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Title: Reactions of ethanethiol and related compounds over Co0-Mo03- A1203 and MoS2 catalysts
Author: Williamson, J. G.
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 1979
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The exchange of thiophene with deuterium and reactions of deuterium labelled propene and isobutene, followed by a combination of mass spectrometry and microwave spectroscopy, have been used to characterise the catalytic nature of a commercial Coo-Mo03 Al203 (CMA) catalyst. It was observed in this work that the oxide-CMA was partially sulphided during the initial stages of ethanethiol hydro-desulphurization (hds) or as a result of exposure to hydrogen sulphide. The results of these exchange experiments indicated that the activity of partially sulphided CMA closely resembled that of unsupported molybdenum disulphide (MoS2) but was markedly different from that observed for oxide-CMA. Investigation of the hds of ethanethiol, hydrogenation of ethane, hds of diethylsulphide and some relevant exchange reactions with deuterium over oxide-CMA, partially sulphided CMA and unsupported MoS2 furnished a similar conclusion i.e. during hds, the partially sulphided CMA may be described as MoS2 supported on, and stabilized by, alumina. Furthermore, by comparison of the relative rates of the various reactions on partially sulphided-CMA and MoS2, it was possible to establish, in outline, a mechanistic scheme for the hds of ethanethiol: ethene, produced by p14m+nation of hydrogen sulphide, was the major product of the hds reaction while ethane, involving hydrogenation, was produced in much lesser quantities. In contrast, during the decomposition of ethanol, the oxygen analogue of ethanethiol, the CMA catalyst remained in the oxide form and the decomposition was found to occur by two alternative routes i.e. dehydrogenation to ethanol, which subsequently coupled to give butane as a secondary decomposition product, or dehydration to diethylether. The higher surface charge density of oxide-CMA relative to partially sulphided CMA is believed to be the major contributor to the differences between the two catalyst systems.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available