Selective collection of selenium(IV) on anion-exchange resin with azothiopyrine disulphonic acid

Azothiopyrine disulphonic acid (ATPS) has been shown to be terfunctional, namely it can form a selenotrisulphide by reaction of its thiol group with selenium(IV), bind to an anion-exchange resin by ion-exchange through its sulphonate group, and be strongly physically adsorbed on the ion-exchange resin, ATPS adsorbed on the resin does not bleed into solution even in the presence of sodium chloride and hydrochloric acid. The collection of seleniurn(IV) is practically complete when ATPS is added to a selenium(IV) solution and the reaction product is collected on the anion-exchange resin. Selenium(IV) is not satisfactorily collected, however, by reaction with anion-exchange resin loaded with ATPS. The sorbed selenium can be eluted [as Se(IV)] with 13M nitric acid and directly determined fluorometrically in the eluate.     

Spectrophotometric determination of traces of selenium(IV) in various environmental samples using the flow-injection technique (FIT)

A simple, sensitive, and rapid flow-injection spectrophotometric method was developed for the determination of trace amounts of selenium(IV). The method is based on the oxidation reaction of 3-methyl-2-benzothiazolinone hydrazone hydrochloride (MBTH) by selenium(IV) followed by the coupling reaction with chromotropic acid (4.5-dihydroxy naphthalene-2.7-disulphonic acid) in a basic medium (phosphate buffer, pH 10.5) to give a pink derivative with λ_max 530 nm that is stable for more than 7 days at 35°C. The reaction and flow conditions of the full experimental design were optimized. A detection limit (2s) of 0.25 μg/L Se(IV) was obtained at a sampling rate of 10 samples per hour. Beer’s law is obeyed for a Se(IV) concentration range of 0.05–0.5 μg/mL at the wavelength of maximum absorption. The detailed study of various interference ions indicates that the method is highly selective. The method was successfully applied to the determination of traces of selenium(IV) in various water samples. The results obtained were in good agreement with those obtained by the reported methods at the 95% confidence level. The text was submitted by the authors in English.     

Spectrofluorimetric kinetic determination of selenium (IV) by flow injection analysis in cationic micellar medium

A sensitive catalytic kinetic spectrofluorimetric method for determining ng ml(-1) of selenium by flow injection analysis has been developed. The method, based on the catalytic effect of Se (IV) on the reduction of resorufin by sulphide, in the presence of cetylpyridinium chloride, is monitored spectrofluorimetrically (lambda(ex)=480 nm; lambda(em)=583 nm). The linearity range of the calibration graph is dependent on the concentration of sulphide. The variables affecting the rate of the reaction were investigated. The method is simple, rapid, precise, sensitive, and widely applicable. The limit of detection is 1 ng ml(-1) Se (IV), and the calibration range is 5-1000 ng ml(-1). Sampling rate is 60 samples h(-1), and the relative standard deviation of 12 determinations of 100 ng ml(-1) Se was 0.76%. The determination of Se (IV) in the presence of Se (VI) and total selenium is described. The method was applied to the determination of Se in selenium tablets, and several synthetic samples.     

Determination of selenium by means of computerized flow constant-current stripping at carbon fibre electrodes. : Application to human whole blood and milk powder.

The main features of the flow constant-current stripping analysis for selenium(IV) are formation of a mercury film on a carbon fibre sensor in a chloride medium containing mercury(II), electrolysis in the sample at ?0.20 V vs. SCE for 15–60 s, and subsequent stripping (reduction) of the mercury(II) selenide formed on the electrode surface, by means of a constant current of 0.40 μA in an acidic magnesium chloride solution containing Triton X-100. During stripping, the potential vs. time gradient is monitored at a real-time measuring rate of 25.6 kHz. All experimental parameters are under computer control. A standard addition method is used and the results are calculated and reported, both digitally and graphically. Equations relating the magnitude of the constant current to the concentration of reducible species, and, in particular, of dissolved dioxygen, are derived. Milk powder and whole blood reference samples were analyzed by high-pressure digestion in nitric acid and dilution with hydrochloric acid, in order to reduce selenium(VI) to selenium(IV), and then constant-current stripping. The results obtained by this method were lower than those obtained by the reference technique, but the values agreed within one standard deviation of the two techniques. Ions, such as iron(III) and lead(II), known to interferè with electrochemical stripping for selenium(IV) in batch analysis did not interfere in the flow approach.     

