Extraction of Ag(I), Cd(II), In(III), Sn(II), Sn(IV), Sb(III), and U(VI) from aqueous solutions by ketone solutions using single-step batch and continuous SISAK methods1,2

The extraction properties of Ag(I), Cd(II), In(III), Sn(II), Sn(IV), Sb(III), and U(VI) from aqueous KI/H₂SO₄ solution into a mixture of 4-methyl-2-pentanone (methyl isobutyl ketone, MIBK) and cyclohexanone (CHO) were studied. Both single-step batch and SISAK² methods were used. The oxidation of Sn(II) to Sn(IV) by iodine and complexation of Sn(IV) by 2,3-dimercapto-propanol-1 (BAL) were also investigated. A method for rapid and continuous separation of indium from tin was developed for investigation of short-lived indium fission products.     

Determination of indium and tin by activation analysis using replacement substoichiometry

A new method for the determination of indium by activation analysis has been developed. It is based on the replacement of indium from indium dithizonate (in carbon tetrachloride) by a substoichiometric amount of aqueous mercury(II) solution. Preliminary steps are the extraction of indium from alkaline cyanide solution with an excess of dithizone solution and washing the extract with buffer solution. The time necessary for the separation is 10-20 min. With this method indium can be determined by using either short ((116m)In, t(1 2 ) = 54 min) or long-lived radioisotopes ((114m)In, t(1 2 = 50 d). As by the reaction (112)Sn (n, gamma)) (113)Sn (119d) --> (113)In (104 min), indium-113m is formed, which has a different gamma-spectrum from that of indium-114m, the determination of both indium and tin is possible. The proposed method has been applied to the determination of indium and tin in granite and gallium.     

Determination of trace impurities in tin by neutron activation analysis

Two methods are described to determine indium and managenese in high-purity tin. In the first method indium and manganese are separated from the tin and antimony matrix activities on Dowex 1X8 anion exchanger. Tin and antimony are adsorbed in 10M HF while indium and manganese are eluted. In the second method the incident γ-ray intensity due to the tin matrix is reduced by placing a lead absorber between the sample and the detector. The reproducibility and the sensitivity of both methods are of the order of 10 ppb for manganese and of 1 ppb for indium for 1 g samples and a neutron flux of 10¹¹ n·cm⁻²·sec⁻¹. Aspirant of the N. F. W. O.     

Subtoichiometric determination of indium and tin by radioactivation analysis

A method of radioactivation analysis has been developed for the determination of indium and tin. It is based on substoichiometric extraction of indium diethyldithiocarbamate into carbon tetrachloride from a slightly ammoniacal solution in the presence of potassium cyanide. With this method, indium can be determined via^116m In (T=54 min) and tin via^113m In (T=104 min) which is formed by the reaction¹¹²Sn(n, ψ)¹¹³Sn. The method has been applied to the determination of indium in metallic zinc and of tin in tin-doped gallium arsenide, and 0.4 ppb of indium was analyzed in a zinc sample.     

Separation of gram quantities of uranium from fission products by extraction chromatography

The separation of gram quantities of uranium from fission products has been investigated by extraction chromatography. The separation which is based on the difference in distribution coefficients between uranium and the fission products on a tributyl phosphate (TBP) resin in nitric acid medium, was carried out by means of high acidity feed and stepwise elution on a TBP chromatography column. The results show that this technique is capable to separate 5 g of uranium from a large quantity of fission products. The recovery of uranium is more than 99%. The decontamination factors of g- and b-activities were 2.1^.10³ and 2.3^.10³, respectively.     

Nuclear decay studies of rare-earth fission-product nuclides using fast radiochemical separation techniques

A facility for the rapid radiochemical separation of individual rare-earth fission product nuclides from mixed fission products has been developed at the Idaho National Engineering Laboratory (INEL). This facility, called the INEL ESOL (elemental separation on-line) facility, includes an electroplated spontaneously fissioning²⁵²Cf source, a He jet transport system to deliver short half-life fission products from the²⁵²Cf hot cell to the radiochemistry laboratory, and a high pressure liquid chromatograph for the individual separation of rare-earth radioelemental fractions. The fission product collection and separation instrumentation is interfaced to a microprocessor that controls valves, motors and other devices and monitoring instrumentation. The data acquistion instrumentation can be controlled from a signal originating from the microprocessor or initiated manually. The results of some recent decay scheme studies on¹⁵³Pm and¹⁵⁴Pm are reported.     

Adsorption of several tracer cations and separation of234Th from238U and113mIn from113Sn on tin dioxide

The uptake of 22 cations at tracer concentrations has been studied over hydrous tin dioxide exchanger material. A granular variety of tin dioxide was prepared from the reaction of tin(IV) chloride with NaOH solution, and the formula of the material was ascertained to be SnO₂·1.7 H₂O. Radiochemical separation of carrier-free²³⁴Th from²³⁸U and^113mIn from¹¹³Sn was achieved over a tin dioxide column. The separated products were of high radionuclidic purity. The overall separation procedures are very simple and quick with quantitative yield.     

