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1.
Extraction behavior of 1 × 10−2–0.1 M U(VI) from aqueous phases containing 0.86 M Th(IV) at 4 M HNO3 in 1.1 M tributyl phosphate (TBP) and 1.1 M N,N-dihexyl octanamide (DHOA) solutions in different diluents viz. n-dodecane, 10% 1-octanol + n-dodecane, and decahydronaphthalene (decalin) was studied. Third-phase formation was observed in both the extractants using n-dodecane as diluent. There was a gradual decrease in Th(IV) concentration in the third-phase (heavy organic phase, HOP) with increased aqueous U(VI) concentration [0.71 M (no U(VI))–0.61 M (0.1 M U(VI)) for TBP; 0.27 M (no U(VI))–0.22 M (0.1 M U(VI)) for DHOA]. The HOP volume in case of DHOA was ~2.2 times of that of TBP. Uranium concentration in HOP increased with its initial concentration in the aqueous phase [from 1.8 × 10−2 M (0.01 M U(VI))–0.162 M (0.1 M U(VI)) for TBP; from 1.4 × 10−2 M (0.01 M U(VI))–0.14 M (0.1 M U(VI)) for DHOA] suggesting that Th(IV) was being replaced by U(VI). An empirical correlation was developed for predicting the concentrations of uranium and thorium in HOP for both the extractants. No third-phase appeared during the extraction of uranium and thorium from the aqueous phases employing 10% 1-octanol + n-dodecane, or decalin as diluents, and therefore, were better choices as diluent for alleviating the third-phase formation during the reprocessing of spent thorium based fuels, and for the recovery of thorium from high-level waste solutions.  相似文献   

2.
A sensitive and selective solid phase extraction procedure for the determination of trace of uranium(VI) has been developed. An alumina-sodium dodecyl sulfate coated on with pyrocatechol violet was used for preconcentration and determination of uranyl ions by spectrophotometry method using Arsenazo III reagent. Sorbed ions were quantitatively eluted using 5 mL of 0.25 mol L−1 HNO3. The effects of parameters such as pH, amount of alumina, amount of ligand, flow rate, type and concentration of elution agent were examined. The capacity of the sorbent for U(VI) was found to be 0.92 mmol g−1. The relative standard deviation was 1.28% for 10 replicate determinations of U(VI) ion in a solution with a concentration of 1.0 μg mL−1. The practical applicability of the developed sorbent was examined using synthetic and real samples such as standard reference material 2709 (San Joaquin Soil) and 2711 (Montana Soil).  相似文献   

3.
 Simple, rapid, sensitive and selective methods for the determination of Cr(III) and W(VI) with flavonol derivatives in the presence of surface-active agents are proposed. In the pH ranges 3.4–4.2 and 1.9–2.5, the molar absorptivities of Cr(III)-morin-emulsifier S (EFA) and W(VI)-morin-polyvinylpyrrolidone (PVP) systems are 1.13×105 and 2.13×104 L mol−1 cm−1 at 435 and 415 nm, respectively. The Cr(III)-quercetin-PVP and W(VI)-quercetin-cetylpyridinium bromide (CPB) systems are formed in the pH ranges 4–4.6 and 2.2–2.8 with molar absorptivities 1.02×105 and 9.02×104 L. mol−1 cm−1 at 441 and 419 nm, respectively. The linear dynamic ranges for the determination of Cr(III) and W(VI) with morin in the presence of EFA and PVP are 0.03–0.46 and 0.71–8.1 μg mL−1, respectively. The corresponding ranges with quercetin are 0.04–0.54 and 0.14–2.1 μg mL−1 of Cr(III) and W(VI), respectively. The r.s.d (n = 10) for the determination of 0.25 and 3.7 μg mL−1 of Cr(III) and W(VI) with morin and their detection limits are 0.88 and 0.99% and 0.016 and 0.63 μg mL−1, respectively. Using quercetin, the r.s.d (n = 10) for 0.22 and 1.2 μg mL−1 of Cr(III) and W(VI) and their detection limits are 0.92 and 0.91% and 0.015 and 0.08 μg mL−1, respectively. The critical evaluation of the proposed methods is performed by statistical analysis of the experimental data. The proposed methods are applied to determine Cr in steel, non-ferrous alloys, wastewater and mud filtrate and to the determination of W in steel. Received March 8, 1999. Revision January 21, 2000.  相似文献   

