Adsorption behaviors of trivalent actinides and lanthanides on pyridine resin in lithium chloride aqueous solution

The adsorption behaviors of trivalent actinides and lanthanides on pyridine resin in lithium chloride aqueous solution were investigated. The adsorbed amounts of lanthanides and the degree of mutual separation of lanthanides increased with an increase in the concentration of lithium chloride in aqueous solution. The group separation of the trivalent actinides and lanthanides was observed. This separation phenomenon is similar in a hydrochloric acid solution. However, the adsorption behavior of lanthanides in lithium chloride is different from their behavior in a hydrochloric acid solution. This fact shows that the adsorption mechanisms of lanthanides in a lithium chloride aqueous solution and in a hydrochloric acid solution are different; the adsorption mechanisms are attributed to the ion exchange in a hydrochloric acid solution, and to the complex formation with pyridine group in a lithium chloride solution.     

Rapid ion-exchange separations of actinides

For the purpose of studying short-lived actinide nuclides, three methods for rapid ion exchange separation of actinide elements with mineral acid-alcohol mixed media have been developed: (1) anion exchange with nitric acid-methyl alcohol mixed media to separate the transplutonium and rare earth elements from target material, U or Pu, and Al catcher foils; (2) anion exchange with hydrochloric acid-methyl alcohol media to separate Am+Cm, Bk and Cf+Fm from the target, catcher foils and major fission products; (3) cation exchange with hydrochloric acid-methyl alcohol media and with concentrated hydrochloric acid to separate the transplutonium elements as a group from the rare earths after eliminating the large amounts of U, Al, Cu, Fe etc. The methods enable one to perform rapid and effective separation at elevated temperature (90 °C) and immediate source preparation for alpha-ray spectrometry.     

Extraction of thorium and cerium (III) chlorides by neutral organophosphorus solvents

Summary The extraction of thorium and trivalent cerium chlorides by tri-n-butyl phosphate and di-isoamylmethyl phosphonate has been investigated as a function of hydrochloric acid molarity in the aqueous phase and solvent concentration in the organic phase. The comparative stability of the extractable metal complexes with the two solvents has been also estimated. The second solvent has been recommended, instead of the first, for the separation of thorium and the rare earth elements from hydrochloric acid media.

---

Zusammenfassung Die Extraktion von Thorium- und Cer(III)-chloriden mit Hilfe von Tri-n-butylphosphat und Di-isoamylmethyl-phosphonat wurde in Abhängigkeit von der HCl-Konzentration in der wäßrigen und der Lösungsmittelkonzentration in der organischen Phase untersucht. Die Stabilität der gebildeten Metallkomplexe wurde bestimmt. Zur Abtrennung von Thorium und Seltenen Erden aus salzsaurem Medium wird Di-isoamylmethyl-phosphonat empfohlen.

     

Extraction of rare earth elements by high molecular weight amines from nitric acid solutions

Extraction of trivalent rare earth elements by a high molecular weight primary amine /decylamine/ from 0.5–3M nitric acid solutions, containing potassium phosphotungstate /K₁₀P₂W₁₇O₆₁/, has been investigated. The effect of nitric acid and potassium phosphotungstate concentration of the organic solvent, and lanthanides ionic radii upon distribution coefficients has been studied. It has been established that decylamine solutions in chloroform can be used for the group isolation of rare earth elements and for their separation.     

Preorganized, cone-conformational calix[4]arene possessing four propylenephosphonic acids with high extraction ability and separation efficiency for trivalent rare earth elements

p-t-Octylcalix[4]arene with tetraphosphonic acid at lower rim in cone conformation has been designed and synthesized as a new extraction reagent to investigate the extraction behavior of the nine trivalent rare earth elements: La, Pr, Nd, Sm, Eu, Gd, Ho, Y, and Er. The extraction of rare earth metals with the present extractant occurs by a simple ion-exchange mechanism. The stoichiometry of the extractant to rare earth metal ion was determined to be 2:1 based on the extraction equation, half pH values, pH_1/2, and the difference in the values of the extraction equilibrium constants of nine trivalent rare earth elements and separation factors between adjacent rare earth elements. This allowed for comparison of the estimated extraction efficiency and selectivity. The present extractant exhibited extremely high extractability and sufficiently high separation efficiency of rare earth metals, compared with calix[4]arene tetraphosphonic acid at upper rim, calix[4]arene tetraacetic acid at lower rim as previously reported and the commercial extraction reagent. This results was attributed to size and multidentate effects based on the preorganized cyclic structure of calix[4]arene and to the original selectivity of functional group for heavier rare earth elements.     

