Thermodynamic study of extraction of cerium(III) and yttrium(III) with tributyl phosphate

To increase the efficiency of hydrometallurgical processing of lean rare-earth raw material, the effect of salt anion and metal cation on the characteristics of Ce(III) and Y(III) recovery from dilute aqueous solutions with tri-n-butyl phosphate was studied on the basis of the thermodynamic theory of extraction.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 9, 2004, pp. 1430–1434.Original Russian Text Copyright © 2004 by Chirkst, Litvinova, Chistyakov, Ionova.     

Extraction of pertechnetate anion as a ligand in a cerium(IV) tributyl phosphate complex

Extraction of technetium has been studied in the tributyl phosphate—dodecanenitric acid—cerium(IV) system. It is established that in the system under study, technetium is extracted as a mixed solvate with cerium(IV) with a component ratio equal to 1. It is shown on the basis of studying the effect of the TBP concentration on the extraction of technetium and cerium(IV) that technetium is extracted as a monosolvate, while cerium(IV) is extracted as a disolvate.     

Extraction of zinc thiocyanate complex by tributyl phosphate in benzene

The species extracted is shown to be Zn(SCN)X.2TBP, where X is a common anion. Good separation factors are obtained for extraction of zinc from solutions containing silver(I), manganese(II), cobalt(II), cadmium(II), mercury(II) and thallium(III).     

Extraction of tetravalent berkelium by tributyl phosphate from nitric acid solutions

Extraction of Bk(IV), Ce(IV), Pu(IV) and Zr by tributyl phosphate from 2M to 16M nitric acid solutions has been studied. Using the data on the effect of the extractant, nitric acid and nitrate ion concentrations on the distribution coefficients of Bk(IV) and Ce(IV), the mechanism of Bk(IV) extraction by tributyl phosphate from nitric acid solutions is considered.     

Synthesis and characterization of cerium and yttrium alkoxide complexes supported by ferrocene-based chelating ligands

Two series of Schiff base metal complexes were investigated, where each series was supported by an ancillary ligand incorporating a ferrocene backbone and different N=X functionalities. One ligand is based on an imine, while the other is based on an iminophosphorane group. Cerium(IV), cerium(III), and yttrium(III) alkoxide complexes supported by the two ligands were synthesized. All metal complexes were characterized by cyclic voltammetry. Additionally, NMR, Mo?ssbauer, X-ray absorption near-edge structure (XANES), and absorption spectroscopies were used. The experimental data indicate that iron remains in the +2 oxidation state and that cerium(IV) does not engage in a redox behavior with the ancillary ligand.     

Extraction of certain elements from aqueous methanol, ethanol and acetone by tridodecylamine and tributyl phosphate

The extraction of silver, mercury, selenium, zinc, cobalt and iron with tridodecylamine (TDA) and tributyl phosphate (TBP) from hydrochloric acid solutions in aqueous methanol, ethanol and acetone is reported. The presence of these additives increases extraction for some elements and decreases it for others. The effect is generally greater with TDA than with TBP.     

Extraction of beryllium(II) from iodide solutions by tributyl phosphate

The distribution of beryllium between aqueous sulfuric acid/potassium iodide solutions and organic phases of tributyl phosphate is described. The dependence of extraction on the pH of the aqueous phase, metal and extractant concentration, diluent type and organic additive, has been investigated. Extraction mechanism is discussed on the basis of results obtained. A method for the separation and determination of beryllium, in a mixture of beryllium and aluminium (with other contaminants) is outlined.     

Anion-exchange separation of scandium from yttrium,lanthanum, cerium and other elements in malonic and ascorbic acid media

Summary The anion-exchange behaviour of scandium was studied in malonate and ascorbate media on Dowex 2×8 colums (1.4×18 cm). It forms anionic complexes with 8% malonic acid at pH 5.0 and 5% ascorbic acid at pH 6.5. Various eluants such as mineral acids and their corresponding salts were tested eluants and their efficiencies evaluated. Scandium was separated from alkali metals, alkaline earth metals Tl(I), Hg(II) and Fe(II). It was separated from Co, Ni, Pd, Mn, Cd and Zn by selective washing of the column and from other elements by selective elution in both systems. The separation of scandium from Y, La, Ce, Pr, Nd, Sm, Gd and Dy were a remarkable feature of the method.     

