Studies and microdetermination of some organic sulfur functions by reduction with titanium(III) sulfate solution

Micromethods are described for the determination of organic sulfoxides and disulfides based on reduction with titanium (III) sulfate solution, the excess of which is titrated with standard ferric alum as usual. The procedures developed depended on the nature of the compound whether aromatic or aliphatic. Quantitative reduction of sulfoxides was achieved in presence of ammonium thiocyanate and sodium acetate but whereas aryl sulfoxides required heating at 70 °C for 30 minutes, the alkyl members demanded heating at 90 °C for one hour. Complete reduction of disulfides was possible in presence of acetate buffer and heating at 50 °C for 15 minutes for aromatic disulfides and at 80 °C for 30 minutes in case of the aliphatic ones. a Calculated by dividing the total titer in a ratio of 2:12. b Calculated using the total titer consumed. Sulfonyl halides, thiocyanates, and isothiocyanates do not react with the titanium(III) solution. The effect of the various sulfur functions on the determination of the nitro group with titanium(III) was also studied and various nitro-substituted sulfur compounds were successfully analyzed.