Extraction and separation of heavy rare earth (III) with Extraction Resin containing di(2,4,4-trimethyl pentyl) phosphinic acid (Cyanex 272)

Extraction resins, of the type of;levextrel, (which is a collective term for styrene/divinylbenzene based copolymers of predominantly macroporous structure that contain a selective extractant) are important for the recovery and separation of metal ions, as they combine features of solvent extraction and ion exchange resins. This paper presents the results of the adsorption of heavy rare earth ions (Ho(III), Er(III), Tm(III), Yb(III), Lu(III) and Y(III)) from hydrochloric acid solutions at 0.2 mol/L ionic strength and 50 degrees C by the extraction resin containing di (2,4,4-trimethyl pentyl) phosphinic acid (Cyanex 272) and the chromatographic separation of (Er(III), Tm(III) and Yb(III)). Technological separation products, with purity and yield of Tm2O3 >99.97%, >80%, Er2O3 >99.9%, >94% and Yb2O3 >99.8%, >80% respectively, have been obtained from a feed having the composition Tm2O3 60%, Er2O3 10%, and Yb2O3 3%, the others 27%. The distribution coefficients, extraction equilibrium constants and separation factors have been determined as a function of acidity, loading of the resin and rare earths, flow rates and column ratios. The resolutions and efficiencies of separation of Er/Tm/Yb each other have been calculated. The stoichiometry of the extraction of rare earth ions has been suggested as well.

Luminescence properties of the Langmuir-Blodgett film of terbium(III) stearoylanthranilate

Terbium(III) stearoylanthranilate has been prepared as a high property Z-type Langmuir-Blodgett (LB) film on various substrates by a vertical transfer process. The UV-visible absorption spectra and the low angle X-ray diffraction peaks have been collected in order to investigate the molecular arrangement and aggregation in the LB films. The average molecular orientation in multilayer stacking was determined by Attenuated Total Reflection Spectroscopy. The influence of the chemical environment of terbium within the LB films on the luminescence properties has been discussed. (C) 1997 Elsevier Science S.A.

Ab initio study on the interaction of La (III) with adrenaline

The interaction of La(III) with adrenaline was studied using Ab initio method. The geometry of the complex of La (III) with adrenaline was optimized, and the La(III) bonding site in adrenaline was ascertained.

Investigation on molecular and crystal structures of metal complexes with aminopolycarboxylic acids .1. Synthesis and structure of Na-2[Fe-III(ida)(2)](2)center dot 3H(2)O

The crystal structure of the title complex salt has been determined by single-crystal X-ray structure analysis. The crystal data areas follows; Monoclinic, P2(1)/c, a=15.6480(10)Angstrom, b=16.7870(10)Angstrom, c=10.347(2)Angstrom, beta=90.790(10), V=2717.7(6)Angstrom(3), Z=3, and R=0.0333 for 4789 unique reflections. The complex anion has a pseudo-octahedral structure distorted more than the Cr-III and Co-III analogs, in which each, iminodiacetato ligand (ida(2-)) is coordinated in a facial fashion with the two N atoms in a cis configuration, resulting in an unsym-fac structure.

Studies on synergistic extraction of Sc(III) with HBTMPTP and Cyanex 925

The synergistic extraction of Sc(III) from H2SO4 solution with bis(2, 4, 4-trimethylpentyl)monothiophosphinic acid(HBTMPTP, HL) and branched chain alkyl phosphine oxide mixture (Cyanex 925, B) in n-hexane has been investigated, The results indicated that synergistic effect was showed in low acidity (c(H2SO4) < 0.25 mol/L). The composition of the extracted complex of Sc(III) has been determined to be Sc(HL2)(2)B-3(SO4)(1/2) by the method of slope analysis, The mechanism of the synergistic extraction of Sc(III) may be : Sc3+ + 2(HL)(2(O)) + 3B((O)) + 1/2SO(4)(2-)reversible arrow(K12)Sc(HL2)(2)B-3(SO4)(1/2(O)) + 2H(+) ScL(HL2)(2(O)) + 3B((O)) + H+ + 1/2SO(4)(2-)reversible arrow(beta')Sc(HL2)(2)B-3(SO4)(1/2(O)) + 1/2(HL)(2(O)) Sc(SO4)(1.5)B-2(O) + B-(O) + 2(HL)(2(O))reversible arrow(beta')Sc(HL2)(2)B-3(SO4)(1/2(O)) + 2H(+) + SO42- Their equilibrium constants have been calculated to be lgK(13)=6.77+/-0.12, lg beta'=7.71, lg beta '' = 0.10, respectively, The IR spectra and FAB-MS of the saturated synergistic extraction complex of Sc(III) have been discussed as well.

