Cation Exchange Separation of Protactinium from Tantalum with Sulfuric Acid-Alcohol Mixed Solvent System

Distributions of protactinium and tantalum between strongly acidic cation exchange resin and sulfuric acid-mixed organic solvent system were studied with Pa-233 and Ta-182 as radioactive tracers. Methyl, ethyl and isopropyl alcohols were used as miscible organic solvents and Dowex 50 W-X 2, Dowex 50 W-X 12, Bio Rad AG 50 W-X 4 and AG 50 W-X 12 were used for different cross linking cation exchange resin. Distribution ratios were plotted against acidities by keeping compositions constant or against compositions by keeping acidities constant. From these plot tings, different trends of these two metals were found. With the use of the property of especially strong absorption of protactinium in methyl alcohol solution by resin having higher degree of cross linking, AG 50 W-X 12, tantalum could be completely separated from protactinium.     

Solvent extraction study of protactinium(V) with methyl-iso-butyl carbinol and methyl-iso-butyl ketone

In order to study the extraction pattern of protactinium in different types of extracting agents and compare the similarity of patterns of extraction with dubnium and thereby unraveling its chemistry, solvent extraction of protactinium(V) with methyl-iso-butyl carbinol (MIBC) and methyl-iso-butyl ketone (MIBK) was studied using ²³³Pa as a radiotracer. The extraction efficiencies of Pa were determined as a function of shaking time, concentrations of mineral acids, and extractant concentrations using the two extractants. The results show that MIBK is more suitable for the extraction of protactinium than MIBC in benzene. Furthermore, the effect of the F anion is also discussed. The text was submitted by the authors in English.     

Use of tetracycline as complexing agent in radiochemical separations

The use of the antibiotic agent tetracycline for analytical purposes in solvent extraction procedures is presented. Individual extraction curves for the lanthanides, zinc, scandium, uranium, thorium, neptunium and protactinium were obtained. Separation of those elements one from another, and of uranium from selenium, bromine, antimony, barium, tantalum and tungsten was carried out. In all cases benzyl alcohol was the diluent used to dissolve tetracycline hydrochloride. Sodium chloride was used as supporting electrolyte for the lanthanide separations and sodium perchlorate for the other elements mentioned. Stability or formation constants for the lanthanide complexes as well as for thorium complex with tetracycline were determined by using the methods of average number of ligands, the limiting value (for thorium), the two parameters and the weighted least squares. For the lanthanides, the stability constants of the complexes Ln(TC)₃ go from 9.35±0.22 for lanthanum up to 10.84±0.11 for lutetium. For the Th(TC)₄ complex the formation constant is equal to 24.6±0.3. Radioisotopes of the respective elements were used for the determinations. When more than one radioelement was present in an experiment, a multichannel analyser coupled to Ge(Li) or NaI(Tl) detectors was used for counting the activities. When only one radioisotope was used, counting of the radioisotopes was made with a single-channel analyser (integral mode counting) coupled to a NaI(Tl) detector. Uranium was determined by activation analysis (epithermal neutrons). Radioisotopes of the elements were obtained by irradiation in the IPEN swimming-pool reactor. The natural radioisotope^{2 3 4}Th was used as label in the thorium experiments. In some separation procedures such as in the case of the pair uranium-neptunium, and of the pair scandium-zinc, the separation was obtained by properly adjusting the pH value of the aqueous phases, before the extraction operation. In other cases, addition of masking agents to the extraction system was required in order to perform the separation between the elements under study. In this way ethylenediaminetetraacetic acid (EDTA) was used as masking agent for scandium and the lanthanides in order to allow separation of uranium from those elements. Diethylenetriaminepentaacetic acid (DTPA) was used as masking agent for thorium in order to extract uranium into the organic phase. Separations of protactinium from thorium, and of uranium from protactinium and thorium, were accomplished by using sodium fluoride as masking agent for protactinium and DPTA as masking agent for thorium and protactinium at the same time. In the case of the separation of the lanthanides one from another it is necessary to resort to a multi-stage extraction procedure since the stability constants for those elements are too close.     

Separation of protactinium from uranium and other reaction products in the reaction of 60 MeV/nucleon 18O with natural uranium

Protactinium was produced by the reaction of 60 MeV/nucleon ¹⁸O with natural uranium. A simple, relatively fast radiochemical procedure was developed, which can be used for the extraction separation of protactinium from uranium and from the complex reaction products using 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone and tri-iso-octylamine as extractants. Measurements of the gamma-ray spectra for the separated protactinium fractions were performed with a HPGe detector. The measured g-ray spectrum of protactinium shows that the decontamination from the main impurity elements, especially zirconium and niobium, is quite satisfactory.     

