Electromigration of Bk(IV) and some other tetravalent cations in nitric acid solutions

Electromigration of Bk(IV) and Ce(IV) in mixed HNO₃−HClO₄ solutions at constant total acid concentration of 6M has been investigated. Comparative electromigration of Bk(IV), Pu(IV), Th(IV) and Ce(IV) has been studied in nitric acid solutions at concentrations from 2M to 16M. Comparison of the obtained values of mobility shows that the ability to form negatively charged hexanitrato complexes in nitric acid solutions decreases with a decrease in ionic radius of the cations: Ce(IV), Th(IV), Pu(IV), Bk(IV). The mobility corresponding to negatively charged ions in the case of Bk(IV) appears only at HNO₃ concentrations higher than 10M. This fact allowed to explain the specific features of ion-exchange and solvent extraction behaviour of Bk(IV).     

In situ electro-oxidation and liquid-liquid extraction of cerium(IV) from nitric acid medium using tributyl phosphate and 2-ethylhexyl hydrogen 2-ethylhexyl phosphonate

The process of in situ electro-oxidation of Ce(III) to Ce(IV) followed by its extraction into the organic phase has been investigated for its applicability in the separation of Ce from nitrate medium. Solvent extraction of cerium from nitric acid after its electro-oxidation to fourth valency state was carried out using tributyl phosphate (TBP) and 2-ethylhexyl hydrogen 2-ethylhexyl phosphonate (KSM-17, equivalent to PC-88A). The efficiency of the extractants at different aqueous phase nitric acid concentrations and different electrode potentials were determined. Various reducing agents such as hydroxylamine hydrochloride, sodium nitrite, ferrous sulphate as well as complexing agents like EDTA, oxalic acid etc, were studied as strippants for the back extraction of cerium from the loaded organic phase. The method developed for the extraction of cerium was further extended to the partitioning of cerium from Ce-Am mixture obtained during the KSM-17 based extraction chromatographic elemental fractionation of PUREX High Activity Waste (HAW) solutions. Recovery of Ce obtained in the extraction experiments by batch as well as by continuous flow organic phase was >95% with good radiochemical purity.     

Kinetic studies on the solvent extraction of uranium (IV), thorium (IV) and uranium (VI) from nitric acid solutions with tributyl phosphate

The kinetics of solvent extraction of U (IV), Th (IV) and U (VI) from nitric acid solution with tributyl phosphate (TBP) in kerosene and cyclohexane have been studied using the single drop technique. The effects of concentrations of U (IV), Th (IV), U (VI), nitric acid, nitrate, TBP and temperature on the extraction rates of U (IV), Th (IV) and U (VI) have been examined. The mechanisms for the three extraction processes are discussed.     

Extraction of trivalent lanthanum,cerium and yttrium thiocynate complexes by tributyl phosphate

The distribution of La(III), Ce(III) and Y(III) from potassium thiocyanate solutions by tributyl phosphate is described. The dependence of extraction on pH, thiocyanate concentration, metal and extractant concentration, diluent type and temperature, was thoroughly investigated. Solvation numbers and thermodynamic data were calculated and discussed. A method has been suggested for the separation of Th(IV) from such elements.     

N-oxides of 4-(5-nonyl)pyridine and trioctylamine as extractants for cerium(IV) and its separation from thorium(IV)

Trace level cerium has been oxidized to the quadrivalent state with potassium dichromate and shown to be preferentially extracted from very dilute mineral acid solutions and also from moderate nitric acid media by 0.1M solutions of 4-(5-nonyl)pyridine oxide and trioctylamine oxide dissolved in xylene. The dependence of extraction on the type of N-oxide, acid concentration and the N-oxide concentration has been investigated. The influence of the concentration of salting-out agents is described. Separation factors for a number of metal ions relative to cerium(IV) are reported for 0.1 M 4-(5-nonyl)pyridine oxide/xylene-0.1M sulphuric acid system. The ratio of the D for Ce(IV) to that of Ce(III) is greater than 10⁵, and the D for Ce(IV) is much greater than that for thorium(IV). Separation of cerium(IV) from thorium has been achieved from 0.1M sulphuric acid solutions using 0.1M 4-(5-nonyl)pyridine oxide/xylene as an extractant.     

Extraction of molybdenum(VI) from fluoride niobium-tantalum solutions with a high content of titanium(IV)

Distribution of molybdenum(VI) (0.05 M) upon extraction with tributyl phosphate from fl uoride solutions with a content of titanium(IV), niobium(V), and tantalum(V) of up to 3.0, 0.7, and 0.7 M, respectively, was studied.     

