Zur Bestimmung kleinster Mengen Schwefel in Selen

Zusammenfassung Es wird ein Analysenverfahren beschrieben, das es gestattet, in relativ kurzer Zeit eine genaue Spurenanalyse von Schwefel in Selen durchzufÜhren. Die Probe wird mit Salpetersäure oxydierend gelÖst. Die dabei entstehende Schwefelsäure wird durch zugefÜgtes Bariumchlorid als Bariumsulfat fixiert, während das als selenige Säure vorliegende Selen durch Eindampfen der LÖsung zur Trockne und Abrauchen entfernt wird. Das Bariumsulfat wird mit einer Mischung aus Zinn(II)-chlorid und konz. Phosphorsäure zu Schwefelwasserstoff reduziert. Der Schwefelwasserstoff wird in ZinkacetatlÖsung Übergetrieben, das Zinksulfid mit Dimethyl-p-phenylendiaminlÖsung zu Methylenblau umgesetzt und photometrisch bestimmt. Nach dieser Methode sind noch 2–10 ppm Schwefel in Selen bei einer Einwaage von 2 g zu bestimmen. Die aus Modellanalysen berechnete Standardabweichung beträgt bei 5 ppm Schwefel 0,6 ppm, was einer Varianz von 12% entspricht. Nach dieser Methode sind 0,5 ppm Schwefel noch nachweisbar. Der Zeitbedarf fÜr eine Bestimmung beträgt etwa 4–5 Std.

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Summary A method is described for the rapid determination of traces of sulphur in selenium. The sample is oxidized by dissolution in nitric acid whereby sulphur is converted to sulphuric acid and selenium to selenous acid. Sulphate is then precipitated as BaSO₄ and selenium is removed by evaporating to fumes. BaSO₄ is reduced to hydrogen sulphide by a mixture of stannous chloride and conc. phosphoric acid, the H₂S is passed into zinc acetate solution and the ZnS formed is determined photometrically by reaction with dimethyl-p-phenylendiamine to methylene blue. 1–20 ppm of sulphur can be determined in a sample of 2 g. The standard deviation is 0.6 ppm for 5 ppm of S, corresponding to a variation of 12%. The limit of detection is 0.5 ppm of S. The time required for a single determination is 4–5 hours.

     

On the Determination of Ultra-trace Amounts of Selenium Using the Twice Hydride Generation -Gaseous Phase Enrichment Techniques and Atomic Fluorescence Spectrometry

Selenium is the one of the most particularly element to human health. This property has been recognized as an essential nutrient and toxicity at same time for humans. The toxicity and essential nature of Se depend on its concentration, which is within a very narrow range from 0.005 ppm to 3.0 ppm. It is strongly required often to investigate the trace selenium in order to understand the processes of elemental cycles in real samples. However,the direct determination of selenium content and chemical species is very difficult because of their extremely low concentrations and complicated characteristics. Hydride generation technique, which offers the advantages of chemical pre-separation from matrix, more efficient sample introduction, has been widely used in real sample analysis. However, except the so-called "in situ pre-concentration techniques" (trapped in graphite furnace and determined by AAS), the investigation of other gaseous phase enrichment techniques has not been noticed enough.     

Rapid and precise determination of total sulphur in soda-lime-silica glasses

A method is described for the determination of total sulphur in small amounts of soda-lime-silica glasses (100 mg or less). The crushed glass is mixed with vanadium pentoxide and decomposed at 1450 degrees under oxygen. The sulphur is quantitatively removed from the glass and determined by a conductometric technique. The method is standardized by accurately injecting sulphur dioxide into the furnace tube. The analysis time is about 10 min and the overall precision (2s) is of the order of 5%.     

Thermal behaviours of sulphur-selenium mixtures

The thermal behaviours of sulphur, selenium and their mixtures have been studied over the range 40–450?. It has been shown that the polymerization threshold temperature of sulphur,T _Ø, decreases with increasing selenium content and follows the equilibrium copolymerization model proposed by Tobolsky and Owen. The formation of octa-atomic species Se_8?xS_x, where 8 >x > 4, takes place only after sulphur is in the liquid state. The rate of polymerization is enhanced by the addition of increasing amounts of selenium and this is reflected in the higher polymerization peak temperatures. The X-ray powder diffractograms show that all the sulphur-selenium melts belong to the same phase as that of SeS, though the constituent atoms are randomly distributed.     

