Sulfur reduction potentials

Addition of sodium dithionite to formaldehyde yields the sodium salt of hydroxymethanesulfinic acid [79-25-4] H0CH2S02Na, which retains the useful reducing character of the sodium dithionite although somewhat attenuated in reactivity. The most important organic chemistry of sodium dithionite involves its use in reducing dyes, eg, anthraquinone vat dyes, sulfur dyes, and indigo, to their soluble leuco forms (see Dyes, anthraquinone). Dithionite can reduce various chromophores that are not reduced by sulfite. Dithionite can be used for the reduction of aldehydes and ketones to alcohols (348). Quantitative studies have been made of the reduction potential of dithionite as a function of pH and the concentration of other salts (349,350). 

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... 

J. A. CavaHaro and co-workers. Sulfur and A.sh Reduction Potential and Selected Chemical and Physical Properties of United States Coals, DOE/PETC-91 / 2, Jan. 1990. 

The sulfur content of U.S. coals varies widely, ranging from a low of 0.2 percent to as much as 7 percent by weight, on a diy Basis. The estimated remaining U.S. coal reserves of all ranks, by sulfur content, are shown in Fig. 27-1. Extensive data on sulfur and sulfur reduc tion potential, including washability, in U.S. coals are given in Sulfur and Ash Reduction Potential and Selected Chemical and Physical Properties of United States Coal (U.S. Dept, of Energy, DOE/PETC, TR-90/7, 1990 TR-91/1 andTR-91/2, 1991). 

Table 15.19 Some standard reduction potentials of sulfur species (25°, pH 0)...

The exact mechanisms of the Raney nickel reactions are still in doubt, though they are probably of the free radical type. It has been shown that reduction of thiophene proceeds through butadiene and butene, not through 1-butanethiol or other sulfur compounds, that is, the sulfur is removed before the double bonds are reduced. This was demonstrated by isolation of the alkenes and the failure to isolate any potential sulfur-containing intermediates. 

Note A HiPIP stands for high potential iron sulfur protein, a trivial name to indicate that the reduction potential of this type of small ET proteins is relatively high +0. < +0.5 volts. Formally,... 

A sulfur analogue of EC, ethylene sulfite (ES), was proposed as an additive for PC-based electrolytes by Winter and co-workers,apparently because of its structural similarity to EC and its potential, under reductive conditions, to release SO2, a known additive that effectively suppresses PC decomposition. As the voltammetry in Figure 39 shows, ES in only 5% presence successfully eliminated the exfoliation of the graphite anode, whereas 10% SO2 failed. The irreversible process corresponding to the reduction of ES occurred at --"2.0 V, lower than that of SO2 by 0.80 V however, the quantity of charge associated was much lower. According to the authors, the above apparent gap between the reduction potentials of ES... 

In this flow sheet, the aqueous raffinate from extraction is acidified to 5-6 mol dm with hydrochloric acid to optimize platinum extraction by the solvating extractant TBP. The coextraction of iridium is prevented by reduction with sulfur dioxide, which converts the iridium(IV) to the (III) species, which is not extractable. Once again, kinetics are a factor in this reduction step because, although the redox potentials are quite similar, [Ir(IV)/(III) —0.87 V Pt(IV)/(II) —0.77 V], iridium(IV) has a relatively labile configuration, whereas platinum(IV) has the inert arrangement. The species H2PtCl6 is extracted by TBP, from which platinum can be stripped by water and recovered by precipitation as (NH3)2PtCl2. 

The half-wave reduction potentials (HWP) of dibenzothiophene and some of its derivatives have been measured for comparison with those of dibenzofuran and dibenzoselenophene. A shift to more negative HWP was observed for all of the methyl derivatives studied, the magnitude of which depended on the position of substitution. These shifts are in accord with LCAO molecular orbital theory predictions if the sulfur d orbitals are excluded from the calculations (Section III, A). ... 

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