连二亚硝酸钠

连二亚硝酸钠
英文名	Sodium hyponitrite
识别
CAS号	60884-94-8（水合物）
PubChem	24869787 10034601, 24869787
ChemSpider	8210166
SMILES	N(=N[O-])[O-].[Na+].[Na+];
InChI	1S/H2N2O2.2Na/c3-1-2-4;;/h(H,1,4)(H,2,3);;/q;2*+1/p-2;
InChIKey	HLJWMCUZPYEUDI-UHFFFAOYSA-L
性质
化学式	Na2N2O2
摩尔质量	105.99 g·mol⁻¹
外观	无色晶体
密度	2.466 g/cm3
熔点	100 °C（373 K）
沸点	335 °C（608 K）（分解）
溶解性（水）	可溶
溶解性	不溶于乙醇
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

连二亚硝酸钠是一种固态的离子化合物，化学式 Na
2N
2O
2或(Na+
)₂[ON=NO]²⁻。^[1]

连二亚硝酸钠中的连二亚硝酸根离子 N
2O2−
2有顺反异构。反式异构体更常见，但顺式异构体也是可被制备的，反应性比反式异构体高。^[1]^[2]

反式异构体

反式连二亚硝酸钠是无色的，可溶于水，不溶于乙醇和乙醚。^[3]^[4]

制备

反式连二亚硝酸钠可以由亚硝酸钠被钠汞齐还原而成。^[5]^[6]^[7]

2 NaNO₂ + 4 Na(Hg) + 2 H₂O → Na₂N₂O₂ + 4 NaOH + 4 Hg

反式连二亚硝酸钠是在1927年由A. W. Scott首次合成的。它反应了亚硝酸酯、羟胺盐酸盐和乙醇钠。^[4]^[8]

RONO + NH₂OH + 2 EtONa → Na₂N₂O₂ + ROH + 2 EtOH

一种较早的方法由David Mendenhall（英语：David Mendenhall）于1974年发表，为一氧化氮 (NO)和金属钠在乙二醇二甲醚、甲苯和二苯基甲酮的反应。这种盐之后通过水提取。^[9]

水合物

反式连二亚硝酸钠的一系列水合物 Na
2N
2O
2(H
2O)_x已被报告，其中x 可以是2、3.5、4、5、6、7、8和9，^[10]^[3]^[11]但有一些争议。^[12]

其中的结晶水只是困在晶格中，而不是和离子配位。^[12]通过在五氧化二磷上干燥水合物，然后将它们加热至120°C，可以获得无水物。^[12]

反应

反式连二亚硝酸钠溶液会和空气中的二氧化碳 CO
2 反应，形成碳酸钠。^[13]

液态N₂O₄会氧化反式连二亚硝酸钠，形成过氧连二亚硝酸钠 Na2+
2[ON=NOO]²⁻)。^[14]^[1]

顺式异构体

顺式连二亚硝酸钠是一种白色晶体，不溶于极性非质子溶剂。不像反式异构体，它在水或质子溶剂中分解。^[2]

制备

顺式连二亚硝酸钠可以由一氧化氮 (NO)通过 −50 °C的液氨中的钠而成。^[1]

顺式连二亚硝酸钠是在1996年由Claus Feldmann和Martin Jansen通过在77 kPa的笑气 N
2O中把氧化钠 Na
2O加热到360 °C两小时而成。反应产生的顺式连二亚硝酸钠是白色微晶体。^[8]^[2]

性质和反应

顺式连二亚硝酸钠在325 °C以上分解成氮气和原亚硝酸钠：^[2]

3 Na
2N
2O
2 → 2 Na
3O(NO
2) + 2 N
2

它的反应性比反式异构体高。^[1]

参见

连二亚硝酸

参考资料

^ ^1.0 ^1.1 ^1.2 ^1.3 ^1.4 Egon Wiberg, Arnold Frederick Holleman (2001) Inorganic Chemistry, Elsevier ISBN 0-12-352651-5
^ ^2.0 ^2.1 ^2.2 ^2.3 Claus Feldmann, Martin Jansen (1996), "cis-Sodium Hyponitrite - A New Preparative Route and a Crystal Structure Analysis". Angewandte Chemie International Edition in English, volume 35, issue 15, pages 1728–1730. doi:10.1002/anie.199617281
^ ^3.0 ^3.1 Trambaklal Mohanlal Oza, Rajnikant Hariprasad Thaker (1955), "The Thermal Decomposition of Silver Hyponitrite". Journal of the American Chemical society, volume 77, issue 19, pages 4976–4980. doi:10.1021/ja01624a007
^ ^4.0 ^4.1 A. W. Scott (1927), "Sodium Hyponitrite". J. Am. Chem. Soc., volume = 49, issue 4, pages = 986–987. doi:10.1021/ja01403a502
^ Addison, C. C.; Gamlen G. A.; Thompson, R. 70. The ultra-violet absorption spectra of sodium hyponitrite and sodium α-oxyhyponitrite : the analysis of mixtures with sodium nitrite and nitrate. J. Chem. Soc. 1952: 338. doi:10.1039/jr9520000338.
^ Neumann, R. C., Jr. Bussey, R. J. High pressure studies. V. Activation volumes for combination and diffusion of geminate tert-butoxy radicals. J. Am. Chem. Soc. 1970, 92 (8): 2440. doi:10.1021/ja00711a039.
^ Greenwood, N. N.; Earnshaw, A. Chemistry of the Elements 2nd. Oxford:Butterworth-Heinemann. 1997. ISBN 0-7506-3365-4.
^ ^8.0 ^8.1 Catherine E. Housecroft; Alan G. Sharpe. Chapter 15: The group 15 elements. Inorganic Chemistry 3rd. Pearson. 2008: 468. ISBN 978-0-13-175553-6.
^ G. David Mendenhall (1974), "Convenient synthesis of silver hyponitrite". Journal of the American Chemical society, volume 96, issue 15, page 5000. doi:10.1021/ja00822a054
^ James Riddick Partington and Chandulal Chhotalal Shah (1931), "Investigations on hyponitrites. Part I. Sodium hyponitrite: preparation and properties". Journal of the Chemical Society (Resumed), paper CCLXXXII, pages 2071-2080. doi:10.1039/JR9310002071
^ C.N. Polydoropoulos, S.D. Voliotis (1967), "Sodium hyponitrite hexahydrate". Journal of Inorganic and Nuclear Chemistry, volume 29, issue 12, pages 2899–2901. doi:10.1016/0022-1902(67)80121-0
^ ^12.0 ^12.1 ^12.2 Gary L. Stucky, Jack L. Lambert, R. Dean Dragsdorf (1969), "The hydrates of sodium hyponitrite". Journal of Inorganic and Nuclear Chemistry, volume 31, issue 1, pages 29–32 doi:10.1016/0022-1902(69)80050-3
^ Charlotte N. Conner, Caroline E. Donald, Martin N. Hughes, Christina Sami (1989), "The molar absorptivity of sodium hyponitrite". Polyhedron, volume 8, issue 21, pages 2621-2622. doi:10.1016/S0277-5387(00)81166-3
^ M. N. Hughes and H. G. Nicklin (1969), "The action of dinitrogen tetroxide on sodium hyponitrite". Journal of the Chemical Society D: Chemical Communications, volume 1969, issue 2, page 80a. doi:10.1039/C2969000080A