Electrochemical Behavior of Ce(IV)/Ce(III) Couple in N,N-Di(2-ethylhexyl)-n-butanamide (DEHBA), N,N-Di(2-ethylhexyl)-iso-butanamide (DEHiBA), and N,N-Di(2-ethylhexyl)-3,3-dimethyl Butanamide (DEHDMBA)

In this work we report on the electrochemical behavior of Ce(IV)/Ce(III) redox couple in pure N,N-dialkyl amides (N,N-DA), namely N,N-di(2-ethylhexyl)-n-butanamide (DEHBA), N,N-di(2-ethylhexyl)-iso-butanamide (DEHiBA), and N,N-di(2-ethylhexyl)-3,3-dimethyl butanamide (DEHDMBA) equilibrated with nitric aqueous solutions as an entry to the direct electrochemical characterization of plutonium in these extractants. Ce(IV)/Ce(III) redox process was used as a model. Its potential (E_1/2≅1.02 V/SCE) is not affected by the temperature and the nature of the N,N-DA and this clearly indicates that the functionalities of these extractants produce the same relative effect on both +IV and +III oxidation states of the cerium cation. Linear variations of the current intensity of the reduction peak of Ce(IV) with the concentration of Ce(IV)/N,N-DAs/HNO₃(5 M) solutions were obtained from cyclic voltammograms recorded at 25 °C and 40 °C. Due to the poor definition of the voltammograms in DEHiBA and DEHDMBA, such characterization allows only the evaluation of the performances of the chemical extraction of Ce(IV) from aqueous nitric acid solution by the undiluted DEHBA. To our knowledge, the electrochemical behavior of Ce(IV)/Ce(III) in N,N-DAs was not previously studied and our findings will for sure open the door for further investigations in this field.     

On Production of Cerium Dioxide

The possibility of obtaining cerium dioxide by recovery of Ce(IV) phosphate from acid nitrate solutions with subsequent conversion of Ce(IV) phosphate to Ce(III) oxalate was studied.     

Influence of fluoroelement acids on extraction of Group IV–VI element fluorides

Effect of titanium(IV) and silicon(IV) on extraction of Ti(IV), Nb(IV), Ta(V), and W(VI) with octanol and tributyl phosphate from fluoride solutions was studied.     

Isolation and separation of transplutonium and rare-earth elements in unusual oxidation states on ion exchangers in inorganic acid solutions

The behaviour of transplutonium and rare-earth elements on anion and cation exchangers in solutions of H₃PO₄ and H₂SO₄ in the presence of oxidants (KBrO₃, PbO₂, (NH₄)₂S₂O₈) and in HCl solutions in the presence of reducing agents [Zn(Hg), Eu²⁺] depending on acid concentration as well as on oxidant content and nature in solution or in resin and other factors has been studied. Effective methods of Bk(IV), Ce(IV), Am(VI), Eu(II) and Md(II) separation from trivalent TPE and REE, as well as continuous methods of isolation of isotopically pure radionuclides²⁵⁰Bk,¹⁴⁴Pr by using ion exchangers and inorganic acid solutions have been developed.     

Extraction of actinides and fission products by octyl(phenyl)-N,N-diisobutylcarbamoylmethyl-phosphine oxide from nitric acid media

Extraction of promethium(III), uranium(VI), plutonium(IV), americium(III), zirconium(IV), ruthenium(III), iron(III) and palladium(II) has been carried out with a mixture of octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) and tributyl phosphate (TBP) in dodecane. The effects of nitric acid, TBP and CMPO concentrations on the extraction of these metal ions have been studied. The nature of the species of the above metal ions extracted into the organic phase has been suggested.     

Quantitative separation of carrier-free cerium from fission products

The extraction of Ce (IV) by di-(2-ethylhexyl)-phosphoric acid (HDEHP) has been studied as a function of nitric acid concentration. Using the distribution coefficient data, the optimum conditions for recovery of Ce (IV) from nitric acid medium were arrived at. Under the conditions employed for Ce(IV), a small percentage of Ru was also found to be extracted. Cerium could be selectively stripped from the organic phase with 8M HNO₃/30% H₂O₂ solution. This procedure led to the recovery of¹⁴⁴Ce free of¹⁰⁶Ru. Based on the solvent extraction data, an extraction-chromatographic procedure employing HDEHP (40% w/w) loaded on Amberlite XAD-7 as the stationary phase was developed for the isolation of pure, carrier-free¹⁴⁴Ce from the spent fuel solution.     

Recovery of Thorium(IV) in Utilization of Solutions Formed in Sulfuric Acid Breakdown of Perovskite

Extraction of thorium(IV) with di-2-ethylhexyl hydrogen phosphate, octanol, and tributyl phosphate in sulfuric acid processing of perovskite was studied. The main stages of utilization of waste hydrochloric acid solutions were considered.     

