On the different adsorption behavior of bismuth,sulfur, selenium and tellurium on a Pt(775) stepped surface

The deposition behavior of sulfur, selenium, tellurium and bismuth on the Pt(775) surface has been studied by cyclic voltammetry. It has been found that bismuth and tellurium deposit preferentially on the step sites. Once the step sites are fully covered by these adatoms, the deposition on the terrace starts. Conversely, step decoration cannot be achieved with sulfur and selenium. For these adatoms, the deposition takes place preferentially on the terrace. The different behavior of the adatoms is related to differences in their electronic properties.     

电感耦合等离子体发射光谱法测定粗二氧化碲中 铜、铅、锑、铋、砷和硒

粗二氧化碲作为碲精炼或碲化工产品生产的重要原料,其中共存元素铜、铅、砷、锑、铋、硒含量的准确测定对于生产过程质量控制和贸易结算具有重要意义,但目前没有粗二氧化碲中铜、铅、砷、锑、铋、硒含量检测的标准分析方法。采用王水和饱和氟化氢铵分解试样,在王水和酒石酸介质中,选用Cu 327.393 nm、Pb 220.353 nm、Sb 217.582 nm、Bi 223.061 nm、As 193.696 nm、Se 196.026 nm为分析谱线,采用电感耦合等离子体发射光谱(ICP-AES)法测定粗二氧化碲中铜、铅、锑、铋、砷和硒含量。各元素校准曲线的相关系数均大于0.999;铜、铅、锑、铋、砷和硒的检出限分别为0.0004%、0.0005%、0.0006%、0.0007%、0.0004%和0.0007%,定量检出限分别为0.0012%、0.0016%、0.0020%、0.0025%、0.0013%和0.0025%。按照实验方法测定5个粗二氧化碲样品中铜、铅、锑、铋、砷和硒,测定结果的相对标准偏差(RSD,n=7)为0.79%~4.8%,加标回收率为96.0%~103%。方法简单,精密度和准确度较高,可用于测定粗二氧化碲中铜、铅、砷、锑、铋、硒含量。     

STUDIES ON THE EXTRACTION OF SELENIUM AND TELLURIUM FROM COPPER ELECTROLYTIC SLIMES BY SUBLIMATION IN VACUUM

Abstract

Anode slimes obtained from the electrolytic refining of copper contain selenium and tellurium in the form of selenides and tellurides of metals, e.g., copper and silver. The slimes were treated with sulfur under vacuum; selenides and tellurides decomposed to give selenium and tellurium in metallic form which condensed on a cooler zone. Various parameters studied were temperature, time, sulfur addition, briquetting pressure, and fineness of sulfur added. The X-ray diffraction studies carried out on treated and then on untreated slime proved the reaction of sulfur with selenide and telluride of copper to give copper sulfide, selenium, and tellurium. Sulfurization at around 475°C for 60 min gives optimum recoveries.     

电感耦合等离子体原子发射光谱法测定纯银中镉、铋、铁、铅、锑、钯、硒、碲

样品用硝酸溶解,加入过量盐酸沉淀分离银,过滤后利用电感耦合等离子体原子发射光谱法测定镉、铋、铁、铅、锑、钯、硒、碲,方法检出限分别为:0.0028,0.0075,0.0036,0.011,0.010,0.021,0.0075,0.0039μg/mL;加标回收率为98.1%～114.3%;RSD小于4.2%,方法能同时准确测定镉、铋、铁、铅、锑、钯、硒、碲,满足日常分析要求。     

Activation analysis for selenium and tellurium trace impurities in gallium, arsenic and gallium arsenide

Destructive and non-destructive activation analysis for selenium and tellurium has been studied. In destructive analysis the selenium and tellurium activities are co-extracted from the irradiated and dissolved matrix elements with dithizone/CCl(4), reagent in a hot-chamber by remote manipulation, then separated from each other by diethylammonium-N,N-diethyldithiocarbamate/CCl(4) extraction, tellurium going into the organic phase and selenium being retained by the aqueous phase. The sensitivity of the method is 10(-8)g for both elements. By non-destructive methods, selenium can be determined down to 10(-6)g on short irradiation, and down to 3 x 10(-8) g on long irradiation and cooling, and tellurium down to 10(-6) g with long irradiation and cooling.     

