Acids of Selenium

For the hydride transfer the effect of the selenium substitution goes in the opposite direction compared to the H-H bond cleavage, with a 1.5 kcal/mol lower barrier for the selenium case. This effect can be explained by a larger mobility and acidity of selenium. The mobility is indicated by the bond distance to nickel which is 2.30 A for the hydride in the sulfur case and 2.40 A for the selenium case. At the transition states the Ni-S and Ni-Se distances increase to 2.44 A and 2.61 A, respectively. It is also interesting to note that the Se-H distance of 1.71 A at the transition state is shorter than the S-H distance of 1.83 A. Since selenium is more acidic this indicates a dominating hydride character of the hydrogen at the transition state. 

Give the names and formulas of the oxides and oxygen acids of selenium and tellurium. 

C. Acute inhalation of hydrogen selenide produces dyspnea, abdominal cramps, and diarrhea. Inhalation of selenium hexafluoride produces severe corrosive injury and systemic toxicity from acids of selenium plus fluoride ion toxicity. Selenium salt inhalation causes dyspnea and skin and mucous membrane irritation. 

Write the name and formula of the -ic acid of selenium (Se, Z = 34) and the name and formula of the anion formed by its total ionization (the loss of all hydrogens in the original acid). 

The -ic acid of selenium will have the same number of hydrogens and oxygens as the -ic acid of sulfur. Write its formula and name. 

Then cool the reaction-mixture, filter it at the pump, leaving a black residue of selenium, and wash out the flask twice with 2x5 ml. of acetic acid, passing the washings also through the filter. Dilute the united filtrates with water, and make the solution alkaline with 10% aqueous sodium hydroxide, which precipitates the camphorquinone. Cool, filter off the yellow camphorquinone at the pump, wash with water and drain thoroughly. 

Digestion. 20-25 mg. of the substance whose nitrogen content is to be estimated are weighed out in a stoppered weighing-tube and then transferred to the flask L that has been previously dried in an oven at izo C. With care, the substance may be transferred directly into the bulb of the flask without any adhering to the sides. If any material sticks on the way down, the flask should be tapped gently to cause the substance to fall to the bottom. 2 G. of the catalyst mixture (32 g. of potassium sulphate, 5 g. of mercury sulphate and ig. of selenium powder, well mixed) are added and 3 ml. of A.R. cone, sulphuric acid are measured out carefully and poured into the digestion... 

Selenium dioxide. The compound is conveniently prepared by the oxidation of selenium with nitric acid, followed by dehydration of the selenious acid thus formed by cautious heating ... 

Medicated Dandruff Shampoos. Dandmff is a scalp condition characterized by the production of excessive cellular material (18). A number of shampoos have been marketed which are designed to control and alleviate this condition, and many additives have been included in shampoo compositions to classify them as treatment products for dandmff. These additives include antimicrobial additives, eg, quaternary ammonium salts keratolytic agents, eg, saUcychc acid and sulfur heavy metals, eg, cadmium sulfide coal tar resorcinol and many others. More recent (ca 1993) systems use selenium sulfide [7488-56-4] or zinc pyrithione [13463-41 -7] as active antidandmff shampoo additives. Both of these additives are classified as dmgs, but can be found in over-the-counter products. A stronger version, incorporating the use of higher levels of selenium sulfide in a shampoo, is available but requires a prescription for purchase. 

Sulfation Roasting. Acid roasting technology (Fig. 2) rehes on differences in the volatiUty of the tetravalent oxides of selenium and tellurium at roasting temperatures of 500—600°C to selectively volatilise selenium from slimes. Acid roasting uses sulfuric acid as the oxidant for the conversion of selenium/selenides and tellurium/teUurides to their respective tetravalent oxides. Typical oxidation reactions are as foUow ... 

Selenium tetrachloride hydrolyzes to form hydrochloric acid, the degree of hydrolysis depending on the acidity of the solution. 

