Topics in Current Chemistry

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Liquid Sulfur 113 peratures higher than 157 􏰹C mainly consists of long chains together with a certain percentage of very large rings. However, never has any author report- ed a qualitative difference in the properties of polymeric sulfur isolated from below or above the “polymerization temperature” of ca. 157 􏰹C, respectively. Finally, it should be mentioned that several times species with four-coor- dinate sulfur atoms (tetrathiasulfuranes) have been claimed to be present in polymeric sulfur [134] or to be intermediates in the interconversion of sulfur rings and chains [135, 136]. However, recent high-level ab initio MO calcula- tions [137] demonstrated that tetrathiasulfuranes like S(SH)4 are much too unstable (endothermic) to play any role in liquid sulfur. Acknowledgement I am grateful to Dr. Yana Steudel for assistance with the figures. This work has been supported by the Deutsche Forschungsgemeinschaft and the Verband der Chemischen Industrie. References 1. W. Botsch, Chemie unserer Zeit 2001, 35, 324. 2. R. Steudel, Chemie unserer Zeit 1996, 30, 226 and Chemie unserer Zeit 1980, 14, 73. 3. For color pictures of the melt at different temperatures, see ref [2]. 4. F. Bacon, R. Fanelli, J. Am. Chem. Soc. 1943, 65, 639. 5. T. Doi, Rev. Phys. Chem. Japan 1963, 33, 41. 6. J. Ruiz-Garcia, E. M. Anderson, S. C. Greer, J. Phys. Chem. 1989, 93, 6980. 7. A. Eisenberg, J. Chem. Phys. 1963, 39, 1852. 8. G. C. Vezzoli, P. J. Walsh, High Temp. High Pressure 1977, 9, 345. 9. K. Bröllos, G. M. Schneider, Ber. Bunsenges. Phys. Chem. 1974, 78, 296. 10. M. Kuballa, G. M. Schneider, Ber. Bunsenges. 1971, 75, 513. 11. F. FehØr, E. Hellwig, Z. Anorg. Allg. Chem. 1958, 294, 63. 12. H. Patel, L. B. Borst, J. Chem. Phys. 1971, 54, 822. 13. K. M. Zheng, S. C. Greer, J. Chem. Phys. 1992, 96, 2175. 14. F. FehØr, E. Hellwig, Z. Anorg. Allg. Chem. 1958, 294, 71. 15. M. E. Baur, D. A. Horsma, J. Phys. Chem. 1974, 78, 1670. 16. S. C. Greer, J. Chem. Phys. 1986, 84, 6984. 17. A. Smith, Z. Physik. Chem. 1906, 54, 257. 18. For an extensive review, see R. Steudel, Z. Anorg. Allg. Chem. 1981, 478, 139. 19. P. W. Schenk, Z. Anorg. Allg. Chem. 1955, 280, 1. 20. A. H. W. Aten, Z. Phys. Chem. 1913, 83, 442. 21. A. H. W. Aten, Z. Phys. Chem. 1914, 86, 1. 22. D. L. Hammick, W. R. Cousins, E. L. Langford, J. Chem. Soc. 1928, 797. 23. J. Schenk, Physica 1957, 23, 325, 546. 24. J. C. Koh, W. Klement, J. Phys. Chem. 1970, 74, 4280. 25. U. Thümmler, Doctoral Dissertation. Freie Universität Berlin 1959. 26. P. W. Schenk, U. Thümmler, Z. Elektrochem. Ber. Bunsenges. Phys. Chem. 1959, 63, 1002. 27. E. Beckmann, C. Platzmann, Z. Anorg. Allg. Chem. 1918, 102, 201. 28. T. K. Wiewiorowski, A. Parthasarathy, B. L. Slaten, J. Phys. Chem. 1968, 72, 1890. 29. F. FehØr, G. P. Görler, H. D. Lutz, Z. Anorg. Allg. Chem. 1971, 382, 135. 30. M. Thackray, J. Chem. Eng. Data 1970, 15, 495. 31. E. D. West, J. Am. Chem. Soc. 1959, 81, 29. 32. M. F. Churbanov, I. V. Skripachev, G. G. Devyatykh, Russ. J. Inorg. Chem. 1976, 21, 1272. 33. P. W. Schenk, U. Thümmler, Z. Anorg. Allg. Chem. 1962, 315, 271.

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