For faster navigation, this Iframe is preloading the Wikiwand page for 無機非水溶劑.

無機非水溶劑

無機非水溶劑(inorganic nonaqueous solvent)就是指不是,也不是有機化合物溶劑。此類溶劑會在化學研究以及化工領域中,會用在一些有水時無法發生的化學反應或是需要特殊條件的化學反應。無機非水溶劑可以分成兩類:質子溶劑(protic solvent)或是非質子溶劑(aprotic solvents)。早期對無機非水溶劑的研究主要是在液氨氟化氫硫酸,也包括一些特殊的溶劑,像是聯氨二氯氧化硒[1]

屬於質子溶劑的無機非水溶劑

[编辑]

主要的有:氟化氫硫酸氰化氫。氨(以及許多胺類)適合產生高還原性的化學溶液,因為N-H鍵不會被還原。像电子盐鹼化物的化學都是在胺類溶劑下發生。

HF和SbF5的混合物是超强酸溶液的基礎。利用此混合物,可以分離出硫化氫的共軛酸:

H2S + HF + SbF5 → [H3S]SbF6

自偶電離

[编辑]

這類溶劑中的限制酸是溶劑陽離子,像是水中的H3O+水合氢离子)。若比限制酸還容易提供氫離子的酸,就會是此溶劑下中的強酸,大部份(其至完全)會以解離態存在。而這類溶劑中的限制鹼是溶劑陰離子,像是水中的OH-氫氧根離子)。比限制鹼還容易吸引質子的鹼無法存在在此溶液中,因為會和溶劑反應。

例如,液氨中的可以存在的最强酸是其自偶电离产生的阳离子,即離子NH4+,其在水中的pKa值為9.25;可以存在的最强鹼是NH2-,NH2離子是比氫氧根更強的鹼,因此不會存在在水溶液中。氨的pKa估計會到34(作為比較,水是14[2][3])。

屬於非質子溶劑的無機非水溶劑

[编辑]

主要的有:二氧化硫磺酰氟氯四氧化二氮三氯化銻三氟化溴。這類溶劑適用研究高親電性或是高氧化性的化合物或是離子。其中許多(像SO2、SO2ClF、N2O4)在室溫下是氣態,因此需要用舒伦克线(vacuum-line)處理方式。

可以用[IS7]+和[BrS7]+的製備來說明。這些高親電性的鹽是在SO2溶液中製備[4]。[SBr3]+鹽的製備也需要用SO2和SO2FCl的混合物作為溶劑[5]。磺酰氟氯常用來合成稀有气体化合物[6]

化合物的製備常需要在氟化氫或是五氟化溴中進行,這些物質會溶解二氟化氙以及其衍生物[7]磺酰氟氯也常作為強氧化劑[8]

若要處理強氧化劑時,可以用磺酰氟氯作溶劑。例如可以用磺酰氟氯溶劑來產生(及研究)游離態的碳正离子[9]芳基正離子[10]

自偶電離

[编辑]

許多無機溶劑都會有自偶電離反應。依照酸和鹼的溶劑系統定義,溶劑的自偶電離會產生酸和鹼。相關的自偶電離如下:

2BrF3 ⇌} BrF2+ + BrF4
N2O4 ⇌ NO+亚硝𬭩离子)+ NO3 (硝酸根離子)
2SbCl3 ⇌ SbCl2+ + SbCl4
2POCl3 ⇌ POCl2+ + POCl4

依照溶剂理论,酸是會增加溶劑正離子(solvonium)的物質,鹼是會增加溶劑負離子(solvate)的物質,而溶劑正離子和溶劑負離子會在純溶劑中解離而平衡。

二氧化硫溶劑SO2結構相對簡單,因此不會自偶電離。

相關條目

[编辑]