4.
Extraction behavior of U(VI) and Th(IV) from nitric acid medium is investigated using organo-phosphorous extractant, tri(butoxyethyl) phosphate in n-paraffin at room temperature (27 ± 1 °C). The effect of diluents, nitric acid concentration as well as extractant concentration on extraction of U(VI) and Th(IV) are evaluated. Extraction of U(VI) and Th(IV) from nitric acid medium proceeds via solvation mechanism. Slope analysis technique showed the formation of neutral complexes of the type of UO2(NO3)2·2TBEP and Th(NO3)4·3TBEP with U(VI) and Th(IV) respectively in the organic phase. The FTIR data showed shifting of P=O stretching frequency from 1,282 to 1,217 cm−1 indicating the strong complexation of P=O group with UO2 2+ ions in the organic phase. Effect of stripping agents, other metal ions and their separation with respect to U(VI) extraction has also been investigated.  相似文献   

5.
A sensitive and non chromatographic analytical procedure for the separation of inorganic selenium species in natural water has been performed. A combination of APDC coprecipitation and determination by an absolute thin layer Energy dispersive X-ray fluorescence spectrometry method was used. The influence of various analytical parameters such as element concentration, oxidation states and pH on the recoveries of Se (IV) was examined. The presence of organic matter and bicarbonate anions, typical components in Cuban groundwater samples, was also tested. Negligible matrix effects were observed. At pH 4 a 100% recovery was found for Se (IV). The coprecipitation recovery of the oxidized selenium species (Se (VI)) was null for the selected concentration range (5–100 μg L−1). When the Se (VI) was reduced by heating the solution with 4 mol L−1 HCl, quantitative recovery was also obtained. The determination of total selenium was conducted by the application of the oxidation–reduction process and the analytical procedure for Se (IV). Se (VI) content was calculated as the difference between total selenium and Se (IV). The detection limit was 0.13 μg L−1. The relative standard deviation was lower than 3.5% for 5 μg L−1 of Se (IV). The trueness of the method was verified by using standardized hydride generation-atomic absorption spectrometry technique. The results obtained using the EDXRF technique were in good agreement with the ones determined by HG-AAS. The proposed method was applied to the determination of Se (IV) in surface water and groundwater samples.  相似文献   

6.
A simple, fast, low cost, and precise direct β-correction spectrophotometric method was developed for thorium determination in water. The method is based on the reaction of Th(IV) with 4-(2-pyridylazo)-resorcinol (PAR) in aqueous solution of pH 5–6 and measuring the absorbance of the resulting red-colored complex at λmax 497 nm. The effective molar absorptivity of the Th(IV)-PAR complex was 2.52 × 104 L mol−1 cm−1. Beer’s law and Ringbom plots were obeyed in the concentration range 0.04–2.0 and 0.07–1.2 μg mL−1 of thorium ions using β-correction spectrophotometry, respectively. The limits of detection and quantification of Th(IV) were 0.02 and 0.066 μg mL−1, respectively. The developed method was applied for the analysis of thorium in certified reference material (IAEA-soil-7), tap-, underground- and Red-sea water samples. The validation of the method was also tested by comparison with data obtained by ICP-MS. The method is convenient, less sensitive to common interfering species and less laborious than most of published methods. The statistical treatment of data in terms of Student t-tests and variance ratio f-tests has revealed no significance differences. The structure of the Th(IV)-PAR complex was determined with the aid of spectroscopic measurements (UV–Visible and Fourier Transform Infrared Spectroscopy).  相似文献   

