Reductions selenium, sodium hydride

Reductions. Elemental selenium can be reduced using sodium hydride. The resulting sodium diselenide (Na2Se2) can be used to prepare dialkyl selenides (eq 55). Similarly, elemental sulfur can be reduced to diatomic sulfur by sodium hydride in the presence of a phase transfer catalyst,... 

Nakashima et al. [719] detail a procedure for preliminary concentration of 16 elements from coastal waters and deep seawater, based on their reductive precipitation by sodium tetrahydroborate, prior to determination by graphite-furnace AAS. Results obtained on two reference materials are tabulated. This was a simple, rapid, and accurate technique for determination of a wide range of trace elements, including hydride-forming elements such as arsenic, selenium, tin, bismuth, antimony, and tellurium. The advantages of this procedure over other methods are indicated. 

The optimal reaction conditions for the generation of the hydrides can be quite different for the various elements. The type of acid and its concentration in the sample solution often have a marked effect on sensitivity. Additional complications arise because many of the hydrideforming elements exist in two oxidation states which are not equally amenable to borohydride reduction. For example, potassium iodide is often used to pre-reduce AsV and SbV to the 3+ oxidation state for maximum sensitivity, but this can also cause reduction of Se IV to elemental selenium from which no hydride is formed. For this and other reasons Thompson et al. [132] found it necessary to develop a separate procedure for the determination of selenium in soils and sediments although arsenic, antimony and bismuth could be determined simultaneously [133]. A method for simultaneous determination of As III, Sb III and Se IV has been reported in which the problem of reduction of Se IV to Se O by potassium iodide was circumvented by adding the potassium iodide after the addition of sodium borohydride [134], Goulden et al. [123] have reported the simultaneous determination of arsenic, antimony, selenium, tin and bismuth, but it appears that in this case the generation of arsine and stibene occurs from the 5+ oxidation state. 

All four dissolution procedures studied were found to be suitable for arsenic determinations in biological marine samples, but only one (potassium hydroxide fusion) yielded accurate results for antimony in marine sediments and only two (sodium hydroxide fusion or a nitricperchloric-hydrofluoric acid digestion in sealed Teflon vessels) were appropriate for determination of selenium in marine sediments. Thus, the development of a single procedure for the simultaneous determination of arsenic, antimony and selenium (and perhaps other hydride-forming elements) in marine materials by hydride generation inductively coupled plasma atomic emission spectrometry requires careful consideration not only of the oxidation-reduction chemistry of these elements and its influence on the hydride generation process but also of the chemistry of dissolution of these elements. 

Nitric-perchloric acid digestion HCI reduction sodium borohydride reduction measure selenium hydride HGAAS No data 33-73% Oster and Prellwitz 1982... 

The question arises as to whether the formation of organometallic compounds during electrolysis of aqueous solutions of acrylonitrile is not due to cyanoethylation of hydrides formed initially at the electrode. In Table 5 data on the electrochemical reduction of tin, sulfur, selenium, and tellurium in aqueous solutions of sodium sulfate with and without acrylonitrile are compared [40]. 

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