硝酸钚(IV)

硝酸钚(IV)
英文名	Plutonium(IV) nitrate
别名	四硝酸钚
识别
CAS号	13823-27-3 ; 53745-09-8（238Pu） ; 13968-56-4（239Pu） ; 55252-44-3（水合） ; 159472-02-3（三水） ; 61204-24-8（五水）
PubChem	150308
SMILES	[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[Pu+4];
性质
化学式	Pu(NO3)4
摩尔质量	492.028（无水）; 582.108（五水） g·mol⁻¹
外观	绿色晶体（五水）
密度	2.90 g·cm−3（五水）
溶解性（水）	可溶
相关物质
其他阴离子	硫酸钚(IV)
其他阳离子	硝酸镎(IV)
相关化学品	硝酸钚(VI)酰
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

硝酸钚(IV)是一种具有强放射性的无机化合物，化学式为Pu(NO₃)₄，可以形成水合物，^[1]其外观为深绿色晶体。^[3]^[4]

制备

硝酸钚(IV)可由二氧化钚溶于硝酸得到，^[5]从其溶液中可以结晶出正交晶系的五水合物（Pu(NO₃)₄·5H₂O）。^[2]

性质

硝酸钚(IV)可溶于水和一部分有机溶剂^[1]，其水溶液可被磷酸三丁酯萃取。^[6]它也能溶于熔融的硝酸铀酰六水合物，若在体系中加入1~6 M HNO₃，它会歧化为Pu(III)和Pu(VI)，若提高HNO₃浓度至10 M以上，则只会生成配阴离子[Pu(NO₃)₆]²⁻。^[7]它在1.5~7.1 M的硝酸溶液中，可以Pu(NO₃)_n⁽⁴⁻ⁿ⁾⁺（n=1, 2, 3, 4, 5）的形式存在，7.1 M以上时，以[Pu(NO₃)₆]²⁻的形式存在，^[8]超过11 M时，以H₂[Pu(NO₃)₆]的形式存在。^[9]在碱性溶液中，它以PuO₂·xH₂O的形式沉淀出来。^[10]

它可以被氨基胍硫酸盐或抗坏血酸还原为Pu(NO₃)₃。^[11]向其溶液通入臭氧，它可以经PuO₂⁺氧化至PuO₂²⁺。^[12]

{\mathsf {Pu(NO_{3})_{4}+O_{3}+H_{2}O\ {\xrightarrow {}}\ PuO_{2}(NO_{3})_{2}+2HNO_{3}+O_{2}\uparrow }}

