Liquid-liquid extraction of 99Mo and 187W with trioctylamine

Molybdenum and tungsten can be separated from each other by extraction with trioctylamine in hydrochloric acid medium.     

Extraction chromatographic separation of99Mo and187W with trioctylamine

⁹⁹Mo and¹⁸⁷W have been separated by reversed phase extraction chromatographic technique, using 1M TOA impregnated on kieselguhr in a column and 4N HCl, respectively, as stationary and mobile phase.     

Extraction of Mo, W and Tc with polyurethane foam and with cyclic polyether from SCN-/HCL medium

The extraction of molybdenum, tungsten and technetium by polyether-based polyurethane foam and by a cyclic polyether from aqueous thiocyanate solutions is described. The influence of the reductants stannous chloride and ascorbic acid has also been studied. The possibilities of the polyurethane foam for preconcentration and determination of molybdenum are discussed.     

High‐field 95Mo and 183W static and MAS NMR study of polyoxometalates

The potential of high‐field NMR to measure solid‐state ⁹⁵Mo and ¹⁸³W NMR in polyoxometalates (POMs) is explored using some archetypical structures like Lindqvist, Keggin and Dawson as model compounds that are well characterized in solution. NMR spectra in static and under magic angle spinning (MAS) were obtained, and their analysis allowed extraction of the NMR parameters, including chemical shift anisotropy and quadrupolar coupling parameters. Despite the inherent difficulties of measurement in solid state of these low‐gamma NMR nuclei, due mainly to the low spectral resolution and poor signal‐to‐noise ratio, the observed global trends compare well with the solution‐state NMR data. This would open an avenue for application of solid‐state NMR to POMs, especially when liquid‐state NMR is not possible, e.g., for poorly soluble or unstable compounds in solution, and for giant molecules with slow tumbling motion. This is the case of Keplerate where we provide here the first NMR characterization of this class of POMs in the solid state. Copyright © 2017 John Wiley & Sons, Ltd.     

萃淋树脂CL—P507吸附分离钨,钼的研究：Ⅰ.树脂的吸附及分离性能

本文考察了萃淋树脂CL-P507对钨、钼的吸附性能,测定了树脂的饱和吸附容量,得出了在H_2SO_4-EDTA体系中从含大量钨的溶液中分离钼的条件。     

Polymerization of silylacetylenes by W and Mo catalysts

Polymerization of HC?CSiMe₃ homologues (HC?CSiMe₂R; R = n-C₆H₁₃, CH₂CH₂Ph, CH₂Ph, Ph, and t-Bu) was studied by use of W and Mo catalysts. W catalysts provided polymers in good yields from all these monomers. Mo catalysts gave mainly a polymer from HC?CSiMe₂–t-Bu, but virturally only cyclotrimers from sterically less croweded monomers (R = n-C₆H₁₃, CH₂CH₂Ph, CH₂Ph, and Ph). Polymers with flexible R groups (n-C₆H₁₃, CH₂CH₂Ph, and CH₂Ph) were totally soluble, their number-average molecular weights being 7000–18,000. Polymers with inflexible R groups (Ph and t-Bu) were partly insoluble. Every polymer was a yellow rubber or powder, and had the structure, \documentclass{article}\pagestyle{empty}\begin{document}$ \rlap{--} [{\rm CH} = {\rm C}\left( {{\rm SiMe}_{\rm 2} {\rm R}} \right)\rlap{--} ]_n $\end{document}. The results were compared with the polymerization and polymer of HC?CSiMe₃.     

INAA for control of technology in producing Mo and W

INAA technique for the determination of impurities (O, F, Na, Mg, Al, Si, P, S, K, Sc, Cr, Mn, Fe, Co, Ni, etc.) and of some doping elements in molybdenum and tungsten with detections limits between 10^–12 and 10^–6g/g by using a nuclear reactor and a neutron generator have been developed. The methods have been used to control the products of processing of refractory materials, to study the dynamics of impurities and doping elements at all stages of the production process.     

