Abstract
Thiourea is progressively oxidized to sulfonic acid before cleavage of the sulfur-carbon bond and formation of sulfate. A 13-step mechanism is proposed with rate-determining step C102" + SC(NH2)2 + H+ — HOC1 + HOSC(NH)NH2. Computer simulation using this mechanism gives good agreement with experiment.
The chlorite ion is perhaps the most readily available source of nonlinear behavior in chemistry.2'3 In nearly all of its reactions, whether it is acting as an oxidizing or a reducing agent, it presents some degree of unconventional kinetics. Reactions of chlorite ion with the halides bromide4 and iodide5 produce clock reaction characteristics in closed (batch) and oscillatory behavior in open (flow) reactors. With a simple one-electron reductant like hexacyanoferrate(II) ion, one finds autoinhibition and evidence for an interfacial redox reaction at the interface between solution and container.