次錳酸鹽

次錳酸鹽
英文名	Hypomanganate
別名	錳(V)酸鹽
識別
CAS編號	14333-15-4
性質
化學式	MnO3−; 4
摩爾質量	118.94 g·mol⁻¹
	若非註明，所有數據均出自標準狀態（25 ℃，100 kPa）下。

次錳酸根，又稱錳(V)酸根，是一種錳的含氧酸根（英語：Oxyanion），化學式 MnO3−
4，次錳酸鹽則是這種陰離子形成的鹽。

次錳酸鹽通常是亮藍色的。^[1]^[2]最著名的次錳酸鹽是次錳酸鉀 K
3MnO
4，但次錳酸鈉 Na
3MnO
4、次錳酸鋇 Ba
3(MnO
4)
2和鉀鋇鹽 KBaMnO
4都是已知的。^[3]在磷灰石^[4]^[5]和鈣鐵鋁石（英語：brownmillerite）^[6]的人造變種中，次錳酸根可以取代其中的磷酸根 PO3−
4。

歷史[編輯]

次錳酸根於1946年由Hermann Lux首次報告。他通過氧化鈉 Na
2O、二氧化錳 MnO
2和亞硝酸鈉 NaNO
2在500 °C的反應，得到了亮藍色的次錳酸鈉。^[7]^[3]他也從其氫氧化鈉溶液結晶出了十水合物 Na
3MnO
4·10H
2O。

結構和性質[編輯]

次錳酸根是四面體形的含氧酸根（英語：Oxyanion），結構類似硫酸根、錳酸根和高錳酸根。作為d²電子構型的四面體形分子，它在基態下為三線態。^[3]

次錳酸根呈亮藍色，^[1]最大吸收光譜λ_max = 670 nm（ε = 900 dm³ mol⁻¹ cm⁻¹）。^[8]^[9]

穩定性[編輯]

次錳酸鹽不穩定，會歧化成錳酸鹽和二氧化錳。^[10]^[1]在pH 14下，次錳酸鹽預測的電極電勢（英語：electrode potential）如下：^[11]^[12]^[13]

MnO2−
4 + e⁻ ⇌ MnO3−
4 E = +0.27 V

MnO3−
4 + e⁻ + 2 H₂O ⇌ MnO₂ + 4 OH⁻ E = +0.96 V

然而，歧化反應在強鹼性環境下（OH⁻濃度超過5–10 mol/L）會變慢。^[1]^[7]

這個歧化反應被認為有質子化的中間體 HMnO2−
4。^[13]它在反應 HMnO2−
4 ⇌ MnO3−
4 + H⁺中的pK_a為13.7 ± 0.2。^[14]然而，K₃MnO₄已經和Ca₂Cl(PO₄)共結晶，使人們可以研究次錳酸根的紫外-可見分光光度法。^[10]^[15]

製備[編輯]

次錳酸鹽可以由亞硫酸鹽、^[1]過氧化氫^[16]或扁桃酸^[9]小心還原錳酸鹽而成。

用處[編輯]

氟化釩酸鍶 Sr
5(VO
4)
3F中的一些釩酸根被次錳酸根取代後，可能可用於近紅外激光器中。^[17]

次錳酸鋇 Ba
3(MnO
4)
2有有趣的磁性性質。^[18]

參見[編輯]

二錳(III)酸鹽 Mn
2O6−
6
錳酸鹽 MnO2−
4
高錳酸鹽 MnO−
4

參考資料[編輯]

