Electrochemistry of elemental sulfur and sulfur nitrides in liquid SO2 with accessory high-performance voltammetry

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Hahn, Nolan R. J.
University of Lethbridge. Faculty of Arts and Science
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Lethbridge, Alta. : University of Lethbridge, Dept. of Chemistry and Biochemistry
The application of high performance voltammetric methods to binary sulfur-nitrogen heterocycles has enabled the further study of many well-known compounds including S4N4 and elemental S8. A custom electrochemical pressure cell, designed and fabricated by the author for use with (l)SO2 at its room temperature vapor pressure, which enabled these studies, is reported. Within this work, a computational method which allows the electric potentials of redox reactions to be calculated in solution is applied to various SN species using acetonitrile (MeCN) and SO2 as solvents. These computed potentials are compared in this work to previous experimental values for SN systems in the literature and to values reported for the first time in this work. The combination of these computational results and the experimental results from the custom electrochemical pressure cell provide compelling evidence for a chemically irreversible single electron oxidation of both S4N4 and elemental S8 in non-aqueous solvent. This procedure is also applied to various other SN species which are related to the electrochemical narrative of S4N4 and S8.
electrochemistry , voltammetry , sulfur dioxide , SO2 , glassblowing , Electrochemistry--Research , Sulfur compounds--Research , Nitrides--Research , Sulfur dioxide , Voltammetry--Research , Glass blowing and working , Scientific apparatus and instruments--Design and construction , Oxidation-reduction reaction , Chemistry, Inorganic , Dissertations, Academic