五氮化三磷

五氮化三磷
	IUPAC名; Triphosphorus pentanitride
别名	氮化磷; 氮化磷(V)
识别
CAS号	12136-91-3
EINECS	235-233-9
性质
化学式	P3N5
摩尔质量	162.955 g·mol⁻¹
外观	白色固体
密度	α-P3N5：2.77 g/cm3
熔点	850 °C（1123 K）（分解）
溶解性（水）	不溶
相关物质
相关化学品	一氮化磷
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

五氮化三磷是一种无机化合物，化学式 P₃ N₅。它是磷的一种氮化物。虽然已经对其各种应用进行了研究，但这并没有导致五氮化三磷有任何重要的工业用途。它是一种白色固体，尽管样品经常因杂质而呈现其它颜色。

制备

五氮化三磷可以由含有磷(V)的化合物和含有氮阴离子的化合物（例如氨和叠氮化钠）：^[1]

3 PCl₅ + 5 NH₃ → P₃N₅ + 15 HCl

3 PCl₅ + 15 NaN₃ → P₃N₅ + 15 NaCl + 5 N₂

据称，磷和氮的反应会产生五氮化三磷。^[2]类似的方法可以用来制备氮化硼 (BN) 和氮化硅 (Si₃N₄)，不过产物通常是不纯和无定形的。^[1]^[3]

五氮化三磷晶体可以由氯化铵和六氯环三氮磷烷（英语：hexachlorocyclotriphosphazene）^[4]或五氯化磷反应而成：^[1]

(NPCl₂)₃ + 2 NH₄Cl → P₃N₅ + 8 HCl

3 PCl₅ + 5 NH₄Cl → P₃N₅ + 20 HCl

室温下，P₃N₅ 也可以由三氯化磷和氨基钠反应而成。^[5]

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

反应

P₃N₅的热稳定性比 BN 和Si₃N₄低，在超过 850 °C时分解：^[1]

P₃N₅ → 3 PN + N₂

4 PN → P₄ + 2 N₂

五氮化三磷不与弱酸、弱碱反应，不溶于水。它加热水解成(NH₄)₂HPO₄ 和NH₄H₂PO₄。

五氮化三磷和氮化锂、氮化钙反应，产生 PN₄⁷⁻ 和PN₃⁴⁻离子。异相氨解会产生像是 HPN₂ 和HP₄N₇的亚氨基化物。有人提出，这些化合物可用作固体电解质（英语：solid electrolytes）和颜料。^[6]

结构和性质

五氮化三磷的多种同质异形体是已知的。α‑P₃N₅是标准情况下，五氮化三磷的形式。加压到6 GPa时，会转变成γ‑P₃N₅。计算化学显示第三种五氮化三磷的结构 δ‑P₃N₅会在约 43 GPa 时出现，为蓝晶石结构。^[7]

结构	密度(g/cm³)
α‑P₃N₅	2.77
γ‑P₃N₅	3.65
δ‑P₃N₅	4.02

α‑P₃N₅ 的结构已通过单晶 X射线衍射确定，里面含有PN₄四面体和二或三配位的氮离子。^[8]

