The mechanism of the catalytic oxidation of hydrogen sulfide: III. An electron spin resonance study of the sulfur catalyzed oxidation of hydrogen sulfide

Abstract

ESR experiments on the oxidation of hydrogen sulfide were performed in the temperature range 20–150 °C. Alumina, active carbon and molecular sieve zeolite 13X were investigated as catalysts. For zeolite 13X it was demonstrated that the reaction is autocatalytic and that sulfur radicals are the active sites for oxygen chemisorption. The intensity of the sulfur radical ESR signal, which is related to the degree of conversion of these radicals, by oxygen, fits in with an oxidation-reduction mechanism. The sulfur-oxygen radical species, which appear when oxygen is admitted to sulfur radicals, are assigned to sulfur chains containing one or two oxygen atoms at the end of the chain. It is very likely that these sulfur-oxygen radicals are intermediates in the proposed mechanism. The formation of the byproduct SO 2 from S xO 2 · − at temperatures above 175 °C is also visible in the ESR spectrum. On the basis of the experiments it is concluded that in the mechanism of H 2S oxidation on active carbons, carbon radicals do not play an important role.