Triphosphorus pentanitride

Last updated
Triphosphorus pentanitride
P3N5Code236555.png
Names
IUPAC name
Triphosphorus pentanitride
Other names
Phosphorus(V) nitride, Phosphorus nitride
Identifiers
3D model (JSmol)
ECHA InfoCard 100.032.018 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 235-233-9
PubChem CID
  • N1=P23N=P45N2P1(=N4)N35
Properties
P3N5
Molar mass 162.955 g/mol
AppearanceWhite solid
Density 2.77 g/cm3 (α-P3N5)
Melting point 850 °C (1,560 °F; 1,120 K) decomposes
insoluble
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Triphosphorus pentanitride is an inorganic compound with the chemical formula P 3 N 5. Containing only phosphorus and nitrogen, this material is classified as a binary nitride. While it has been investigated for various applications this has not led to any significant industrial uses. It is a white solid, although samples often appear colored owing to impurities.

Contents

Synthesis

Triphosphorus pentanitride can be produced by reactions between various phosphorus(V) and nitrogen anions (such as ammonia and sodium azide): [1]

3 PCl5 + 5 NH3 → P3N5 + 15 HCl
3 PCl5 + 15 NaN3 → P3N5 + 15 NaCl + 20 N2

The reaction of the elements is claimed to produce a related material. [2] Similar methods are used to prepared boron nitride (BN) and silicon nitride (Si3N4); however the products are generally impure and amorphous. [1] [3]

Crystalline samples have been produced by the reaction of ammonium chloride and hexachlorocyclotriphosphazene [4] or phosphorus pentachloride. [1]

(NPCl2)3 + 2 [NH4]Cl → P3N5 + 8 HCl
3 PCl5 + 5 [NH4]Cl → P3N5 + 20 HCl

P3N5 has also been prepared at room temperature, by a reaction between phosphorus trichloride and sodium amide. [5]

3 PCl3 + 5 NaNH2 → P3N5 + 5 NaCl + 4 HCl + 3 H2

Reactions

P3N5 is thermally less stable than either BN or Si3N4, with decomposition to the elements occurring at temperatures above 850 °C: [1]

P3N5 → 3 PN + N2
4 PN → P4 + 2 N2

It is resistant to weak acids and bases, and insoluble in water at room temperature, however it hydrolyzes upon heating to form the ammonium phosphate salts [NH4]2HPO4 and [NH4]H2PO4.

Triphosphorus pentanitride reacts with lithium nitride and calcium nitride to form the corresponding salts of PN7−4 and PN4−3. Heterogenous ammonolyses of triphosphorus pentanitride gives imides such as HPN2 and HP4N7. It has been suggested that these compounds may have applications as solid electrolytes and pigments. [6]

Structure and properties

Several polymorphs are known for triphosphorus pentanitride. The alpha‑form of triphosphorus pentanitride (α‑P3N5) is encountered at atmospheric pressure and exists at pressures up to 11 GPa, at which point it converts to the gamma‑variety (γ‑P3N5) of the compound. [7] [8] Upon heating γ‑P3N5 to temperatures above 2000 K at pressures between 67 and 70 GPa, it transforms into δ-P3N5. [9] The release of pressure on the δ-P3N5 polymorph does not revert it back into γ‑P3N5 or α‑P3N5. Instead, at pressures below 7 GPa, δ-P3N5 converts into a fourth form of triphosphorus pentanitride, α′‑P3N5. [9]

PolymorphDensity (g/cm3)
α‑P3N52.77
α′‑P3N53.11
γ‑P3N53.65
δ‑P3N55.27 (at 72 GPa)

The structure of all polymorphs of triphosphorus pentanitride was determined by single crystal X-ray diffraction. α‑P3N5 and α′‑P3N5 are formed of a network structure of PN4 tetrahedra with 2- and 3-coordinated nitrides, [7] [9] γ‑P3N5 is composed of both PN4 and PN5 polyhedra [8] while δ-P3N5 is composed exclusively of corner- and edge-sharing PN6 octahedra. [9] δ-P3N5 is the most incompressible triphosphorus pentanitride, having a bulk modulus of 313 GPa. [9]

Potential applications

Triphosphorus pentanitride has no commercial applications, although it found use as a gettering material for incandescent lamps, replacing various mixtures containing red phosphorus in the late 1960s. The lighting filaments are dipped into a suspension of P3N5 prior to being sealed into the bulb. After bulb closure, but while still on the pump, the lamps are lit, causing the P3N5 to thermally decompose into its constituent elements. Much of this is removed by the pump but enough P4 vapor remains to react with any residual oxygen inside the bulb. Once the vapor pressure of P4 is low enough, either filler gas is admitted to the bulb prior to sealing off or, if a vacuum atmosphere is desired, the bulb is sealed off at that point. The high decomposition temperature of P3N5 allows sealing machines to run faster and hotter than was possible using red phosphorus.