Separation of selenium(IV) and tellurium(IV) from mixtures by extraction chromatography with trioctylphosphine oxide

The reversed-phase extraction chromatographic separation of selenium(IV) and tellurium(IV) from several elements with trioctylphosphine oxide as extractant is reported. Selenium was extracted from 6M hydrochloric acid containing 7M lithium chloride was stripped with 4M hydrochloric acid, and tellurium was extracted from either the same medium as selenium or from 4M hydrochloric acid, and stripped with 1-2M hydrochloric acid. Selenium and tellurium can be separated from multicomponent mixtures.     

Investigation into the voltammetric behaviour and detection of selenium(IV) at metal electrodes in diverse electrolyte media

The voltammetric behaviour of selenium(IV) was studied at platinum and gold electrodes in sulphuric acid, perchloric acid and potassium chloride media as a basis for its voltammetric detection. The best voltammetric behaviour was recorded at gold electrodes with perchloric acid as the supporting electrolyte. The concomitant presence of metals, such as copper or lead, and of model biomolecules, such as bovine serum albumin, in the solution resulted in a deterioration of the electrochemical response for selenium(IV). Quantitative detection of selenium(IV) by square wave anodic stripping voltammetry at both a millimetre-sized gold disc electrode and a microband electrode array revealed linear responses to selenium concentration in the ranges 5–15 μM and 0.1–10 μM, respectively, with 60 s preconcentration. The sensitivities were 6.4 μA μM⁻¹ cm⁻² and 100 μA μM⁻¹ cm⁻² at the disc and the microband array, respectively. The detection limit at the microband electrode array was 25 nM, illustrating the potentiality of such microelectrodes for the development of mercury-free analytical methods for the trace detection of selenium(IV).     

Flow-injection simultaneous determination of selenium(IV) and selenium(IV + VI) using photooxidative coupling of p-hydrazinobensenesulfonic acid with N-(1-naphthyl)ethylenediamine

A flow-injection spectrophotometric method has been developed for the simultaneous determination of selenium(IV) and (IV + VI) at nanogram per milliliter levels. It is based on the catalytic effect of selenium(IV) on the photooxidative coupling of p-hydrazinobenzenesulfonic acid (HBS) with N-(1-naphthyl)ethylenediamine (NED) to form an azo dye (λ_max = 538 nm). In this reaction, bromide acted as an activator for the catalysis of selenium(IV) and an reducer for selenium(VI) to selenium(IV) in an acidic medium which allowed the determination of selenium(IV + VI). A sample solution, being split by Y-piece into two portions, passed through the low-temperature coil (4 m, 25 °C) and the high-temperature coil (20 m, 100 °C). By monitoring the absorbance of the dye produced in the two portions, selenium(IV) and (IV + VI) in the range of 0.2–6 ng ml⁻¹ were determined simultaneously. The relative standard deviations for 3 ng ml⁻¹ selenium(IV) and (VI) (n = 10) were 1.2 and 1.3%, respectively. There were few interfering ions in the selenium determination. The proposed method was applied to the determination of selenium(IV) and (VI) in natural water samples.     

Sorption of selenium(IV) onto magnetite in the presence of silicic acid

Sorption of selenium(IV) and silicic acid onto magnetite (Fe(3)O(4)) was investigated in binary systems, with concentrations of silicic acid under the solubility limit of amorphous silica. Using the double diffuse layer model (DDLM), surface complexation constants of selenium(IV) and H(4)SiO(4) onto magnetite were extracted using Fiteql 4.0. Then, prediction curves of the sorption of selenium(IV) in the presence of silicic acid onto magnetite were obtained, using the calculated surface complexation constants. Finally, laboratory experiments were performed and showed a competition between selenium(IV) and silicic acid for the surface sites of magnetite. Experimental results matched the model predictions, confirming its ability to model qualitatively and quantitatively the ternary system.     

Determination of selenium(IV) and other forms of selenium dissolved in sea water by anion-exchange resin loaded with sulfonic acid derivative of bismuthiol-II and hydride generation atomic-absorption spectrometry

Summary A sulfonic acid derivative of bismuthiol-II (bisIIS) was synthesized from 4-hydrazinobenzene sulfonic acid and carbon disulfide. Selenium(IV) was adsorbed selectively and quantitatively on the anion-exchange resin loaded with bis-IIS. Selenium adsorbed on the resin was eluted by the use of penicillamine and determined by hydride generation atomic absorption spectrometry (hydride generation/AAS). Selenium(VI) and other forms of selenium, which were not adsorbed onto the resin, were collected on the resin after digestion with nitric acid followed by reduction with hydrochloric acid. Separative preconcentration of selenium(IV), selenium(VI) and other forms of selenium in 0.5 mol/l sodium chloride could be carried out successfully by the proposed procedures. However, in the case of estuarial sea water containing a large quantity of organic substances, selenium(IV) could not be separated, because organic substances interfered with the reduction of selenium(VI) to selenium(IV) by the use of hydrochloric acid. Selenium(IV) and total amount of selenium(VI) and other forms of selenium dissolved in polluted sea water samples were determined by the proposed procedures.

