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| MolarMass = 162.955
| Appearance = White solid
| Density = άα-P<sub>3</sub>N<sub>5</sub> = 2.77 g/cm<sup>3</sup>
| MeltingPt = decomposes at ≥850°C
| Solubility = insoluable}}
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}}
'''Triphosphorus pentanitride''' is an ] with the ] ]]. ItContaining only phosphorus and nitrogen, this material is classified as a ] non-metal nitride;. afamily ofRelated compounds which includesare ] and ]. No applications have been developed for this material, which remains a topic of research. It is a white solid, although samples often appear colored owing to impurities.
== Synthesis ==
Triphosphorus pentanitride can be produced by reactions between various ](V) and various ] compounds,reagents:<ref name=Wolfgang></ref> including a reaction between the elements.<ref>{{cite journal|last=Vepřek|first=S.|author2=Iqbal, Z. |author3=Brunner, J. |author4= Schärli, M. |title=Preparation and properties of amorphous phosphorus nitride prepared in a low-pressure plasma|journal=Philosophical Magazine Part B|date=1 March 1981|volume=43|issue=3|pages=527–547|doi=10.1080/01418638108222114}}</ref> These methods of preparation are similar to those used for ] and ]; however the products are generally impure and ].<ref name=Wolfgang>{{cite journal|last=Schnick|first=Wolfgang|title=Solid-State Chemistry with Nonmetal Nitrides|journal=Angewandte Chemie International Edition in English|date=1 June 1993|volume=32|issue=6|pages=806–818|doi=10.1002/anie.199308061}}</ref>
:3 ] + 5 ] → P<sub>3</sub>N<sub>5</sub> + 15 ]
:3 PCl<sub>5</sub> + 15 ] → P<sub>3</sub>N<sub>5</sub> + 15 ] + 5 N<sub>2</sub><ref>{{cite journal|last=Meng|first=Zhaoyu|author2=Peng, Yiya |author3=Yang, Zhiping |author4= Qian, Yitai |title=Synthesis and Characterization of Amorphous Phosphorus Nitride.|journal=Chemistry Letters|date=1 January 2000|issue=11|pages=1252–1253|doi=10.1246/cl.2000.1252}}</ref>
Similar methods are used to prepared ] and ]; however the products are generally impure and ].<ref name=Wolfgang>{{cite journal|last=Schnick|first=Wolfgang|title=Solid-State Chemistry with Nonmetal Nitrides|journal=Angewandte Chemie International Edition in English|date=1 June 1993|volume=32|issue=6|pages=806–818|doi=10.1002/anie.199308061}}</ref><ref>{{cite journal|last=Meng|first=Zhaoyu|author2=Peng, Yiya |author3=Yang, Zhiping |author4= Qian, Yitai |title=Synthesis and Characterization of Amorphous Phosphorus Nitride.|journal=Chemistry Letters|date=1 January 2000|issue=11|pages=1252–1253|doi=10.1246/cl.2000.1252}}</ref>
Pure, ],triphosphorussamples pentanitride hashave been produced by reactionsthe reaction betweenof ] and ]:<ref>{{cite journal |doi=10.1021/cm950385y |title=Phosphorus Nitride P3N5: Synthesis, Spectroscopic, and Electron Microscopic Investigations |year=1996 |last1=Schnick |first1=Wolfgang |last2=Lücke |first2=Jan |last3=Krumeich |first3=Frank |journal=Chemistry of Materials |volume=8 |pages=281}}</ref> or ].<ref name=Wolfgang></ref>
:] + 2 NH<sub>4</sub>Cl → P<sub>3</sub>N<sub>5</sub> + 8 HCl
:3 ] + 5 NH<sub>4</sub>Cl → P<sub>3</sub>N<sub>5</sub> + 20 HCl
P<sub>3</sub>N<sub>5</sub> has also been prepared at room temperature, by a reaction between ] and ].<ref>{{cite journal |doi=10.1016/j.inoche.2004.03.009 |title=Room temperature route to phosphorus nitride hollow spheres |year=2004 |last1=Chen |first1=Luyang |last2=Gu |first2=Yunle |last3=Shi |first3=Liang |last4=Yang |first4=Zeheng |last5=Ma |first5=Jianhua |last6=Qian |first6=Yitai |journal=Inorganic Chemistry Communications |volume=7 |issue=5 |pages=643}}</ref>
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== Reactions ==
P<sub>3</sub>N<sub>5</sub> is thermally less stable than either BN or Si<sub>3</sub>N<sub>4</sub>, with ] to the elements occurring at temperatures above 850 °C.:<ref name = Wolfgang></ref>
:2 P<sub>3</sub>N<sub>5</sub> → 6 PN + 2 N<sub>2</sub> :2 PN → 3 P<sub>2</sub> + 5 N<sub>2</sub>
It is resistant to weak acids and bases, and insoluble in water at room temperature, however it will react with water] upon heating to form various ammonium] phosphateand salts].