Related halogen containing cyclic polymers, trimeric hexabromophosphazene (PNBr2)3 (melting point 192 °C) and tetrameric octabromophosphazene (PNBr2)4 (melting point 202 °C) find similar lamp gettering applications for tungsten halogen lamps, where they perform the dual processies of gettering and precise halogen dosing. [10]

Triphosphorus pentanitride has also been investigated as a semiconductor for applications in microelectronics, particularly as a gate insulator in metal-insulator-semiconductor devices. [11] [12]

As a fuel in pyrotechnic obscurant mixtures, it offers some benefits over the more commonly used red phosphorus, owing mainly to its higher chemical stability. Unlike red phosphorus, P3N5 can be safely mixed with strong oxidizers, even potassium chlorate. While these mixtures can burn up to 200 times faster than state-of-the-art red phosphorus mixtures, they are far less sensitive to shock and friction. Additionally, P3N5 is much more resistant to hydrolysis than red phosphorus, giving pyrotechnic mixtures based on it greater stability under long-term storage. [13]

Patents have been filed for the use of triphosphorus pentanitride in fire fighting measures. [14] [15]

See also

Related Research Articles

<span class="mw-page-title-main">Acetyl chloride</span> Organic compound (CH₃COCl)

Acetyl chloride is an acyl chloride derived from acetic acid. It belongs to the class of organic compounds called acid halides. It is a colorless, corrosive, volatile liquid. Its formula is commonly abbreviated to AcCl.

<span class="mw-page-title-main">Thionyl chloride</span> Inorganic compound (SOCl2)

Thionyl chloride is an inorganic compound with the chemical formula SOCl2. It is a moderately volatile, colourless liquid with an unpleasant acrid odour. Thionyl chloride is primarily used as a chlorinating reagent, with approximately 45,000 tonnes per year being produced during the early 1990s, but is occasionally also used as a solvent. It is toxic, reacts with water, and is also listed under the Chemical Weapons Convention as it may be used for the production of chemical weapons.

<span class="mw-page-title-main">Phosphorus pentachloride</span> Chemical compound

Phosphorus pentachloride is the chemical compound with the formula PCl5. It is one of the most important phosphorus chlorides/oxychlorides, others being PCl3 and POCl3. PCl5 finds use as a chlorinating reagent. It is a colourless, water-sensitive solid, although commercial samples can be yellowish and contaminated with hydrogen chloride.

<span class="mw-page-title-main">Bismuth(III) oxide</span> Chemical compound

Bismuth(III) oxide is a compound of bismuth, and a common starting point for bismuth chemistry. It is found naturally as the mineral bismite (monoclinic) and sphaerobismoite, but it is usually obtained as a by-product of the smelting of copper and lead ores. Dibismuth trioxide is commonly used to produce the "Dragon's eggs" effect in fireworks, as a replacement of red lead.

<span class="mw-page-title-main">Phosphoryl chloride</span> Chemical compound

Phosphoryl chloride is a colourless liquid with the formula POCl3. It hydrolyses in moist air releasing phosphoric acid and fumes of hydrogen chloride. It is manufactured industrially on a large scale from phosphorus trichloride and oxygen or phosphorus pentoxide. It is mainly used to make phosphate esters.

<span class="mw-page-title-main">Silicon nitride</span> Compound of silicon and nitrogen

Silicon nitride is a chemical compound of the elements silicon and nitrogen. Si
3
N
4
is the most thermodynamically stable and commercially important of the silicon nitrides, and the term ″Silicon nitride″ commonly refers to this specific composition. It is a white, high-melting-point solid that is relatively chemically inert, being attacked by dilute HF and hot H
3
PO
4
. It is very hard. It has a high thermal stability with strong optical nonlinearities for all-optical applications.