---

Bestimmung von Selen (IV) und anderen in Meereswasser gelösten Selenformen mit Hilfe eines mit dem Sulfonsäurederivat von Bismuthiol-II beladenen Anionenaustauschers und der Hydrid-AAS

     

Kinetic determination of trace levels of selenium(IV) and total selenium by Nile Blue A/hydrogen peroxide method

A kinetic method for the determination of selenium(IV) traces is proposed, based on its inhibitory action on the oxidation of Nile Blue A by hydrogen peroxide in phosphate buffer (pH 10.5). A linear dependence was established between the rate of the proposed indicator reaction and selenium concentration in the range 9.5 × 10^–2-1.58 ng cm^–3. The experimental conditions of maximal selenium effect were established. Selenium, determined by the tangent method, was determined at concentrations over the range 0.22–1.26 ng cm^–3, with relative standard deviations up to 4.5%. The reaction rate was followed spectrophotometrically. The effect of foreign ions on the accuracy of this method was also investigated. The method was applied to the determination of selenium in pharmaceutical preparations and wheat flour.     

Interference from iodide in the determination of trace level selenium

The rate of the reaction between iodide and selenium(IV) at trace levels to form selenium and iodine has been determined in 1-6M hydrochloric acid. The reaction rate increases rapidly with acidity. When hydrochloric acid is added to reduce selenate to selenite prior to the determination of total selenium, some selenium may be lost by reduction to the element if iodide is present. A table of half-lives of the selenite-iodide reaction under various conditions is presented. A method for removal of iodide is suggested.     

Determination of selenium(IV) and tellurium(IV) by differential pulse polarography

Differential pulse polarographic methods for the determination of selenium(IV) and tellurium(IV) in nitric acid medium are described. The peak current is maximal when 0.25M nitric acid medium is used, the DPP peaks for Se(IV) and Te(IV) being at -0.54 and -0.8 V vs. Ag/AgCl respectively. The peak current is a linear function of selenium concentration over three ranges, 5.1 x 10(-6)-1.3 x 10(-5), 1.27 x 10(-5)-1.27 x 10(-4) and 1.27 x 10(-4)-7.60 x 10(-4)M Se(IV), with different slopes. The plot for Te(IV) is linear over the range 0.78 x 10(-6)-9.40 x 10(-5)M.     

Kinetic determination of selenium using the reduction of nile blue with sulfide ions

The catalytic effect of Se(IV) was first observed in the reaction of the reduction of Nile Blue with sulfide ions. Optimal conditions for the determination of selenium by this reaction were found. The dependence of the reaction rate on the concentration of Se(IV) was linear in the concentration range 0.008-0.16 μg/mL. Solvent extraction with dithiophosphoric acids was proposed for the separation of selenium from the interferents. A procedure for the extraction-kinetic determination of selenium with the detection limit 0.006 μg/mL was developed.     

Anion-exchange resin modified with bismuthiol-II, as a new functional resin for the selective collection of selenium(IV)

A functional resin for the collection of selenium(IV) has been prepared simply by the conversion of a common ion-exchange resin with bismuthiol-II which has three functional properties, namely the capabilities of selective reaction with selenium(IV), ion-exchange reaction with ion-exchange resin and strong physical sorption to the ion-exchange resin matrix. The binding ratio of selenium(IV) to bismuthiol-II on the resin was confirmed to be 1:4. The reaction was represented as follows: 4RSH + H(2)SeO(3)--> R-S-Se-S-R + R-S-S-R + 3H(2)O. Highly selective sorption of selenium(IV) was achieved, based on the formation of stable selenotrisulphide on the resin. Selenium(IV) sorbed on bismuthiol-II resin was eluted effectively with 8-13M nitric acid or some thiols, such as cysteine and penicillamine. In the cases of thiols, the elution of selenium was found to be also based on the formation of selenotrisulphide, and the bismuthiol-II resin was regenerated. Satisfactory results were obtained when this resin was applied to the determination of selenium(IV) in river, estuarine or sea water samples.     