Extraction of antimony and tantalum from aqueous fluoride solutions by n-octanol and tributyl phosphate

¹⁹F and ²¹Sb NMR spectroscopy and chemical analysis were used to study the composition and structure of fluoride complexes of antimony(V) and tantalum(V) in organic and aqueous phases in extraction by tributyl phosphate (TBP) and n-octanol. It is found that extraction from solutions containing a single element or both elements occurs via the hydrate-solvate mechanism. The possibility of separating tantalum(V) and antimony(V) by extraction from fluoride solutions is shown. The efficiency of tantalum(V) and antimony(V) separation by extraction from fluoride solutions is enhanced at a transition from TBP to n-octanol.     

Thermal decomposition of yttrium,lanthanum and lanthanide complexes of square acid in air atmosphere

The conditions of thermal decomposition of the Y, La and lanthanide complexes of square acid in air atmosphere have been studied. On heating, the complexes of Y, La, Ce(III), Pr(III), Nd, Sm, Eu(III), Gd, Tb(III) and Ho decompose in two steps. First, the hydrated complexes lose crystallization water to form anhydrous salts. The complexes of Dy and Er decompose in three steps; they are dehydrated in two steps to form anhydrous salts. The complexes of Tm, Yb and Lu are dehydrated in three steps; in two steps they lose water molecules to form octahydrates, which in the third step are dehydrated during decomposition. On heating, the anhydrous complexes of Y, Ce(III), Pr(III), Eu(III), Gd, Tb(III), Dy, Ho and Er and the octahydrated salts of Tm, Yb and Lu decompose directly to the oxides Ln₂O₃, CeO₂, Pr₆O₁₁ and Tb₄O₇. The anhydrous complexes of La, Nd and Sm decompose to Ln₂O₃ with intermediate formation of Ln₂O₂CO₃.

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Zusammenfassung Die thermische Zersetzung von Komplexen von Y, La und Lanthaniden mit Squaresäure in Luft wurde untersucht. Beim Erhitzen zerfallen die Komplexe von Y, La, Ce(III), Pr(III), Nd, Sm, Eu(III), Gd, Tb(III) und Ho in zwei Schritten. Die hydrierten Komplexe geben zuerst Wasser ab und bilden wasserfreie Salze. Die Komplexe von Dy und Er zerfallen in drei Schritten, wobei sie in zwei Schritten zu wasserfreien Salzen dehydriert werden. Die Komplexe von Tm, Yb und Lu werden in drei Schritten dehydriert. Sie geben in zwei Schritten einige Wassermoleküle ab, um Octahydrate zu bilden, die dann während des Zerfalles dehydriert werden. Die wasserfreien Komplexe von Y, Ce(III), Pr(III), Eu(III), Gd, Tb(III), Dy, Ho und Er sowie die Octahydratsalze von Tm, Yb, und Lu zerfallen beim Erhitzen direkt zu den Oxiden Ln₂O₃, CeO₂, Pr₆O₁₁ und Tb₄O₇. Die wasserfreien Komplexe von La, Nd und Sm zerfallen über das Zwischenprodukt Ln₂O₂CO₃ zu Ln₂O₃.

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, . , , , , , , , . , . . . , . , , . , , , , , , , , , , Ln₂O₃, CeO₂, Pr₆O₁₁ Tb₄O₇. , Ln₂O₃ Ln₂O₂CO₃.

     

The determination of lanthanum,cerium and thorium without separations: The determination of lanthanum and cerium in thorium

A method is proposed for the spectrophotometric determination of small quantities of lanthanum, cerium and thorium in the presence of one another without separations. Cerium is estimated from its absorption peak in the ultraviolet region, thorium with thorin, and the 3 elements together with arsenazo. The lanthanum is calculated after subtraction of the combined absorbances of the arsenazo complexes of the thorium and cerium. The procedure can be readily applied to the determination of microgram amounts of the 2 rare earths in thorium. In this case the majority of the thorium is removed from the solution by solvent extraction with TTA before the estimation of the rare earths. The interference of iron is considered and proposals made for its removal.     

