Spectrophotometric determination of niobium(V) with n-propyl 3,4,5-trihydroxybenzoate

The use of n-propyl 3,4,5-trihydroxybenzoate (PTB) for the spectrophotometric determination of niobium is investigated. PTB yields a yellowish-orange ML(2) chelate with Nb(V) at pH 6.1. The formation constant at pH 6.1 is about 10(10). Beer's law is obeyed over the range 0-100 mug of Nb per ml.     

Separation of rare earth elements from uranium by solvent extraction and ion exchange

The detection limit of⁹⁹Tc in (,) radio-activation analysis was determined in the presence of molybdenum and compared with that of⁹⁹Tc in pure materials in the previous paper. The isotopic ratio of molybdenum in a⁹⁹Mo–^99mTc generator column could be simultaneously determined by photon activation analysis.     

Separation of uranium(VI) as chloride complex by solvent extraction with dicyclohexyl-18-crown-6

Uranium(VI) was quantitatively extracted from 6 to 8M hydrochloric acid with 0.02M DC-18-crown-6 in chloroform. It was stripped from the organic phase with 0.5M hydrochloric acid and determined as its Arsenazo-III complex at 665 nm. Uranium(VI) was separated from several elements such as thorium, zirconium, scandium, yttrium, thallium and tin in complex mixtures. The method was extended for analysis of uranium in monazite and rock sample.     

A precise uranium assay using solvent extraction and spectrophotometry

The uranium spectrophotometric measurement using the uranylnitrate-quaternaryamine solvent extraction method is investigated to identify factors that affect precision and accuracy of the uranium determination. The inherent spectrophotometric precision was measured with neutral density filters in the sample light path and was found to be <0.1% relative standard deviation (RSD). Under selected experimental conditions, temperature instability has a –0.02% effect on the extraction, and a –0.4% effect on the absorbance of the uranium extract in 2-nitropropane (2-NP) or methyl isobutyl ketone (MIBK) solvents. Under optimum conditions at the 10 mg uranium level, RSDs of 0.1% resulted.     

Separation of rhenium from molybdenum and vanadium by extraction with amyl alcohol

Summary A method is described for the separation of rhenium from molybdenum and vanadium by extraction with amyl alcohol. The sample solution containing Re^VII, Mo^VI, and V^V is boiled with hydrazine sulphate in order to obtain Mo^V and V^IV (Re remains in the heptavalent state). Rhenium is quantitatively extracted into amyl alcohol from this solution, along with very slight amounts of molybdenum and vanadium. After back-extraction, the residual molybdenum is completely removed by extraction of its thiocyanate with amyl acetate. The accompanying vanadium is usually too small to interfere in the thiocyanate method of rhenium estimation. The method is simple, rapid and applicable to all Mo:Re ratios generally met with.

---

Zusammenfassung Ein Verfahren zur Abtrennung des Rheniums von Molybdän und Vanadium durch Extraktion mit Amylalkohol wird beschrieben. Rhenium soll als Re^VII, Molybdän als Mo^V und Vanadium als V^IV vorliegen (Mo^VI und V^V werden mit Hydrazinsulfat reduziert). Geringe Mengen Mo und V werden mitextrahiert. Nach Rückextraktion wird Mo vollständig durch Extraktion des Thiocyanats mit Amylacetat entfernt. Die vorhandenen Vanadiummengen sind zu gering, um die nachfolgende Rheniumbestimmung (nach der Thiocyanatmethode) zu stören. Das Verfahren ist einfach und rasch durchführbar und für alle üblichen Mo:Re-Verhältnisse anwendbar.

---

---

Our sincere thanks are due to Prof. S. M. Mukherji, Head of the Chemistry Department, for facilities.     

Organic solvent extraction of uranium from alkaline nuclear waste

There are proliferation issues with the Plutonium Uranium Redox Extraction process due to the possibility of recovering plutonium. The objective of this research was to evaluate different organic extraction ligands that can remove uranium from the nuclear waste and to determine the most effective organic solvent for extracting uranium only, from alkaline media. The results indicate that Alamine 336 in xylene has zero (0%) extraction capability for surrogate fission products at an optimum extraction time of 15 min. Aliquat 336 in xylene has an extraction percentage of 72% for uranium in 60 min. However, Aliquat 336 in toluene extracted 82% of the uranium from the feed solution after 30 min, decreasing to 76% after 60 min.