Radiochemical investigation of the electron exchange reaction between tin(II) and tin(IV) in hydrochloric acid solutions

This paper is concerned with the study of isotope exchange reaction between Sn(II) and Sn(IV) in hydrochloric acid solutions. The kinetics of the exchange reaction of tin in these solutions were studied by extraction of Sn(IV)-hydroxyquinolate into chloroform.¹¹³Sn tracer, initially in the Sn(IV) state, was used. The rate of exchange reaction was determined at 22°C in a wide range of hydrochloric acid concentrations (2.8–12M). The dependence of the exchange rate on the concentration of chloride and hydrogen ions in these solutions (ionic strength: I∼8 and I∼12) are given. The activation energy dependence on chloride ion concentration at I∼12 was determined. The possible mechanism of the exchange reaction between tin(II) and tin(IV) is discussed on the basis of these data.     

Kinetics and mechanism of the oxidation of selenium(IV) by permanganate

Summary The oxidation of selenium(IV) by permanganate has been studied kinetically in acid, neutral and alkaline media. The reaction exhibits unit-order dependence on selenium(IV) and permanganate in all the three media. Manganese(VI) retards the reaction in alkaline medium. The rate-limiting step is the same in all the three media, but the stoichiometry is different, being 2:1 in alkaline medium, 2:3 in neutral medium and 2:5 in acid medium. Evidence has been obtained for a one electron-transfer in the rate-determining step.     

Kinetic-spectrophotometric determination of selenium in natural water after preconcentration of elemental selenium on activated carbon

A simple, accurate, sensitive and selective method is described for rapid determination of ultra-trace quantities of selenium. Selenium (IV) was collected on activated carbon after reduction to elemental Se by l-ascorbic acid. The collected selenium was then determined based on its accelerating effect on the oxidation reaction of methyl orange with bromate in acidic media. Total amount of Se(IV) and Se(VI) were collected on AC after their reduction by hydrazine. Se(IV), Se(VI) and total selenium could be determined by the method. Selenium in the range 10-10 000 ng could be determined by the method. The method was used to the determination of Se(IV), Se(VI) and total selenium in natural water with satisfactory results.     

Determination of submicrogram amounts of selenium(IV) by means of the catalytic reduction of 1,4,6,ii-tetraaza- naphthacene

In the presence of glyoxal and hypophosphorous acid 1,4,6II-tetraazanaph-thacene is reduced to I,6-dihydro-I,4,6,II-tetraazanaphthacene. The reaction is catalyzed by selenium(IV). By means of this catalytic reaction, submicrogram amounts of selenium(IV) can easily be determined. The method is simple and sensitive, and there are few interferences.     

Fabrics and papers modified with analytical reagents for the test determination of selenium(IV) and tellurium(IV)

It is shown that Malachite Green and Crystal Violet immobilized on viscose fabrics can be used as reagents for the rapid determination of selenium(IV) and tellurium(IV). Selenium is determine by the color intensity of ion associates formed by the reagents with the triiodide ion formed upon the reduction of selenium(IV) with potassium iodide and tellurium, by the color intensity of reagent ion associates with telluromolybdic heteropoly acid. The analytical ranges for selenium and tellurium(IV) were 0.005–0.5 and 0.01–0.1 mg/L upon passing 20 and 100 mL of a test solution through the indicator matrix, respectively. The duration of analysis does not exceed 15–20 min. The relative standard deviation is 50%. Test strips were proposed for determining 0.1–100 mg/L selenium(IV) and 1–1000 mg/L tellurium(IV) by the length of the colored zone. The determination of selenium(IV) is based on the oxidation of 4-nitrophenylgydrazine to its diazonium salt and salt interaction with naphthylamine chemically immobilized on paper with the formation of a red azo compound. The determination of tellurium(IV) is based on its reaction with Bismuthol II immobilized on a paper.     

Spectrophotometric determination of selenium with dithizone

Microgram amounts of selenium(IV) are determined by measuring the decrease in absorbance of dithizone in carbon tetrachloride solution at 620 nm. Relative standard deviations for samples containing 0.20 and 1.00 μg of selenium(IV) are 0.6% and 0.4%, respectively. Of several metals tested only copper (at the 1.0-μg level) and iron (at the 100-μg level) interfere but high concentrations of nitric or perchloric acid cause low results. A reinvestigation of the reaction of selenium(IV) with dithizone suggests a formula Se(HDz)₄ for the dithizonate.