Difference between revisions of "Manganese tetrafluoride"
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==Preparation== | ==Preparation== | ||
Manganese tetrafluoride was first unequivocally prepared in 1961{{#tag:ref|Reports of the preparation of MnF<sub>4</sub> date back to the nineteenth century,<ref>{{citation | first = W. H. | last = Melville | title = Contribution towards the History of the Fluorides of Manganese | journal = Proc. Am. Acad. Arts Sci. | volume = 12 | year = 1876 | pages = 228–34 | url = http://www.jstor.org/stable/25138452}}.</ref> but are inconsistent with the now-known chemistry of the genuine compound. However, the more stable hexafluoromanganate(IV) compounds were prepared as early as 1899.<ref>{{citation | first1 = R. F. | last1 = Weinland | first2 = O. | last2 = Lauenstein | journal = Z. Anorg. Allg. Chem. | year = 1899 | volume = 20 | page = 40}}.</ref>|group=Note}} by the reaction of [[manganese(II) fluoride]] (or other Mn<sup>II</sup> compounds) with a stream of [[fluorine]] gas at 550 °C: the MnF<sub>4</sub> sublimes into the gas stream and condenses onto a [[cold finger]].<ref>{{citation | title = Mangantetrafluorid, MnF<sub>4</sub> | first1 = Rudolf | last1 = Hoppe | first2 = Wolfgang | last2 = Dähne | first3 = Wilhelm | last3 = Klemm | journal = Naturwissenschaften | year = 1961 | volume = 48 | issue = 11 | page = 429 | doi = 10.1007/BF00621676}}.</ref><ref>{{citation | first1 = Rudolf | last1 = Hoppe | first2 = Wolfgang | last2 = Dähne | first3 = Wilhelm | last3 = Klemm | title = Mangantetrafluorid mit einem Anhang über LiMnF<sub>5</sub> und LiMnF<sub>4</sub> | journal = Justus Liebigs Ann. Chem. | volume = 658 | issue = 1 | pages = 1–5 | year = 1962 | doi = 10.1002/jlac.19626580102}}.</ref> This is till the commonest method of preparation, although the sublimation can be avoided by operating at increased fluorine pressure and mechanically agitating the powder to avoid sintering of the grains.<ref name="AstorPrepn"/><ref name="SolvayPrepn">{{citation | inventor1-last = Seseke-Koyro | inventor1-first = Ulrich | inventor2-last = Garcia-Juan | inventor2-first = Placido | inventor3-last = Palsherm | inventor3-first = Stefan | inventor4-last = Schulz | inventor4-first = Alf | assignee = Solvay Fluor | title = Method for preparing manganese tetrafluoride | country-code = WO | description = PCT Appl. | publication-number = 2009074560 | publication-date = 2009-06-18}}.</ref> The reaction can also be carried out starting from [[manganese]] powder in a [[fluidized bed]].<ref>{{citation | first1 = H. | last1 = Roesky | first2 = O. | last2 = Glemser | title = A New Preparation of Manganese Tetrafluoride | journal = Angew. Chem., Int. Ed. Engl. | volume = 2 | issue = 10 | page = 626 | year = 1963 | doi = 10.1002/anie.196306262}}.</ref><ref>{{citation | first1 = Herbert W. | last1 = Roesky | first2 = Oskar | last2 = Glemser | first3 = Karl-Heinz | last3 = Hellberg | title = Darstellung von Metallfluoriden in der Wirbelschicht | journal = Chem. Ber. | volume = 98 | issue = 6 | pages = 2046–48 | year = 1965 | doi = 10.1002/cber.19650980642}}.</ref> | Manganese tetrafluoride was first unequivocally prepared in 1961{{#tag:ref|Reports of the preparation of MnF<sub>4</sub> date back to the nineteenth century,<ref>{{citation | first = W. H. | last = Melville | title = Contribution towards the History of the Fluorides of Manganese | journal = Proc. Am. Acad. Arts Sci. | volume = 12 | year = 1876 | pages = 228–34 | url = http://www.jstor.org/stable/25138452}}.</ref> but are inconsistent with the now-known chemistry of the genuine compound. However, the more stable hexafluoromanganate(IV) compounds were prepared as early as 1899.<ref>{{citation | first1 = R. F. | last1 = Weinland | first2 = O. | last2 = Lauenstein | journal = Z. Anorg. Allg. Chem. | year = 1899 | volume = 20 | page = 40}}.</ref>|group=Note}} by the reaction of [[manganese(II) fluoride]] (or other Mn<sup>II</sup> compounds) with a stream of [[fluorine]] gas at 550 °C: the MnF<sub>4</sub> sublimes into the gas stream and condenses onto a [[cold finger]].<ref>{{citation | title = Mangantetrafluorid, MnF<sub>4</sub> | first1 = Rudolf | last1 = Hoppe | first2 = Wolfgang | last2 = Dähne | first3 = Wilhelm | last3 = Klemm | journal = Naturwissenschaften | year = 1961 | volume = 48 | issue = 11 | page = 429 | doi = 10.1007/BF00621676}}.