     

In-line phase separator for microfluidic solvent extraction of uranium

Experiments are carried out to study the separation of liquid-liquid dispersion generated at a microfluidic junction by using an in-line phase separator. The phase separator comprises a metallic mesh sandwiched between two flow channels. Dispersion generated at the microfluidic junction is fed to the upper flow channel of the in-line phase separator. Continuous phase permeates through the metallic mesh into the lower flow channel and gets separated from the dispersed phase. The effects of operating parameters (flow rates of the aqueous and organic phases), flow channel geometry and mesh properties (pore size and thickness) on phase separation are studied. After identification of operating window in which complete phase separation is achieved, mass transfer experiments are performed to demonstrate intensified uranium extraction using a micromixer and in-line phase separator.

     

Separation of rhenium from molybdenum, tungsten, vanadium, platinum metals and other elements by reduction and solvent extraction

Reduction in 1 M H(2)SO(4) with liquid zinc amalgam and extraction with isopentanol from 3M H(2)SO(4), separates rhenium from almost all the interfering elements of importance in rhenium determination. The small amounts of Mo, U, Fe and Ru still accompanying rhenium are removed by the thiocyanate-pentyl acetate or the oxine-chloroform extraction. The method is simple, rapid and of very wide applicability. It is particularly useful in the determination of rhenium in various alloys and tungsten-containing samples.     

Spectrophotometric determination of tetraphenyl-arsonium salts by solvent extraction with vanadium—par complex

An extraction-visible spectrophotometric method for the determination of tetraphenylarsonium salts is described. The method is based on the extraction of the ion-pair formed between the tetraphenylarsonium cation and the anionic vanadium(V)– 4-(2-pyridylazo)resorcinol complex, followed by the spectrophotometric measurements of the coloured organic phase at 560 nm. The method can be applied to micro amounts of tetraphenylarsonium salt or to very dilute solutions (10^-6 – 10^-5M). It is more sensitive and less subject to interferences than the direct u.v. method.     

Recovery of uranium and thorium from zirconium oxychloride by solvent extraction

A solvent extraction process is proposed to recover uranium and thorium from the crystal waste solutions of zirconium oxychloride. The extraction of iron from hydrochloride medium with P350, the extraction of uranium from hydrochloride with N235, and the extraction of thorium from the mixture solutions of nitric acid and the hydrochloric acid with P350 was investigated. The optimum extraction conditions were evaluated with synthetic solutions by studying the parameters of extractant concentration and acidity. The optimum separation conditions for Fe (III) are recognized as 30% P350 and 4.5 to 6.0 M HCl. The optimum extraction conditions for U (VI) are recognized as 25% N235 and 4.5 to 6.0 M HCl. And the optimum extraction conditions for Th (VI) are recognized as 30% P350 and 2.5 to 3.5 M HNO₃ in the mixture solutions. The recovery of uranium and thorium from the crystal waste solutions of zirconium oxychloride was investigated also. The results indicate that the recoveries of uranium and thorium are 92 and 86%, respectively.     

The separation of titanium from vanadium and molybdenum by cupferron solvent extraction

The isolation of small amounts of titanium from vanadium and molybdenum before the spectrophotometric determination of titanium as the “pertitanate” complex has been achieved by a. solvent extraction procedure using cupferron and chloroform at pH 6 in the presence of EDTA.     

Separation of uranium from vanadium by ion exchange: with special reference to the determination of small amounts of uranium

An ion exchange method has been worked out for the separation of milligram quantities of uranium from large amounts of vanadium. A solution containing vanadium and uranium and excess sodium carbonate is passed through a column filled with an anion exchanger in the chloride form. All the uranium and part ot the vanadium arc adsorbed by the resin. The adsorbed vanadium is first elutcd with 10 % sodium carbonate solution leaving uranium in the column. Uranium is then cluted with sodium chloride and estimated colorimctrically.     