^ ^1.0 ^1.1 ^1.2 ^1.3 ^1.4 Greenwood, Norman N.; Earnshaw, A. Chemistry of the Elements. Oxford: Pergamon. 1984: 1221–22. ISBN 0-08-022057-6. .
^ Reinen, D.; Rauw, W.; Kesper, U.; Atanasov, M.; Güdel, H.U.; Hazenkamp, M.; Oetliker, U. Colour, luminescence and bonding properties of tetrahedrally coordinated chromium(IV), manganese(V) and iron(VI) in various oxide ceramics. Journal of Alloys and Compounds (Elsevier BV). 1997, 246 (1-2): 193–208. ISSN 0925-8388. doi:10.1016/s0925-8388(96)02461-9.
^ ^3.0 ^3.1 ^3.2 zur Loye, K. D.; Chance, W. M.; Yeon, J.; zur Loye, H.-C. Synthesis, Crystal Structure, and Magnetic Properties of the Oxometallates KBaMnO₄ and KBaAsO₄. Solid State Sciences. 2014, 37: 86–90. Bibcode:2014SSSci..37...86Z. doi:10.1016/j.solidstatesciences.2014.08.013 .
^ Dardenne, K.; Vivien, D.; Huguenin, D. Color of Mn(V)-Substituted Apatites A10((B, Mn)O4)6F2, A=Ba, Sr, Ca; B=P, V. Journal of Solid State Chemistry (Elsevier BV). 1999, 146 (2): 464–472. ISSN 0022-4596. doi:10.1006/jssc.1999.8394.
^ Grisafe, D.A.; Hummel, F.A. Pentavalent ion substitutions in the apatite structure part A. Crystal chemistry. Journal of Solid State Chemistry (Elsevier BV). 1970, 2 (2): 160–166. ISSN 0022-4596. doi:10.1016/0022-4596(70)90064-2.
^ Jiang, Peng; Li, Jun; Ozarowski, A.; Sleight, Arthur W.; Subramanian, M. A. Intense Turquoise and Green Colors in Brownmillerite-Type Oxides Based on Mn5+ in Ba2In2–xMnxO5+x. Inorganic Chemistry (American Chemical Society (ACS)). 2013-01-18, 52 (3): 1349–1357. ISSN 0020-1669. doi:10.1021/ic3020332.
^ ^7.0 ^7.1 Herrman Lux (1946): "Über Salze des fünfwertigen Mangans （頁面存檔備份，存於互聯網檔案館）." Zeitschrift für Naturforschung, volume 1, pages 281-283.
^ Carrington, A.; Symons, M. C. R., Structure and reactivity of the oxy-anions of transition metals. Part I. The manganese oxy-anions, J. Chem. Soc., 1956: 3373–80, doi:10.1039/JR9560003373
^ ^9.0 ^9.1 ^9.2 Lee, Donald G.; Chen, Tao, Reduction of manganate(VI) by mandelic acid and its significance for development of a general mechanism of oxidation of organic compounds by high-valent transition metal oxides, J. Am. Chem. Soc., 1993, 115 (24): 11231–36, doi:10.1021/ja00077a023 .
^ ^10.0 ^10.1 Cotton, F. Albert; Wilkinson, Geoffrey, Advanced Inorganic Chemistry 4th, New York: Wiley: 746, 1980, ISBN 0-471-02775-8 .
^ Weast, Robert C. (編). CRC Handbook of Chemistry and Physics 62nd. Boca Raton, FL: CRC Press. 1981: D-134. ISBN 0-8493-0462-8. .
^ Manganese – compounds – standard reduction potentials, WebElements, [2010-06-26], （原始內容存檔於2021-01-17） .
^ ^13.0 ^13.1 Sekula-Brzezińska, K.; Wrona, P. K.; Galus, Z., Rate of the MnO₄⁻/MnO₄²⁻ and MnO₄²⁻/MnO₄³⁻ electrode reactions in alkaline solutions at solid electrodes, Electrochim. Acta, 1979, 24 (5): 555–63, doi:10.1016/0013-4686(79)85032-X .
^ ^14.0 ^14.1 Rush, J. D.; Bielski, B. H. J., Studies of Manganate(V), -(VI), and -(VII) Tetraoxyanions by Pulse Radiolysis. Optical Spectra of Protonated Forms, Inorg. Chem., 1995, 34 (23): 5832–38, doi:10.1021/ic00127a022 .
^ Carrington, A.; Symons, M. C. R., Structure and reactivity of the oxy-anions of transition metals. Part I. The manganese oxy-anions, J. Chem. Soc., 1956: 3373–80, doi:10.1039/JR9560003373 .
^ Lee, Donald G.; Chen, Tao, Oxidation of hydrocarbons. 18. Mechanism of the reaction between permanganate and carbon-carbon double bonds, J. Am. Chem. Soc., 1989, 111 (19): 7534–38, doi:10.1021/ja00201a039 .
^ Merkle, Larry D.; Guyot, Yannick; Chai, Bruce H. T. Spectroscopic and laser investigations of Mn5+:Sr5(VO4)3F. Journal of Applied Physics (AIP Publishing). 1995-01-15, 77 (2): 474–480. ISSN 0021-8979. doi:10.1063/1.359585.
^ Stone, M. B.; Lumsden, M. D.; Qiu, Y.; Samulon, E. C.; Batista, C. D.; Fisher, I. R. Dispersive magnetic excitations in theS=1antiferromagnetBa3Mn2O8. Physical Review B (American Physical Society (APS)). 2008-04-02, 77 (13). ISSN 1098-0121. doi:10.1103/physrevb.77.134406.

[G&E-1] 1.0 ^1.1 ^1.2 ^1.3 ^1.4 Greenwood, Norman N.; Earnshaw, A. Chemistry of the Elements. Oxford: Pergamon. 1984: 1221–22. ISBN 0-08-022057-6. .

[Reinen-2] Reinen, D.; Rauw, W.; Kesper, U.; Atanasov, M.; Güdel, H.U.; Hazenkamp, M.; Oetliker, U. Colour, luminescence and bonding properties of tetrahedrally coordinated chromium(IV), manganese(V) and iron(VI) in various oxide ceramics. Journal of Alloys and Compounds (Elsevier BV). 1997, 246 (1-2): 193–208. ISSN 0925-8388. doi:10.1016/s0925-8388(96)02461-9.

