalocyaninato)europium(III) and bis(tetra-tert-butylnaphthalocyaninato)europium(III) complexes

Bis(substituted-2,3-naphthalocyaninato)europium(III) complexes: bis(octakis(dodecylthio)-2,3-naphthalocyaninato)europium(III) (Eu[2,3-Nc(SC12H25)8]2, 1) and bis(tetra-tert-butyl-2,3- naphthalocyaninato)europium(III) (Eu[2,3-Nc(t-Bu)4]2, 2) have been synthesized by cyclic tetramerization of naphthalonitriles with Eu(acac)3.H2O in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in refluxing n-octanol. These compounds were characterized by UV-visible, magnetic circular dichroism (MCD), near-IR, IR, EPR, and mass spectroscopies. The absorption and MCD spectra of 1 showed splitting of the Q band, with peaks at 700 and 784 nm, red shifted from the Q band of 2 at 763 nm. The absorption and MCD spectral band deconvolution calculations of complex 1 gave two A terms in the Q-band region. The A terms are assigned to 2A2-->2E1 transitions. Cyclic voltammograms of 1 and 2 showed reversible oxidation couples at E1/2 = -0.28 V (for 2) and -0.25 V (for 1) vs ferrocenium/ferrocene (Fc+/Fc). The second oxidation exhibited a complicated behavior for both complexes. The reduction couples for 2 were observed at E1/2 = -0.61, -1.64, -1.97, and -2.42 V, and for 1 they were observed at E1/2 = -0.62, -1.60, -1.86, and -2.27 V vs Fc+/Fc. Spectral changes observed on chemical oxidation and reduction of the complexes are presented, and the behaviors of 1 and 2 are compared.     

Stability of plutonium(IV) and plutonium(VI) in nitric acid solutions under strong α-irradiation

Plutonium(IV) oxidation has been studied in 1 to 20 mol/1 HNO₃ under 1 to 14 W/1 internal alpha-irradiation and at plutonium concentrations from 2 to 100 mmol/1. Curium isotopes have been used as the basic alpha-irradiation sources. It has been established that in the systems investigated both oxidation of plutonium(IV) and reduction of plutonium(VI) take place, resulting with time in reaching the equilibrium between plutonium(IV) and plutonium(VI). The presence of plutonium(IV) enhances the reduction of plutonium(VI). The rate constants for plutonium(IV) oxidation and plutonium(VI) reduction have been estimated and their dependences upon the concentrations of nitric acid, plutonium(IV) and plutonium(VI) as well as upon the dose rate investigated. An equation has been derived which permits to calculate the concentrations of plutonium(IV) and plutonium(VI) at any desired time.     

Photochemical behavior of luminescent compositions based on antimony(III) and europium(III) complexes in high-pressure polyethylene

Luminescent and photochemical properties of polymer compositions based on the Eu(NO₃)₃(Phen)₂ complex and complexes of antimony(III) halides with diphenylguanidine are investigated. It is found that high-pressure polyethylene (HPPE) containing europium(III) and antimony(III) complexes in combination exhibits efficient transfer of electronic excitation energy from antimony(III) levels to europium(III) levels and photosensitization of europium(III) luminescence. It is shown that the europium(III) and antimony(III) complexes increase the stability of HPPE to UV radiation.