Non-chromatographic hydride generation atomic spectrometric techniques for the speciation analysis of arsenic,antimony, selenium,and tellurium in water samples—a review

Hydride generation (HG) coupled with AAS, ICP–AES, and AFS techniques for the speciation analysis of As, Sb, Se, and Te in environmental water samples is reviewed. Careful control of experimental conditions, offline/online sample pretreatment methods employing batch, continuous and flow-injection techniques, and cryogenic trapping of hydrides enable the determination of various species of hydride-forming elements without the use of chromatographic separation. Other non-chromatographic approaches include solvent extraction, ion exchange, and selective retention by microorganisms. Sample pretreatment, pH dependency of HG, and control of NaBH₄/HCl concentration facilitate the determination of As(III), As(V), monomethylarsonate (MMA), and dimethylarsinate (DMA) species. Inorganic species of arsenic are dominant in terrestrial waters, whereas inorganic and methylated species are reported in seawater. Selenium and tellurium speciation analysis is based on the hydrides generation only from the tetravalent state. Se(IV) and Se(VI) are the inorganic selenium species mostly reported in environmental samples, whereas speciation of tellurium is rarely reported. Antimony speciation analysis is based on the slow kinetics of hydride formation from the pentavalent state and is mainly reported in seawater samples.     

Novel multi-chalcogen ring systems with three different chalcogen atoms: synthesis,structure and redox property of five-membered trichalcogenaheterocycles

The molecular structure of novel five-membered trichalcogenaheterocycles with three different chalcogen atoms, sulfur, selenium and tellurium, has been determined by crystallographic studies.     

Qualitative and Quantitative Study on Internal Rotation During Tautomerization of Thione,Selenone, and Tellurone

Internal rotation during the tautomerization of simple acetone analogues of sulfur, selenium, and tellurium is investigated in detail both qualitatively and quantitatively. An enhanced HOMO-LUMO gap and thus, an increased stability in the product, which is evident from the qualitative analysis of frontier molecular orbitals of different rotamers of enol analogues, can be attributed to the consequences of this internal rotation. The effect of various substituents on the reaction mechanism and tautomerization energy is also investigated.     

Nanotube formation favored by chalcogen-chalcogen interactions

Close contacts between sulfur, selenium, and tellurium centers are used to construct nanotubes in the solid state which are able to host other molecules.     

Donor Acceptor Complexes between the Chalcogen Fluorides SF2, SeF2, SeF4 and TeF4 and an N-Heterocyclic Carbene

The majority of binary chalcogen fluorides are fiercely reactive and extremely difficult to handle. Here, we show that access to crystalline donor-acceptor complexes between chalcogen difluorides (sulfur, selenium) and tetrafluorides (selenium, tellurium) with the N-heterocyclic carbene (NHC) 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) is possible conveniently and safely without the need to generate the highly unstable EF₂ (E=S, Se) or the very toxic and corrosive SeF₄.     

Macro micro separation of selenium and tellurium: Application to NAA</p> </p>

Summary A simple pre-irradiation separation approach has been worked out for the determination of traces of tellurium in high purity selenium followed by neutron activation analysis (NAA) for the end determination of the analyte/s. The difference in volatilities of these elements has been utilized for the separation of the analyte from the matrix. The complete volatility of selenium at ~600 °C was established using neutron activation analysis and selenium radiotracer. Standard addition was used to validate the results. The proposed method of separation of selenium prior to irradiation could make the determination of tellurium possible and also improved the detection limit by several folds.</p> </p>     

Three-component reaction of imidazoles,cyanophenylacetylene, and chalcogens: stereoselective synthesis of 3-alkenyl-2-imidazolethiones and -selones

The three-component reaction of 1-substituted imidazoles, cyanophenylacetylene, and elemental sulfur or selenium proceeds readily (for sulfur at room temperature without solvent, and for selenium in boiling MeCN) to stereoselectively afford 3-(Z)-cyanophenylethenyl-2-imidazolethiones or -selones in yields ranging 39–97% (for thiones) and 39–84% (for selones). In this reaction, tellurium is inactive both under the above conditions and upon heating (50–55 °C) in DMSO, instead, only the C(2)-vinylation of the imidazole ring in up to 98% yield takes place. The Z-stereoselectivity of the reaction is close to 100% (for sulfur) and reaches 91–99% (for selenium). The reaction involves the zwitterionic adduct of imidazoles with cyanophenylacetylene, which converts to the carbene via proton transfer (from the imidazole 2 position to the carbanionic site of the zwitterion) further reacting with chalcogens.     

Vertical and nonvertical participation by sulfur,selenium, and tellurium

The mechanism of stabilization of positive charge on carbon by sulfur, selenium, or tellurium at the beta-position has been investigated kinetically, by measurement of rate enhancements, and structurally, by variation of the bond strength to the leaving group. Stabilization can occur either nonvertically with formation of a bridged intermediate or vertically through hyperconjugation within an open carbocation. We observed large rate enhancements (10(5) for S, 10(6) for Se) in 97% aqueous trifluoroethanol with trifluoroacetate as the leaving group. These enhancements are consistent with either mechanism. Product structures also are consistent with either mechanism. Nine crystal structures revealed that the bond to the leaving group (C-O) is lengthened by the presence of S or Se at the beta-position, in proportion to the basicity of the leaving group. This lengthening is not accompanied by angle distortions expected for the bridging mechanism. The crystallographic data support vertical (hyperconjugative) character along the reaction coordinate, more so for selenium than sulfur.     

