Selenium, reduction potentials

Although it is only slowly oxidized in moist air at ambient temperature, cadmium forms a fume of brown-colored cadmium oxide [1306-19-0] CdO, when heated in air. Other elements which react readily with cadmium metal upon heating include the halogens, phosphoms, selenium, sulfur, and tellurium. The standard reduction potential for the reaction... 

Conditions such as pH, oxidation-reduction potential, and the presence of metal oxides affect the partitioning of the various compounds of selenium in the environment. In general, elemental selenium is stable in soils and is found at low levels in water because of its ability to coprecipitate with sediments. The soluble selenates are readily taken up by plants and converted to organic compounds such as selenomethionine, selenocysteine, dimethyl selenide, and dimethyl diselenide. Selenium is bioaccumulated by aquatic organisms. Very low levels of selenium are found in ambient air. 

This illustrates that the deposited metal dissolves in the mercury electrode. Other elements, such as selenium, arsenic, mercury, silver, gold, or tellurium, which either do not form amalgam or oxidize at potentials anodic to that of mercury can be measured by ASV using a variety of solid electrodes. The deposition step is usually carried out under conditions of forced convection to facilitate the transport of the metal ions to the electrode surface. The convective transport is achieved mainly by electrode rotation, solution stirring, and flow. The deposition potential (Ed in Figure 1) should be 0.3-0.4V more negative than the reduction potential of the metal ion to ensure an efficient deposition process. The duration of the preconcentration step is selected according to the... 

For chalcogenide films, a suitable complex of metal ions and selenium (HjSeOj) or a sulfur source is allowed to reduce simultaneously. The role of the complexing agent is twofold (a) it avoids the reaction between the precursors in the bulk solution and (b) it helps in shifting the reduction potential of the metal ions to an optimum value so that one... 

The co-reduction of copper and selenium is considered as an exception to Kroger s theory. Current-potential curves in the literature show that deposition of copper is rather compulsory to make the deposition of selenium possible. In fact, although the standard potential for Se(IV) reduction is more positive than that of copper (0.741 and 0.340 V vs. SHE, for selenous acid and cupric ion, respectively), it turns out that Se(IV) alone is reduced at more negative potentials than Cu(II). In the presence of copper, the order is reversed. 

Certain trace substances such as selenium (IV) can be determined by differential cathodic stripping voltammetry (DPCSV). For selenium a rather positive preconcentration potential of-0.2 V is adjusted. Selenium (IV) is reduced to Se2", and Hg from the electrode is oxidised to Hg2+ at this potential. It forms, with Se2" on the electrode, a layer of insoluble HgSe, and in this manner the preconcentration is achieved. Subsequently the potential is altered in the cathodic direction in the differential pulse mode. The resulting mercury (II) peak produced by the Hg11 reduction is proportional to the bulk concentration of SeIV in the analyte. 

Reduction is used for carbonyl functionalities [71, 230] such as thioesters [231], amides [232], and carbamates [233], as well as for sulfur [234] and selenium [122] compounds. Recently, the synthesis of a potential carbohydrate vaccine is described via an reduction-oxidation sequence [235]. An efficient solid-phase synthesis of pyrimidine derivatives that involved reduction of the corresponding nitro derivatives was developed by Makara et al. in 2001 (Scheme 3.9) [236]. 

Anaerobic metabolism occnrs nnder conditions in which the diffusion rate is insufficient to meet the microbial demand, and alternative electron acceptors are needed. The type of anaerobic microbial reaction controls the redox potential (Eh), the denitrification process, reduction of Mu and SO , and the transformation of selenium and arsenate. Keeney (1983) emphasized that denitrification is the most significant anaerobic reaction occurring in the subsurface. Denitrification may be defined as the process in which N-oxides serve as terminal electron acceptors for respiratory electron transport (Firestone 1982), because nitrification and NOj" reduction to produce gaseous N-oxides. hi this case, a reduced electron-donating substrate enhances the formation of more N-oxides through numerous elechocarriers. Anaerobic conditions also lead to the transformation of organic toxic compounds (e.g., DDT) in many cases, these transformations are more rapid than under aerobic conditions. 

There is increased interest in the use of Ru-based systems as catalysts for oxygen reduction in acidic media, because these systems have potential applications in practicable direct methanol fuel cell systems. The thermolysis of Ru3(CO)i2 has been studied to tailor the preparation of such materials [123-125]. The decarbon-ylation of carbon-supported catalysts prepared from Ru3(CO)i2 and W(CO)6, Mo(CO)is or Rh(CO)is in the presence of selenium has allowed the preparation of catalysts with enhanced activity towards oxygen reduction, when compared with the monometallic ruthenium-based catalyst [126],... 

Triphenyl sulphur, selenium and telurium cations are reductively cleaved at less negative potentials, moving down the periodic table (Table 5.4). At the first po-larographic wave, a one-electron process results in the formation of phenyl radicals, probably adsorbed on the mercury surface. Only the reaction of triphenylsul-phonium ions has been studied in detail and the products are diphenylsulphide and diphenylmercury. A second polarographic wave has E/, = -1.33 to -1,39 V vs. see over the range of pH 5 to 12 and reduction at the plateau of this wave gives diphenylsulphide and benzene [53]. 

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