Determination of low molecular weight alcohols including fusel oil in various samples by diethyl ether extraction and capillary gas chromatography

Low molecular weight alcohols including fusel oil were determined using diethyl ether extraction and capillary gas chromatography. Twelve kinds of alcohols were successfully resolved on the HP-FFAP (polyethylene glycol) capillary column. The diethyl ether extraction method was very useful for the analysis of alcohols in alcoholic beverages and biological samples with excellent cleanliness of the resulting chromatograms and high sensitivity compared to the direct injection method. Calibration graphs for all standard alcohols showed good linearity in the concentration range used, 0.001-2% (w/v) for all alcohols. Salting out effects were significant (p < 0.01) for the low molecular weight alcohols methanol, isopropanol, propanol, 2-butanol, n-butanol and ethanol, but not for the relatively high molecular weight alcohols amyl alcohol, isoamyl alcohol, and heptanol. The coefficients of variation of the relative molar responses were less than 5% for all of the alcohols. The limits of detection and quantitation were 1-5 and 10-60 microg/L for the diethyl ether extraction method, and 10-50 and 100-350 microg/L for the direct injection method, respectively. The retention times and relative retention times of standard alcohols were significantly shifted in the direct injection method when the injection volumes were changed, even with the same analysis conditions, but they were not influenced in the diethyl ether extraction method. The recoveries by the diethyl ether extraction method were greater than 95% for all samples and greater than 97% for biological samples.     

Extraction of gold(III) from hydrochloric acid solutions with high-molecular aliphatic alcohols

Experiments on extraction of gold(III) from hydrochloric acid solutions with isomeric aliphatic alcohols containing 6–12 carbon atoms showed that secondary alcohols recover AuCl_4? from acid solutions with higher distribution ratios than primary alcohols do. The best alcohol that can be recommended for the extraction of gold(III) from 3–6 M HCl solutions, taking into account the solubility and extraction ability of alcohols, is 2-octanol. The possibility of efficient stripping of gold(III) from the 2-octanol phase with ammonia or thiourea solutions was demonstrated.     

Liquid-liquid extraction of some actinides with polyethyleneglycol and its derivatives

Polyethyleneglycol (PEG) and its derivatives of high molecular weight were found to be employed as useful extractants for the solvent extraction of uranium. The extraction behaviors of uranium and neptunium were investigated, particularly concerning the dependence of the extractibility of uranium(VI) on the molecular weight of PEG. A dominating species of the extracted uranium(VI) thiocyanate complexes was assumed to be NH₄ UO₂(SCN)₃·(PEG). The extraction of protactinium was also preliminarily studied. The extraction of these actinides from an acidic thiocyanate solution increased in the order: uranium(VI)>protactinium(V)>neptunium(V).     

Rapid extraction of microamounts of protactinium from hydrochloric acid solutions by morin-isoamylol

A new extractant for protactinium has been studied. This paper describes the extraction behaviour of Pa from HCl system by morin-isoamylol. The whole procedure can be completed in 100 sec., yield of extraction is 99.2%.     

Liquid-liquid extraction of 233Pa(V) with Aliquat 336</p> </p>

Summary The extraction of protactinium with Aliquat 336 (methyl-tri-caprylyl ammonium chloride) in toluene, cyclohexane and chloroform from HCl, HNO₃, H₂SO₄, HClO₄, HF and mixed HCl-HF media was investigated by radioactive tracer technique. Distribution ratios of protactinium between the aqueous solution and the organic phase were determined as a function of shaking time, concentrations of acid in aqueous solution phase, extractant concentration and type of diluents in the organic phase. Aliquat 336 can almost quantitatively extract protactinium from strong HCl solution. At the same time, small amounts of HF in HCl solutions have a strong effect on Pa distribution.</p> </p>     

Extraction of Nitric Acid and Np(IV) by some aliphatic ketones and alcohols

The extraction behaviour of HNO₃ and Np(IV) from aqueous nitrate solutions with some aliphatic alcohols and ketones using hexane, carbon tetrachloride, benzene and chloroform as diluents was studied. The acid concentration in the aqueous phase varied from 0.25 to 10 M and that of the extractant in the organic phase varied from 0.5 M to the undiluted fraction. In the alcohol systems, solutions of the same alcohol in the diluents CCl₄ and CHCl₃ showed similar capacity for acid extraction, and also in the same diluents, solutions of diisopropyl and diisobutyl alcohol showed similar capacity for extraction. Extraction of Np(IV) with the different ketones and alcohols used follow the same pattern as HNO₃.     