Synthesis of 2,3,7,8-tetramethoxydibenzotellurophene and its thio and seleno analogues

The title compounds 5 were obtained from the reaction of 3,3′,4,4′-tetramethoxybiphenyl ( 6 ) or its 2,2′-dilithio derivative 8 with various chalcogen electrophiles (sulfur dichloride, selenium tetrachloride, selenium oxychloride and tellurium tetrachloride).     

Spectrophotometric determination of traces of selenium with diaminobenzidine

Diaminobenzidine is suitable for the spectrophotometric determination of traces of selenium. The reaction is very sensitive, the molecular extinction coefficient being as high as 10,200. The reaction is specific, the most common ions causing no perturbation. The procedure is especially valuable for the determination of traces selenium in tellurium and in sulfur, provided that the latter is present in the sulfate form.     

Rapid determination of selenium and tellurium by atomic-absorption spectrophotometry

A rapid method has been developed for the determination of selenium and tellurium in geological and biological samples. It involves acid digestion of the sample with mineral acids, addition of arsenic as a carrier, reduction of arsenic to co-precipitate selenium and tellurium, dissolution of the precipitate in dilute nitric acid and subsequent determination of selenium and tellurium by conventional atomic-absorption spectrophotometry. Selenium and tellurium have been measured on a routine basis, down to 0.1 ppm.     

Molecular emission cavity analysis: Part 14. Determination of Selenium Utilizing Hydrogen Selenide Generation

Selenium (0.02–2 ppm), after conversion to hydrogen selenide -with sodium tetrahydroborate, can be determined by molecular emission cavity analysis. The detection limit is 7 ng of selenium. The effects of 26 ions are reported. The depressive effects of arsenic and antimony can be removed by selective volatilisation, and the enhancing effects of tellurium and sulphite by addition of tellurium to standards and by oxidation to sulphate, respectively.     

A multidimensional gas chromatography method for the analysis of hydrogen sulfide in crude oil and crude oil headspace

Two‐dimensional heart‐cutting gas chromatography is used to analyze dissolved hydrogen sulfide in crude samples. Liquid samples are separated first on an HP‐PONA column, and the light sulfur gases are heart‐cut to a GasPro column, where hydrogen sulfide is separated from other light sulfur gases and detected with a sulfur chemiluminescence detector. Heart‐cutting is accomplished with the use of a Deans switch. Backflushing the columns after hydrogen sulfide detection eliminates any problems caused by high‐boiling hydrocarbons in the samples. Dissolved hydrogen sulfide is quantified in 14 crude oil samples, and the results are shown in this work. The method is also applicable to the analysis of headspace hydrogen sulfide over crude oil samples. Gas hydrogen sulfide measurements are compared to liquid hydrogen sulfide measurements for the same sample set. The chromatographic system design is discussed, and chromatograms of representative gas and liquid measurements are shown.     

Studies of the naturally occurring biomethylation of selenium and the determination of the products

A systematic study of the biomethylation of selenium and the determination of the methylated species indicates preliminarily that selenium is susceptible to natural biomethylation under certain environmental conditions. Detectable levels of methylated selenium species, including dimethyl selenide [(CH₃)₂Se], dimethyl diselenide [(CH₃)₂Se₂] and dimethylselenone [(CH₃)₂SeO₂] have been detected by gas chromatography – graphite furnace atomic absorption spectrophotometry (GC – GF AA) from a variety of environmental samples. Findings of naturally methylated selenium species from both soil samples and related air samples suggest that there may exist a localized cycle of selenium between ground soil and the ambient air. Factors that influence the sensitivity and accuracy for the determination of alkyl selenide compounds by GC – GF AA have also been investigated. Flashlike injection mode and addition of about 10% of hydrogen gas to the argon carrier gas provide for highly sensitive detection. Reproducible determination can be obtained with a precision of about 6% and the detection limits are 0.3 ng Se m^?3.     

Determination of selenium and tellurium in air by atomic-absorption spectrometry

Elemental selenium and tellurium, and gaseous inorganic forms of Se(IV), Se(VI), Te(IV) and Te(VI) have been determined after their adsorption on gold-coated beads. After leaching, with water and dilute hydrochloric and nitric acids, the different chemical species in each acid fraction were separated with an anion-exchange resin (Bio-Rad AG-1X8) and a cation-exchange resin (Amberlite IR-120 Plus) by varying the acidity of the leaching agent. Subsequent analysis was by graphite-fumace atomic-absorption spectrometry. The lower detection limit for Se and Te was 0.03 ng/M(3) with a precision of +/- 5%. The average amounts of selenium in interior and exterior air samples were about 4.73 and 1.93 ng/m(3) respectively. For tellurium the corresponding values were about 0.78 and 0.24 ng/m(3).