Chemistry:Disulfur diiodide

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Disulfur diiodide
Disulfur-diiodide-3D-balls.png
  Sulfur, S
  Iodine, I
Names
IUPAC name
Diiododisulfane
Other names
Sulfur monoiodide (incorrect name)
Identifiers
3D model (JSmol)
ChemSpider
EC Number
  • 258-458-4
Properties
S
2I
2
Molar mass 317.93 g·mol−1
Appearance Reddish-brown solid
Melting point −30 °C (−22 °F; 243 K) (decomposes)
Solubility Soluble in carbon tetrachloride, slightly soluble in pentane
Structure
C2
2 at sulfur atoms
gauche
Related compounds
Related compounds
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Disulfur diiodide is an unstable inorganic chemical compound with the chemical formula S
2I
2. Its empirical formula is SI. It is a red-brown solid that decomposes above −30 °C to elemental sulfur and iodine.[1]

Production

Reaction of sulfur and iodine

The first attempt and claim to produce a sulfur iodide were made in 1813 by Bernard Courtois when exploring the properties of his newly discovered element, iodine. He reacted to sulfur and iodine, claiming they had made a compound. However, this production was doubted by Gay-Lussac. Between 1827 and 1896, more attempts were made to make sulfur iodide by combining the elements; however, all were inconclusive on the existence of the compound or failed. Later, when thermal analysis was developed, it was shown that when the elements were combined, it only resulted in a mixture, not a compound.[2]

Production by double replacement

When attempts to produce sulfur iodide by the direct combination of the elements failed to overcome the low thermodynamic stability of the compound, production by double replacement was attempted between 1833 and 1886. Some reactions that were attempted was the reaction of disulfur dichloride and hydroiodic acid:[2]

S
2Cl
2 + 2 HI → S
2I
2 + 2 HCl

The reaction of hydrogen sulfide and iodine trichloride:

3 H
2S + 2 ICl
3 → S
3I
2 + 6 HCl

The reaction of hydroiodic acid and sulfur:

2 HI + 3 S → H
2S + S
2I
2

The reaction of disulfur dichloride and potassium iodide:

S
2Cl
2 + 2 KI → S
2I
2 + 2 KCl

and more, all assumed to have failed to produce sulfur iodide. However, the reaction between S
2Cl
2 and HI attempted in 1835 was later proven to have produced disulfur diiodide.[2]

In 1940, another production was attempted with the fourth reaction and was reported to have detected various sulfur iodides, such as disulfur diiodide and sulfur diiodide (SI
2). When observing the reaction of very dilute disulfur dichloride in carbon tetrachloride and potassium iodide:[2][3]

S
2Cl
2 + 2 KI → 2 S + I
2 + 2 KCl

they observed a color change from yellow to reddish-brown to finally violet, which was assumed to be evidence for the formation of sulfur iodides. The compound was found to decompose at room temperature slowly in a solution, with the decomposition rate increasing with increasing temperature.[3]

Isolation

Disulfur diiodide was first isolated by the reaction of disulfur dichloride and potassium iodide, sodium iodide, or hydrogen iodide in pentane at −90 °C, and verified by infrared spectroscopy.[4][5]

Properties

Disulfur diiodide is light-sensitive and is soluble in various haloalkanes, such as carbon tetrachloride.[3]

Other sulfur iodides

Sulfur diiodide (SI
2) has finally been reported in an argon matrix at 9 K by the reaction of sulfur dichloride and iodine; however, this has been disputed.[6]

Sulfur and iodine react in antimony pentafluoride or arsenic trifluoride to form the S
7I+
 ion, which is stable at room temperature, unlike other sulfur-iodine compounds.[7]

References

  1. ↑ Wiberg, Egon; Nils Wiberg; Arnold Frederick Holleman (2001). Inorganic chemistry. Academic Press. p. 529. ISBN 978-0-12-352651-9. https://books.google.com/books?id=LxhQPdMRfVIC&pg=PA1263. 
  2. ↑ 2.0 2.1 2.2 2.3 William B. Jensen (2016) (in en). The Search for Sulfur Iodide : Notes from the Oesper Collections, No. 37. University of Cincinnati. https://drc.uc.edu/handle/2374.UC/747827?submit=Go&query=sulfur&focusscope=&mode=search. 
  3. ↑ 3.0 3.1 3.2 M. R. Aswathanarayana Rao (1940). "Investigations on the Iodides of Sulphur" (in en). Proceedings of the Indian Academy of Sciences 11 (3): 162-174. https://www.ias.ac.in/article/fulltext/seca/011/03/0162-0174. 
  4. ↑ Gisela Vahl; Priv.-Doz. Dr. Rolf Minkwitz (1978). "Beiträge zur Chemie der Schwefelhalogenide. IV. Über Versuche zur Darstellung von festem Dijoddisulfan bei tiefen Temperaturen" (in de). Zeitschrift für anorganische und allgemeine Chemie (Wiley) 443 (1): 217-224. doi:10.1002/zaac.19784430124. 
  5. ↑ Gisela Krummel; Rolf Minkwitz (1977). "Infrared-spectroscopic investigations on solid disulfurdiiodine" (in en). Inorganic and Nuclear Chemistry Letters 13 (5): 213-215. doi:10.1016/0020-1650(77)80096-2. 
  6. ↑ Martin Feuerhahn; Gisela Vahl (1980). "Infrared spectra of matrix isolated sulfur dibromide and sulfur diiodide" (in en). Inorganic and Nuclear Chemistry Letters 16 (1): 5-8. doi:10.1016/0020-1650(80)80082-1. 
  7. ↑ T. Klapoetke; J. Passmore (1989). "Sulfur and selenium iodine compounds: from non-existence to significance" (in en). Accounts of Chemical Research (ACS Publications) 22 (7): 234–240. doi:10.1021/ar00163a002. 
HI He
LiI BeI2 BI3 CI4 NI3 I2O4,
I2O5,
I4O9 		IF,
IF3,
IF5,
IF7 		Ne
NaI MgI2 AlI3 SiI4 PI3,
P2I4 		S ICl,
ICl3 		Ar
KI CaI2 Sc TiI4 VI3 CrI3 MnI2 FeI2 CoI2 NiI2 CuI ZnI2 Ga2I6 GeI2,
GeI4 		AsI3 Se IBr Kr
RbI SrI2 YI3 ZrI4 NbI5 Mo Tc Ru Rh Pd AgI CdI2 InI3 SnI4,
SnI2 		SbI3 TeI4 I Xe
CsI BaI2   HfI4 TaI5 W Re Os Ir Pt AuI Hg2I2,
HgI2 		TlI PbI2 BiI3 Po AtI Rn
Fr RaI2   Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
↓
La Ce Pr Nd Pm SmI2 Eu Gd TbI3 Dy Ho Er Tm Yb Lu
Ac ThI4 Pa UI3,
UI4 		Np Pu Am Cm Bk Cf EsI3 Fm Md No Lr



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