参考文献

^ ^1.0 ^1.1 ^1.2 Ahrland, S.; Bagnall, K.W.; Brown, D. The Chemistry of the Actinides: Comprehensive Inorganic Chemistry. Elsevier Science. 2016: 292 [2021-08-18]. ISBN 978-1-4831-5934-8. （原始内容存档于2021-08-18）（英语）.
^ ^2.0 ^2.1 Staritzky, Eugene. Crustallographic Data. 142. Plutonium Tetranitrate Pentahydrate, Pu(NO₃)₄·5H₂O. Analytical Chemistry (American Chemical Society (ACS)). 1956-12-01, 28 (12): 2021–2022. ISSN 0003-2700. doi:10.1021/ac60120a063 （英语）.
^ Allen, P. G.; Veirs, D. K.; Conradson, S. D.; Smith, C. A.; Marsh, S. F. Characterization of Aqueous Plutonium(IV) Nitrate Complexes by Extended X-ray Absorption Fine Structure Spectroscopy. Inorganic Chemistry. 1996-01, 35 (10): 2841–2845 [2021-08-16]. doi:10.1021/ic9511231. （原始内容存档于2022-01-27）.
^ Kubic, William; Jackson, J. A thermodynamic model of plutonium (IV) nitrate solutions. Journal of Radioanalytical and Nuclear Chemistry. 2012-03-09, 293 (2): 601–612 [2021-08-16]. ISSN 1588-2780. S2CID 94704456. doi:10.1007/s10967-012-1703-4. （原始内容存档于2022-01-27）.
^ George, Kathryn; Muller, Julie; Berthon, Laurence; Berthon, Claude; Guillaumont, Dominique; Vitorica-Yrezabal, Iñigo J.; Stafford, H. Victoria; Natrajan, Louise S.; Tamain, Christelle. Exploring the Coordination of Plutonium and Mixed Plutonyl–Uranyl Complexes of Imidodiphosphinates. Inorganic Chemistry (American Chemical Society (ACS)). 2019-04-26, 58 (10): 6904–6917. ISSN 0020-1669. doi:10.1021/acs.inorgchem.9b00346 （英语）.
^ Healy, T. V.; McKay, H. A. C. The extraction of nitrates by tri-n-butyl phosphate (TBP). Part 2.—The nature of the TBP phase. Trans. Faraday Soc. (Royal Society of Chemistry (RSC)). 1956, 52 (0): 633–642. ISSN 0014-7672. doi:10.1039/tf9565200633 （英语）.
^ Kulyako, Yu. M.; Trofimov, T. I.; Samsonov, M. D.; Shadrin, A. Yu.; Myasoedov, B. F. Solubility of plutonium nitrate in uranyl nitrate hexahydrate melt. Radiochemistry (Pleiades Publishing Ltd). 2008, 50 (3): 250–252. ISSN 1066-3622. doi:10.1134/s1066362208030053 （英语）.
^ Lipis, L. V.; Pozharskii, B. G.; Fomin, V. V. Spectrophotometric investigation of the formation of complexes of quadrivalent Pu in nitrate solutions. Zhurnal Strukturnoi Khimii. 1960, (2): 135-144. ISSN 0136-7463 （俄语）.
^ Brothers, J.A.; Hart, R.G.; Mathers, W.G. The nitrate complexes of tetravalent plutonium. Journal of Inorganic and Nuclear Chemistry (Elsevier BV). 1958, 7 (1-2): 85–93. ISSN 0022-1902. doi:10.1016/0022-1902(58)80031-7 （英语）.
^ Delegard, C. H. Effects of aging on PuO₂·xH₂O particle size in alkaline solution. Radiochimica Acta (Walter de Gruyter GmbH). 2013-04-29, 101 (5): 313–322. ISSN 2193-3405. doi:10.1524/ract.2013.2034 （英语）.
^ Burney, G. A.; Tober, F. W. Precipitation of Plutonium Trifluoride. Industrial & Engineering Chemistry Process Design and Development (American Chemical Society (ACS)). 1965, 4 (1): 28–32. ISSN 0196-4305. doi:10.1021/i260013a009 （英语）.
^ Conroy, Nathan A.; Wylie, E. Miller; Powell, Brian A. A Novel Method for Tracer Concentration Plutonium(V) Solution Preparation. Analytical Chemistry (American Chemical Society (ACS)). 2016-03-28, 88 (8): 4196–4199. ISSN 0003-2700. doi:10.1021/acs.analchem.6b00229 （英语）.

拓展阅读

Balasubramonian, S.; Pandey, N. K.; Subba Rao, R. V. Thermodynamic modeling of Pu(IV) and nitric acid extraction by 1.1 M tri-iso-amyl phosphate in n-dodecane. Journal of Radioanalytical and Nuclear Chemistry (Springer Science and Business Media LLC). 2020-08-12, 326 (1): 105–113. ISSN 0236-5731. doi:10.1007/s10967-020-07338-8 （英语）.
Kaplan, Daniel I.; Demirkanli, Deniz I.; Gumapas, Leo; Powell, Brian A.; Fjeld, Robert A.; Molz, Fred J.; Serkiz, Steven M. Eleven-Year Field Study of Pu Migration from Pu III, IV, and VI Sources. Environmental Science & Technology (American Chemical Society (ACS)). 2005-12-06, 40 (2): 443–448. ISSN 0013-936X. doi:10.1021/es050073o （英语）.

[Ahrland-1] 1.0 ^1.1 ^1.2 Ahrland, S.; Bagnall, K.W.; Brown, D. The Chemistry of the Actinides: Comprehensive Inorganic Chemistry. Elsevier Science. 2016: 292 [2021-08-18]. ISBN 978-1-4831-5934-8. （原始内容存档于2021-08-18）（英语）.