Species dependent extraction of 99Mo

The liquid–liquid extraction profile of molybdenum has been studied with di-(2-ethylhexyl) phosphoric acid from different HCl media. The careful study of extraction profile clearly indicates various species of molybdenum at different acid strengths, which have been interpreted with reference to established data.     

Solvent extraction of Mo(V) and Mo(VI) from hydrochloric acid into Aliquat 336 chloroform solution

Solvent extraction of macro amounts of Mo(V) and Mo(VI) from HCl using Aliquat 336 in chloroform was performed for the electrochemistry of Sg. The extraction reaction attained equilibrium with a shaking time of 10 s in higher than 8 M HCl. The D values of Mo(V) obtained by the electrochemical reduction of Mo(VI) were in good agreement with those obtained by the extraction of MoCl₅, and the D values of Mo(V) were higher than those of Mo(VI). These results suggested that the reduction behavior of Sg might be studied by electrochemical reduction combined with the present solvent extraction.     

Reactivity and electronic property of decaphenylmetallocenes of Mo and W atoms

The perphenylmetallocene complexes (η⁵-C₅Ph₅)₂W (1), [(η⁵-C₅Ph₅)₂W]⁺I₃⁻ (1⁺I₃), (η⁵-C₅Ph₅)₂Mo (2) and [(η⁵-C₅Ph₅)₂Mo]⁺I₃⁻ (2⁺I₃) have been prepared. Hydrogenation of 1 in THF produces (η⁵-C₅Ph₅)₂WH₂ (4), while (η⁵-C₅Ph₅)₂WHCl (3) is afforded in 1,2-dichloroethane solvent. Carbonylation of 1 produces (η⁵-C₅Ph₅)₂W(CO) (5). Treatment of 1 with the strong acid CF₃SO₃H leads to the dicationic species [(η⁵-C₅Ph₅)₂W]⁺²[CF₃SO₃]⁻₂ (1⁺²Tf₂) after crystallization. The structures of 2⁺I₃ and 1⁺²Tf₂ have been determined by an X-ray diffraction study. The magnetic susceptibility study indicates a ³E_2g ground-state for 1 and 2, and a ⁴A_2g ground-state for 1⁺ and 2⁺.     

99Mo提取后的裂变残液中铀回收技术初步研究

本文对裂变99Mo提取后残液中铀的回收进行了不同类型萃取溶液的效率对比,最终选择了萃取效率最好的30%二-(2-乙基乙基)磷酸的正十二烷溶液进行了条件实验,结果表明体系的HNO3浓度在4.0mol/L附近铀的分配比达到最大值,萃取过程为放热反应,且提高搅拌强度有利于加快萃取速率。     

Cloud point extraction of 99Mo with Triton X-114

This paper reports the cloud point extraction (CPE) extraction behaviour of ⁹⁹Mo in non-ionic Triton X-114 (TX-114), sodiumdodecyl sulphate (SDS) + TX-114 and sodium diethyldithiocarbamate (DDTC) + TX-114. The high extraction of ⁹⁹Mo observed in all the CPE systems in pH 5 or less. The extent of extraction was almost unchanged with addition of SDS and DDTC in TX-114. Extraction behaviour was also studied in presence of common salts. It was observed the presence of salts dramatically decreased the amount of molybdenum extraction in the surfactant-rich phase.     

Liquid-liquid extraction of Mo(VI) and V(V) by Primene JMT

The extraction equilibrium of pentavalent vanadium and hexavalent molybdenum with a benzene solution of primary amine Primene JMT sulphate has been investigated. The comparison of the extraction of aqueous solutions containing the salts of the elements and the solutions containing the mixture of Mo(VI) and V(V) was carried out. The attention was directed to the pH 2–6 region in which the heptamolybdates and decavanadates in prevail aqueous phase and to the region ≈1M H₂SO₄ which was suitable for the extraction separation of Mo(VI). The mechanism of extraction is discussed.     