Extraction of rare earth elements by primary high molecular weight amines from hydrochloric acid solutions

Extraction of trivalent lanthanides: La, Ce, Nd, Eu, Tb, Tm, Yb by primary high molecular weight amines from 0.5–3M hydrochloric acid solutions, containing complex-forming agent potassium phosphotungstate /K₁₀P₂W₁₇O₆₁/ has been investigated. The effect of hydrochloric acid, potassium phosphotungstate and amine concentration, the length of primary amine alkyl chain, organic solvents nature and elements ionic radii on distribution coefficients have been studied. It has been established that the system can be used for group isolation and separation of rare earth elements.     

Separation of rare earth elements by high-speed counter-current chromatography

Besides being widely used in electronic and glass industries, rare earth elements have recently been found to have important biological effects including the ability to stabilize and enhance interferon activity [J.J. Sedmak and S.E. Grossberg, J. Gen. Virol, 52 (1981) 195]. In this paper, the rare earth elements have been separated using a high-speed counter-current chromatography (HSCCC) centrifuge equipped with three multilayer coils connected in series. Two-phase solvent systems were composed of n-heptane containing di-(2-ethylhexyl)phosphoric acid (stationary phase) and dilute hydrochloric acid (mobile phase) where the partition coefficient of each can be optimized by selecting the proper hydrochloric acid concentration. The mobile phase was eluted through the column at a flow-rate of 5 ml/min, while the apparatus was rotated at 900 rpm. Continuous detection of the rare earth elements was effected by means of a post-column reaction with arsenazo III and the elution curve was obtained by on-line monitoring at 650 nm. Excellent isocratic separations of closely related rare earth elements were achieved at high partition efficiencies up to several thousand theoretical plates. Versatility of the present method was demonstrated in an exponential gradient elution of hydrochloric acid concentration where fourteen rare earth elements were all resolved in about 4.5 h.     

Cation Exchange Chromatographic Separation Of Lead From Mixed Solvents

Abstract

The cation exchange separation of lead from associated elements on Dowex 50W-X8, was carried out in mixed solvent systems. Elution behaviour was studied with 0.75 M HCl in the presence of various concentrations of solvents such as methanol, ethanol, 2-propanol, acetone, 1, 4 dioxane and tetrahydrofuran. Tetrahydrofuran, 1, 4 dioxane and acetone were effective in the presence of hydrochloric acid. At low concentrations of methanol, ethanol and 2-propanol in hydrochloric acid were useful for the separation of ions from lead. Lead was separated from binary and as well as multicomponent mixtures. The method was extended to the separation of lead from lead base alloys.     

Thermodynamic Approach for Predicting Actinide and Rare Earth Concentrations in Leachates from Radioactive Waste Glasses

Studies aimed primarily at determining leach rates of different elements from doped glasses have resulted in computerized models for predicting leachate concentrations. However, leach rate related data should be limited to predicting the stability behavior of the glass matrix; the radionuclide release data based on these studies are empirical and are highly dependant on many variables and processes which have not been systematically evaluated and thus do not provide a reliable method of predicting leachate concentrations. A better approach is available for those elements that can readily form relatively insoluble solids during preparation of glass or glass/water interactions. This alternate approach relies on the experimental solubilities of pulverized doped glasses, in a wide range of well-controlled important variables such as pH and pe, and their comparisons at the given aqueous composition to predicted solubilities of known solid phases from the thermodynamic data. These comparisons are used to indirectly identify specific solubility-controlling solids in doped glass/water systems to determine scientifically defensible aqueous concentrations of different elements for any given groundwater composition, independent of glass dissolution kinetics and independent of time. This paper summarizes data available for the application of this alternate approach to reliably predict concentrations of thorium, uranium, neptunium, plutonium, and trivalent actinides and rare earth elements leachable from the doped glasses. The thermodynamic data, in addition to that reported in recent critical reviews, includes new data that were developed for the solubility products of Th₃(PO₄)₄(s) and the solid solutions of trivalent actinides and rare earth hydroxides. Thermodynamic interpretations of the doped glass solubility data show specifically that tetravalent actinide hydrous/crystalline oxides and solid solutions of trivalent actinides and rare earths hydroxides in non-phosphate glasses and Th₃(PO₄)₄(s) and MPO₄(s), where M denotes trivalent actinides or rare earths, in phosphate-containing glasses are the dominant solubility-controlling solids. Needed future research in this area is briefly outlined.     