Preparation and properties of yttrium,lanthanum, and lanthanidem-nitrobenzoates

The conditions of the formation of rare earth elementm-nitrobenzoates were studied and their quantitative composition and solubilities in water and benzene at 298 K were determined (their solubilities are in the orders of 10^–3 mol dm^–3 and 10^–4 mol dm^–3, respectively). From the values of solubilities in water the solubility products were established (they are in the orders of 10^–10 mol⁴ dm^–12).The IR and X-ray spectra for the prepared complexes and the dehydrated rare earthm-nitrobenzoates were recorded. All obtained complexes were found to be crystalline compounds. The conditions of thermal decomposition for complexes were also studied. It was found that on heating above 573 K the complexes decompose explosively and undergo a melting process at the same time. Therefore the thermal decomposition was carried out in the temperature range 273–573 K. The obtained results show that during dehydration process no transformation of the nitro group to nitrito occurs.

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Darstellung und Eigenschaften von Y, La und Lanthaniden-meta-Nitrobenzoaten

Zusammenfassung Die Bedingungen zur Darstellung von Y-, La- und Lanthanidenmeta-Nitrobenzoaten wurden untersucht. Ihre quantitative Zusammensetzung und ihre Wasserlöslichkeit bei 298K wurden bestimmt (die Löslichkeit ist in der Größenordnung 10^–3 mol dm^–3). Die Infrarot- und Röntgenspektren der erhaltenen Komplexe sowie derm-Nitrobenzoate der seltenen Erden nach der Dehydratisierung wurden gemessen und dabei festgestellt, daß es sich stets um kristalline Verbindungen handelt. Das thermische Verhalten der erhaltenen Komplexe wurde festgestellt: Sie zerfallen über 573 K explosiv und schmelzen zugleich. Der thermische Zerfall der erhaltenenm-Nitrobenzoate der seltenen Erden wurde im Temperaturbereich von 273–573 K untersucht. Es wurde festgestellt, daß die Y-, La- und Lanthaniden-m-Nitrobenzoate bei Temperaturzunahme oder im Dehydratisierungsprozeß keiner Umgruppierung in entsprechende Nitritoverbindungen unterliegen.

     

Preparation and properties of yttrium,lanthanum and lanthanideo-nitrobenzoates

The conditions of the formation of yttrium, lanthanum and lanthanideo-nitrobenzoates were studied and their quantitative composition and solubilities in water at 298 K were determined (their solubilities are of the order of 10^–2 mol dm^–3). The IR and X-ray spectra for the obtained complexes and the dehydrated rare earth elemento-nitrobenzoates were recorded; all prepared complexes are crystalline compounds. The conditions of thermal decomposition of the complexes were also studied. It was found that on heating above 523 K the complexes decompose explosively and undergo a melting process at the same time. Therefore the thermal decomposition for complexes being studied was carried out in the temperature range 273–523 K. From the results it appears that during the dehydration process or with the increase of temperature no transformation of the nitro group to nitrito occurs.

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Darstellung und Eigenschaften von Y, La und Lanthanidenorthonitrobenzoaten

Zusammenfassung Die Bedingungen zur Darstellung von Y-, La- und Lanthanidenorthonitrobenzoaten wurden untersucht. Ihre quantitative Zusammensetzung und ihre Wasserlöslichkeit bei 298 K wurde bestimmt; die Löslichkeit ist in der Größenordnung 10^–2 mol dm^–3. Die Infrarot- und Röntgenspektren der erhaltenen Komplexe sowie der Orthonitrobenzoate der seltenen Erden nach der Dehydratisierung wurden gemessen und dabei festgestellt, daß es sich um kristalline Verbindungen handelt. Das thermische Verhalten der erhaltenen Komplexe wurde festgestellt: sie zerfallen über 523 K explosiv und schmelzen zugleich. Der thermische Zerfall der erhaltenen Orthonitrobenzoate der seltenen Erden wurde im Temperaturbereich von 273–523 K untersucht. Es wurde festgestellt, daß die Y-, La- und Lanthanidenorthonitrobenzoate bei Temperaturzunahme oder im Dehydratisierungsprozeß keiner Umgruppierung in entsprechende Nitritoverbindungen unterliegen.

