Abstract
The products of the interaction of ethyl xanthate (CH<sub>3</sub>CH<sub>2</sub>OCS<sup>-</sup><sub>2</sub>) with copper and chalcocite (Cu<sub>2</sub>S) electrodes at a controlled potential have been investigated by <i>ex situ</i> infrared spectroscopy. The disappearance of bands assigned to dixanthogen over time indicated that additional reactions were occurring subsequent to the initial interaction. These reactions were also followed by gas-phase infrared photoacoustic spectroscopy (PAS), which suggested the formation of CO<sub>2</sub> and COS. The PAS technique was also employed to identify the gas-phase species produced from a variety of powdered minerals [heazlewoodite (Ni<sub>3</sub>S<sub>2</sub>), chalcocite (Cu<sub>2</sub>S), chalcopyrite (CuFeS<sub>2</sub>), pyrite (FeS<sub>2</sub>), pyrrhotite (Fe<sub>1-<i>x</i></sub>S<sub><i>x</i></sub>), pentlandite ([Fe,Ni]S), galena (PbS), sphalerite ([Zn,Fe]S), and arsenopyrite ([Fe,As]S)] when treated with ethyl and isobutyl xanthates. The main species produced were COS, CO<sub>2</sub>, and H<sub>2</sub>0 , with CS<sub>2</sub> and C<sub>2</sub>H<sub>5</sub>OH being observed for ethyl xanthate in certain cases. The results show that the xanthate films decompose over time. The following decomposition pathways could account for the products observed: elimination of the triatomics from metal–xanthate complexes; decomposition of dixanthogen; formation of radicals; and pyrolysis of the xanthate complexes.
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