Abstract
SINCE the discovery that blue solutions of sulphur in oleum contain a paramagnetic species1,2, theories regarding its identity have abounded. Recently two accounts of the e.s.r. spectra of the interesting blue solutions formed by dissolution of elemental sulphur in 65% oleum have appeared3–5. In the first, for which sulphur enriched with 25% 33S was used, a seven line e.s.r. spectrum was interpreted in terms of the ion S8+, because a simulation of the spectrum seemed to favour eight equivalent sulphur atoms rather than the four required by S4+. The differences were small, however, and more weight was placed on the results at 77 K which clearly required that the sulphur atoms were not equivalent. This seemed to rule out S4+. Only S4+ and S8+ were seriously considered because of the convincing work of Gillespie et al.6, who consider that the blue oleum solutions contain S4+ rather than S8+.
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References
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Gillespie, R. J., Passmore, J., Ummat, P. K., and Vaidya, O. C., Inorg. Chem., 10, 1327 (1971).
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SYMONS, M., WILKINSON, J. Nature of the Paramagnetic Cation in Solutions of Sulphur in Oleum. Nature Physical Science 236, 126–127 (1972). https://doi.org/10.1038/physci236126a0
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DOI: https://doi.org/10.1038/physci236126a0