7.
During this work selective separation of uranium from rock phosphate and columbite mineral was done before its quantitative estimation by using Inductively Coupled Plasma Optical Emission Spectrometery (ICP-OES). Uranium from the rock phosphate and columubite was extracted by sodium peroxide fusion followed by leaching in 2 M HNO3. To avoid spectral interference in the estimation of uranium by ICP-OES, the selective separation of uranium from the leachate was carried out by using two different extractants, 30% Tributyl Phophates (TBP) in CCl4 and a equi-volume mixture of Di(2-ethylhexyl) phosphoric acid (D2EHPA) & TBP in petrofin. Uranium was stripped from the organic phase by using 1 M ammonium carbonate solution. Determination of uranium by ICP-OES was done after dissolving the residue left after evaporation of ammonium carbonate solution in 4% HNO3. The concentration of the uranium observed in the rock phosphates samples was 40–200 μg g−1 whereas in columbite samples the concentration range was 100–600 μg g−1. Uranium concentration evaluated by ICP-OES was complimented by gamma & alpha spectrometry. Concentration of uranium evaluated by gamma spectrometry in case of rock phosphate and coulmbite was in close agreement with the uranium content obtained by ICP-OES. Uranium determination by alpha spectrometry showed only minor deviation (1–2%) from the results obtained by ICP-OES in case of rock phosphates whereas in case of coulmbites results are off by 20–30%.  相似文献   

8.
In geochemistry, the distribution of the Rare Earth Elements (REEs) in earth crust and mantle allows to understand geochemical cycles and origin and age of igneous rocks. In this article REEs (Ce, Dy, Eu, La, Nd, Sm, Tb, and Yb), Th and U in ores of the North-Latium (Bracciano area, Ceriti Mt., Fate Mt., Sabatini Mt., Vulsini Mt., Acqua Rossa basin), have been investigated for evaluating the extraction feasibility for industrial applications. 107 samples were irradiated in the rotating rack of the TRIGA Mark II reactor of the R.C. Casaccia (ENEA) at neutron flux of 2.6 × 1012 n × cm−2 × s−1 for 12 h together with primary and secondary standards. The gamma spectrometry measurements were performed after 8 h, 3 and 30 days of decay by means of HPGe detector (FWHM 1.75 keV at 1332.5 keV, peak/Compton ratio 55.1, relative efficiency of 22%) connected to a multi-channel analyzer. The total REE mean content is 105 μg g−1, ranging widely between 2.23 and 410.5 μg g−1 (average coefficient of variation 112%). A similar behavior is found for Th and U: their average levels are 13.5 and 6.0 μg g−1, respectively. A quite good correlation between REEs and Th (and U) is found for Ceriti Mt. (r 2 > 0.8) whereas for the other areas the correlation is <0.7. The results obtained evidence the low U content in the investigated locations.  相似文献   

9.
This paper reports silica gel loaded with p-tert-butylcalix[8]arene as a new solid phase extractor for determination of trace level of uranium. Effective extraction conditions were optimized in column methods prior to determination by spectrophotometry using arsenazo(III). The results showed that U(VI) ions can be sorbed at pH 6 in a mini-column and quantitative recovery of U(VI) (>95–98%) was achieved by stripping 0.4 mol L−1 HCl. The sorption capacity of the functionalized sorbent is 0.072 mmol uranium(VI) g−1 modified silica gel. The relative standard deviation and detection limit were 1.2% (n = 10) for 1 μg uranium(VI) mL−1 solution and 0.038 μg L−1, respectively. The method was employed to the preconcentration of U(VI) ions from spiked ground water samples.  相似文献   

