Difference between revisions of "Manganese tetrafluoride"
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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. | + | Other preparations of MnF<sub>4</sub> include the fluorination of MnF<sub>2</sub> with [[krypton difluoride]],<ref>{{citation | first1 = Karel | last1 = Lutar | first2 = Adolf | last2 = Jesih | first3 = Boris | last3 = Žemva | title = KrF<sub>2</sub>/MnF<sub>4</sub> adducts from KrF<sub>2</sub>/MnF<sub>2</sub> interaction in HF as a route to high purity MnF<sub>4</sub> | journal = Polyhedron | volume = 7 | issue = 13 | year = 1988 | pages = 1217–19 | doi = 10.1016/S0277-5387(00)81212-7}}.</ref> or with F<sub>2</sub> in liquid [[hydrogen fluoride]] solution under [[ultraviolet light]].<ref>{{citation | first = Z. | last = Mazej | title = Room temperature syntheses of MnF<sub>3</sub>, MnF<sub>4</sub> and hexafluoromanganete(IV) salts of alkali cations | journal = J. Fluorine Chem. | volume = 114 | issue = 1 | year = 2002 | pages = 75–80 | doi = 10.1016/S0022-1139(01)00566-8}}.</ref> 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.<ref>{{citation | first = Karl O. | last = Christe | year = 1986 | title = Chemical synthesis of elemental fluorine | journal = Inorg. Chem. | volume = 25 | issue = 21 | pages = 3721–24 | doi = 10.1021/ic00241a001}}.</ref> |
==Chemistry== | ==Chemistry== | ||
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===Other reactions=== | ===Other reactions=== | ||
| + | |||
| + | ==Applications== | ||
==Fluoromanganate(IV) complexes== | ==Fluoromanganate(IV) complexes== | ||
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===References=== | ===References=== | ||
| − | {{reflist}} | + | {{reflist|2}} |
===Further reading=== | ===Further reading=== | ||
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*{{citation | first1 = T. C. | last1 = Ehlert | first2 = M. | last2 = Hsia | title = Mass spectrometric and thermochemical studies of the manganese fluorides | journal = J. Fluorine Chem. | volume = 2 | issue = 1 | year = 1972 | pages = 33–51 | doi = 10.1016/S0022-1139(00)83113-9}}. | *{{citation | first1 = T. C. | last1 = Ehlert | first2 = M. | last2 = Hsia | title = Mass spectrometric and thermochemical studies of the manganese fluorides | journal = J. Fluorine Chem. | volume = 2 | issue = 1 | year = 1972 | pages = 33–51 | doi = 10.1016/S0022-1139(00)83113-9}}. | ||
*{{citation | first1 = R. | last1 = Hoppe | first2 = B. | last2 = Müller | first3 = J. | last3 = Burgess | first4 = R. D. | last4 = Peacock | first5 = R. | last5 = Sherry | title = The enthalpy of formation of manganese tetrafluoride | journal = J. Fluorine Chem. | volume = 16 | issue = 2 | year = 1980 | pages = 189–91 | doi = 10.1016/S0022-1139(00)82393-3}}. | *{{citation | first1 = R. | last1 = Hoppe | first2 = B. | last2 = Müller | first3 = J. | last3 = Burgess | first4 = R. D. | last4 = Peacock | first5 = R. | last5 = Sherry | title = The enthalpy of formation of manganese tetrafluoride | journal = J. Fluorine Chem. | volume = 16 | issue = 2 | year = 1980 | pages = 189–91 | doi = 10.1016/S0022-1139(00)82393-3}}. | ||
| − | |||
*{{citation | first1 = M. | last1 = Adelhelm | first2 = E. | last2 = Jacob | title = MnF<sub>4</sub>: preparation and properties | journal = J. Fluorine Chem. | volume = 54 | issue = 1–3 | year = 1991 | page = 21 | doi = 10.1016/S0022-1139(00)83531-9}}. | *{{citation | first1 = M. | last1 = Adelhelm | first2 = E. | last2 = Jacob | title = MnF<sub>4</sub>: preparation and properties | journal = J. Fluorine Chem. | volume = 54 | issue = 1–3 | year = 1991 | page = 21 | doi = 10.1016/S0022-1139(00)83531-9}}. | ||
| − | |||
==External links== | ==External links== | ||
Revision as of 09:44, 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,[10] or with F2 in liquid hydrogen fluoride solution under ultraviolet light.[11] 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.[12]
Chemistry
Decomposition
Other reactions
Applications
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.
- ↑ Lutar, Karel; Jesih, Adolf; Žemva, Boris KrF2/MnF4 adducts from KrF2/MnF2 interaction in HF as a route to high purity MnF4. Polyhedron 1988, 7 (13), 1217–19. DOI: 10.1016/S0277-5387(00)81212-7.
- ↑ 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.
- ↑ Christe, Karl O. Chemical synthesis of elemental fluorine. Inorg. Chem. 1986, 25 (21), 3721–24. DOI: 10.1021/ic00241a001.
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.
- Adelhelm, M.; Jacob, E. MnF4: preparation and properties. J. Fluorine Chem. 1991, 54 (1–3), 21. DOI: 10.1016/S0022-1139(00)83531-9.
External links
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See also the corresponding article on Wikipedia. |
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