Titanium(III) chloride is the inorganic compound with the formula TiCl3. At least four distinct species have this formula; additionally hydrated derivatives are known. TiCl3 is one of the most common halides of titanium and is an important catalyst for the manufacture of polyolefins.

<span class="mw-page-title-main">Hexachlorophosphazene</span> Chemical compound

Hexachlorophosphazene is an inorganic compound with the chemical formula (NPCl2)3. The molecule has a cyclic, unsaturated backbone consisting of alternating phosphorus and nitrogen atoms, and can be viewed as a trimer of the hypothetical compound N≡PCl2. Its classification as a phosphazene highlights its relationship to benzene. There is large academic interest in the compound relating to the phosphorus-nitrogen bonding and phosphorus reactivity.

<span class="mw-page-title-main">Thiophosphoryl chloride</span> Chemical compound

Thiophosphoryl chloride is an inorganic compound with the chemical formula PSCl3. It is a colorless pungent smelling liquid that fumes in air. It is synthesized from phosphorus chloride and used to thiophosphorylate organic compounds, such as to produce insecticides.

<span class="mw-page-title-main">Allotropes of sulfur</span> Class of substances

The element sulfur exists as many allotropes. In number of allotropes, sulfur is second only to carbon. In addition to the allotropes, each allotrope often exists in polymorphs delineated by Greek prefixes.

<span class="mw-page-title-main">Magnesium hydride</span> Chemical compound

Magnesium hydride is the chemical compound with the molecular formula MgH2. It contains 7.66% by weight of hydrogen and has been studied as a potential hydrogen storage medium.

Iron nitrides are inorganic chemical compounds of iron and nitrogen.

<span class="mw-page-title-main">Phosphoryl chloride difluoride</span> Chemical compound

Phosphoric chloride difluoride POF2Cl is a colourless gas. At one atmosphere pressure the gas condenses to a liquid at 3.1 °C and freezes at −96.4. Alternate names are difluorophosphoryl chloride or phosphoryl chloride difluoride.

In chemistry, aluminium(I) refers to monovalent aluminium (+1 oxidation state) in both ionic and covalent bonds. Along with aluminium(II), it is an extremely unstable form of aluminium.

The nitridosilicates are chemical compounds that have anions with nitrogen bound to silicon. Counter cations that balance the electric charge are mostly electropositive metals from the alkali metals, alkaline earths or rare earth elements. Silicon and nitrogen have similar electronegativities, so the bond between them is covalent. Nitrogen atoms are arranged around a silicon atom in a tetrahedral arrangement.

The nitridogermanates are chemical compounds containing germanium atoms bound to nitrogen. The simplest anion is GeN48−, but these are often condensed, with the elimination of nitrogen.

A chloride nitride is a mixed anion compound containing both chloride (Cl) and nitride ions (N3−). Another name is metallochloronitrides. They are a subclass of halide nitrides or pnictide halides.

A nitridophosphate is an inorganic compound that contains nitrogen bound to a phosphorus atom, considered as replacing oxygen in a phosphate.

<span class="mw-page-title-main">Rubidium ozonide</span> Chemical compound

Rubidium ozonide is an oxygen rich compound of rubidium. It is an ozonide, meaning it contains the ozonide anion (O3).

An iodide nitride is a mixed anion compound containing both iodide (I) and nitride ions (N3−). Another name is metalloiodonitrides. They are a subclass of halide nitrides or pnictide halides. Some different kinds include ionic alkali or alkaline earth salts, small clusters where metal atoms surround a nitrogen atom, layered group 4 element 2-dimensional structures, and transition metal nitrido complexes counter-balanced with iodide ions. There is also a family with rare earth elements and nitrogen and sulfur in a cluster.