Crystal structure of a Pr-III complex with a novel macrocyclic ligand

The crystal structure of a novel macrocyclic ligand complex of Pr-III, C112H178O52N8S4Pr2, [Pr2L2(HL)(2)(H2O)(6)]. 22H(2)O is reported. The macrocyclic ligand has pendant acetic acid through which the ligand is coordinated to the Pr-III ion. For the dimeric unit, [Pr2L2(HL)(2)(H2O)(6)], two Pr-III ions are connected by two bridging-chelating carboxyl groups and two bridging carboxyl groups of the ligands, and each Pr-III ion is also bonded to a unidentate carboxyl group of the ligand and three water molecules. The dimeric units are bridged by four ligands through their carboxyl groups to form an infinite one-dimensional chain. The coordination number of the Pr-III ion is nine, with a distorted tricapped trigonal prismatic configuration. (C) 1997 Elsevier Science Ltd.

Studies on synergistic extraction of rare earths(III) with HBTMPTP and primary amine N1923

The synergistic extraction of rare earths(III) with binary systems containing HBTMPTP and primary amine N1923 from sulfuric acid medium was observed, The syner gistic extraction factor(R) decreased with increasing atomic number of lanthanides. Through the methods of slope analysis, constant mole and saturation titration, the synergistic extraction stoichiometry was obtained, The thermodynamic function was calculated, The IR spectra of the saturated synergistic extraction completely confirmed the mechanism.

Kinetics of electrocatalytic ascorbic acid at ultramicroelectrode modified by Eastman-AQ polymer containing tris(2,2-'-bipyridine) osmium(III/II) complexes as electron-transfer centers

The theoretical model[17] of an ultramicroelectrode modified with a redox species film is used as the diagnostic tool to characterize the catalytic oxidation of ascorbic acid at carbon fiber ultramicrodisk electrodes coated with an Eastman-AQ-Os(bpy)(3)(2+) film. The electrocatalytic behavior of ascorbic acid at the ultramicroelectrode modified by an Eastman-AQ polymer containing tris(2,2'-bipyridine) osmium(III/II) as mediators is described. In order to determine the five characteristic currents quantitatively, the radius of the ultramicroelectrode and the concentration of ascorbic acid are varied systematically. The kinetic zone diagram has been used to study the electrocatalytic system. This system with 0.5-2.75 mM ascorbic acid belongs to SR + E case, and the concentration profiles of the catalyst in the film are given in detail. Finally, optimizing the design of catalytic system is discussed.

TETRAKIS(MU-DL-ALANINE-O-O')OCTA-AGUADIERBIUM(III) HEXAPERCHLORATE

The structure of the title compound, [Er-2(C3H7NO2)(4)- (H2O)(8)](ClO4)(6), consists of dimeric [Er-2(DL-alanine)(4)-(H2O)(8)](6+) cations and perchlorate anions. The four alanine molecules act as bridging ligands linking two Er3+ ions through their carboxyl O atoms. Each Er3+ ion is also coordinated by four water molecules to complete eightfold coordination in a square antiprism fashion. The perchlorate anions and the methyl groups of the alanine ligands are disordered.

STUDIES ON THE COORDINATION OF TB(III) AND CA(III) WITH AMINO-ACID UNDER THE PHYSIOLOGICAL CONDITION

Tb(Ca)-glycine, Tb(Ca)-alanine, Tb(Ca)-glycine-alanine systems were studied by potentiometry (37%, I = 0.15 mol/L NaCl). The stability constants of complexes and distribution of species in ternary system were obtained. The results show CaTb for the ternary complexes. The species convert each other with changing pH values.