10.
Solvent extraction of U(VI) with di-isodecyl phosphoric acid (DIDPA)/dodecane from nitric acid medium has been investigated for a wide range of experimental conditions. Effect of various parameters including nitric acid concentration, DIDPA concentration, temperature, stripping agents, and other impurities like rear earths, transition metal ion, boron, aluminum ion on U(VI) extraction has been studied. The species extracted in the organic phase is found to be UO2(NO3)(HA2)·H2A2 at lower acidity (<3.0 M HNO3). Increase in temperature lead to the decrease in extraction with the enthalpy change by ∆H = −16.27 kJ/mol. Enhancement in extraction of U(VI) from nitric acid medium was observed with the mixture of DIDPA and tri butyl phosphate (TBP). The stripping of U(VI) from organic phase (DIDPA–U(VI)/dodecane) with various reagents followed the order: 4 M H2SO4 > 5% (NH4)2CO3 > 8 M HCl > 8 M HNO3 > Water. High separation factors between U(VI) and impurities suggested that the use of DIDPA for purification of uranium from multi elements bearing solution.  相似文献   

11.
The World Health Organization states that envenomation is responsible for a high number of deaths per year, especially in equatorial areas. The only effective specific treatment is the use of hyperimmune serum (antivenom). In Brazil, Crioula breed horses are used for antivenom production, with great importance in the maintenance of public health programs. A strict biochemical and metabolic control is required to attain specificity in antiserum. Inorganic elements represent only a small fraction of whole blood. Nonetheless, they play important roles in mammalian metabolism, being responsible for controlling enzymatic reactions, respiratory and cardiac functions and ageing. In this work, whole blood samples from Crioula breed horses were analyzed by EDXRF technique. The reference interval values were determined for the elements Na (1955–2013 μg g−1), Mg (51–75 μg g−1), P (523–555 μg g−1), S (1628–1730 μg g−1), Cl (2388–2574 μg g−1), K (1649–1852 μg g−1), Ca (202–213 μg g−1), Cu (4.1–4.5 μg g−1) and Zn (2.4–2.8 μg g−1) and a comparative study with NAA results was outlined. The samples were obtained from Instituto Butantan. Both techniques showed to be appropriate for whole blood sample analyses and offer a new perspective in Veterinary Medicine.  相似文献   

12.
5,10,15,20-tetrakis(phenoxy acetic acid) porphyrin (PAAP) was covalently linked to Merrifield chloromethylated resin. Characterization of PAAP and the modified polymeric matrix were performed by 1H NMR, FTIR and elemental analysis. The sorbent was used for the separation and enrichment of the d-electron metals (Mn(II), Co(II), Ni(II), Cu(II) and Zn(II)) at pH 6–8 and of the f-electron metals U(VI) and Th(IV) at pH 4–5. The metals ions were preconcentrated with a concentration factor range of 115–215 and then determined by flame atomic absorption spectrometry or visible spectrophotometry using Arsenazo(III). The retained metals were eluted with 2.0 mol L−1 HNO3 in the case of the d-electron metals and 0.1/0.25 mol L−1 HCl in the case of the f-electron metals. The procedure was validated by analyzing the NIST standard reference material 2709 (San Joaquin Soil). Correspondence: Melek Merdivan, Chemistry Department, Faculty of Arts and Sciences, Dokuz Eylul University, 35160 Buca, Izmir, Turkey  相似文献   

13.
The extraction order of Th(IV), U(VI) and Mo(VI) based on pH0.5 values is Mo(VI)>U(VI)>Th(IV). Quantitative extraction has been observed for U(VI) by mixture of 10% (v/v) LIX 84 and 0.1M dibenzoylmethane at pH 4.2 and by mixture of 10% LIX 84 and 0.05M HTTA in the pH range 5.5–7.3 and for Mo(VI) by 10% LIX 84 from chloride media at pH 1.5. The order of extraction of Mo(VI) from 1N acid solutions is HCl>H2SO4>HNO3>HClO4 and extraction decreases very rapidly with increase in the concentration of HCl as compared to that from H2SO4, HNO3 and HClO4 acid solutions. The diluents C6H6, CCl4 and CHCl2 are found to be superior ton-butyl alcohol and isoamyl alcohol for extraction of Mo(VI). Influence of concentration of different anions on the extraction of U(VI) and Mo(VI) has been studied. Very little extraction has been observed in case of Th(IV) by LIX 84 or its mixtures with other chelating extractants or neutral donors.  相似文献   