Extraction of vanadium(V) from acid solutions with octyl alcohol isomers

Vanadium(V) extraction with octyl alcohol isomers from acid solutions was studied. Two areas are determined, wherein the vanadium(V) extraction in relation to acidity of the aqueous phase is maximal. The opposite effects of temperature on the extraction are found. The mechanism of the vanadium(V) extraction with high molecular weight alcohols from weakly acid solutions was suggested.     

Trace analysis of surfactants derived from fatty alcohols I. Optimization of derivatization reaction

Summary Pre-column derivatization of the primary hydroxyl group in fatty alcohols and fatty alcohol ethoxylates using carbazole-9-carbonyl chloride (CC−Cl) and FMOC-Cl is described and compared with derivatization with 1-naphthoyl chloride (N−Cl). As the excess of derivatization reagent leads to a broad and strongly tailing reagent peak, it hinders trace determination of fatty alcohols and fatty alcohol ethoxylates. Therefore, an off-line as well as an on-line solid-phase extraction (SPE) method for removal of excess reagent are described. The on-line method which is based on column switching, shows better reproducibility higher pre-concentration, lower risk of contamination and can be easily automated, while the off-line method is better suited for the analysis of derivatized, fatty alcohol ethoxylates. An example of the trace analysis of fatty alcohols with a concentration of 2 ppb is given.     

Thermodynamical and structural study of protactinium(V) oxalate complexes in solution

The complexation of protactinium(V) by oxalate was studied by X-ray absorption spectroscopy (XAS), density functional theory (DFT) calculations, capillary electrophoresis coupled with inductively coupled plasma mass spectrometry (CE-ICP-MS) and solvent extraction. XAS measurements showed unambiguously the presence of a short single oxo-bond, and the deduced structure agrees with theoretical calculations. CE-ICP-MS results indicated the formation of a highly charged anionic complex. The formation constants of PaO(C(2)O(4))(+), PaO(C(2)O(4))(2)(-), and PaO(C(2)O(4))(3)(3-) were determined from solvent extraction data by using protactinium at tracer scale (C(Pa) < 10(-10) M). Complexation reactions of Pa(V) with oxalate were found to be exothermic with relatively high positive entropic variation.     

Tensammetric studies of alcohols with reference to their structural influence on surface activity

Summary This work relates to the tensametric studies of various aliphatic alcohols with a view to see if this technique can be used to assess the structural influence on surface activity. From the study of the homologous series of aliphatic alcohols, it is seen that the surface activity increases with increase in chain length of the alcohols. With lower members of the series the desorption peak is not sharp. There is no regular shift of peak potential from methanol to amylalcohol. For the same alcohol the surface activity increases if the carbon atoms are in a straight chain but decreases if they are branched. Primary alcohols are more surface active than secondary and secondary are more surface active than tertiary alcohols. The peak potential is more negative for normal alcohol than that of tertiary alcohol. Saturated alcohols are more surface active than unsaturated ones having the same number of carbon atoms. The peak potential is also more negative with saturated than with unsaturated. Monohydric alcohols are more surface active than dihydric and dihydric is more surface active than trihydric alcohol having the same number of carbon atoms as in monohydric and dihydric alcohols and in this case the peak potential is more negative with trihydric than with monohydric alcohol.     

Alcohol modifiers in MEKC with SDS as surfactant. Study on the influence of the alcohol chain length (C1?C12)

The influence of alcohol modifiers with different chain length on the migration time window in micellar electrokinetic chromatography (MEKC) has been studied. Highly polar alcohols like methanol and 1-propanol are typical aqueous phase modifiers. Higher alcohols like 1-butanol, 1-pentanol and 1-hexanol influence the micellar structure and are considered as micellar phase modifiers. The effect of long chain alcohols is small because of their low applicable concentrations.     

