Selenium chromatography

Selenium(IV) reacts with substituted 1,2-diaminobenzene or 2,3-diamlnonaphthalene in acidic solution to form stable cyclic derivatives which can t>e extracted into an organic solvent and analyzed by gas or liquid chromatography [682,683]. With chloro-, bromo-, or nitro-substituents the plazselenols can be determined with an electron-capture detector at the low picogram level. Se(VI) does not form piazselenol derivatives so the reaction with diaminobenzene can be used to determine the concentration of Se(IV) and Se(VI). Selenium(VI) may be redu to Se(IV) with... 

Selenurane oxides are also one of the hypervalent selenium compounds. Recently, the enantiomers of chiral selenurane oxide 38 were isolated for the first time by enantioselective liquid chromatography of the racemate or by spontaneous resolution occurring during slow evaporation of its acetonitrile solution or slow crystallization from the same solvent.57 The absolute configurations of the enantiomers were determined by X-ray crystallographic analysis (Scheme 17). 

Other methods reported for the determination of beryllium include UV-visible spectrophotometry [80,81,83], gas chromatography (GC) [82], flame atomic absorption spectrometry (AAS) [84-88] and graphite furnace (GF) AAS [89-96]. The ligand acetylacetone (acac) reacts with beryllium to form a beryllium-acac complex, and has been extensively used as an extracting reagent of beryllium. Indeed, the solvent extraction of beryllium as the acety-lacetonate complex in the presence of EDTA has been used as a pretreatment method prior to atomic absorption spectrometry [85-87]. Less than 1 p,g of beryllium can be separated from milligram levels of iron, aluminium, chromium, zinc, copper, manganese, silver, selenium, and uranium by this method. See also Sect. 5.74.9. 

Measures and Burton [556] used gas chromatography to determine selenite and total selenium in seawater. 

Shimoishi [ 555 ] determined selenium by gas chromatography with electron capture detection. To 50-100 ml seawater was added 5 ml concentrated hydrochloric acid and 2 ml 4-nitro-o-phenylenediamine (1%) and, after 2 hours, the product formed was extracted into 1 ml of toluene. The extract was washed with 2 ml of 7.5 M hydrochloric acid, then a sample (5 pi) was injected into a glass gas-liquid chromatography column (lm x 4 mm) packed with 15% of SE-30 on Chromosorb W (60-80 mesh) and operated at 200 °C with nitrogen (53 ml/min) as carrier gas. There is no interference from other substances present in seawater. The detection limit is 5 ng/1 with 200 ml samples, and the precision at a Se level of 0.025 pg/1 is 6%. 

Selenium Selenium co-precipitated with Fe(OH)3, precipitate dissolved in hydrochloric acid, converted to 5-nitro- piazselenol Gas chromatography with electron capture detector 5 ng/1 [907]... 

Selenium Selenium complexed with 4-nitro-o-phenylenediamine, extracted into toluene Gas chromatography — [555]... 

Hasunuma, R., T. Ogawa, Y. Fujise, and Y. Kawanashi. 1993. Analysis of selenium metabolites in urine samples of minke whales (Balaenoptera acutorostrata) using ion exchange chromatography. Comp. Biochem. Physiol. 104C 87-89. 

Biospecific adsorption, 6 396-397, 399 Biospecific binding, in microarray fabrication, 16 385 Biospecific elution, in affinity chromatography, 6 398 Biosphere, selenium occurrence in, 22 78. 

It is seen by examination of Table 1.11(b) that a wide variety of techniques have been employed including spectrophotometry (four determinants), combustion and wet digestion methods and inductively coupled plasma atomic emission spectrometry (three determinants each), atomic absorption spectrometry, potentiometric methods, molecular absorption spectrometry and gas chromatography (two determinants each), and flow-injection analysis and neutron activation analysis (one determinant each). Between them these techniques are capable of determining boron, halogens, total and particulate carbon, nitrogen, phosphorus, sulphur, silicon, selenium, arsenic antimony and bismuth in soils. 

Siu and Berman [163] determined selenium in marine sediments in amounts down to 0.2pg (or 20ng g 1 of sediment) with a precision of 7%. This method is based on the fact that 1,2 diaminobenzene (o-phenylene diamine) and its derivatives react selectively and quantitatively with selenium IV (average accuracy 94 5%) to form piazselenols that are both volatile and stable. Piazselenols can be determined by electron capture gas chromatography. The sediments were digested as follows. A 0.5g sample was placed in a poly(tetrafluoroethylene) pressure decomposition vessel. A... 

Oxidation with bis(p-methoxyphenyl) telluroxide (general procedure All the reactions are performed at room temperature under Nj in CHCI3 or CHjClj. Approximately 10 mL of solvent is used for every 100 mg of substrate. For thiocarbonyl derivatives, 1.1 equiv of the reagent is used, for thiols 0.55 equiv. The mixtures are concentrated by evaporation and submitted to thin layer or column chromatography to isolate the products. An2Te is always recovered in a yield of 64-96%, while sulphur or selenium is always recovered in near quantitative yields from reaction with thio- or selenocarbonyl derivatives. 

Chromatographic methods seem to offer the only possibility to provide pure stoichiometric selenium sulfides as fractional crystallization and sublimation result in more or less complicated mixtures. Conventional column chromatography has turned out to be unsuccessful, but recently it has been shown that high-pressure liquid... 

The application of high temperatures to increase the speed of HPLC separation extends to ion chromatography and to inorganic analysis. Le et al. [18,19] reported a 50% reduction in analysis time when a number of selenium and arsenic species including inorganic forms, organometallics, and compounds with amino acids and sugars were analyzed at 70°C. 

On-line anion exchange LC/ICP-MS methods for selenium and chromium speciation have been published [30], In studies of selenium speciation in environmental samples LC/ICP-MS and LC/ ESI-MS methods have been used for the determination of both inorganic and organic selenium species [43]. For the determination of methyl selenide, strong anion exchange and RP chromatography have been employed [43], while for the determination of seleno-aminoacids, IP RP chromatography with on-line detection based on ICP-MS has been successfully employed [44],... 

Gas chromatography and mass spectroscopy (GC/MS) of inorganic and organometallic compounds, 18 273-276 Gaseous hydroxides, 5 215-258 dimerization of, 5 224 mass spectrometric study of, 5 220-225 metalic, 5 220 nonmetallic, 5 217-220 study of in oxyhydrogen flame, 5 225-226 types of, 5 215-217 Gases, see also specific substances high ternperamre species from, 14 137-139 thermal decomposition of, 17 90-93 Gas phase electron resonance spectra, of sulfur and selenium fluorides, 24 190... 

NMR spectroscopy ( Se, /= 1/2, 7%) is a powerful technique for identifying cyclic selenium molecules, especially the heteroatomic ring systems that contain sulfur or tellurium in addition to selenium, for which several isomers are possible for most compositions (Section 12.1.2). Solutions of monoclinic selenium in CS2 have been shown by high-performance liquid chromatography to form an equilibrium mixture of cyclo-Seg, cyclo-Sey and cyclo-Se6. The Se NMR spectra of such solutions show two singlets that are attributable to cyclo-Seg and cyclo-Se with relative intensities that correspond to a molar ratio of ca 6 No resonance is observed for cyclo-Sey presumably as a result of the fluxional behaviour (pseudorotation) of the seven-membered ring (Section 12.1.2). 

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