Isolation of radiocesium from a fission product mixture

A method of¹³⁷Cs isolation from strongly, acidic solutions of fission products is described, in which vanadyl ferrocyanide is used as a selective ion exchanger for cesium. The effects of the acidity of medium and the carrier concentration on the quantitative yield of separation have been studied and convenient conditions have been found for¹³⁷Cs isolation from the solution of fission products formed after irradiating uranium with neutrons.     

The role of NAA in nuclear chemistry education

One of the missions of our Institute is the promotion of basic nuclear teaching for students as well as professional teaching for workers in nuclear industry and research. For nuclear chemistry education, we present here a one day teaching course on radioactive decay and nuclear reactions, and a two or three days course based on reactor irradiation of uranium oxide, instrumental and radiochemical analysis of fission products. In the first experiment, the neutron capture is presented as an example of nuclear reaction; the neutron activation of a silver coin with a Am-Be neutron source, followed by γ-ray spectrometry, is used to identify three radionuclides of silver and to calculate their half-lives. In the second experiment, our teaching reactor is used as a neutron source with a flux about 10¹⁰ n·cm⁻²·s⁻¹ at a low thermal power (10 kW). This low flux allows us to irradiate a small uranium sample which is usable for spectrometry after a short cooling time of about two hours. The first day is reserved for instrumental analysis of the fission products and a second day for the radiochemical separation of a fission radionuclides. With these experimental results, the students have to calculate the number of fissions in the irradiated sample. On optional third day for postgraduate students is devoted to the presentation of NAA and some applications as uranium determination by the fission product spectrometry.     

The determination of fission products in irradiated uranium by electrophoretic focussing of ions

Electrophoretic focussing of ions was applied to the separation of fission products present in solutions of nuclear uranium fuel irradiated in various European reactors. By combining two separation methods, all the long-lived fission products could be determined individually and quantitatively by counting with a NaI(T1) and a GM detector of known detection efficiency. Radiography and autoradiography were used for semi-quantitative purposes. The concentrations of²³⁵U and²³⁸U were determined from a short post-irradiation of the fuel solution and counting of¹⁴⁰Ba−¹⁴⁰La and²³⁹Np, respectively. An iterative calculus method is presented which allows calculation of the irradiation history of the fuel solution from the above analyses. without any a priori knowledge.     

Specific activities of radioactive elements from fission product mixtures

Specific activities of radioactive elements at the time of chemical separation from fission product mixtures produced by thermal neutron fission of²³⁵U were computed byBateman's and other equations on an electronic computer. Computations were made for two fission times: fission was assumed to be complete in a few minutes in one case, and over a period of a year in the other case. It was also assumed that each element was separated instantly after allowing the fission products to decay for 1∼10 000 000 hrs (1 140 years). The computations were applied to 12 important elements: Ru, Zr, Nb, Cs, Sr, Pm, Tc, Ba, La, Ce, Kr and Y. Results are given as a diagram for each element. The diagrams are intended to be helpful in the chemical processing of a large quantity of fission products, and industrial or tracer application of these elements.     

Determination of traces of antimony and tin in copper by anodic stripping voltammetry

The determination of antimony and tin impurities in copper by anodic stripping voltammetry on a hanging mercury drop electrode is described. Antimony and tin were previously separated from copper by distillation with hydrobromic acid or a mixture of hydrobromic acid and hydrochloric acid. The method was applied to the analysis of various high-purity copper samples, commercially available, showing satisfactory sensitivity and precision. The determination limit was about 1.4· 10^-9M for antimony and 7·10^-10M for tin in solution, for pre-electrolysis times of respectively 15 and 25 min; this corresponds to 0.8 p.p.b. of antimony and 0.3 p.p.b. of tin for a 2-g sample and a final volume of 10 ml after separation.     

钾锰氧化物：电化学控制合成及其电容器性质

Potassium manganese oxides were prepared by cathodic deposition from aqueous KMnO4 solution on an indium tin oxide slide. The products were characterized by XRD, XPS and SEM techniques. The as-prepared products were potassium manganese oxides with different manganese valence states. The component, morphology and size of the products could be controlled through adjusting the preparation parameters such as deposition potential, deposition time and acidity of the electrolyte. The results show that the deposition of potassium manganese oxide from aqueous KMnO4 is a pH value dependent procedure. Due to the facilitating of intercalation and deintercalation of cations, the specific capacitance of the products deposited for 500 s is higher than that indicate that the reversibility and performance of these potassium manganese oxides are also changed with the deposition time.     

Production of87Br for studying neutron decay

An improved gas flow system is described for the production of⁸⁷Br through a fast radiochemical separation of fission products from a solution of²³⁵U irradiated with thermal neutrons. It can produce⁸⁷Br with a higher yield relative to⁸⁸Br than was previously possible for measurement of neutron energy distribution. Contrary to previous indication, large amounts of iodine fission products have been found to come out of the irradiation cell in the gas stream necessitating their isolation.     