Chromium(VI) oxide oxidation of non‐ethoxylated and ethoxylated alcohols for determination by electrospray ionization mass spectrometry

A new derivatization procedure to increase the sensitivity of electrospray ionization mass spectrometry (ESI‐MS) to non‐ethoxylated and ethoxylated alcohols was investigated. The analytes were oxidized with chromium(VI) oxide and the resulting carboxylic and ethoxy‐carboxylic acids were isolated by extraction with ethyl acetate; the extracts were alkalinized and infused into the ESI‐MS system working in the negative‐ion mode. The yields of the combined oxidation‐extraction were ca. 100% for non‐ethoxylated fatty alcohols dissolved in acetone and they decreased moderately in samples containing increasing amounts of water (e.g., a 75% yield was obtained with 50% water). Ethoxylated alcohols with more than two ethylene oxide units resulted in yields of ca. 60%. Low limits of detection (LODs) were obtained when the procedure was applied to the analysis of body‐care products and cosmetics containing fatty alcohols, e.g., in a varicose‐vein cream, the LODs were 25 µg cetyl alcohol and 7.5 µg stearyl alcohol (detected as palmitic acid and stearic acid, respectively) per gram of sample. High molecular mass alcohols were also detected in seawater after pre‐concentration by solid‐phase extraction. Thus, the proposed method is particularly valuable for use in industrial samples having complex matrices and in environmental samples and it is competitive with other methods for the analysis of trace amounts of fatty alcohols. Copyright © 2010 John Wiley & Sons, Ltd.     

Liquid-liquid extraction of protactinium(V) using tri-iso-octylamine

Solvent extraction of protactinium with tri-iso-octyl-amine (TIOA) in xylene, benzene, carbon tetrachloride and chloroform from HCl, HF, HNO₃, HClO₄ and H₂SO₄ media was studied using ²³³Pa as a radiotracer. The extraction efficiencies of protactinium were determined as a function of shaking time, concentrations of mineral acids in aqueous phase, extractant concentrations and diluents in organic phase. The extraction mechanism was discussed. The results show that the extracted species in the organic phase is [(R₃N⁻H)_nPa(OH)_xCl _y ^5−x−y ].     

Na促进的CuCoMn催化剂催化生物质合成气合成高醇

研究钠促进的CuCoMn催化剂的特性及其在生物质气化合成气合成高醇中的应用. 研究了催化剂中Na含量及合成条件(温度、压力和空速)对生物质基合成气合成高醇性能的影响. 发现CuCoMnNa_0.1催化剂较适合高醇合成, 在300 °C以下, 随着温度的上升, 碳转化率增大, 而醇选择性降低. 压力的增加有利于醇的合成, 增大空速会明显降低碳转化率, 但醇时空产率则因转换频率的增加而增大. 在所考察的范围内, 醇产率最高达到304.6 g·kg^-1·h^-1, 其中C₂₊高醇(C₂-C₆醇)占64.4% (w, 质量分数). 醇产物和烃产物均符合ASF (Anderson- Schulz-Flory)分布关系. 根据催化剂性能与表征分析, Na的加入有利于提高生物质气化合成气合成高醇的选择性和活性元素Cu、Co的分散性. X射线光电子谱(XPS)测试结果显示反应后的催化剂表面上, Cu以Cu⁺和Cu⁰的混合形式存在, 而Co则是Co²⁺/Co³⁺和Co⁰的混合物. 增加Na的含量, Cu⁰/Cu⁺比率和Co⁰的强度均随之减小.     

Neutron activation analysis by standard addition and solvent extraction : Determination of traces of thorium in aluminium by extraction of protactinium-233

A rapid and selective radiochemical separation for protactinium-233 is suggested. The method is based on extraction of protactinium with 0.3 M tridodecylamine from 4.5 M HCl-1.5 M AlCl₃ solution, stripping with 1.35 M HCl followed by another extraction with 0.5 M 2-thenoyltrifluoroacetone. The separation, coupled with the application of the standard addition technique, is applied to the determination of traces of thorium in aluminium by neutron activation.     

液相色谱-串联质谱法同时测定蔬菜中7种三唑醇类杀菌剂的残留量

采用高效液相色谱-串联质谱(HPLC-MS/MS)建立了同时测定蔬菜中环唑醇、三唑醇、粉唑醇、戊唑醇、己唑醇、烯唑醇和联苯三唑醇残留量的分析方法.样品经甲醇提取,分散固相萃取净化后,采用C8色谱柱(150 mm×2.1 mm,3 μm)分离,以甲醇-0.05%甲酸梯度洗脱,串联质谱测定,外标法定量.在优化实验条件下,7...