Conversion of Tantalum(V), Niobium(V), and Titanuim(IV) Sulfates and Chlorides to Their Fluorides

A process was developed for converting tantalum(V), niobium(V), and titanium(IV) sulfate and chloride to their fluorides in order to improve separation of these elements.     

Processing of Precipitates of Hydrated Tantalum(V), Niobium(V), and Titanium(IV) Oxides in Loparite Technology

Conditions were studied for the dissolution in HF of hydrated tantalum(V), niobium(V), and titanium(IV) oxides, which are formed by acid decomposition of loparite, and also for the selective extraction of Ta(V) with octanol from the resulting fluotitanic solutions.     

Studies on Simultaneous Fluorescence-Spectrophotometric Determination of Ultratrace Niobium(V), Tantalum(V), and Zirconium(IV) Using Partial Least-Squares Algorithm

In the presence of cetyltrimethylammonium bromide, a cationic surfactant, highly sensitive molecular fluorescence reactions occur between Nb(V), Ta(V), and Zr(IV) ions and morin (3, 5, 7, 2′, 4′-pentahydroxyflavone) in acidic medium to form stable ternary micellar complexes. Their λ_ex(max)/λ_em(max)values are 421.0/492.2, 416.2/489.6, and 424.2/507.8 nm, respectively, and their λ_em(max)values are 490.5, 488.6, and 507.2 nm, respectively, at the same fixed λ_exof 420.5 nm, indicating their seriously overlapping fluorescence excitation spectra and fluorescence emission spectra. The linear ranges of their regression calibration curves are 0 to 0.20, 0 to 0.50, and 0 to 0.20 mg/liter, respectively, with 0.5 ng/ml for all of sensitivities. The simultaneous molecular fluorescence-spectrophotometric determination of ultratrace or trace Nb(V), Ta(V), and Zr(IV) without separation was made using a partial least-squares (PLS) algorithm and other algorithms. The optimum PLS computation conditions are wavelength point number of 25 and corresponding wavelength range from 450 to 550 nm oriented from λ_em500 nm to two sides at combined intervals of 2.5 and 5.0 nm at a fixed λ_exof 420.5 nm with an optimum calibration sample number of 14 and respective optimum abstracted factor numbers of 6, 4, and 3. With respect to both accuracy and precision of the obtained results, the PLS algorithm is superior to the ordinary least-squares algorithm.     

Electron Transfer Spectra of Some Adducts of Niobium (V), Tantalum (V), Titanium (IV) and Zirconium (IV) Halides with Lewis Bases

The electron transfer spectra of adducts of the title metal halides with a series of ligands (nitriles, dialkylchalcogenides, phosphoryl and thiophosphoryl ligands and phosphines) have been studied. The effect of halogen substitution on the halogen metal transitions is discussed by comparing the spectra of the adducts with those of the hexahalometalates. The origin of the two ligand-metal transitions observed in most adducts is discussed, and the splitting of the metal d levels in these almost octahedral adducts is estimated. For each metal halide, the series of adducts with dialkyl chalcogenides show a linear relationship of slope one between the ligand ionisation potential and the ligand-metal charge transfer energy. The ligand optical electronegativities have been estimated.     

Pseudo-Halide Complexes of Biscyclopentadienyl Niobium(IV) and Bisindenyl Niobium(IV) Dichloride

Reactions of biscyclopentadienyl niobium(IV) dichloride and bisindenyl niobium(IV) dichloride with sodium or potassium salts of various pseudohalides have been studied and the pseudohalide complexes so formed of the formulae (C₅H₅)₂Nb(Ps)₂ and (C₂H₇)₂Nb(Ps)₂ where Ps may be NC, NCO, NCS, or N₃, have been isolated. The complexes have been characterised on the basis of physical measurements, analytical data and infrared spectral studies.     

Nb(x)()Ru(6)(-)(x)()Te(8), New Chevrel-Type Clusters Containing Niobium and Ruthenium(,)

Phases of composition Nb(x)()Ru(6)(-)(x)()Te(8) were prepared by reacting stoichiometric mixtures of the elements at high temperature in evacuated silica ampules. The structure of Nb(3.33)Ru(2.67)Te(8) was refined from X-ray powder data using the Rietveld method. Nb(3.33)Ru(2.67)Te(8) crystallizes isotypic with Mo(6)Q(8) (Q = S, Se, Te) in the rhombohedral space group R&thremacr; with the hexagonal lattice parameters a = 10.34106(5) ?, c = 11.47953(7) ?, and Z = 3. Its structure consists of M(6)Te(8) mixed-metal clusters (M = Nb, Ru) which are connected by intercluster M-Te bonds to form a three-dimensional network. Metal-metal bonding in these phases is analyzed in terms of Pauling bond orders and found to be weaker compared to that in related cluster compounds. Nb(x)()Ru(6)(-)(x)()Te(8) are the first representatives of Chevrel-type cluster phases with complete substitution of Mo by other metals. The chemical perspectives arising from this substitution are discussed.     