14.
The extractive properties of the ortho-aminophenol reagent upon U(VI) were investigated in two solvents: 4-chlor-acetophenone and acetylacetone, in a water-organic solvent system. The method here proposed is based on the complexation reaction of the uranyl ion, UO2 2+, with ortho-aminophenol dissolved in 4-chlor-acetophenone, at room temperature, over a pH interval = 4–6, followed by spectro-photometry of the organic phase, involving measuring of absorbancy at 569.6 nm. The Beer law is valid over the 1–12 μg U(VI)/mL concentration interval, with molar absorbtivity εmax = 4.3 × 105 mol−1 cm2 and Sandell sensitivity = 0.0526 μg cm−2. The structure, stability and solubility of the formed complex was studied by UV–VIS and IR spectrometry, diffractometry and scanning electron microscopy. The mixed complex formed between the uranyl ion and the ortho-aminophenol dissolved in 4-chlor-acetophenone, [UO2.(L)2.(S)4], is characterized by the following parameters: metal/ligand combination ratio: M/L = 1/2, stability constant β = 2.06 × 106, distribution coefficient D = 66.56 (Vorg = Vaq), percentage extraction E% = 98.52, and recovery factor, R%, ranging between 99.48 and 99.85%.  相似文献   

15.
New complexes of MoO2(VI), WO2(VI), Th(IV) and UO2(VI) with aroyl hydrazones have been prepared and characterized by various physicochemical methods. Elemental analysis suggested 1 : 1 metal : ligand stoichiometry for MoO2(VI), WO2(VI), and UO2(VI) complexes whereas 1 : 2 for Th(VI) complexes. The physicochemical studies showed that MoO2(VI), Th(IV) and UO2(VI) complexes are octahedral. The electrical conductivity of these complexes lies in the range 1.00 × 10−7−3.37 × 10−11Ω−1 cm−1 at 373 K. The complexes were found to be quite stable and decomposition of the complexes ended with respective metal oxide as a final product. The thermal dehydration and decomposition of these complexes were studied kinetically using both Coats-Redfern and Horowitz-Metzger methods. It was found that the thermal decomposition of the complexes follow first order kinetics. The thermodynamic parameters of the decomposition are also reported. The biological activities of ligands and their metal complexes were tested against various microorganisms.  相似文献   

16.
Liquid-liquid extraction of Th(IV) and U(VI) has been investigated by commercial extractant PC-88A in toluene. The optimum conditions for extraction of these metals have been established by studying the various parameters like acid concentration/pH, reagent concentration, diluents and shaking time. The extraction of Th(IV) was found to be quantitative with 0.1–1.0M HNO3 acid and in the pH range 1.0–4.0 while U(VI) was completely extracted in the pH range 1.0–3.5 with 2.5·10–2M and 2.·10–2M PC-88A in toluene, respectively. The probable extracted species have been ascertained by log D-log C plot as ThR4·4HR and UO2R2·2HR, respectively. The method permits separation of Th(IV) and U(VI) from associated metals with a recovery of 99.0%.  相似文献   

