Trisulfur

Trisulfur
Names
IUPAC name
Trisulfur
Identifiers
[1] 12597-03-4[2]
ChEBI CHEBI:29388
ChemSpider 62201
Jmol interactive 3D Image
Properties
S3
Molar mass 96.198 g/mol
Structure
bent
Related compounds
Related compounds
 ozone
Disulfur monoxide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

The S
3 molecule or trisulfur or sulfur trimer or thiozone or triatomic sulfur is an allotrope of sulfur. It occurs as a mixture in liquid and gaseous sulfur and also at cryogenic temperatures as a solid. Under standard conditions it is unstable and self reacts to solid sulfur cyclooctasulfur. The molecule shape is similar to ozone.[3] S
3 is found in sulfur vapour, comprising 10% of vapour species at 713 K (440 °C; 824 °F) and 1,333 Pa (10.00 mmHg; 0.1933 psi). It is cherry red in colour, with a bent structure, similar to ozone, O
3.[3] The bonds between the atoms are not full double bonds (as this would require two fewer electrons, similar to carbon disulfide), and the molecule can be thought of as a resonance between two states, in each of which one of the end atoms has a negative formal charge while the central atom has a positive formal charge.

The molecule has a distance between sulfur atoms of 191.7 ± .01 pm (1.9170 ± 0.0001 Å) and angle at the central atom of 117.36°±0.006°.[4] However, cyclic S
3, where the sulfur atoms are arranged in an equilateral triangle with three bonds (similar to cyclic ozone), should in theory be lower in energy than the bent structure actually observed.[5]

The name thiozone was invented by Hugo Erdmann in 1908 who hypothesized that S
3 made up a large proportion of liquid sulfur.[6] However its existence was unproven until the experiments of J. Berkowitz in 1964.[7] Using mass spectrometry, he showed that sulfur vapour contains the S
3 molecule. Above 1,200 °C (2,190 °F) S
3 is the second most common molecule after S
2 in sulfur gas.[7] In liquid sulfur the molecule is not common until the temperature is high, such as 500 °C (932 °F). However, small molecules like this contribute to most of the reactivity of liquid sulfur.[7] S
3 has an absorption peak of 425 nm with a tail extending into blue light.[7]

S
3 can also be made by photolysis of S
3Cl
2 embedded in a glass or matrix of solid noble gas.[7]

Natural occurrence

It occurs naturally on Io in volcanic emissions. Also S
3 is likely to appear in the atmosphere of Venus at heights of 20 to 30 km (12 to 19 mi), where it is in thermal equilibrium with S
2 and S
4.[8] The reddish colour of Venus atmosphere at lower levels is likely to be due to S
3.[9]

Reactions

S
3 reacts with carbon monoxide CO to make carbon oxysulfide and S
2.

Tungsten and group-8 metal carbonyls, for example iron carbonyl, in theory can replace a carbonyl group with S
3.[5]

Formation of compounds with a defined number of sulfur atoms is possible:

S
3 + S−
2 → S−
5 (ring)[10]

Radical anion

Lazurite contains S3−.

S
3 can form the radical anion S−
3, which has an intense blue colour. The ion is also called thiozonide,[11] by analogy with the ozonide anion, O−
3. The gemstone lapis lazuli and the mineral lazurite (from which the pigment ultramarine is derived) contain S−
3. International Klein Blue, developed by Yves Klein, also contains the S−
3 radical anion.[12] This is valence isoelectronic with the ozonide ion. The spectrum of the colour shows a strong absorption band at 610–620 nm or 2.07 eV.[13] The blue colour is due to the C2A2 transition to the X2B1 electronic state in the ion.[11] The Raman frequency is 523 cm−1 and another infrared absorption is at 580 cm−1.[7]

The S−
3 ion has been shown to be stable in aqueous solution under pressure of 0.5 GPa (73,000 psi), and is expected to occur naturally at depth in the earth's crust where subduction or high pressure metamorphism occurs.[14] This ion is probably important in movement of copper and gold in hydrothermal fluids.

Lithium hexasulfide (which contains S−
6, another polysulfide radical anion) with tetramethylenediamine solvation reacts with acetone or donor solvents to form S−
3.[15]

The S−
3 radical anion was also made by reducing sulfur gas with Zn2+
 in a matrix. The material is strongly blue coloured when dry and changes colour to green and yellow in the presence of trace amounts of water.[16] Another way to make it is with polysulfide dissolved in hexamethylphosphoramide where it gives a blue colour.[17]

Other methods of production of S−
3 include reacting sulfur with slightly dampened magnesium oxide.[13]

Raman spectroscopy can be used to identify S−
3, and it can be used non-destructively in paintings. The bands are 549 cm−1 for symmetric stretch, 585 cm−1 for asymmetric stretch, and 259 cm−1 for bending.[18] Natural materials can also contain S−
2 which has an optical absorption at 390 nm and Raman band at 590 cm−1.[18]

Trisulfide ion

The trisulfide ion, S2−
3 is part of the polysulfide series. The sulfur chain is bent at an angle of 107° 53'.[7] SrS
3 has a bond length in the trisulfide ion of 0.205 nm.[7] The bonds are single. It is isoelectronic to sulfur dichloride.

