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] This yellow solid is one of two commercially produced phosphorus sulfides. It is a component of "strike anywhere" matches.

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). Unlike some other phosphorus sulfides, P₄S₃ is slow to hydrolyze and has a well-defined melting point.

Structure and synthesis

The molecule has C_3v 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.^[3] Under higher temperatures, mixed chalcogenide molecules P₄S₂Se and P₄SSe₂ will form.^[4]

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.^[5]

Applications

P₄S₃ and potassium chlorate, together with other materials, comprises the heads of "strike-anywhere matches".^[6]

Safety

Its flash point is about 100 °C.

Health Effects

Exposure to "strike anywhere" matches containing phosphorus sesquisulfide can cause contact dermatitis, usually in the pocket area but also on the face.^[7] 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.^[8]

References

This article contains public domain text from the NOAA as cited.

1 2 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.
↑ US patent 614350, Seyene, H.; Cahen, E. D., "Match Composition", issued 1898-11-15
↑ Burns, G.R., and Sarfati, J.D., "Raman spectra of tetraphosphorus triselenide doped in tetraphosphorus trisulphide", Solid State Communications 66(4):347–49, April 1988 | doi:10.1016/0038-1098(88)90854-X
↑ Burns, G.R., Rollo, J.R., and Sarfati, J.D.: "Raman spectra of the tetraphosphorus trichalcogenide cage molecules P₄S₂Se and P₄SSe₂", Inorganica Chimica Acta 161(1):35–38, 3 July 1989 | doi:10.1016/S0020-1693(00)90111-7
↑ Bettermann, G.; Krause, W.; Riess, G.; Hofmann, T. (2005), "Phosphorus Compounds, Inorganic", Ullmann's Encyclopedia of Industrial Chemistry, Weinheim: Wiley-VCH, doi:10.1002/14356007.a19_527
↑ 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.
↑ 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. Retrieved 2013-12-06.
↑ BURGESS, J. Frederick (December 1951). "Phosphorus Sesquisulphide Poisoning". Can Med Assoc J. Canadian Medical Association. 65 (6): 567–568. PMC 1822299. PMID 14886853.

Phosphorus compounds

PBr₃ PBr₅ PCl₃ PCl₅ PF₃ PF₅ PI₃ InP PH₃ PN P₃N₅ P₂O₃ P₂O₄ P₂O₅ P₄S₃ P₄S₁₀ AlP HfP FeP Fe₃P BP Ca₃P₂ CuP₂

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