</ref><ref>{{citation | first1 = Rudolf | last1 = Hoppe | first2 = Wolfgang | last2 = Dähne | first3 = Wilhelm | last3 = Klemm | title = Mangantetrafluorid mit einem Anhang über LiMnF<sub>5</sub> und LiMnF<sub>4</sub> | journal = Justus Liebigs Ann. Chem. | volume = 658 | issue = 1 | pages = 1–5 | year = 1962 | doi = 10.1002/jlac.19626580102}}.</ref> This is till the commonest method of preparation, although the sublimation can be avoided by operating at increased fluorine pressure and mechanically agitating the powder to avoid sintering of the grains.<ref name="AstorPrepn"/><ref name="SolvayPrepn">{{citation | inventor1-last = Seseke-Koyro | inventor1-first = Ulrich | inventor2-last = Garcia-Juan | inventor2-first = Placido | inventor3-last = Palsherm | inventor3-first = Stefan | inventor4-last = Schulz | inventor4-first = Alf | assignee = Solvay Fluor | title = Method for preparing manganese tetrafluoride | country-code = WO | description = PCT Appl. | publication-number = 2009074560 | publication-date = 2009-06-18}}.</ref> The reaction can also be carried out starting from [[manganese]] powder in a [[fluidized bed]].<ref>{{citation | first1 = H. | last1 = Roesky | first2 = O. | last2 = Glemser | title = A New Preparation of Manganese Tetrafluoride | journal = Angew. Chem., Int. Ed. Engl. | volume = 2 | issue = 10 | page = 626 | year = 1963 | doi = 10.1002/anie.196306262}}.</ref><ref>{{citation | first1 = Herbert W. | last1 = Roesky | first2 = Oskar | last2 = Glemser | first3 = Karl-Heinz | last3 = Hellberg | title = Darstellung von Metallfluoriden in der Wirbelschicht | journal = Chem. Ber. | volume = 98 | issue = 6 | pages = 2046–48 | year = 1965 | doi = 10.1002/cber.19650980642}}.</ref> | ||
| + | |||
| + | Other preparations of MnF<sub>4</sub> include the fluorination of MnF<sub>2</sub> with [[krypton difluoride]], or with F<sub>2</sub> in liquid [[hydrogen fluoride]] solution under [[ultraviolet light]]. Manganese tetrafluoride has also been prepared (but not isolated) in an acid–base reaction between [[antimony pentafluoride]] and K<sub>2</sub>MnF<sub>6</sub> as part of a chemical synthesis of elemental fluorine. | ||
| + | |||
| + | ==Chemistry== | ||
| + | ===Decomposition=== | ||
| + | |||
| + | ===Other reactions=== | ||
| + | |||
| + | ==Fluoromanganate(IV) complexes== | ||
==Notes and references== | ==Notes and references== | ||
Revision as of 08:36, 12 September 2010
| Manganese tetrafluoride | |
|---|---|
| IUPAC name | manganese tetrafluoride |
| Other names | manganese(IV) fluoride |
| Identifiers | |
| InChI | InChI=1/4FH.Mn/h4*1H;/q;;;;+4/p-4 |
| Standard InChI | InChI=1S/4FH.Mn/h4*1H;/q;;;;+4/p-4 |
| Standard InChIKey | KWKYNMDHPVYLQQ-UHFFFAOYSA-J |
| CAS number | [] |
| Properties | |
| Chemical formula | MnF4 |
| Molar mass | 130.93 g mol−1 |
| Appearance | blue solid |
| Melting point |
70 °C decomp. |
| Solubility in water | reacts violently |
| Related compounds | |
| Other cations | Manganese(II) fluoride Manganese(III) fluoride |
| Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa) | |
Manganese tetrafluoride, MnF4, is the highest fluoride of manganese. It is used as a powerful oxidizing agent and as a means of purifying elemental fluorine.[1][2]
Contents
Preparation
Manganese tetrafluoride was first unequivocally prepared in 1961[Note 1] by the reaction of manganese(II) fluoride (or other MnII compounds) with a stream of fluorine gas at 550 °C: the MnF4 sublimes into the gas stream and condenses onto a cold finger.[5][6] This is till the commonest method of preparation, although the sublimation can be avoided by operating at increased fluorine pressure and mechanically agitating the powder to avoid sintering of the grains.[1][7] The reaction can also be carried out starting from manganese powder in a fluidized bed.[8][9]
Other preparations of MnF4 include the fluorination of MnF2 with krypton difluoride, or with F2 in liquid hydrogen fluoride solution under ultraviolet light. Manganese tetrafluoride has also been prepared (but not isolated) in an acid–base reaction between antimony pentafluoride and K2MnF6 as part of a chemical synthesis of elemental fluorine.