Separation of95Zr and95Nb from each other and from other fission products by adsorption and desorption on silica gel using hydrochloric acid solutions

The silica gel adsorption behaviour of zirconium, niobium, ruthenium and cerium in hydrochloric acid has been investigated by batch and column techniques. A satisfactory radiochemical separation of zirconium and niobium from each other and from other fission products has been achieved by a two column technique. The recommended procedure consists of sorption of all the nuclides on a primary silica gel column. Fifteen per cent of⁹⁵Nb, all of the zirconium and all of the other fission products are eluted first by washing with 5.5 M HCl. A second elution with concentrated hydrochloric acid then recovers the⁹⁵Nb (free from other products). The solution from the first elution after evaporation to 1 ml is then passed through another silica gel column and successively washed with 0.5M HCl, 5.5M HCl and concentrated HCl to obtain three fractions—other fission products—⁹⁵Zr free from other products—⁹⁵Nb free from other products, respectively.     

Instrumental activation analysis for determining the composition of micro-ingots of multi-constituent alloys

A procedure for the instrumental neutron activation analysis of micro-ingots of alloys containing In, Sb, Au, Ga, Ni, Sn and Bi is proposed. The non-destructive analysis of the irradiated samples is performed by γ-spectrometry techniques including one-crystal scintillation detectors, dual-crystal sum-coincidence scintillation detectors and Ge(Li) semiconductor detectors. As a result, the cumbersome operations of radiochemical separation can be eliminated. The sensitivity of quantitative determinations using scintillation detectors in alloys of the above composition is 10⁻¹⁰ g for indium, gold, antimony and gallium and 10⁻⁶ g for nickel and tin. The use of semiconductor detectors yields sensitivities of 10⁻¹⁰ g for indium and gold and 10⁻⁹ g for gallium and antimony.     

Elemental analysis of biological tissues of Dmdmdx/J and C57BL/6J mice strains investigated by neutron activation analysis

Radioactivity measurement of short-lived nuclides is the basis of decay data measurement, which requires rapid separation and purification of the interested nuclides from complicated fission products. A rapid separation system based on SISAK and extraction chromatography technique was established to isolate ⁹⁵Y, which half-life is 10.3 min. With the best conditions studied in this paper, ⁹⁵Y was separated successfully from complicated fission products under the mini-reactor in the China Institute of Atomic Energy. Decontamination factors to other nuclides except ⁹⁴Y are higher than 2 × 10³.     

Separation of heavier rare earths from neutron irradiated uranium targets

A radiochemical method is described for the separation of heavier rare earths from the fission of uranium. The method is particularly suitable for the separation of low yield (10⁻⁵%–10⁻⁷%), highly asymmetric rare earth fission products viz.^179,177Lu,¹⁷⁵Yb,¹⁷³Tm,^172,171Er,¹⁶⁷Ho and^161,160Tb in the neutron induced fission of natural and depleted uranium targets. Additional separation steps have been incorporated for decontamination from²³⁹Np (an activation product) and^93-90Y (a high fission-yield product) which show similar chemical behaviour to rare earths. Separation of individual rare earths is achieved by a cation exchange method performed at 80°C by elution with α-hydroxyisobutyric acid (α-HIBA).     

Room temperature deposition of nanocrystalline cadmium peroxide thin film by electrochemical route

Nanocrystalline cadmium peroxide thin film has been electrodeposited on indium doped tin oxide glass substrate from aqueous solution at room temperature. The grain size of the nanocrystals of the film is estimated from XRD and is about 14 nm. The deposits are decomposed at 228 °C by formation of CdO, releasing plentiful heat at same time. The band-gap of the nanocrystalline CdO film made from decomposition of electrodeposited CdO₂ is around 2.4 eV.     

Cyclic and stripping voltammetry of tin at mercury hanging drop and film electrodes in acidic o-diphenol media in the presence of lead and cadmium

The influence of catechol, gallic acid and tiron on the voltammetric behaviour of tin(IV) in the presence of lead(II) and cadmium(II) was investigated at hanging drop and mercury film electrodes in perchloric acid, oxalic acid and formate supporting electrolytes. Under cyclic conditions, well separated peaks of tin, lead and cadmium are obtained in oxalic acid and formate solutions containing gallic acid or catechol; tiron suppresses the tin peaks significantly. The efficiency of the deposition of tin in the presence of catechol or gallic acid is less than that of lead, particularly at long deposition time. The best separation of the stripping peaks of tin, lead and cadmium is obtained in oxalic acid solution containing gallic acid or catechol. In perchloric acid solution containing gallic acid or catechol the second peak corresponding to tin oxidation is useful for determinations of tin in the presence of lead. Tin(IV) at the 10^-8 mol l^-1 level can be detemined in various salt solutions and in water samples in the presence of five-fold amounts of lead and cadmium.