Sulfur oxidation-reduction

FIGURE 11.21 Schematic showing sulfur oxidation-reduction at the sediment-water interface. 

Sulfur Dioxide Reductant. The Mathieson process uses sulfur dioxide, sodium chlorate, and sulfuric acid to produce chlorine dioxide gas with a much lower chlorine content. The sulfur dioxide gas reductant is oxidized to make sulfuric acid, reducing the overall acid requirement of the process. Air is used to dilute the chlorine dioxide produced by this process. The exit gases flow through a scmbber to which chlorate is added in order to remove any unreacted sulfur dioxide. Spent Hquor, containing some unreacted chlorate, sulfuric acid, and sodium sulfate, continuously overflows from this process. 

General 1. Use cokeless iron- and steel-making processes, such as the direct reduction process, to eliminate the need to manufacture coke. 2. Use beneficiation (preferably at the coal mine) and blending processes that improve the quality of coal feed to produce coke of desired quality and reduce emissions of sulfur oxides and other pollutants. 

These reactions differ from those of sulfur tetrafluoride with carbonyl compounds in that a formal oxidation-reduction of the sulfur atoms m the thiocarbonyl compound and sulfur tetrafluoride molecule occurs, resulting in the formation of free sulfur and the complete utilization of the fluorine atoms in sulfur tetrafluoride. 

The formal interrelationship between the various oxoacids of sulfur can also be illustrated in a. scheme which places less emphasis on oxidation-reduction reactions but which is useful in suggesting possible alternative synthetic routes... 

Verify that reaction (23) is an oxidation-reduction reaction and that the oxidation number change of carbon is balanced by the oxidation number change of the sulfur. 

In an electrochemical cell, electrical work is obtained from an oxidation-reduction reaction. For example, consider the process that occurs during the discharge of the lead storage battery (cell). Figure 9.3 shows a schematic drawing of this cell. One of the electrodes (anode)q is Pb metal and the other (cathode) is Pb02 coated on a conducting metal (Pb is usually used). The two electrodes are immersed in an aqueous sulfuric acid solution. 

SOLUTION The process is oxidation if the oxidation number of sulfur increases, reduction if it decreases. We need to assign the oxidation numbers of sulfur in S02 and S042, then compare them. To assign an oxidation number to sulfur we represent that number by x and solve for x, by using the rules in Toolbox K.l. The oxidation number of oxygen is —2 in both compounds. 

This key enzyme of the dissimilatory sulfate reduction was isolated from all Desulfovibrio strains studied until now 135), and from some sulfur oxidizing bacteria and thermophilic Archaea 136, 137). The enzymes isolated from sulfate-reducing bacteria contain two [4Fe-4S] clusters and a flavin group (FAD) as demonstrated by visible, EPR, and Mossbauer spectroscopies. With a total molecular mass ranging from 150 to 220 kDa, APS reductases have a subunit composition of the type 012)32 or 02)3. The subunit molecular mass is approximately 70 and 20 kDa for the a and )3 subunits, respectively. Amino-acid sequence data suggest that both iron-sulfur clusters are located in the (3 subunit... 

Because of their multiple oxidation states, the chalcogens, particularly sulfur, can engage in numerous redox couples participating in acid-base, oxidation-reduction, precipitation, and complexation equilibria. 

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