Chemistry
Decomposition
Other reactions
Fluoromanganate(IV) complexes
Notes and references
Notes
References
- ↑ 1.0 1.1 Torisu, Junichi; Oka, Masakazu; Kuznetsov, Andrey Sergeyevich, et al. (Astor Electronics/Showa Denko) Method of manufacturing manganese tetrafluoride. WO PCT Appl. 2006033480, published 30 March 2006.
- ↑ Seseke-Koyro, Ulrich; Garcia-Juan, Placido; Palsherm, Stefan, et al. (Solvay Fluor) Process for the purification of elemental fluorine. WO PCT Appl. 2009074562, published 18 June 2009.
- ↑ Melville, W. H. Contribution towards the History of the Fluorides of Manganese. Proc. Am. Acad. Arts Sci. 1876, 12, 228–34, <http://www.jstor.org/stable/25138452>.
- ↑ Weinland, R. F.; Lauenstein, O. Z. Anorg. Allg. Chem. 1899, 20, 40.
- ↑ Hoppe, Rudolf; Dähne, Wolfgang; Klemm, Wilhelm Mangantetrafluorid, MnF4. Naturwissenschaften 1961, 48 (11), 429. DOI: 10.1007/BF00621676.
- ↑ Hoppe, Rudolf; Dähne, Wolfgang; Klemm, Wilhelm Mangantetrafluorid mit einem Anhang über LiMnF5 und LiMnF4. Justus Liebigs Ann. Chem. 1962, 658 (1), 1–5. DOI: 10.1002/jlac.19626580102.
- ↑ Seseke-Koyro, Ulrich; Garcia-Juan, Placido; Palsherm, Stefan, et al. (Solvay Fluor) Method for preparing manganese tetrafluoride. WO PCT Appl. 2009074560, published 18 June 2009.
- ↑ Roesky, H.; Glemser, O. A New Preparation of Manganese Tetrafluoride. Angew. Chem., Int. Ed. Engl. 1963, 2 (10), 626. DOI: 10.1002/anie.196306262.
- ↑ Roesky, Herbert W.; Glemser, Oskar; Hellberg, Karl-Heinz Darstellung von Metallfluoriden in der Wirbelschicht. Chem. Ber. 1965, 98 (6), 2046–48. DOI: 10.1002/cber.19650980642.
Further reading
- Gubkina, N. I.; Sokolov, Sergey V.; Krylov, E. I. Fluorides of High Oxidising Power and Their Application to the Preparation of Organic Fluorine Compounds. Russ. Chem. Rev. 1966, 35 (12), 930–41. DOI: 10.1070/RC1966v035n12ABEH001550.
- Ehlert, T. C.; Hsia, M. Mass spectrometric and thermochemical studies of the manganese fluorides. J. Fluorine Chem. 1972, 2 (1), 33–51. DOI: 10.1016/S0022-1139(00)83113-9.
- Hoppe, R.; Müller, B.; Burgess, J.; Peacock, R. D.; Sherry, R. The enthalpy of formation of manganese tetrafluoride. J. Fluorine Chem. 1980, 16 (2), 189–91. DOI: 10.1016/S0022-1139(00)82393-3.
- Christe, Karl O. Chemical synthesis of elemental fluorine. Inorg. Chem. 1986, 25 (21), 3721–24. DOI: 10.1021/ic00241a001.
- Adelhelm, M.; Jacob, E. MnF4: preparation and properties. J. Fluorine Chem. 1991, 54 (1–3), 21. DOI: 10.1016/S0022-1139(00)83531-9.
- Mazej, Z. Room temperature syntheses of MnF3, MnF4 and hexafluoromanganete(IV) salts of alkali cations. J. Fluorine Chem. 2002, 114 (1), 75–80. DOI: 10.1016/S0022-1139(01)00566-8.
External links
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See also the corresponding article on Wikipedia. |
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