KINETIC-STUDY OF ELECTROCATALYTIC REDUCTION OF HYDROGEN-PEROXIDE AT IRON(III) PORPHYRIN MODIFIED GLASSY-CARBON ELECTRODE IN ALKALINE-MEDIUM USING THE ROTATION-SCAN METHOD

Reduction of hydrogen peroxide at a glassy carbon (GC) electrode modified with sigma-bonded pyrrole iron(III) octaethylporphyrin complex, (OEP)Fe(Pyr), was studied by cyclic voltammetry and a rotating disk electrode. In 0.1N NaOH solution, it is shown that such an (OEP)Fe(Pyr)/GC electrode has a significant catalytic activity towards hydrogen peroxide reduction (E(D) = -0.80 V, k = 0.066 cm s(-1)); however, the electrode stability is low. The deactivation is observed when the reaction charge (Q) is passing through the (OEP)Fe(Pyr)/GC disk electrode. A linear rotation scan method is applied to study the kinetic process by determining the disk electrochemical response (i(D)) to rotation rate (omega) at a definite disk potential (E(D)). Considering that the number of adsorbed electroreduced catalyst molecules (Red) varies according to the disk potential, a factor theta(= Gamma(Red)/(Gamma(Red) + Gamma(Ox))) is introduced to describe the electrode surface area fraction for electroreduced species. The obtained Koutecky-Levich equation is applicable whatever the potential is.

IN-SITU SCANNING-TUNNELING-MICROSCOPY IMAGE OF A HIGHLY ORIENTED PYROLYTIC-GRAPHITE ELECTRODE MODIFIED WITH POTASSIUM BIS(11-MOLYBDOSILICATO) DYSPROSATE(III) IN SODIUM-SULFATE SOLUTION

The variation in molecule adsorption mode on pretreated highly oriented pyrolytic graphite electrodes, modified with the title complex K10H3[Dy(SiMo11O39)(2)] by cyclic voltammetry in the title complex solution, was observed in situ by electrochemical scanning tunnelling microscopy (ECSTM) with molecular resolution in sodium sulphate solution. According to the ECSTM images and the known molecular structure we conclude that the adsorption mode of the title complex modified electrode changed during potential cycling from ''vertical'' to ''inclined'' and then ''horizontal'' or ''flat'' mode, i.e. the title complex adsorbed on the surface of electrode by one ligand of the complex at first, then began to incline and was finally adsorbed by two ligands of the complex. This result indicates that the adsorption mode on the modified electrode surface changed during potential cycling in the sulphate solution and a much more stable molecular layer was formed. The change in adlattice of adsorbates on the modified electrode surface from hexagonal to rectangular was also observed by ECSTM. A plausible model was given to explain this process.

COMPARATIVE-STUDIES ON PERIODATOCUPRATE(II, III) AND TELLURATOCUPRATE(II, III)

The crystal structures, electronic spectra, and Cu2p XPS of Cu(III) complexes Na4H[Cu(H2TeO6)(2)]. 17H(2)O and Na4K[Cu(HlO(6))(2)]. 12H(2)O have been described. The characterizations of a Cu(III) atom in a complex are as follows: (i) In a square-planar coordination, the average bond length of Cu-O is 0.183 nm, shorter than the 0.190-0.200 nm found for a Cu(II) complex. (2) The ''blue shift'' occurs for d-d transitions in the electronic spectrum of the Cu(III) complex compared to those of its related Cu(II) complex, resulting from the higher valence state. (3) Cu(III) compounds with CuO4 square-planar coordination are expected to be diamagnetic whereas Cu(II) compounds to be paramagnetic. (4) Comprehensive investigations on Cu2p XPS show that the binding energy of Cu2p(3/2) of a pure Cu(III) compound is about 2.0 eV higher than that of its corresponding Cu(II) compound: the shake-up satellites do not appear in the Cu2p XPS for a pure diamagnetic Cu(III) compound, the same as found for a diamagnetic Ni(II) compound: the FWHM of the signal of Cu2p XPS may become broader for Cu(III) compound because its core hole's lifetime shortens due to the higher valence state of copper. (C) 1995 Academic Press, Inc.