Dithiocarbamate extraction of trace amounts of selenium from biological samples for neutron activation analysis

A three-step method has been developed for extracting trace amounts of selenium from biological samples for neutron activation analysis /NAA/. After acid digestion, the sample is first extracted with lead diethyldithiocarbamate at pH 4 to remove a number of interfering elements. Next, selenium is extracted with sodium diethyldithiocarbamate into chloroform at pH 1.5. Finally, selenium is back-extracted with concentrated nitric acid for NAA. Analysis of selenium extracted from four standard reference materials resulted in excellent agreement with the certified values of selenium concentration. A detection limit of 0.05 g has been achieved.     

Determination of trace quantities of selenium by indirect atomic-absorption spectrophotometry

The selenium(IV)-iodide interaction in acid medium, leading to the liberation of iodine, has been utilized for the indirect determination of selenium by atomic-absorption spectrophotometry (AAS). The iodine is extracted into benzene and subsequently reductively stripped into an aqueous solution of ascorbic acid. After extraction of the resulting iodide as tris(1,10-phenanthroline)cadmium(II) iodide into nitrobenzene, the cadmium content of the organic extract is determined by AAS. Beer's law is applicable up to 0.75 ppm of selenium. The few interferences are readily overcome. The chemical yield in the system is about 80% overall.     

The application of ion-exchanger foils in the determination of trace amounts of some metals in water by means of the non-dispersive X-ray fluorescence method

Preliminary enrichment by means of strong acid ion-exchanger foils has been used to determine trace amounts of metals in water. The kinetics of the exchange reaction between the hydrogen ions in the cation-exchanger foil and metal ions in the solution has been studied. The time needed for the attainment of equilibrium and the values of the distribution coefficients have been determined for Fe²⁺, Zn²⁺, Pb²⁺, Ca²⁺, Cd²⁺ and Ba²⁺ ions. The metal contents in the cation-exchanger foil were determined by means of non-dispersive X-ray fluorescence. The feasibility of the method was determined on the examples of Pb, Zn and Cd ions. The method permits trace amounts of these elements to be determined above 0.01 ppm in the solution. No significant matrix effect due to the presence of Ca and Ba was found for concentration in the solution below 60 ppm.     

二氧化硒催化过氧化氢氧化萘丙醛制萘丙酸的研究

萘丙酸((±)-2-(6-甲氧基-2-萘基)-丙酸)的右旋体有解热镇痛特效,国内生产中由萘丙醛氧化成酸系采用多伦试剂,耗费大量硝酸银。我们采用过氧化氢作氧化剂,结果表明,制得的产品纯度高,而且成本低。     

Spectrographic estimation of Ga, In and Tl in semiconductor grade selenium

Summary An emission spectrographic method for the estimation of Ga, In and Tl in semiconductor grade selenium at less than a ppm concentration has been developed. The impurities were separated from 1 g of selenium by volatilizing it from its solution in nitric acid and sulphuric acid. The residue containing the impurities was dissolved in small amounts of 6 M HCl and was loaded along with the washings on 10 mg mixture containing graphite (90%) and sodium chloride carrier (10%) in the electrode crater. The spectra were excited in a d.c. arc carrying 13 A current. The detection limits lie in the range of 0.0025–0.005 ppm. The precision of the method ranges from 7–12% for these elements. The recoveries of impurities from selenium were confirmed using radioactive tracers.

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Spektrographische Bestimmung von Gallium, Indium und Thallium in Halbleiterselen

Zusammenfassung Eine 1 g-Probe wird in Salpeter- und Schwefelsäure gelöst und die Verunreinigungen durch Verflüchtigung des Selens isoliert. Sie werden in 6 M HCl gelöst und zusammen mit einem Graphit/NaCl-Gemisch (91) in die Elektrode eingebracht. Zur Anregung dient ein Gleichstrombogen (13 A). Die Nachweisgrenzen liegen im Bereich von 0.0025–0.005 ppm, der Variationskoeffizient bei 7–12%. Die Wiedergewinnung der Verunreinigungen wurde mit Hilfe von Radioindicatoren geprüft.

     

Determination of Fluorine in Vegetation by Proton Activation Analysis

Abstract

Techniques have been developed for proton activation analysis using the ¹⁹F(p,p′y)¹⁹F reaction to measure the fluorine content of pulverized samples of vegetation which have been exposed to fluorides in the atmosphere or soil. The method is non-destructive and neither the chemical form of fluorine in the sample nor the type of vegetation analyzed appears to affect results. Calibration is performed by analyzing samples to which known amounts of fluorine are added. The fluorine content of 11 vegetation samples was determined by proton activation analysis and by standard chemical techniques. The values obtained by the two methods were in generally good agreement. Fluorine concentrations greater than 1 ppm can be measured with uncertainties ranging from about 50% at 5 ppm to less than 10% at concentrations above 50 ppm.     