參考資料

[编辑]
  1. ^ Audrieth, Ludwig Frederick. Non-aqueous Solvents; Applications as Media for Chemical Reactions. Wiley. 1953. 
  2. ^ Meister, Erich C.; Willeke, Martin; Angst, Werner; Togni, Antonio; Walde, Peter. Confusing Quantitative Descriptions of Brønsted-Lowry Acid-Base Equilibria in Chemistry Textbooks – A Critical Review and Clarifications for Chemical Educators. Helvetica Chimica Acta. 2014, 97 (1): 1–31. ISSN 1522-2675. doi:10.1002/hlca.201300321 (英语). 
  3. ^ Silverstein, Todd P.; Heller, Stephen T. pKa Values in the Undergraduate Curriculum: What Is the Real pKa of Water?. Journal of Chemical Education. 2017-06-13, 94 (6): 690–695. Bibcode:2017JChEd..94..690S. ISSN 0021-9584. doi:10.1021/acs.jchemed.600623. 
  4. ^ Murchie, M. P.; Passmore, J.; Wong, C.-M. Iodine and Bromine Polysulfur Hexafluoroarsenate(V) and Hexafluoroantimonate(V). Inorganic Syntheses. Inorganic Syntheses 27. 1990: 332–339. ISBN 9780470132586. doi:10.1002/9780470132586.ch67. 
  5. ^ Murchie, Mike; Passmore, Jack. Tribromosulfur(IV) Hexafluoroarsenate(V). Inorganic Syntheses. Inorganic Syntheses 24. 1986: 76–79. ISBN 9780470132555. doi:10.1002/9780470132555.ch23. 
  6. ^ Koppe, Karsten; Bilir, Vural; Frohn, Hermann-J.; Mercier, Hélène P. A.; Schrobilgen, Gary J. Syntheses, Solution Multi-NMR Characterization, and Reactivities of [C6F5Xe]+Salts of Weakly Coordinating Borate Anions, [BY4] (Y = CF3, C6F5, CN, or OTeF5). Inorganic Chemistry. 2007, 46 (22): 9425–9437. PMID 17902647. doi:10.1021/ic7010138. 
  7. ^ Pointner BE, Suontamo RJ, Schrobilgen GJ. Syntheses and X-ray crystal structures of alpha- and beta-[XeO
    2
    F][SbF
    6
    ]
    , [XeO
    2
    F][AsF
    6
    ]
    , [FO
    2
    XeFXeO
    2
    F][AsF
    6
    ]
    , and [XeF
    5
    ][SbF
    6
    )]·XeOF
    4
    and computational studies of the XeO
    2
    F+
    and FO
    2
    XeFXeO
    2
    F+
    cations and related species. Inorg Chem. 2006 Feb 20;45(4):1517-34.
  8. ^ Mercier HP, Moran MD, Sanders JC, Schrobilgen GJ, Suontamo RJ. "Synthesis, structural characterization, and computational study of the strong oxidant salt [XeOTeF
    5
    ][Sb(OTeF
    5
    )
    6
    ]·SO
    2
    ClF
    ." Inorg Chem. 2005 Jan 10;44(1):49-60.
  9. ^ Mercier HP, Moran MD, Schrobilgen GJ, Steinberg C, Suontamo RJ. The syntheses of carbocations by use of the noble-gas oxidant, [XeOTeF
    5
    ][Sb(OTeF
    5
    )
    6
    ]
    : the syntheses and characterization of the CX+
    3
    (X = Cl, Br, OTeF
    5
    ) and CBr(OTeF
    5
    )+
    2
    cations and theoretical studies of CX+
    3
    and BX
    3
    (X = F, Cl, Br, I, OTeF
    5
    ). J Am Chem Soc. 2004 May 5;126(17):5533-48.
  10. ^ V D Shteingarts, Polyfluorinated Arenonium Ions, Russ. Chem Rev 1981;50(8):735-748.

外部連結

[编辑]


{{bottomLinkPreText}} {{bottomLinkText}}
無機非水溶劑
Listen to this article

This browser is not supported by Wikiwand :(
Wikiwand requires a browser with modern capabilities in order to provide you with the best reading experience.
Please download and use one of the following browsers:

This article was just edited, click to reload
This article has been deleted on Wikipedia (Why?)

Back to homepage

Please click Add in the dialog above
Please click Allow in the top-left corner,
then click Install Now in the dialog
Please click Open in the download dialog,
then click Install
Please click the "Downloads" icon in the Safari toolbar, open the first download in the list,
then click Install
{{::$root.activation.text}}

Install Wikiwand

Install on Chrome Install on Firefox
Don't forget to rate us

Tell your friends about Wikiwand!

Gmail Facebook Twitter Link

Enjoying Wikiwand?

Tell your friends and spread the love:
Share on Gmail Share on Facebook Share on Twitter Share on Buffer

Our magic isn't perfect

You can help our automatic cover photo selection by reporting an unsuitable photo.

This photo is visually disturbing This photo is not a good choice

Thank you for helping!


Your input will affect cover photo selection, along with input from other users.

X

Get ready for Wikiwand 2.0 🎉! the new version arrives on September 1st! Don't want to wait?