Selenium and precious metals can be removed selectively from the chlorination Hquor by reduction with sulfur dioxide. However, conditions of acidity, temperature, and a rate of reduction must be carefliUy controlled to avoid the formation of selenium monochloride, which reacts with elemental selenium already generated to form a tar-like substance. This tar gradually hardens to form an intractable mass which must be chipped from the reactor. Under proper conditions of precipitation, a selenium/precious metals product substantially free of other impurities can be obtained. Selenium can be recovered in a pure state by vacuum distillation, leaving behind a precious metals residue. 

Comprehensive accounts of the various gravimetric, polarographic, spectrophotometric, and neutron activation analytical methods have been pubHshed (1,2,5,17,19,65—67). Sampling and analysis of biological materials and organic compounds is treated in References 60 and 68. Many analytical methods depend on the conversion of selenium in the sample to selenous acid, H2Se02, and reduction to elemental selenium when a gravimetric deterrnination is desired. 

A number of substances, such as the most commonly used sulfur dioxide, can reduce selenous acid solution to an elemental selenium precipitate. This precipitation separates the selenium from most elements and serves as a basis for gravimetry. In a solution containing both selenous and teUurous acids, the selenium may be quantitatively separated from the latter by performing the reduction in a solution which is 8 to 9.5 W with respect to hydrochloric acid. When selenic acid may also be present, the addition of hydroxylamine hydrochloride is recommended along with the sulfur dioxide. A simple method for the separation and deterrnination of selenium(IV) and molybdenum(VI) in mixtures, based on selective precipitation with potassium thiocarbonate, has been developed (69). 

A widely used procedure for determining trace amounts of selenium involves separating selenium from solution by reduction to elemental selenium using tellurium (as a carrier) and hypophosphorous acid as reductant. The precipitated selenium, together with the carrier, are collected by filtration and the filtered soflds examined directly in the wavelength-dispersive x-ray fluorescence spectrometer (70). Numerous spectrophotometric and other methods have been pubHshed for the deterruination of trace amounts of selenium (71—88). 

Selenium. Selenium is determined by atomic absorption after the organoselenides are broken down with acidic persulfate and all forms of selenium have been converted to H2Se. The reduction is brought about in acidic solution of KI—SnCl2 or borohydride, and H2Se is generated by addition... 

The possibility of preconcentration of selenium in form of SeO by evaporation of low alkali water solution (for 20-1000 J.g/L) has been investigated. Considerable losses of selenium have been observed during evaporation of acidic and neutral solutions owing to volatility of selenium compounds. During evaporation of low alkali solutions at ph 9-10 there are no losses of selenium. Relative error of selenium determination is 1-2% for 1000 P-g/L solution and 3-5% for 20-100 p.g/L. Concentration factor is 10. 

The possibility of preconcentration of selenium (IV) by coprecipitation with iron (III) hydroxide and lanthanum (III) hydroxide with subsequent determination by flame atomic absorption spectroscopy has been investigated also. The effect of nature and concentration of collector and interfering ions on precision accuracy and reproducibility of analytical signal A has been studied. Application of FefOH) as copreconcentrant leads to small relative error (less than 5%). S, is 0.1-0.2 for 5-100 p.g Se in the sample. Concentration factor is 6. The effect of concentration of hydrochloric acid on precision and accuracy of AAS determination of Se has been studied. The best results were obtained with HCl (1 1). 

A constant problem in the use of selenium dioxide is the removal of selenium-containing contaminants in the above example it was found necessary to treat the product with chromic acid to remove materials which otherwise poisoned subsequent hydrogenation steps. 

Estr-5(10)-en-3-ones also react with methanol to give dimethyl ketals. Weak acid catalysts such as malonic and oxalic acid or selenium dioxide, which are unable to promote conjugation of the double bond, are conveniently used. ... 

An alternative synthetic route is described in U.S, Patent 2,900,398 as follows. A suspension of 30 g of 17a-methyI-testosterone and 10 g of selenium dioxide in 600 cc of tertiary amyl alcohol is treated with 60 g of magnesium powder and 6 cc of glacial acetic acid. 

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