Triphosphorus pentanitride can reactreacts with ] and ] to form athe varietycorresponding salts of compounds including LiPN<sub>74</sub>PN<subsup>47-</subsup> and CaPN<sub>23</sub>PN<subsup>34-</subsup>. Heterogenous ammonolyses of triphosphorus pentanitride can from triphosphorus pentanitridegives immidesimides such as HPN<sub>2</sub> and HP<sub>4</sub>N<sub>7</sub>. It has been suggested that these compounds may have applications as ] and ]s.<ref>{{cite journal|last=Schnick|first=Wolfgang|title=Phosphorus(V) Nitrides: Preparation, Properties, and Possible Applications of New Solid State Materials with Structural Analogies to Phosphates and Silicates|journal=Phosphorus, Sulfur, and Silicon and the Related Elements|year=1993|volume=76|issue=1-4|pages=183–186|doi=10.1080/10426509308032389}}</ref>▼:P<sub>3</sub>N<sub>5</sub> + 12 H<sub>2</sub>O → 3 ] + 5 ] → 2 ] + ]▲Triphosphorus pentanitride can react with ] and ] to form a variety of compounds including Li<sub>7</sub>PN<sub>4</sub> and Ca<sub>2</sub>PN<sub>3</sub>. Heterogenous ammonolyses of triphosphorus pentanitride can from triphosphorus pentanitride immides such as HPN<sub>2</sub> and HP<sub>4</sub>N<sub>7</sub>. It has been suggested that these compounds may have applications as ] and ]s.<ref>{{cite journal|last=Schnick|first=Wolfgang|title=Phosphorus(V) Nitrides: Preparation, Properties, and Possible Applications of New Solid State Materials with Structural Analogies to Phosphates and Silicates|journal=Phosphorus, Sulfur, and Silicon and the Related Elements|year=1993|volume=76|issue=1-4|pages=183–186|doi=10.1080/10426509308032389}}</ref>
== Structure and properties ==
There are severalSeveral different ] ofare known for triphosphorus pentanitride, which occur at different ]s. The alpha‑form of triphosphorus pentanitride (ά‑Pα‑P<sub>3</sub>N<sub>5</sub>) is the form encountered at atmospheric pressure and exists at pressures up to 6 ], at which point it converts to the gamma‑variety (γ‑P<sub>3</sub>N<sub>5</sub>) of the compound. ] indicates that a third, delta‑variety (δ‑P<sub>3</sub>N<sub>5</sub>), will form at around 43 Gpa with a ]-like structure.<ref>{{cite journal |pmid=12203333 |year=2002 |last1=Kroll |first1=P |last2=Schnick |first2=W |title=A density functional study of phosphorus nitride P3N5: Refined geometries, properties, and relative stability of alpha-P3N5 and gamma-P3N5 and a further possible high-pressure phase delta-P3N5 with kyanite-type structure |volume=8 |issue=15 |pages=3530–7 |doi=10.1002/1521-3765(20020802)8:15<3530::AID-CHEM3530>3.0.CO;2-6 |journal=Chemistry}}</ref>▼Although white when of high purity, triphosphorus pentanitride can take on a number of subtle buff shades if not highly pure.▲There are several different ] of triphosphorus pentanitride, which occur at different ]s. The alpha‑form of triphosphorus pentanitride (ά‑P<sub>3</sub>N<sub>5</sub>) is the form encountered at atmospheric pressure and exists at pressures up to 6 ], at which point it converts to the gamma‑variety (γ‑P<sub>3</sub>N<sub>5</sub>) of the compound. ] indicates that a third, delta‑variety (δ‑P<sub>3</sub>N<sub>5</sub>), will form at around 43 Gpa with a ]-like structure.<ref>{{cite journal |pmid=12203333 |year=2002 |last1=Kroll |first1=P |last2=Schnick |first2=W |title=A density functional study of phosphorus nitride P3N5: Refined geometries, properties, and relative stability of alpha-P3N5 and gamma-P3N5 and a further possible high-pressure phase delta-P3N5 with kyanite-type structure |volume=8 |issue=15 |pages=3530–7 |doi=10.1002/1521-3765(20020802)8:15<3530::AID-CHEM3530>3.0.CO;2-6 |journal=Chemistry}}</ref>
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The structure of ά‑Pα‑P<sub>3</sub>N<sub>5</sub> has been determined by ] ], which showed a network structure of edge‑sharing PN<sub>4</sub> tetrahedra.<ref>{{cite journal|last=Horstmann|first=Stefan|author2=Irran, Elisabeth |author3=Schnick, Wolfgang |title=Synthesis and Crystal Structure of Phosphorus(V) Nitrideα-P3N5|journal=Angewandte Chemie International Edition in English|year=1997|volume=36|issue=17|pages=1873–1875|doi=10.1002/anie.199718731}}</ref>
== Applications ==
Triphosphorus pentanitride is an inorganic compound with the chemical formulaP3N5. Containing only phosphorus and nitrogen, this material is classified as a binary nitride. Related compounds are boron nitride and silicon nitride. No applications have been developed for this material, which remains a topic of research. It is a white solid, although samples often appear colored owing to impurities.