The Constitution of Niobium(IV) Chloride Vapour

Die Konstitution des Niob(IV)-chlorid-Dampfes Durch Vergleich der Diffusionskoeffizienten der Gaspaare NbCl₄/NbCl₅ und ZrCl₄/NbCl₅ ergibt sich, daß NbCl₄-Dampf bei 618 ± 6 K dimer ist.     

Niobium(V) Recovery from Titanium-Containing Sulfate Solutions

The separation of niobium(V) from titanium(IV) by extraction with tributyl phosphate containing an amine, followed by precipitation from sulfate media with organic coagulants, was studied.     

Organic acid solutions in the chromatography of inorganic ions VIII. Cation-exchange of Mn(II), Cd(II), Co(II), Ni(II), Zn(II), Cu(II), Fe(III), Sc(III), Y(III), Eu(III), Dy(III), Ho(III), Yb(III), Ti(IV) and Nb(V) in malate media

Summary The cation-exchange behaviour of Mn(II), Cd(II), Co(II), Ni(II), Zn(II), Cu(II), Fe(III), Sc(III), Y(III), Eu(III), Dy(III), Ho(III), Yb(III), Ti(IV) and Nb(V) in malate media at various concentrations and pH, was studied with Dowex 50 WX8 resin (200–400 mesh) in the ammonium form. Separation of Fe(III)/Cu(II), Fe(III)/Cu(II)/Zn(II), Fe(III)/Co(II)/Mn(II), Cu(II)/Ni(II)/Mn(II), Fe(III)/Cu(II)/Co(II)/Mn(II), Fe(III)/Cu(II)/Ni(II)/Cd(II), Yb(III)/Eu(III), Sc(III)/Y(III),Sc(III)/Yb(III)/Dy(III) and Nb(V)/Yb(III)/Ho(III) has been achieved, among others.This work was supported by C.N.R. of Italy.     

Some Cyclopentadienyl and Indenyl Niobium(V) Phenoxides

Some cyclopentadienyl and indenyl niobium(V) phenoxides are reported in this communication. The effect of different types of groups in the phenoxide ring is related with the stability of the compounds. It has been established that only those phenols which have two hydroxyl groups in the ortho position are able to form chelates. The cyclopentadienyl and the indenyl rings are π-bonded to niobium atom. The complexes have been characterised by elemental analysis and i.r. spectra.     

Cation Exchange in Oxohydroxide Matrices of Niobium(V)

Exchange of lithium, sodium, and potassium cations for hydrogen ions in oxohydroxide matrices of niobium(V), with alkali metal to niobium ratio of 1, was studied potentiometricaly. The possibility is considered of predicting the content of various singly charged cations in the case of their simultaneous presence in a complex hydrated oxide based on niobium(V).     

Chemistry of Trivalent Niobium

A stable compound of lower valent niobium viz. KKb(SO₄)₂ · 4 H₂O in which Nb is in +3 oxidation state has been isolated pure. It has been characterised by its chemical properties, UV, visible and i.r. spectral studies and also by polarographic investigations.     

On the character and products of the thermal decomposition of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) formates

The character and products of the thermal decomposition of metal formate dihydrates of Mn-Zn series were studied in carbon dioxide atmosphere under different pressures.     

Interaction of Aluminium (III) with the f-Family Ions Np(VI), Pu(VI), Np(V), Np(IV), Pu(IV), Nd(III), and Am(III) in the Course of Simultaneous Hydrolysis

The interaction of Np(VI), Pu(VI), Np(V), Np(IV), Pu(IV), Nd(III), and Am(III) with Al(III) in solutions at pH 0–4 was studied by the spectrophotometric method. It was shown that, in the range of pH 3–4, the hydrolyzed forms of neptunyl and plutonyl react with the hydrolyzed forms of aluminium. In the case of Pu(VI), the mixed hydroxoaqua complexes (H₂O)₃PuO₂(-OH)₂Al(OH)(H₂O)₃ ²⁺ or (H₂O)₄PuO₂OAl(OH)(H₂O)₄ ²⁺ are formed at the first stage of hydrolysis. Np(VI) also forms similar hydroxoaqua complexes with Al(III). The formation of the mixed hydroxoaqua complexes was also observed when Np(IV) or Pu(IV) was simultaneously hydrolyzed with Al(III) at pH 1.5–2.5. The Np(IV) complex with Al(III) has, most likely, the formula (H₂O) _n (OH)Np(-OH)₂Al(OH)(H₂O)₃ ³⁺. At pH from 2 to 4.1 (when aluminium hydroxide precipitates), the Np(V) or Nd(III) ions exist in solutions with or without Al(III) in similar forms. When pH is increased to 5–5.5, these ions are almost not captured by the aluminium hydroxide precipitate.     