参见

聚磷氮烯（英语：Polyphosphazene）

参考资料

^ ^1.0 ^1.1 ^1.2 ^1.3 Schnick, Wolfgang. Solid-State Chemistry with Nonmetal Nitrides (PDF). Angewandte Chemie International Edition in English. 1 June 1993, 32 (6): 806–818 [2021-07-25]. doi:10.1002/anie.199308061. （原始内容 (PDF)存档于2017-08-13）.
^ Vepřek, S.; Iqbal, Z.; Brunner, J.; Schärli, M. Preparation and properties of amorphous phosphorus nitride prepared in a low-pressure plasma. Philosophical Magazine B. 1 March 1981, 43 (3): 527–547. Bibcode:1981PMagB..43..527V. doi:10.1080/01418638108222114.
^ Meng, Zhaoyu; Peng, Yiya; Yang, Zhiping; Qian, Yitai. Synthesis and Characterization of Amorphous Phosphorus Nitride.. Chemistry Letters. 1 January 2000, 29 (11): 1252–1253. doi:10.1246/cl.2000.1252.
^ Schnick, Wolfgang; Lücke, Jan; Krumeich, Frank. Phosphorus Nitride P3N5: Synthesis, Spectroscopic, and Electron Microscopic Investigations. Chemistry of Materials. 1996, 8: 281–286. doi:10.1021/cm950385y.
^ Chen, Luyang; Gu, Yunle; Shi, Liang; Yang, Zeheng; Ma, Jianhua; Qian, Yitai. Room temperature route to phosphorus nitride hollow spheres. Inorganic Chemistry Communications. 2004, 7 (5): 643. doi:10.1016/j.inoche.2004.03.009.
^ Schnick, Wolfgang. 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. 1993, 76 (1–4): 183–186. doi:10.1080/10426509308032389.
^ Kroll, P; Schnick, W. 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. 2002, 8 (15): 3530–7. PMID 12203333. doi:10.1002/1521-3765(20020802)8:15<3530::AID-CHEM3530>3.0.CO;2-6.
^ Horstmann, Stefan; Irran, Elisabeth; Schnick, Wolfgang. Synthesis and Crystal Structure of Phosphorus(V) Nitrideα-P3N5. Angewandte Chemie International Edition in English. 1997, 36 (17): 1873–1875. doi:10.1002/anie.199718731.

[Wolfgang-1] 1.0 ^1.1 ^1.2 ^1.3 Schnick, Wolfgang. Solid-State Chemistry with Nonmetal Nitrides (PDF). Angewandte Chemie International Edition in English. 1 June 1993, 32 (6): 806–818 [2021-07-25]. doi:10.1002/anie.199308061. （原始内容 (PDF)存档于2017-08-13）.

[2] Vepřek, S.; Iqbal, Z.; Brunner, J.; Schärli, M. Preparation and properties of amorphous phosphorus nitride prepared in a low-pressure plasma. Philosophical Magazine B. 1 March 1981, 43 (3): 527–547. Bibcode:1981PMagB..43..527V. doi:10.1080/01418638108222114.

[3] Meng, Zhaoyu; Peng, Yiya; Yang, Zhiping; Qian, Yitai. Synthesis and Characterization of Amorphous Phosphorus Nitride.. Chemistry Letters. 1 January 2000, 29 (11): 1252–1253. doi:10.1246/cl.2000.1252.

[4] Schnick, Wolfgang; Lücke, Jan; Krumeich, Frank. Phosphorus Nitride P3N5: Synthesis, Spectroscopic, and Electron Microscopic Investigations. Chemistry of Materials. 1996, 8: 281–286. doi:10.1021/cm950385y.

[5] Chen, Luyang; Gu, Yunle; Shi, Liang; Yang, Zeheng; Ma, Jianhua; Qian, Yitai. Room temperature route to phosphorus nitride hollow spheres. Inorganic Chemistry Communications. 2004, 7 (5): 643. doi:10.1016/j.inoche.2004.03.009.

[6] Schnick, Wolfgang. 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. 1993, 76 (1–4): 183–186. doi:10.1080/10426509308032389.

[7] Kroll, P; Schnick, W. 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. 2002, 8 (15): 3530–7. PMID 12203333. doi:10.1002/1521-3765(20020802)8:15<3530::AID-CHEM3530>3.0.CO;2-6.

[8] Horstmann, Stefan; Irran, Elisabeth; Schnick, Wolfgang. Synthesis and Crystal Structure of Phosphorus(V) Nitrideα-P3N5. Angewandte Chemie International Edition in English. 1997, 36 (17): 1873–1875. doi:10.1002/anie.199718731.

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