References

  1. 1 2 3 4 Schnick, Wolfgang (1 June 1993). "Solid-State Chemistry with Nonmetal Nitrides" (PDF). Angewandte Chemie International Edition in English. 32 (6): 806–818. doi:10.1002/anie.199308061.
  2. Vepřek, S.; Iqbal, Z.; Brunner, J.; Schärli, M. (1 March 1981). "Preparation and properties of amorphous phosphorus nitride prepared in a low-pressure plasma". Philosophical Magazine B. 43 (3): 527–547. Bibcode:1981PMagB..43..527V. doi:10.1080/01418638108222114.
  3. Meng, Zhaoyu; Peng, Yiya; Yang, Zhiping; Qian, Yitai (1 January 2000). "Synthesis and Characterization of Amorphous Phosphorus Nitride". Chemistry Letters. 29 (11): 1252–1253. doi:10.1246/cl.2000.1252.
  4. Schnick, Wolfgang; Lücke, Jan; Krumeich, Frank (1996). "Phosphorus Nitride P3N5: Synthesis, Spectroscopic, and Electron Microscopic Investigations". Chemistry of Materials. 8: 281–286. doi:10.1021/cm950385y.
  5. Chen, Luyang; Gu, Yunle; Shi, Liang; Yang, Zeheng; Ma, Jianhua; Qian, Yitai (2004). "Room temperature route to phosphorus nitride hollow spheres". Inorganic Chemistry Communications. 7 (5): 643. doi:10.1016/j.inoche.2004.03.009.
  6. Schnick, Wolfgang (1993). "Phosphorus(V) Nitrides: Preparation, Properties, and Possible Applications of New Solid State Materials with Structural Analogies to Phosphates and Silicates". Phosphorus, Sulfur, and Silicon and the Related Elements. 76 (1–4): 183–186. doi:10.1080/10426509308032389.
  7. 1 2 Horstmann, Stefan; Irran, Elisabeth; Schnick, Wolfgang (1997). "Synthesis and Crystal Structure of Phosphorus(V) Nitrideα-P3N5". Angewandte Chemie International Edition in English. 36 (17): 1873–1875. doi:10.1002/anie.199718731.
  8. 1 2 Landskron, Kai; Huppertz, Hubert; Senker, Jürgen; Schnick, Wolfgang (2001). "High-Pressure Synthesis of γ-P3N5 at 11 GPa and 1500 °C in a Multianvil Assembly: A Binary Phosphorus(V) Nitride with a Three-Dimensional Network Structure from PN4 Tetrahedra and Tetragonal PN5 Pyramids". Angewandte Chemie. 40 (14): 2643–2645. doi:10.1002/1521-3773(20010716)40:14<2643::AID-ANIE2643>3.0.CO;2-T.
  9. 1 2 3 4 5 Laniel, Dominique; Trybel, Florian; Néri, Adrien; Yin, Yuqing; Aslandukov, Andrey; Fedotenko, Timofey; Khandarkhaeva, Saiana; Tasnádi, Ferenc; Chariton, Stella; Giacobbe, Carlotta; Bright, Eleanor Lawrence; Hanfland, Michael; Prakapenka, Vitali; Schnick, Wolfgang; Abrikosov, Igor A. (2022-11-07). "Revealing Phosphorus Nitrides up to the Megabar Regime: Synthesis of α′-P 3 N 5, δ-P 3 N 5 and PN 2". Chemistry – A European Journal. 28 (62): e202201998. doi:10.1002/chem.202201998. ISSN   0947-6539. PMC   9827839 . PMID   35997073. S2CID   251743071.
  10. S.T. Henderson and A.M. Marsden, Lamps and Lighting 2nd Ed., Edward Arnlold Press, 1975, ISBN   0 7131 3267 1
  11. Hirota, Yukihiro (1982). "Chemical vapor deposition and characterization of phosphorus nitride (P3N5) gate insulators for InP metal-insulator-semiconductor devices". Journal of Applied Physics. 53 (7): 5037–5043. Bibcode:1982JAP....53.5037H. doi:10.1063/1.331380.
  12. Jeong, Yoon-Ha; Choi, Ki-Hwan; Jo, Seong-Kue; Kang, Bongkoo (1995). "Effects of Sulfide Passivation on the Performance of GaAs MISFETs with Photo-CVD Grown P3N5 Gate Insulators". Japanese Journal of Applied Physics. 34 (Part 1, No. 2B): 1176–1180. Bibcode:1995JaJAP..34.1176J. doi:10.1143/JJAP.34.1176. S2CID   67837168.
  13. Koch, Ernst-Christian; Cudziło, Stanisław (2016), "Safer Pyrotechnic Obscurants Based on Phosphorus(V) Nitride", Angewandte Chemie International Edition, 55 (49): 15439–15442, doi:10.1002/anie.201609532, PMID   27862760
  14. Phosphorus nitride agents to protect against fires and explosions
  15. Manufacture of flame-retardant regenerated cellulose fibres, December 20, 1977