Single column ion exchange separation of the transplutonium elements from uranium targets bombarded with heavy ions and catcher foils

A simple pressurized ion exchange apparatus has been devised for rapid ion exchange separation of transplutonium elements synthesized by heavy ion bombardment. Cation exchange with mixed media of mineral acids and organic solvents at elevated temperature was used to separate the transplutonium elements from uranium targets and/or catcher foils (aluminium and copper) dissolved in aqua regia. The transplutonium elements were strongly adsorbed on the cation exchange column and separated in a group from rare earths by elution with hydrochloric acid or mutually separated with 2-hydroxy-2-methylpropionate solution. It has been successfully applied to separate and identify²⁵⁰Fm and²⁴⁶Cf synthesized by the¹⁶O+²³⁸U reaction.     

Cation-exchange separation of hafnium and zirconium from accompanying ions

Hafnium and zirconium are not retained on the strongly acidic cation-exchange resin Dowex 50 from a mixture consisting of methanol and 12M nitric acid (19:1) which is 0.1M in trioctylphosphine oxide. On the other hand most other elements investigated are strongly adsorbed on the resin from this medium so that they are readily separated from hafnium and zirconium. These elements include titanium, rare earths, alkali metals, alkaline earth metals, iron, cobalt, manganese and zinc. This separation technique has been found to be suitable for the separation of tracer and milligram amounts of hafnium and zirconium from accompanying metal ions. If in place of methanol other organic solvents such as acetone, tetrahydrofuran and methyl glycol are used the selectivity of the separation of zirconium and hafnium from the other elements is decreased. The same effect is observed when hydrochloric acid is used in the mixtures instead of nitric acid.     

5709萃淋树脂色层分离稀土元素的研究

研究了在盐酸体系中十四个钢系元素和钇被５７０９萃淋树脂吸附的分配系数和相邻两元素的分离系数．测量了Ｌａ、Ｅｕ、Ｙｂ在树脂上吸附平衡时间．结果表明，随着原子库数的增加，稀土元素达到平衡吸附所需时间愈短．     

Continuous separation of Sr, Y and some actinides by mixed solvent anion exchange and determination of 89,90Sr, 238,239Pu and 241Am in soil and vegetation samples

Methodology for the determination of ^89,90Sr, Am and Pu isotopes in complex samples is given. Methodology is based on simultaneous isolation of Sr, Y and actinides from samples by mixed solvent anion exchange chromatography, mutual separation of ^89,90Sr and ⁹⁰Y from actinides, mutual separation of Th, Pu and Am by extraction chromatography, quantitative determination of ^89,90Sr by Cherenkov counting and quantitative determination of Pu and Am isotopes in soil and vegetation samples by alpha spectrometry. It is shown that Y and Sr can be efficiently separated from alkaline, alkaline earth and transition elements as well as from lanthanides and actinides on the column filed by strong base anion exchanger in nitrate form and 0.25?M HNO₃ in mixture of ethanol and methanol as eluent. It is also shown that Pu, Am and Th strongly binds on the mentioned column, can be separated from number of elements and easily be eluted from column by water. After elution actinides were mutually separated on TRU column and electrodeposited on stainless steel disc. Examination of conditions of electrodeposition was shown that chloride-oxalate electrolyte with addition of DTPA in presence of sodium hydrogen sulphate in cell with cooling and rotating platinum anode enables deposition of actinides within 1?h by 0.8?A?cm^?2 current density. Obtained peaks FWHM for Pu, Am and Th isotopes are between 27 and 40?keV. Scanning electron microscopy picture and ED XRF analysis of electroplated discs showed that actinide deposition is followed by iron oxide formation on disc surface. The methodology was tested by determination of ^89,90Sr, Am and Pu isotopes in ERA proficiency testing samples (low level activity samples). Obtained results shows that ^89,90Sr, ²⁴¹Am and ^238,239Pu can be simultaneously separated on anion exchange column, ^89,90Sr can be determined by Cherenkov counting with a satisfactory accuracy and limit of determination within 1?C3?days after separation. ²⁴¹Am and ^238,239Pu can easily be separated on TRU column and determined after electrodeposition with acceptable accuracy within 1?day.     

Determination of individual rare earth elements in Vietnamese monazite by radiochemical neutron activation analysis

Radiochemical neutron activation analysis (RNAA) has been applied for determination of rare earth elements (REE) in Vietnamese monazite. The chemical separation procedure used is based on the chromatographic elution of rare earth groups, after the separation of²³³Pa(Th) in irradiated monazite samples by coprecipitation with MnO₂, the rare earth elements were retained by Biorad AG1×8 resin column in 10% 15.4M HNO₃-90% methanol solution. The elution of heavy rare earth (HREE) and middle rare earth (MREE) groups was carried out with 10% 1M HNO₃-90% methanol and 10% 0.05M HNO₃-90% methanol solution, respectively; while the light rare earths (LREE) were eluted from the column by 0.1M HNO₃ solution. The accuracy of the method was checked by the analysis of granodiorite GSP-I and the rare earth values were in good agreement.     