[Wiberg&Holleman-1] 1.0 ^1.1 ^1.2 ^1.3 ^1.4 Egon Wiberg, Arnold Frederick Holleman (2001) Inorganic Chemistry, Elsevier ISBN 0-12-352651-5

[feld-2] 2.0 ^2.1 ^2.2 ^2.3 Claus Feldmann, Martin Jansen (1996), "cis-Sodium Hyponitrite - A New Preparative Route and a Crystal Structure Analysis". Angewandte Chemie International Edition in English, volume 35, issue 15, pages 1728–1730. doi:10.1002/anie.199617281

[tram-3] 3.0 ^3.1 Trambaklal Mohanlal Oza, Rajnikant Hariprasad Thaker (1955), "The Thermal Decomposition of Silver Hyponitrite". Journal of the American Chemical society, volume 77, issue 19, pages 4976–4980. doi:10.1021/ja01624a007

[scott-4] 4.0 ^4.1 A. W. Scott (1927), "Sodium Hyponitrite". J. Am. Chem. Soc., volume = 49, issue 4, pages = 986–987. doi:10.1021/ja01403a502

[5] Addison, C. C.; Gamlen G. A.; Thompson, R. 70. The ultra-violet absorption spectra of sodium hyponitrite and sodium α-oxyhyponitrite : the analysis of mixtures with sodium nitrite and nitrate. J. Chem. Soc. 1952: 338. doi:10.1039/jr9520000338.

[6] Neumann, R. C., Jr. Bussey, R. J. High pressure studies. V. Activation volumes for combination and diffusion of geminate tert-butoxy radicals. J. Am. Chem. Soc. 1970, 92 (8): 2440. doi:10.1021/ja00711a039.

[7] Greenwood, N. N.; Earnshaw, A. Chemistry of the Elements 2nd. Oxford:Butterworth-Heinemann. 1997. ISBN 0-7506-3365-4.

[InorgChem-8] 8.0 ^8.1 Catherine E. Housecroft; Alan G. Sharpe. Chapter 15: The group 15 elements. Inorganic Chemistry 3rd. Pearson. 2008: 468. ISBN 978-0-13-175553-6.

[mend-9] G. David Mendenhall (1974), "Convenient synthesis of silver hyponitrite". Journal of the American Chemical society, volume 96, issue 15, page 5000. doi:10.1021/ja00822a054

[partin-10] James Riddick Partington and Chandulal Chhotalal Shah (1931), "Investigations on hyponitrites. Part I. Sodium hyponitrite: preparation and properties". Journal of the Chemical Society (Resumed), paper CCLXXXII, pages 2071-2080. doi:10.1039/JR9310002071

[polyhydr-11] C.N. Polydoropoulos, S.D. Voliotis (1967), "Sodium hyponitrite hexahydrate". Journal of Inorganic and Nuclear Chemistry, volume 29, issue 12, pages 2899–2901. doi:10.1016/0022-1902(67)80121-0

[stucky-12] 12.0 ^12.1 ^12.2 Gary L. Stucky, Jack L. Lambert, R. Dean Dragsdorf (1969), "The hydrates of sodium hyponitrite". Journal of Inorganic and Nuclear Chemistry, volume 31, issue 1, pages 29–32 doi:10.1016/0022-1902(69)80050-3

[conner-13] Charlotte N. Conner, Caroline E. Donald, Martin N. Hughes, Christina Sami (1989), "The molar absorptivity of sodium hyponitrite". Polyhedron, volume 8, issue 21, pages 2621-2622. doi:10.1016/S0277-5387(00)81166-3

[hughN2O4-14] M. N. Hughes and H. G. Nicklin (1969), "The action of dinitrogen tetroxide on sodium hyponitrite". Journal of the Chemical Society D: Chemical Communications, volume 1969, issue 2, page 80a. doi:10.1039/C2969000080A

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