Separation of uranium from different uranium oxide matrices employing supercritical carbon dioxide extraction

Uranium from different uranium oxide matrices was extracted with tri-n-butyl phosphate–nitric acid (TBP–HNO₃) adduct using supercritical carbon dioxide (SC CO₂). While 30 min dissolution time at 323 K was sufficient for U₃O₈ and UO₂ powder, UO₂ granule (at 333 K) and crushed green pellet (at 353 K) required 40 min. Crushed sintered pellet required 60 min at 353 K for complete dissolution. Influence of various experimental parameters such as temperature, pressure, volume of TBP–HNO₃ adduct, acidity of nitric acid used for preparing TBP–HNO₃ adduct and extraction time on uranium extraction efficiency was also investigated. For UO₂ powder, temperature of 323 K, pressure of 15.2 MPa, 1 mL TBP–HNO₃ adduct, 10 M nitric acid and 30 min extraction time was found to be optimum. ~70% uranium extraction efficiency was obtained on extraction with SC CO₂ alone which increased to 90% with the addition of 2.5% TBP in SC CO₂ stream. Extraction efficiency was found to vary linearly with TBP percentage and nearly complete uranium extraction (~99%) was observed with 20% TBP. Nearly complete extraction was also achieved with addition of 2.5% thenoyltrifluoroacetylacetone (TTA) in methanol. The optimized procedure was extended to remove uranium from simulated tissue paper waste matrix smeared with uranium oxide solids.     

Separation of rhodium from ruthenium and iridium by fast solvent extraction with HDEHP

Solvent extraction of rhodium, ruthenium and iridium with di(2-ethylhexyl)phosphoric acid (HDEHP) has been investigated. Under the conditions [Cl^–1]=0.20M, [(HDEHP)₂]=0.30M, pH 4.05, phase contact time 1 minutes, Rh(III) is extracted 90.7%, Ru(III) and Ir(III) 20.0% and 11.5%, respectively, at phase ratio 11. The distribution ratio of rhodium is proportional to [(HDEHP)₂]³ for a freshly prepared aqueous phase with low chloride concentration but might drop to [(HDEHP)₂]^1to2 for an aqueous phase high in chloride concentration and after standing. The spectroscopic studies indicate that the extracted compound of rhodium is Rh(H₂O)_6–x Cl _x [H(DEHP)₂]_3–x (x=0, 1, 2).     

Separation of trivalent actinides from lanthanides by solvent extraction

A method is presented for separating the trivalent actinides, mainly Am and Cm, from trivalent lanthanides by the use of only two solvent extractants. The first solvent removes the heavy lanthanides, leaving the Am, Cm and the lighterlanthanides; the second removes the Am and Cm. Because additional complexing agents are not required, waste-disposal and corrosion problems are reduced. Overall separation factors may be as high as several thousand for the separation of Am and Cm from lanthanides in the fission waste products from reactor fuel processing.     

Separation of thorium from lanthanides by solvent extraction with ionizable crown ethers

Thorium and the lanthanides are extracted by alpha-(sym-dibenzo-16-crown-5-oxy)acetic acid and its analogues in different pH ranges. At pH 4.5, Th is quantitatively extracted by the crown ether carboxylic acids into chloroform whereas the extraction of the lanthanides is negligible. Separation of Th from the lanthanides can be achieved by solvent extraction under this condition. The extraction does not require specific counteranions and is reversible with respect to pH. Trace amounts of Th in water can be quantitatively recovered using this extraction system for neutron activation analysis. The nature of the extracted Th complex and the mechanism of extraction are discussed.     

Determination of alpha-emitting uranium isotopes in soft tissues by solvent extraction and alpha-spectrometry

A radiochemical procedure has been developed for the determination of alpha-emitting isotopes of uranium ((238)U, (235)U and (234)U) in soft tissues. Known amounts of sample are spiked with (232)U internal tracer and wet-ashed. Uranium is co-precipitated with iron hydroxide as carrier, and extracted into 20% trilaurylamine solution in xylene after dissolution of the precipitate in 10M hydrochloric acid. The uranium, after stripping into an aqueous phase, is electro-deposited onto a platinum disc and counted by alpha-spectrometry. The radiochemical recovery ranges from 60 to 85% for bovine liver samples. The average radiochemical recoveries for human tissues vary from 53 to 78%.     

Separation of strontium from nuclear waste solutions by solvent extraction with crown ethers

The possibilities of strontium separation from medium activity waste (MAW) solutions have been investigated. MAW originates from the PUREX process and contains NaNO₃ and HNO₃ in a large excess. By solvent extraction with the crown ether dicyclohexano-18-crown-6 (DC-18-C-6) in 1,1,2,2-tetrachloroethane, separation is possible. The distribution ratio for Sr²⁺ depends on the concentration of HNO₃, NaNO₃ and Pb(NO₃)₂. The extraction system is employed in a continuous counter-current process. After use, the extraction agent can easily be regenerated by reextraction with pure water.