Studies on extraction of indium by tributyl phosphate from thiocyanate solutions

Indium can be quantitatively separated from a large number of elements which are usually associated with it, by extraction with 15% tributyl phosphate solution in kerosene from hydrochloric acid (pH 1)/0.5M potassium thiocyanate medium and stripping with 6M nitric acid. The equilibration takes 20 min.     

Extraction of oxalic acid from solutions of electrolyte mixture

Extraction of oxalic acid with tributyl phosphate and triisoamyl phosphate from solutions of its mixtures with nitric, phosphoric, sulfuric, and hydrochloric acid and with ammonium nitrate and chloride was studied. In the extractability series, oxalic acid occupies the position between nitric and phosphoric acids, with sulfuric and hydrochloric acids acting as strong salting-out agents. Nitric acid salts drastically decrease the distribution ratios of oxalic acid.     

Study of the layering process in extraction systems for optimization of the technology of rare earth elements production

Effect of the contents of non-rare-earth admixtures, in particular calcium, and of the concentration of nitric acid in initial solutions on the rate of layering emulsions was studied the model extraction systems tributyl phosphate, nitric acid REE solutions. The opportunity to reduce areas of settling chambers by a factor of 4–5 at the subsequent steps of the separation and production of individual rare-earth elements.     

Behaviours of trinitratonitrosyl complexes of ruthenium in dilute nitric acid solutions (author's transl)

This study aimed to elucidate the protolysis and condensation processes of the Ru complexes in relation to the concentration of nitric acid. The compositions of the dissociated and undissociated complexes were determined by the extraction with tributyl phosphate (TBP) and absorption spectroscopy in order to follow the rather rapid protolysis reaction of the complexes. The test solutions were prepared by dissolving the freshly obtained complexes into 0.50-0.001 M nitric acid solutions. The amounts of the undissociated complexes were determined at different elapses of time in the test solutions. The protolysis became significant when the concentration was below 0.15 M, and the dissociation rate suddenly increased at this concentration. At the concentrations above 0.2 M, the absorption peak of the complexes at 480 nm survived even after 144 hours. But below 0.15 M, the formation of dissociation products by protolysis was observed after the disappearance of the absorption peak. The amount of dissociation products rapidly increased after the preparation of the test solution as the concentration decreased below 0.15 M.     

Cerium isotope partition in the HCl/TBP extraction system

The^142/140Ce unit separation factor (q) for Ce(III)-Ce(IV) exchange reaction in an extraction system containing Ce(IV) in tri-n-butyl phosphate (TBP) and Ce(III) in hydrochloric acid has been determined. The value of q was found to be 0.9996±0.0001 (2) in the 12M HCl/TBP extraction system. The properties of the extraction systems containing nitric and hydrochloric acids in regard to isotope partition have been discussed.     

Biphasic kinetic investigations on the evaluation of non-salt forming reductants for Pu(IV) stripping from tributyl phosphate and N,N-dihexyl octanamide solutions in n-dodecane

The relative stability of different oxidation states of actinide elements is influenced by the nature of complexes formed and redox equilibria in aqueous/non-aqueous solutions. The reduction/stripping studies on Pu(IV) ions from loaded organic phases of 1.1 M tributyl phosphate and of 1.1 M N,N-dihexyl octanamide in n-dodecane were studied using organic soluble tert-butyl hydroquinone (TBH) and aqueous soluble reductants like acetaldoxime (AX) and hydroxyurea (HU). These studies were carried out as a function of reductant and nitric acid concentration (0.5–4 M HNO₃) and of time. The changes in Pu oxidation states were followed by spectrophotometry for TBH and by distribution ratio values for AX and HU as reductants. Spectrophotometric investigations using TBH as reductant showed that it was desirable to strip Pu(III) formed after reduction of Pu(IV) in the organic phase, which may otherwise be reconverted to extractable Pu(IV) by in situ generated HNO₂ from oxidative degradation of TBH to tert-butyl quinone. Similarly, the biphasic reduction/stripping of Pu(IV) using AX and HU as reductant rate was affected adversely with increased aqueous phase acidity. This data will help in the accurate simulation of Pu separation processes using these reductants in mixer-settlers/pulsed columns or centrifugal contactors.     

Preparation of125I labeled testosterone derivatives for use in radioimmunoassays

A study for separation and sequential recovery of uranium and plutonium from nitric acid solutions by extraction chromatography using tributyl phosphate (TBP)/Amberlite XAD7 as stationary phase is presented. Distribution ratios of actinides, lanthanides and fission products were obtained. The column capacity was investigated and actinides retention conditions were established. Finally, U-Pu sequential separation was studied as well as the U and Pu recovery yields from nitric solutions containing Am/fission products were determined.