     

Preparation and properties of yttrium,lanthanum and lanthanidep-nitrobenzoates

The conditions of the formation of rare earth elementp-nitrobenzoates were studied and their quantitative composition and solubilities in water at 298 K were determined (their solubilities are of the order of 10^–3 mol dm^–3). The IR and X-ray spectra for the prepared complexes and the dehydrated rare earthp-nitrobenzoates were recorded. All obtained complexes are crystalline compounds. The conditions of thermal decomposition of the complexes were also studied. It was found that on heating above 573 K the complexes decompose explosively and undergo a melting process at the same time. Therefore the thermal decomposition for complexes being investigated was carried out in the temperature range 273–573 K. From the obtained results it follows that during the dehydration process no transformation of the nitro group to nitrito occurs.

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Herstellung und Eigenschaften von Y, La und Lanthaniden-p-nitrobenzoaten

Zusammenfassung Die Bedingungen zur Darstellung von Y-, La- und Lanthaniden-p-nitrobenzoaten wurden untersucht. Ihre quantitative Zusammensetzung und ihre Wasserlöslichkeit bei 298 K wurden bestimmt (die Löslichkeit ist in der Größenordnung 10^–3 mol dm^–3). Die Infrarot- und Röntgenspektren der erhaltenen Komplexe sowie derp-Nitrobenzoate der seltenen Erden nach der Dehydratisierung wurden gemessen und dabei festgestellt, daß es sich um kristalline Verbindungen handelt. Das thermische Verhalten der erhaltenen Komplexe wurde untersucht: Sie zerfallen über 573 K explosiv und schmelzen zugleich. Der thermische Zerfall der erhaltenenp-Nitrobenzoate der seltenen Erden wurde im Temperaturbereich von 273–573 K untersucht. Es wurde festgestellt, daß die Y-, La- und Lanthaniden-p-nitrobenzoate bei Temperaturzunahme oder im Dehydratisierungsprozeß keiner Umgruppierung in entsprechende Nitritoverbindungen unterliegen.

     

Extraction of gallium from mixed acid solutions by tributyl phosphate and its application to activation analysis

The extraction of gallium from chloride-containing solutions was investigated in detail. In the main, mixtures of hydrochloric acid and sulfuric acid were used as the aqueous phase, and the optimum extraction conditions have been established. Other acids and neutral salts increase the extraction rate very effectively, but nitric acid exhibits a detrimental effect. The extraction method has been applied successfully to the neutron activation determination of traces of gallium in insoluble aluminium oxide, which can be decomposed only by fusion with sodium pyrosulphate.     

Extraction chromatography of chloride complexes of osmium (III, IV and VI) on paper treated with tributyl phosphate and amberlite LA-1 hydrochloride

The complex anions OsCl₆²⁻, OsO₂Cl₄²⁻ and OsCl₆³⁻ were separated by extraction chromatography on paper treated with tributyl phosphate and developed with hydrochloric acid. The chloride complexes of osmium and ruthenium can also be separated in the system TBP-HCl or Amberlite LA-1 hydrochloride-HCl.     

Phosphoesterase activity and phosphate release from tributyl phosphate by aCitrobacter sp.

Tributyl phosphate (TBP) and other alkyl phosphates represent a class of persistent organophosphorus compounds of widespread use. Biodegradation of the phosphotriesters is postulated to occur through sequential hydrolytic cleavages via the phosphodiester and monoester intermediates to alcohol and inorganic phosphate (P_i). Immobilized cells of aCitrobacter sp. liberated P_i upon challenge with TBP but the reaction was short-lived. In vitro studies with purified phosphomonoesterase (phosphatase) used³¹P nuclear magnetic resonance to demonstrate P_i transfer onto ethanol (phosphotransferase activity). This suggested that in vivo the onset of a futile phosphohydrolytic and transphosphorylation cycle would limit the extent of phosphate production. A mutant deficient in the transphosphorylating phosphomonoesterase showed an extended release of P_i under challenge with TBP that was not subject to the complete and premature reaction termination that precluded application of the parent strain to possible industrial processes for alkyl phosphate biodegradation.