Synthesis
Triphosphorus pentanitride can be produced by reactions between various phosphorus(V) and various nitrogen reagents: including a reaction between the elements.
P3N5 is thermally less stable than either BN or Si3N4, with decomposition to the elements occurring at temperatures above 850 °C:
2 P3N5 → 6 PN + 2 N2
2 PN → P2 + N2
It is resistant to weak acids and bases, and insoluble in water at room temperature, however it hydrolyzes upon heating to form ] and NH4H2PO4.
Triphosphorus pentanitride reacts with lithium nitride and calcium nitride to form the corresponding salts of PN4 and PN3. 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.
Structure and properties
Several different 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 6 GPa, at which point it converts to the gamma‑variety (γ‑P3N5) of the compound. Computational chemistry indicates that a third, delta‑variety (δ‑P3N5), will form at around 43 Gpa with a Kyanite-like structure.
Polymorph
Density (g/cm)
α‑P3N5
2.77
γ‑P3N5
3.65
δ‑P3N5
4.02
The structure of α‑P3N5 has been determined by single crystalX-ray diffraction, which showed a network structure of edge‑sharing PN4 tetrahedra.
Applications
Triphosphorus pentanitride currently has no large scale applications although it had found use as a gettering material for incandescent lamps; replacing various mixtures containing red phosphorus in the late 1960's. The lighting filaments are dipped into a suspension of P3N5 prior to being sealed into the bulb. After bulb closure, but whilst 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 polymers, trimeric bromophosphonitrile, (PNBr2)3, m.p. 192C and tetrameric bromophosphonitrile, (PNBr2)4, m.p. 202C find similar lamp gettering applications for tungsten halogen lamps, where they perform the dual processies of gettering and precise halogen dosing.
^ Schnick, Wolfgang (1 June 1993). "Solid-State Chemistry with Nonmetal Nitrides". Angewandte Chemie International Edition in English. 32 (6): 806–818. doi:10.1002/anie.199308061.
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 Part B. 43 (3): 527–547. doi:10.1080/01418638108222114.
Meng, Zhaoyu; Peng, Yiya; Yang, Zhiping; Qian, Yitai (1 January 2000). "Synthesis and Characterization of Amorphous Phosphorus Nitride". Chemistry Letters (11): 1252–1253. doi:10.1246/cl.2000.1252.
Schnick, Wolfgang; Lücke, Jan; Krumeich, Frank (1996). "Phosphorus Nitride P3N5: Synthesis, Spectroscopic, and Electron Microscopic Investigations". Chemistry of Materials. 8: 281. doi:10.1021/cm950385y.
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.
Kroll, P; Schnick, W (2002). "A density functional study of phosphorus nitride P3N5: Refined geometries, properties, and relative stability of alpha-P3N5 and gamma-P3N5 and a further possible high-pressure phase delta-P3N5 with kyanite-type structure". Chemistry. 8 (15): 3530–7. doi:10.1002/1521-3765(20020802)8:15<3530::AID-CHEM3530>3.0.CO;2-6. PMID12203333.
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.
S.T. Henderson and A.M. Marsden, Lamps and Lighting 2nd Ed., Edward Arnlold Press, 1975, ISBN 0 7131 3267 1
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. doi:10.1063/1.331380.
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. doi:10.1143/JJAP.34.1176.
