Phosphorus pentasulfide

Phosphorus pentasulfide is the inorganic compound with the formula P2S5 or dimer P4S10. This yellow solid is the one of two phosphorus sulfides of commercial value. Samples often appear greenish-gray due to impurities. It is soluble in carbon disulfide but reacts with many other solvents such as alcohols, DMSO, and DMF.[3]

Phosphorus decasulfide
Names
Other names
phosphorus sulfide
sulfur phosphide
phosphorus persulfide
diphosphorus pentasulfide
tetraphosphorus decasulfide
phosphorus decasulfide
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.013.858
EC Number
  • 215-242-4
RTECS number
  • TH4375000
UNII
Properties
P2S5 or dimer P4S10
Molar mass 222.27 g mol
Appearance greenish-gray to yellow solid[1]
Odor rotten eggs[1]
Density 2.09 g/cm3
Melting point 288 °C (550 °F; 561 K)
Boiling point 514 °C (957 °F; 787 K)
hydrolyses
Solubility in other solvents 0.222 g / 100g CS2 (at 17 °C)
Insoluble in C6H6
Insoluble in hot xylene
Insoluble in hot anisole.
Vapor pressure 1 mmHg (300°C)[1]
Structure
triclinic, aP28
P-1, No. 2
Td
Hazards
Lethal dose or concentration (LD, LC):
389 mg/kg (oral, rat)[2]
NIOSH (US health exposure limits):
PEL (Permissible)
 TWA 1 mg/m3[1]
REL (Recommended)
 TWA 1 mg/m3 ST 3 mg/m3[1]
IDLH (Immediate danger)
 250 mg/m3[1]
Related compounds
Related compounds
 P4S3
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Structure and synthesis

Its tetrahedral molecular structure is similar to that of adamantane and almost identical to the structure of phosphorus pentoxide.[4]

Phosphorus pentasulfide is obtained by the reaction of liquid white phosphorus (P4) with sulfur above 300 °C. The first synthesis of P4S10 by Berzelius in 1843 [5][6] was by this method. Alternatively, P4S10 can be formed by reacting elemental sulfur or pyrite, FeS2, with ferrophosphorus, a crude form of Fe2P (a byproduct of P4 production from phosphate rock):

4 Fe2P + 18 S → P4S10 + 8 FeS
4 Fe2P + 18 FeS2 + heat → P4S10 + 26 FeS

Applications

Approximately 150,000 tons of P4S10 are produced annually. The compound is mainly converted to other derivatives for use as lubrication additives such zinc dithiophosphates. It is also used in the production of pesticides such as Parathion and Malathion.[7] It is also a component of some amorphous solid electrolytes (e.g. Li2S-P2S5) for some types of lithium batteries.

Phosphorus pentasulfide is a dual-use material, for the production of early insecticides such as Amiton and also for the manufacture of the related VX nerve agents.

Reactivity

Due to hydrolysis by atmospheric moisture, P4S10 evolves H2S, thus P4S10 is associated with a rotten egg odour. Aside from H2S, hydrolysis of P4S10 eventually gives phosphoric acid:

P4S10 + 16 H2O → 4 H3PO4 + 10 H2S

Other mild nucleophiles react with P4S10, including alcohols and amines. Aromatic compounds such as anisole, ferrocene and 1-methoxynaphthalene react to form 1,3,2,4-dithiadiphosphetane 2,4-disulfides such as Lawesson's reagent.

P4S10 is used as a thionation reagent. Reactions of this type require refluxing solvents such as benzene, dioxane, or acetonitrile with P4S10 dissociating into P2S5. Some ketones, esters, and imides are converted to the corresponding thiocarbonyls. Amides give thioamide. With 1,4-diketones the reagent forms thiophenes. It is also used to deoxygenate sulfoxides. The use of P4S10 has been displaced by Lawesson's reagent P4S10s.[8]

P2S5 reacts with pyridine to form the complex P2S5(pyridine)2.[9]

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References
  1. NIOSH Pocket Guide to Chemical Hazards. "#0510". National Institute for Occupational Safety and Health (NIOSH).
  2. "Phosphorus pentasulfide". Immediately Dangerous to Life and Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  3. Scott D. Edmondson, Mousumi Sannigrahi "Phosphorus(V) sulfide" Encyclopedia of Reagents for Organic Synthesis 2004 John Wiley & Sons. doi:10.1002/047084289X.rp166s.pub2
  4. Corbridge, D. E. C. (1995). Phosphorus: An Outline of its Chemistry, Biochemistry, and Technology (5th ed.). Amsterdam: Elsevier. ISBN 0-444-89307-5.
  5. Berzelius, J. (1843). "Ueber die Verbindungen des Phosphors mit Schwefel". Annalen der Chemie und Pharmacie. 46 (2): 129–154. doi:10.1002/jlac.18430460202.
  6. Berzelius, J. (1843). "Ueber die Verbindungen des Phosphors mit Schwefel". Annalen der Chemie und Pharmacie. 46 (3): 251–281. doi:10.1002/jlac.18430460303. (continuation of p. 154 of the same volume)
  7. Bettermann, G.; Krause, W.; Riess, G.; Hofmann, T. (2002). "Phosphorus Compounds, Inorganic". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a19_527. ISBN 3527306730.
  8. Ozturk, T.; Ertas, E.; Mert, O. (2010). "A Berzelius Reagent, Phosphorus Decasulfide (P4S10), in Organic Syntheses". Chemical Reviews. 110 (6): 3419–3478. doi:10.1021/cr900243d. PMID 20429553.
  9. Bergman, Jan; Pettersson, Birgitta; Hasimbegovic, Vedran; Svensson, Per H. (2011). "Thionations Using a P4S10−Pyridine Complex in Solvents Such as Acetonitrile and Dimethyl Sulfone". The Journal of Organic Chemistry. 76 (6): 1546–1553. doi:10.1021/jo101865y. PMID 21341727.
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