[Loye-3] 3.0 ^3.1 ^3.2 zur Loye, K. D.; Chance, W. M.; Yeon, J.; zur Loye, H.-C. Synthesis, Crystal Structure, and Magnetic Properties of the Oxometallates KBaMnO₄ and KBaAsO₄. Solid State Sciences. 2014, 37: 86–90. Bibcode:2014SSSci..37...86Z. doi:10.1016/j.solidstatesciences.2014.08.013 .

[Dardenne-4] Dardenne, K.; Vivien, D.; Huguenin, D. Color of Mn(V)-Substituted Apatites A10((B, Mn)O4)6F2, A=Ba, Sr, Ca; B=P, V. Journal of Solid State Chemistry (Elsevier BV). 1999, 146 (2): 464–472. ISSN 0022-4596. doi:10.1006/jssc.1999.8394.

[Grisafe-5] Grisafe, D.A.; Hummel, F.A. Pentavalent ion substitutions in the apatite structure part A. Crystal chemistry. Journal of Solid State Chemistry (Elsevier BV). 1970, 2 (2): 160–166. ISSN 0022-4596. doi:10.1016/0022-4596(70)90064-2.

[Jiang-6] Jiang, Peng; Li, Jun; Ozarowski, A.; Sleight, Arthur W.; Subramanian, M. A. Intense Turquoise and Green Colors in Brownmillerite-Type Oxides Based on Mn5+ in Ba2In2–xMnxO5+x. Inorganic Chemistry (American Chemical Society (ACS)). 2013-01-18, 52 (3): 1349–1357. ISSN 0020-1669. doi:10.1021/ic3020332.

[Lux-7] 7.0 ^7.1 Herrman Lux (1946): "Über Salze des fünfwertigen Mangans （頁面存檔備份，存於互聯網檔案館）." Zeitschrift für Naturforschung, volume 1, pages 281-283.

[JCS-8] Carrington, A.; Symons, M. C. R., Structure and reactivity of the oxy-anions of transition metals. Part I. The manganese oxy-anions, J. Chem. Soc., 1956: 3373–80, doi:10.1039/JR9560003373

[Mandelate-9] 9.0 ^9.1 ^9.2 Lee, Donald G.; Chen, Tao, Reduction of manganate(VI) by mandelic acid and its significance for development of a general mechanism of oxidation of organic compounds by high-valent transition metal oxides, J. Am. Chem. Soc., 1993, 115 (24): 11231–36, doi:10.1021/ja00077a023 .

[C&W-10] 10.0 ^10.1 Cotton, F. Albert; Wilkinson, Geoffrey, Advanced Inorganic Chemistry 4th, New York: Wiley: 746, 1980, ISBN 0-471-02775-8 .

[11] Weast, Robert C. (編). CRC Handbook of Chemistry and Physics 62nd. Boca Raton, FL: CRC Press. 1981: D-134. ISBN 0-8493-0462-8. .

[12] Manganese – compounds – standard reduction potentials, WebElements, [2010-06-26], （原始內容存檔於2021-01-17） .

[Epot-13] 13.0 ^13.1 Sekula-Brzezińska, K.; Wrona, P. K.; Galus, Z., Rate of the MnO₄⁻/MnO₄²⁻ and MnO₄²⁻/MnO₄³⁻ electrode reactions in alkaline solutions at solid electrodes, Electrochim. Acta, 1979, 24 (5): 555–63, doi:10.1016/0013-4686(79)85032-X .

[PulseRad-14] 14.0 ^14.1 Rush, J. D.; Bielski, B. H. J., Studies of Manganate(V), -(VI), and -(VII) Tetraoxyanions by Pulse Radiolysis. Optical Spectra of Protonated Forms, Inorg. Chem., 1995, 34 (23): 5832–38, doi:10.1021/ic00127a022 .

[15] Carrington, A.; Symons, M. C. R., Structure and reactivity of the oxy-anions of transition metals. Part I. The manganese oxy-anions, J. Chem. Soc., 1956: 3373–80, doi:10.1039/JR9560003373 .

[H2O2-16] Lee, Donald G.; Chen, Tao, Oxidation of hydrocarbons. 18. Mechanism of the reaction between permanganate and carbon-carbon double bonds, J. Am. Chem. Soc., 1989, 111 (19): 7534–38, doi:10.1021/ja00201a039 .

[Merkle-17] Merkle, Larry D.; Guyot, Yannick; Chai, Bruce H. T. Spectroscopic and laser investigations of Mn5+:Sr5(VO4)3F. Journal of Applied Physics (AIP Publishing). 1995-01-15, 77 (2): 474–480. ISSN 0021-8979. doi:10.1063/1.359585.

[Stone-18] Stone, M. B.; Lumsden, M. D.; Qiu, Y.; Samulon, E. C.; Batista, C. D.; Fisher, I. R. Dispersive magnetic excitations in theS=1antiferromagnetBa3Mn2O8. Physical Review B (American Physical Society (APS)). 2008-04-02, 77 (13). ISSN 1098-0121. doi:10.1103/physrevb.77.134406.

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