A scheme for the analysis of monazite and monazite concentrates

A scheme using ion-exchange methods is described for the analysis of monazites and monazite concentrates. The sample is opened up with concentrated sulphuric acid, and the resultant solution is applied to a column of Zeocarb 225 resin. After phosphate has been washed out, lead, aluminium, titanium, iron, uranium, calcium and magnesium are eluted with N hydrochloric acid and determined by specific, mainly spectrophotometric, methods. Rare earth elements are eluted with 3 N hydrochloric acid. Cerium is separated from the other rare earths by solvent extraction of its nitrate with methyl iso-butyl ketone; both groups are determined gravimetrically. Thorium is eluted from the ion-exchange resin with 3.6 N sulphuric acid and determined spectrophotometrically with thorin.The sulphuric acid-insoluble minerals are brought into solution by a double fusion method, and the determinations are carried out by a combination of ion-exchange and photometric procedures. Silica, phosphorus pentoxide, tin and chromium are determined by photometric methods, using separate portions of the sample.Lanthanum, yttrium and ytterbium are determined in a 1 M perchloric acid solution of the mixed rare earth oxides (less cerium) using flame photometry. Samarium, praseodymium and neodymium are determined by spectrophotometry.     

Adsorption behavior of alkaline earth elements on tertiary pyridine resin

The separation of strontium from other alkaline earth elements and alkali metal elements is necessary for precise strontium isotope measurement in natural samples. The adsorption behavior of alkaline earth elements on tertiary pyridine resin was investigated using the methanol/nitric acid mixed solution, and the feasibility of strontium separation was studied. We found that strontium can be completely separated from other alkaline earth elements and alkali metal elements using the tertiary pyridine resin. The extraction of strontium from coral sample was demonstrated.     

Paper chromatography in the separation of ions

A study has been made of the separation of ions of the alkali metals, alkaline earth metals, elements of groups IIIA and B and of anions, such as arscnate, phosphate, vanadate, molybdate, tungstate and chromate, with solvent mixtures of tert.-butyl alcohol, water and hydrochloric or acetic acid in the ratio of 7:2 1, and with 01 without tartaric, citric or malonic acid. The solvent mixture with hydrochloric acid as one of the components was found to be most effective for the separation of six cations or three anions from their mixtures. The rl and R1 values and the sequences of separations have been recorded     

Reversed-phase thin-layer chromatography of the rare earth elements

Summary Partition chromatographic behaviour of the rare earth elements on C₁₈ bonded silica reversed-phase material has been investigated by thin-layer chromatography in methanol — lactate media. The rare earth lactato complexes are distributed and fractionated on bonded silica layers without ion-interaction reagents. The concentration and pH of lactate solution, methanol concentration and temperature have effects on the migration and resolution of the rare earth elements. The partition system is particularly suited to separate adjacent rare earths of middle atomic weight groups, allowing the separation of gadolinium, terbium, dysprosium, holmium, erbium and thulium to be achieved by development to 18 cm distance.     

Sequential separation of actinides and lanthanides by extraction chromatography using a CMPO-TBP/XAD7 column

CMPO/TBP sorbed on Amberlite XAD7 resin was used for the separation of actinides and lanthanides from nitric acid solutions by extraction chromatography. The distribution ratios of actinides and lanthanide fission products (Ce, Eu) as a function of acid concentration and some complexing agents were determined. In strong HNO₃ medium (>1 mol/l) the tri-, tetra- and hexavalent actinides as well as the lanthanides have shown great affinity for the CMPO/TBP/XAD7 sorbent. The same behavior was found in HCl medium except for trivalent actinides and lanthanides which show lower distribution values in the same acid range. The effect of some complexing agents as DTPA and ammonium oxalate were also investigated. In DTPA only hexavalent actinides showed higher distribution value. On the basis of these differences, an alternative procedure for actinide-lanthanide separation and actinides from each other is proposed.     

Separation of Curium-Californium by Extraction Chromatography

Sequential separation of the trivalent actinides Cm and Cf is investigated by extraction chromatography using the system Alamine 336-LiCl on the diatomaceous earth, Celite 360. The effect of the mobile phase concentration and the acidity on the distribution behaviour of both elements is found almost to parallel that based on simple liquid-liquid extraction. Optimum resolution and efficient decontamination is readily achieved by 11 M LiCl in 0.02 M HC1. The possible use of the same system for the decontamination of the +3 actinides from various foreign ions is also pointed out.