17.
The effect of mM concentrations of K3[Fe(CN)6], Fe(III), Mo(VI), KSCN and KMnO4 on the generation of BiH3 by the reaction of 0.2–10 μg ml−1 Bi(III) with 0.2 M tetrahydroborate(III) at 1 M acidity (HCl or HNO3) was investigated. Chemical vapour generation (CVG) of BiH3 was investigated by atomic absorption spectrometry using a continuous flow reaction system (CF–CVG–AAS) and different mixing sequences and reagent reaction times. Gas chromatography–mass spectrometry (GC–MS) was employed in batch generation experiments with NaBD4. In the absence of additives, the formation of Bi0 at high concentrations of Bi(III) caused rollover of calibration curves and limited the linear range to less than 1 μg ml−1 Bi(III). In the presence of additives, the formation of Bi0 was not observed and the linear range was increased to 5 μg ml−1 of Bi(III) while rollover was completely removed. GC–MS experiments indicated that the presence of additives did not affect the direct transfer of H from boron to bismuth. Experiments with CF–CVG–AAS and different mixing sequences and reagent reaction times suggest that additives act by preventing the formation of Bi0 through the formation of reaction intermediates which evolve towards the formation of BiH3 at elevated Bi(III)/NaBH4 ratios.   相似文献   

18.
175, 181Hafnium(IV) was extracted by HDBP in 2-ethylhexanol from 1–10M solutions of HClO4, HCl and HNO3, and 1–8M H2SO4. As with low polar organic phase diluents, the acidity dependence of the distribution ratio of Hf, D, passes through a minimum for HClO4, HCl, and H2SO4 whereas only an increase of D can be observed with increasing HNO3 concentration. From the slope analysis the following complexes were found to be extracted (HDBP=HA): HfA4 at <4M HClO4 and <5M HCl, lg Kextr=9, HfX4(HA)4 (X=ClO 4 , Cl or NO 3 ) at >5M HClO4, >7M HCl and 1–10M HNO3, Hf(SO4)A2(HA)3–4 at <3M H2SO4, and Hf(SO4)2 (HA)4 at >6M H2SO4. Coextraction of sulphate with hafnium from H2SO4 solutions was evidenced in experiments with macro concentrations of Hf(IV) and35SO 4 2− . Part XX: Coll. Czech. Chem. Commun., 40 (1975) 3617.  相似文献   

19.
A mid-infrared enzymatic assay for label-free monitoring of the enzymatic reaction of fructose-1,6-bisphosphatase with fructose 1,6-bisphosphate has been proposed. The whole procedure was done in an automated way operating in the stopped flow mode by incorporating a temperature-controlled flow cell in a sequential injection manifold. Fourier transform infrared difference spectra were evaluated for kinetic parameters, like the Michaelis–Menten constant (K M) of the enzyme and V max of the reaction. The obtained K M of the reaction was 14 ± 3 g L−1 (41 μM). Furthermore, inhibition by adenosine 5′-monophosphate (AMP) was evaluated, and the K MApp value was determined to be 12 ± 2 g L−1 (35 μM) for 7.5 and 15 μM AMP, respectively, with V max decreasing from 0.1 ± 0.03 to 0.05 ± 0.01 g L−1 min−1. Therefore, AMP exerted a non-competitive inhibition.  相似文献   

20.
The extraction behavior of U(VI) and Th(IV) with tri-isoamyl phosphate–kerosene (TiAP–KO) from nitric acid medium was investigated in detail using the batch extraction method as a function of aqueous-phase acidity, TiAP concentration and temperature, then the thermodynamic parameters associated with the extraction were derived by the second-law method. It could be noted that the distribution ratios of U(VI) or Th(IV) increased with increasing HNO3 concentration until 6 or 5 M from 0.1 M. However, a good separation factor (D U(VI)/D Th(IV)) of 88.25 was achieved at 6 M HNO3, and the stripping of U(VI) from TiAP–KO with deionized water or diluted nitric acid was easier than that of Th(IV). The probable extracted species were deduced by log D-log c plot at different temperatures as UO2(NO3)2·(TiAP)(1–2) and Th(NO3)4·(TiAP)(2–3), respectively. Additionally, △H, △G and △S for the extraction of U(VI) and Th(IV) revealed that the extraction of U(VI) by TiAP was an exothermic process and was counteracted by entropy change, while the extraction of Th(IV) was an endothermic process and was driven by entropy change.  相似文献   

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