References

  1. ↑ http://www.ebi.ac.uk/chebi/searchId.do?chebiId=CHEBI:29388
  2. ↑ http://www.ebi.ac.uk/chebi/searchId.do?chebiId=CHEBI:29388
  3. 1 2 Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. pp. 645–662. ISBN 0-08-037941-9.
  4. ↑ Michael C. McCarthy, Sven Thorwirth, Carl A. Gottlieb, and Patrick Thaddeus (11 March 2004). "The Rotational Spectrum and Geometrical Structure of Thiozone, S3". Journal of the American Chemical Society 126 (13): 4096–4097. doi:10.1021/ja049645f. PMID 15053585.
  5. 1 2 Beate Flemmig, Peter T. Wolczanski, and Roald Hoffmann (1 June 2005). "Transition Metal Complexes of Cyclic and Open Ozone and Thiozone" (PDF). Journal of the American Chemical Society 127 (4): 1278–1285. doi:10.1021/ja044809d. PMID 15669867.
  6. ↑ Hugo Erdmann (1908). "Ueber Thiozonide, ein Beitrag zur Kenntniss des Schwefels und seiner ringförmigen Verbindungen". Justus Liebigs Annalen der Chemie 362 (2): 133–173. doi:10.1002/jlac.19083620202.
  7. 1 2 3 4 5 6 7 8 Beat Meyer (March 1975). "Elemental Sulfur" (PDF). Chemical Reviews 76 (3): 367–388. doi:10.1021/cr60301a003.
  8. ↑ John S. Lewis (2004). Physics and chemistry of the solar system. Academic Press. p. 546. ISBN 9780124467446.
  9. ↑ John S. Lewis (2004). Physics and chemistry of the solar system. Academic Press. p. 539. ISBN 9780124467446.
  10. ↑ Steudel, Ralf; Steudel, Yana (November 2, 2004). "The Thermal Decomposition of S2O Forming SO2, S3, S4 and S5O — An ab initio MO Study". Cheminform 35 (44). doi:10.1002/chin.200444022.
  11. 1 2 Roberto Linguerri, Najia Komiha, Jürgen Fabian und Pavel Rosmus; Komiha; Fabian; Rosmus (2008). "Electronic States of the Ultramarine Chromophore S−
    3    "    . Zeitschrift für Physikalische Chemie 222 (1): 163–176. doi:10.1524/zpch.2008.222.1.163.
  12. ↑ Craig E. Manning (25 February 2011). "Sulfur Surprises in Deep Geological Fluids". Science 331 (6020): 1018–1019. Bibcode:2011Sci...331.1018M. doi:10.1126/science.1202468. PMID 21350156.
  13. 1 2 Ralf Steudel (2003). "Cluster Anions Sn− and Sn2−". Elemental sulfur and sulfur-rich compounds, Volume 2. p. 16. ISBN 9783540403784.
  14. ↑ Gleb S. Pokrovski1 and Leonid S. Dubrovinsky (25 February 2011). "The S3– Ion Is Stable in Geological Fluids at Elevated Temperatures and Pressures". Science 331 (6020): 1052–1054. Bibcode:2011Sci...331.1052P. doi:10.1126/science.1199911. PMID 21350173.
  15. ↑ Tristram Chivers, Ian Manners (2009). Inorganic rings and polymers of the p-block elements: from fundamentals to applications. Royal Society of Chemistry. pp. 295–296. ISBN 9781847559067.
  16. ↑ Qian Gao, Yang Xiu, Guo-Dong Li and Jie-Sheng Chen (2010). "Sensor material based on occluded trisulfur anionic radicals for convenient detection of trace amounts of water molecules". Journal of Materials Chemistry 20 (16): 3307–3312. doi:10.1039/B925233A.
  17. ↑ T. Chivers, I. Drummond; Drummond (October 1972). "Characterization of the trisulfur radical anion S3− in blue solutions of alkali polysulfides in hexamethylphosphoramide". Inorganic Chemistry 11 (11): 2525–2527. doi:10.1021/ic50116a047.
  18. 1 2 Richard R. Hark and Robin J. H. Clark. "Raman Microscopy of Diverse Samples of Lapis Lazuli at Multiple Excitation Wavelengths" (PDF).
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