Bestimmung kleiner Sauerstoffgehalte in Selen

Zusammenfassung Es wird eine Analysenmethode zur Bestimmung von Sauerstoff in Selen beschrieben. Die Abtrennung des Sauerstoffs geschieht über seine Umsetzung mit Schwefel; die Endanzeige des gebildeten Schwefeldioxids erfolgt colorimetrisch mit Parafuchsinchlorid. Mit dem Verfahren werden Gehalte bis 0,5 ppm (w)¹ erfaßt. Die relative Standardabweichung bei Analysen von SeO₂- und TeO₂-dotiertem Selen beträgt ±8%. Die Analysen von 5 Selenproben als Perlen ergaben Gehalte zwischen 4 und 11 ppm (w) Sauerstoff; Selengleichrichterschichten enthielten 1 ppm (w) Sauerstoff.

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Determination of small oxygen contents in selenium

An analysis method for the determination of oxygen in selenium is described. The separation of oxygen is accomplished through its reaction with sulphur. The final measurement of the sulphur dioxide formed is made colorimetrically with parafuchsine chloride. With this method contents as low as 0.5 ppm (w) can be determined. The relative standard deviation for analyses of selenium doped with SeO₂ and TeO₂ is ±8%. The analyses of 5 selenium samples having the form of beads resulted in oxygen contents between 4 and 11 ppm (w), whilst selenium rectifier layers contained 1 ppm (w) of oxygen.

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Die Verfasser bedanken sieh für das fördernde Interesse von Herrn Prof. Dr. W. Gebauhr und Herrn Dr. A. Spang. Zur Arbeit trugen wesentlich die anregenden Diskussionen mit Herrn J. Martin bei.     

Determination of sub microgram amounts of selenium in rocks by atomic-absorption spectroscopy

Atomic-absorption spectroscopy was used to determine trace amounts of selenium accurately in U.S. Geological Survey standard rocks, GSP-1, W-1 and BCR-1. The results obtained were compared with those obtained by neutron-activation analysis and excellent agreement was found; in addition, the selenium:sulphur ratio was calculated and agreed with results obtained by other workers.     

Determination of trace elements and radioactive materials by substoichiometric isotope dilution analysis

Substoichiometric isotope dilution analysis has been applied for the determination of trace elements in liquid samples, of carrier content in radioisotope solution and of concentration of organic reagent. Cu in mineral acids and in ZnSe single crystal was determined by the substoichiometric extraction with dithizone. The values of 1.8 and 0.018 ppm in nitric acid and distilled one and of 1.4 and 0.44 ppm in ZnSe were obtained. Cu and P carrier contents in⁶⁴Cu and³²P solutions were determined by the substoichiometric extractions with dithizone in CCl₄ and with molybdic acid into MIBK in the series of the solutions adding various amounts of Cu or P carrier. An analogous method has been applied for the determination of dithizone and diethyldithiocarbamate solutions. The method was also applied for the determination of⁶⁰Co radioactivity in environmental samples. The analytical result of water samples is described.     

Analysis of low-volatility organic sulphur compounds in wines by solid-phase microextraction and gas chromatography

A method for analysing low-volatility sulphur compounds using solid-phase microextraction has been developed. The analytes were extracted directly from the liquid sample using fibres coated with different stationary phases. The best extraction efficiency was obtained with Carboxen-polydimethylsiloxane coating. Ionic strength, sample volume, time and temperature of the extraction were optimised and the matrix effect studied. The method enables 15 sulphur compounds in wine to be determined at trace levels with recoveries close to 100% and limits of detection between 0.05 and 5 microg/L. The overall method was successfully applied to the determination of the sulphur compounds studied in several red, white and rosé wines.     

Multi-element analysis by isotope dilution-spark source mass spectrometry (ID-SSMS)

Summary Isotope dilution-spark source mass spectrometry (ID-SSMS) has been applied for the simultaneous quantitative determination of about 35 trace elements in rock samples. A precision and an accuracy of better than 5% is obtained for most elements. Concentrations down to 0.01–0.1 ppm can be precisely determined for many trace elements.The application of ID-SSMS in geochemical and cosmochemical research is particularly interesting when concentrations of many elements are desired (e. g., for element correlations) and low detection limits are needed, or when only small amounts of samples are available.

