Phosphorus sesquisulfide

Phosphorus sesquisulfide is the inorganic compound with the formula P4S3. It was developed by Henri Sevene and Emile David Cahen in 1898 as part of their invention of friction matches that did not pose the health hazards of white phosphorus.[2][3] This yellow solid is one of two commercially produced phosphorus sulfides. It is a component of "strike anywhere" matches.

Phosphorus sesquisulfide
Names
IUPAC names
Tetraphosphorus trisulfide
or 3,5,7-trithia-1,2,4,6-tetraphosphatricyclo[2.2.1.02,6]heptane
Other names
phosphorus trisulfide, phosphorus sesquisulfide, phosphorus sulfide
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.013.860
RTECS number
  • TH4330000
UNII
Properties
P4S3
Molar mass 220.093 g/mol
Appearance Yellow, yellow-green or gray solid
Density 2.08 g.cm3,[1] solid
Melting point 172.5 °C (342.5 °F; 445.6 K)
Boiling point 408 °C (766 °F; 681 K)
Structure
orthorhombic, Schönflies notation D2h
Pmnb
C3v
Related compounds
Related compounds
 P4S10
P4O6
Hazards
Main hazards Irritant
GHS pictograms
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
N verify (what is YN ?)
Infobox references

Depending on purity, samples can appear yellow-green to grey. The compound was discovered by G. Lemoine and first produced safely in commercial quantities in 1898 by Albright and Wilson. It dissolves in an equal weight of carbon disulfide (CS2), and in a 1:50 weight ratio of benzene. Unlike some other phosphorus sulfides, P4S3 is slow to hydrolyze and has a well-defined melting point.

Structure and synthesis

The molecule has C3v symmetry. It is a derivative of the tetrahedral (P4) unit from insertion of sulfur into three P-P bonds. The P-S and P-P distances are 2.090 and 2.235 Å, respectively. P4Se3 and P4S3 adopt the same structures.[1] These compounds can be melted together and form mixed crystals of one dissolved in the other.[4] Under higher temperatures, mixed chalcogenide molecules P4S2Se and P4SSe2 will form.[5]

P4S3 is produced by the reaction of red or white phosphorus with sulfur. Excess sulfur gives phosphorus pentasulfide (P4S10). It is estimated that 150 ton/y were produced in 1989.[6]

Applications

P4S3 and potassium chlorate, together with other materials, composes the heads of "strike-anywhere matches".[7]

Safety

Its flash point is about 100 °C.[8]

Health effects

Exposure to "strike anywhere" matches containing phosphorus sesquisulfide can cause contact dermatitis, usually in the pocket area but also on the face.[9] Exposure over a long period of time to burning match tips (containing phosphorus sesquisulfide) can result in a recurring severe primary dermatitis about the eyes and face. Loosening of the teeth has also been reported which may have been due to phosphorus poisoning.[10]

References
  1. Leung, Y. C.; Waser, J.; van Houten, S.; Vos, A.; Wiegers, G. A.; Wiebenga, E. H. (1957). "The Crystal Structure of P4S3". Acta Crystallographica. 10 (9): 574–582. doi:10.1107/S0365110X57002042.
  2. US patent 614350, Seyene, H.; Cahen, E. D., "Match Composition", issued 1898-11-15
  3. US 614350
  4. Burns, Gary R.; Sarfati, Jonathan D. (1988). "Raman spectra of tetraphosphorus triselenide doped in tetraphosphorus trisulphide". Solid State Communications. 66 (4): 347–349. Bibcode:1988SSCom..66..347B. doi:10.1016/0038-1098(88)90854-X.
  5. Burns, Gary R.; Rollo, Joanne R.; Sarfati, Jonathan D. (1989). "Raman spectra of the tetraphosphorus trichalcogenide cage molecules P4S2Se and P4SSe2". Inorganica Chimica Acta. 161: 35–38. doi:10.1016/S0020-1693(00)90111-7.
  6. Bettermann, G.; Krause, W.; Riess, G.; Hofmann, T. "Phosphorus Compounds, Inorganic". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a19_527.
  7. Corbridge, D. E. C. (1995). Phosphorus: An Outline of its Chemistry, Biochemistry, and Technology (5th ed.). Amsterdam: Elsevier. pp. 115–116. ISBN 0-444-89307-5.
  8. Lewis, R.J. Sr (2007). Hawley's Condensed Chemical Dictionary (15th ed.). New York, NY: John Wiley & Sons, Inc. p. 987.
  9. Burgess, J. F.; Forsey, R. Roy (1951). "Contact Dermatitis of the Face Due to Matches". AMA Arch Derm Syphilol. American Medical Association. 64 (5): 636–637. doi:10.1001/archderm.1951.01570110106016.
  10. Burgess, J. Frederick (December 1951). "Phosphorus Sesquisulphide Poisoning". Can Med Assoc J. Canadian Medical Association. 65 (6): 567–568. PMC 1822299. PMID 14886853.

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