Organic acid solutions in the chromatography of inorganic ions. VII. Cation exchange of Mg(II), Ca(II), Sr(II), Ba(II), Mn(II), Cd(II), Co(II), Ni(II), Zn(II), Cu(II) and Fe(III) in succinate media

Summary The cation-exchange behaviour of Mg(II), Ca(II), Sr(II), Ba(II), Mn(II), Cd(II), Co(II), Ni(II), Zn(II), Cu(II) and Fe(III) in succinate media at various concentrations and pH, was studied with Dowex 50 WX8 resin (200–400 mesh) in the NH ₄ ⁺ form. As examples separations of Cd(II)/Co(II), Cd (II)/Ni(II), Fe(III)/Cu(II)/Ni(II) and Mg(II)/Ca(II)/Sr(II)/Ba(II) have been achieved.This work was supported by C.N.R. of Italy.     

Preparation de Complexes Dicyclopentadienyliques Dissymetriques du Niobium(IV)

Dicyclopentadienyl derivatives of niobium(IV) containing two different cyclopentadienyl ligands have been synthesized. The products obtained are characterized by mass and EPR spectroscopy and by elemental analysis. Starting from NbCl₅, unequivocal selective routes proceed via monocyclopentadienyl complexes. The possibility of selectively obtaining several (RCp)NbCl₄ compounds from RC₅H₄SnBu₃ and a heptane suspension of NbCl₅ is presented. Evidence is given for formation of a monocyclopentadienyltrichloroniobium(IV) moiety either by reduction of (RCp)NbCl₄ with aluminium or stannous chloride in acetonitrile or by monosubstitution of niobium tetrachloride with RC₅H₄SnBu₃.     

Determination of Lead(II), Copper(II), Zinc(II), Cobalt(II), Cadmium(II), Iron(III), Mercury(II) using sequential injection extractions

Sequential injection analysis is still dominated by single component analysis. In this proposed robust, economical simple instrumental system seven different metal ions are determined simultaneously using thin-film sequential injection extraction (SIE) with multivariate calibration and multiwavelength detection. Dithizone, in ethanol, is used as extractant and the metal dithizonates’ spectra are generated by a diode array spectrophotometer between 300 and 700 nm. The SI thin-film extraction using water miscible with ethanol works due to the hydrophobic interaction of ethanol with the Teflon wall to create a thin film. A sample frequency of 27 samples per hour was obtained with a sample carry-over of less than 1%. The results of the proposed sequential injection extraction system compare favourably with the results obtained by using standard atomic absorption spectrometry (AAS) methods on conventional extraction samples.     

Modelling the adsorption of Cd(II), Cu(II), Ni(II), Pb(II), and Zn(II) onto Fithian illite

Illite samples from Fithian, IL were purified and saturated with Na(+) ions. The acid-base surface chemistry of the Na-saturated illite was studied by potentiometric titration experiments with 0.1, 0.01, and 0.001 M NaNO(3) solutions as the background electrolyte. Results showed that the titration curves obtained at different ionic strengths did not intersect in the studied pH range. The adsorption of Cd(II), Cu(II), Ni(II), Pb(II), and Zn(II) onto illite was investigated as a function of pH and ionic strength by batch adsorption experiments. Two distinct mechanisms of metal adsorption were found from the experimental results: nonspecific ion-exchange reactions at lower pH values on the basal surfaces and 'frayed edges' and specific adsorption at higher pH values on the mineral edges. Ionic strength had a greater effect on the ion-exchange reactions. The binding constants for the five heavy metals onto illite were determined using the least-square fitting computer program FITEQL. Linear free energy relationships were found between the surface binding constants and the first hydrolysis constants of the metals.     

Convenient Synthesis of Bis(indol)alkanes by Niobium(V) Chloride

Bis(indolyl)alkanes have been synthesized in excellent yields in the presence of a catalytic amount of niobium(V) chloride under solvent-free conditions.