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Multielement-Analyse mit Isotopenverdünnung-Funkenmassenspektrometrie (ID-SSMS)

     

电感耦合等离子体质谱(ICP-MS)法测定高纯砷中痕量磷和硒

通过对样品前处理方式、内标元素及质量数的选择、仪器检测模式等方面进行优化,采用串联四级杆电感耦合等离子体质谱仪直接测定高纯砷中痕量的磷和硒.实验室使用电子级盐酸、硝酸配制王水直接溶解样品,在不除基体的情况下,以铑作为内标补偿校正砷基体的抑制效应,在调试好的仪器上进行测定磷、硒含量.磷、硒的测定结果相对标准偏差(RSD)...     

Activation analysis of Se in biological samples through75Se and77mSe

A method is described to separate trace amounts of selenium in biological samples without using a carrier. This method is based on the adsorption on active carbon of the complex ion formed with APDC /ammonium salt of l-pyrrolidine carbodithioic acid/ at pH 1. The efficiency of the radiochemical separation described is measured by using carrier-free⁷⁵Se labelled solutions of sodium selenite at selenium concentrations from 3.5×10^–8 to 3.5×10^–11 g ml^–1. The results were between 95% and 98% with statistical variations from 2% to 10%. The determination of selenium can be made following this separation either through⁷⁵Se in the traditional way, or through^77mSe if the separation is performed prior to irradiation. The detection limits on the available conditions were 0.01 ppm for⁷⁵Se and 0.1 ppm for^77mSe. When the analysis is performed through⁷⁵Se /t=120 d/, the statistical error is notably smaller because the counting time may be considerable, whereas through^77mSe/t=17.5 s/it is higher than 20%, depending on the concentration and the available neutron flux. However, the advantages of gaining time and the fact of performing the trace separation from a non radioactive material, make both procedures competitive as useful tools for the research on the function of Se in vertebrates.     

Determination of bromine, chlorine, sulphur and phosphorus in peat by X-ray fluorescence spectrometry combined with single-element and multi-element standard addition

Bromine (20-40 ppm), chlorine (200-500 ppm), sulphur (0.2-3%) and phosphorus (300-1000 ppm) in peat have been determined by X-ray fluorescence spectrometry (XRFS) combined with the standard-addition method. Chlorine, sulphur and phosphorus have also been determined by other methods and agreement between the results is good. Theoretical calculations based on the Sherman equation were made to validate the linearity of the standard-addition curves. A multi-element standard-addition technique has been tested with addition of all elements at the same time. The results for chlorine were high but after correction for the difference in attenuation coefficient between the sample and added compound the results agreed with those from single-element standard addition.     

Determination of sulphur and total sulphur dioxide in wines by an ICP-AES method

Sulphur contents of the original sample and the sample free from sulphur dioxide were determined by ICP-AES following nitric acid digestion under high pressure (using PAAR HPA equipment), and the total sulphur content was calculated from the difference between the results obtained. With the aim of preparing a sample free from sulphur dioxide, bound sulphur dioxide was released by sodium hydroxide, then after acidifying by phosphoric acid, boiling was carried out. Relative standard deviations of the results obtained for total sulphur, the sulphur without S(IV) and total sulphur dioxide were lower than 2.5, 3.5 and 5% respectively. Various amounts of sulphur (in the form of Na₂SO₄), added to wine samples, were successfully recovered between 95.5 and 104.9%. Based on comparative analyses performed by a widely accepted classic method, the indirect method developed was found to be adequate for the determination of total sulphur dioxide. The procedure is suitable for serial tests.     

Versuche zur Anreicherung von Edelmetallspuren in Reinstquecksilber durch partielles Lösen der Matrix

Trace impurities of gold and palladium in metallic mercury can be enriched in a simple way by partially dissolving the sample in nitric acid. Practically the whole trace content of the sample will be collected in the residue. Up to at least 100 g Hg the quantity of the mercury sample has no influence on the trace enrichment. After the partial dissolution of the metal the enriched gold was determined photometrically with Rhodamine B as a reagent, Pd was determined as [PdJ₄]^2? complex. For the analysis of metallic mercury containing 0.5 ppm of Au and 2 ppm of Pd the relative standard deviation is 0.046, respectively 0.037. The limit of detection was found to be at 0.2 ppm for both the elements. Using this method, the enrichment of traces of silver in mercury is not possible.