Sulfane sulfur

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This chapter discusses the determination of sulfane sulfur. The term, “sulfane,” designates sulfur atoms that are bonded covalently in chains only to other sulfur atoms. Sulfane atoms are somewhat unstable, readily oxidizing in air, reducing with thiols, and decomposing slowly in dilute acid to release free sulfur. Most sulfane-containing compounds are stable in alkali, but polythionates decompose in strong alkali to form various products including thiosulfate, sulfite, sulfate, and elemental sulfur. Sulfane sulfurs are identified by susceptibility to cyanolysis. The chapter presents the cyanolysis methods used for determination of sulfane sulfur. The first method is cold cyanolysis of thiosulfate that is done if cupric ion is added as a catalyst. Persulfides, polysulfides, aryl thiosulfonates, and higher polythionates react quantitatively with cyanide in alkaline solution, at temperatures between 10° and ambient room temperature. This is known as “cold cyanolysis.” The next method is hot cyanolysis that provides for analysis of alkyl thiosulfonates, thiosulfate, and trithionate, which react too slowly for cold cyanolysis. The third method described in the chapter is cold cyanolysis in presence of cupric ion. Catalysis by cupric ion is necessary for the quantitative conversion of thiosulfate to thiocyanate.

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