[Staritzky-2] 2.0 ^2.1 Staritzky, Eugene. Crustallographic Data. 142. Plutonium Tetranitrate Pentahydrate, Pu(NO₃)₄·5H₂O. Analytical Chemistry (American Chemical Society (ACS)). 1956-12-01, 28 (12): 2021–2022. ISSN 0003-2700. doi:10.1021/ac60120a063 （英语）.

[3] Allen, P. G.; Veirs, D. K.; Conradson, S. D.; Smith, C. A.; Marsh, S. F. Characterization of Aqueous Plutonium(IV) Nitrate Complexes by Extended X-ray Absorption Fine Structure Spectroscopy. Inorganic Chemistry. 1996-01, 35 (10): 2841–2845 [2021-08-16]. doi:10.1021/ic9511231. （原始内容存档于2022-01-27）.

[4] Kubic, William; Jackson, J. A thermodynamic model of plutonium (IV) nitrate solutions. Journal of Radioanalytical and Nuclear Chemistry. 2012-03-09, 293 (2): 601–612 [2021-08-16]. ISSN 1588-2780. S2CID 94704456. doi:10.1007/s10967-012-1703-4. （原始内容存档于2022-01-27）.

[5] George, Kathryn; Muller, Julie; Berthon, Laurence; Berthon, Claude; Guillaumont, Dominique; Vitorica-Yrezabal, Iñigo J.; Stafford, H. Victoria; Natrajan, Louise S.; Tamain, Christelle. Exploring the Coordination of Plutonium and Mixed Plutonyl–Uranyl Complexes of Imidodiphosphinates. Inorganic Chemistry (American Chemical Society (ACS)). 2019-04-26, 58 (10): 6904–6917. ISSN 0020-1669. doi:10.1021/acs.inorgchem.9b00346 （英语）.

[6] Healy, T. V.; McKay, H. A. C. The extraction of nitrates by tri-n-butyl phosphate (TBP). Part 2.—The nature of the TBP phase. Trans. Faraday Soc. (Royal Society of Chemistry (RSC)). 1956, 52 (0): 633–642. ISSN 0014-7672. doi:10.1039/tf9565200633 （英语）.

[7] Kulyako, Yu. M.; Trofimov, T. I.; Samsonov, M. D.; Shadrin, A. Yu.; Myasoedov, B. F. Solubility of plutonium nitrate in uranyl nitrate hexahydrate melt. Radiochemistry (Pleiades Publishing Ltd). 2008, 50 (3): 250–252. ISSN 1066-3622. doi:10.1134/s1066362208030053 （英语）.

[8] Lipis, L. V.; Pozharskii, B. G.; Fomin, V. V. Spectrophotometric investigation of the formation of complexes of quadrivalent Pu in nitrate solutions. Zhurnal Strukturnoi Khimii. 1960, (2): 135-144. ISSN 0136-7463 （俄语）.

[9] Brothers, J.A.; Hart, R.G.; Mathers, W.G. The nitrate complexes of tetravalent plutonium. Journal of Inorganic and Nuclear Chemistry (Elsevier BV). 1958, 7 (1-2): 85–93. ISSN 0022-1902. doi:10.1016/0022-1902(58)80031-7 （英语）.

[10] Delegard, C. H. Effects of aging on PuO₂·xH₂O particle size in alkaline solution. Radiochimica Acta (Walter de Gruyter GmbH). 2013-04-29, 101 (5): 313–322. ISSN 2193-3405. doi:10.1524/ract.2013.2034 （英语）.

[11] Burney, G. A.; Tober, F. W. Precipitation of Plutonium Trifluoride. Industrial & Engineering Chemistry Process Design and Development (American Chemical Society (ACS)). 1965, 4 (1): 28–32. ISSN 0196-4305. doi:10.1021/i260013a009 （英语）.

[12] Conroy, Nathan A.; Wylie, E. Miller; Powell, Brian A. A Novel Method for Tracer Concentration Plutonium(V) Solution Preparation. Analytical Chemistry (American Chemical Society (ACS)). 2016-03-28, 88 (8): 4196–4199. ISSN 0003-2700. doi:10.1021/acs.analchem.6b00229 （英语）.

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