Solvent extraction of W(VI) with rhodamine-B in nitrobenzene

A rapid and selective method has been developed for the extraction of W(VI) with rhodamine-B in nitrobenzene. The extraction coefficient value for the extraction between aqueous solution and nitrobenzene showed a maximum value of E=63 at a pH of 5.0. The stoichiometry of metal to reagent has been determined by the method of substoichiometric extraction and slope ratio method.     

A radical pathway to synthesise Mo and W dithiolene complexes

A new method has been developed to synthesise bis η(5)-cyclopentadienyl dithiolene complexes of molybdenum and tungsten. This procedure involves the in situ thermolysis of the azo compounds, 2,2'-azobisisobutyronitrile (AIBN) or 1,1'-azobiscyclohexanecarbonitrile (ACCN) (R'(2)N(2), R' = CMe(2)CN or C(6)H(10)CN, respectively), which initiates a reaction between [Cp(2)M(S(4))] (M = Mo or W) and an alkyne (HC(2)R, R = Ph, 2-pyridyl or 2-quinoxalinyl) and produce the corresponding [Cp(2)M(S(2)C(2)RR')] compound.     

Radiation reduction of Cr, Mo and W isopolymetalates in aqueous system

The radiation-chemical processes in aqueous solutions of dichromates, isopolymolybdates and isopolytungstates have been studied. The radiation reduction of Cr(VI) to Cr(III), Mo(VI) to Mo(V) and W(VI) to W(V) takes place. Molybdenum and tungsten blues are the products of the last two processes in acid solutions. The yields of reduction decrease significantly with the increase of pH. The mechanisms of the processes have been discussed. The photochemical reduction of Mo(VI) and W(VI) for the production of corresponding 5-valent states have been used to the study of their electron scavenging efficiencies. It has been shown that these efficiencies decrease in the order: Mo(V)>W(V)>Cr(VI)>Mo(VI)>W(VI).     

Group separation by solvent extraction from silicate rock matrix of Nb, Mo, Ta, and W at low levels for ICP-MS

Summary The extraction efficiency from silicate rock solutions in HF of Nb, Mo, Ta, and W as a function of fluoride activity in HCl solution, 3 mol/l, was investigated. At pF 3.5, N-benzoyl N-phenylhydroxylamine (BPHA) dissolved in CHCl₃ proved to be an ideal system for the separation of the four analyte elements from the rock matrix after HF dissolution. All major rock constituents except for titanium are left behind in the aqueous phase. Values for the distribution ratios are 500±100 for all four elements allowing cross calibration in ICP-MS between enriched isotopes of Mo and W added to the samples before dissolution (isotope dilution) and the neighbouring monoisotopic elements Nb and Ta. Previously such high distribution ratios have been reported for Mo only because Nb, Ta, and W are not normally available as reactive ions due to hydrolysis unless directly released from fluoride complexes by downwards adjustment of fluoride activity of the solution in the presence of BPHA. Analytical data from 20 geochemical reference standards document the practical value of the described analytical procedure. Using ICP-MS and BPHA-pentanol solutions standards, superior detection limits are demonstrated by Nb, Ta, and W values in the sub ppm range obtained for some ultrabasic rock standards for which reference values are not yet available. Using ICP-MS and BPHA-pentanol solutions, superior detection limits are demonstrated by concentration values in the sub ppm range obtained for some ultrabasic rock standards for which reference values are not yet available.     

Radiochemical solvent extraction of molybdenum/VI/ using99Mo tracer

A radiochemical solvent extraction method has been developed for the micro determination of Mo/VI/ using⁹⁹Mo tracer. It involves removal of^99mTc by ethyl methyl ketone /EMK/ and extraction of Mo with tri-n-butyl phosphate /TBP/ from 5M HCl. Different parameters affecting the extraction such as pH dependence, nature of solvent and interferences due to other radionuclides have been studied. The method can be used up to 2 g of Mo.