氧的氟化物

氧的氟化物是一类只由氧和氟组成的化合物，通式O_nF₂（n = 1 至 6）。一共有七种氧的氟化物被发现:

二氟化氧 (OF₂)
二氟化二氧 (O₂F₂)
二氟化三氧，又称二氟化臭氧（O₃F₂）^[1]^[2]
二氟化四氧（O₄F₂）^[3]
二氟化五氧（O₅F₂）
二氟化六氧（O₆F₂）^[4]
一氟化二氧自由基（O₂F）

二氟化四氧

氧的氟化物是具有高能量的强氧化剂，可以瞬时或以受控的速率释放其能量。因此，这些化合物作为喷气推进系统中的潜在燃料备受关注。^[5]

性质

这里有三种最常见的氧的氟化物 – 二氟化氧 (OF₂), 二氟化二氧(O₂F₂) 和二氟化三氧(O₃F₂)的性质。

二氟化氧(OF2)

二氟化氧的一般制备方法是用氟单质氟化氢氧化钠而成:

{\ce {2F2 + 2NaOH -> OF2 + 2NaF + H2O}}

OF₂ 是一种无色气体，在128 K以下是一种黄色液体。它有一种不愉快的恶臭，并且有毒。^[3] 它可以和氢卤酸反应，生成相应的卤素单质:

{\ce {OF2 + 4HCl -> 2Cl2 + 2HF + 2H2O}}

它也可以替代卤化物里的卤素离子，生成氟化物。^[3] 它是一种高效的氟化剂和强氧化剂。当和不饱和的氮的氟化物（例如：四氟肼）放电时，会产生三氟化氮和氮氧化物。^[6]^[7]

二氟化二氧(O2F2)

O₂F₂ 是一种橙色固体，由液态 O₂ 和 F₂ 在 -196 °C照射紫外光而成。^[8] 它只在-160 °C 以下稳定。^[9] 氧的氟化物都是由氧气和氟气放电而成，O₂F₂ 也不例外。^[10]

{\ce {{O2}+F2->[{\text{放电}}][{\text{183 °C}}]O2F2}}

它是一种橙色固体，极易分解成 O₂ 和 F₂ ，温度接近于沸点 216 K。^[3]

O₂F₂ 可以和红磷反应, 即使在 -196 °C 仍会爆炸。三氟氯甲烷可以用来减缓爆炸力度。^[9]

二氟化三氧(O3F2)

O₃F₂ 是一种血红色液体。它在 90 K 就是液体，与熔点 109 K 的O₂F₂不同，可用来分辨两者。^[11]^[3]

和其他氧的氟化物一样， O₃F₂ 极易分解，于 115 K 迅速分解，反应如下:

{\ce {2 O3F2 -> O2 + 2O2F2}}

参考资料

[1]
Solomon, I. J. et al. Additional Studies Concerning the Existence of O₃F₂. Journal of the American Chemical Society. 1968, 90 (20): 5408–5411. doi:10.1021/ja01022a014.
[2]
Misochko, Eugenii Ya, Alexander V. Akimov, Charles A. Wight. Infrared spectroscopic observation of the stabilized Intermediate complex FO₃ formed by reaction of mobile Fluorine atoms with ozone molecules Trapped in an Argon Matrix. The Journal of Physical Chemistry A. 1999, 103 (40): 7972–7977. Bibcode:1999JPCA..103.7972M. doi:10.1021/jp9921194.
[3]
Streng, A. G. The Oxygen Fluorides. Chemical Reviews. 1963, 63 (6): 607–624. doi:10.1021/cr60226a003.
[4]
Streng, A. G., A. V. Grosse. Two New Fluorides of Oxygen, O₅F₂ and O₆F₂. Journal of the American Chemical Society. 1966, 88: 169–170. doi:10.1021/ja00953a035.
[5]
Jäger, Susanne et al. Fluorine and Oxygen. Fluorine. Berlin, Heidelberg: Springer. 1986: 1–161.
[6]
Nikitin, Igor Vasil'evich, and V. Ya Rosolovskii. Oxygen Fluorides and Dioxygenyl Compounds. Russian Chemical Reviews. 1971, 40 (11): 889–900. Bibcode:1971RuCRv..40..889N. doi:10.1070/rc1971v040n11abeh001981.
[7]
Lawless, Edward W., Ivan C. Smith. Inorganic high-energy oxidizers: synthesis, structure, and properties. M. Dekker. 1968.
[8]
Marx, Rupert, Konrad Seppelt. Structure investigations on oxygen fluorides. Dalton Transactions. 2015, 44 (45): 19659–19662. PMID 26351980. doi:10.1039/c5dt02247a.
[9]
Solomon, Irvine J. Research on Chemistry of ${\ce {O3F2}}$ and ${\ce {O2F2}}$ . No. IITRI-C227-6. IIT RESEARCH INST CHICAGO IL, 1964.
[10]
Goetschel, Charles T. et al. Low-Temperature Radiation Chemistry. I. Preparation of Oxygen Fluorides and Dioxygenyl Tetrafluoroborate. Journal of the American Chemical Society. 1969, 91 (17): 4702–4707. doi:10.1021/ja01045a020.
[11]
De Marco, Ronald A., and Jean'ne M. Shreeve . "Fluorinated Peroxides." Advances in Inorganic Chemistry and Radiochemistry. Vol. 16. Academic Press, 1974. 109-176.

参见

氯的氧化物

[1] [1]
Solomon, I. J. et al. Additional Studies Concerning the Existence of O₃F₂. Journal of the American Chemical Society. 1968, 90 (20): 5408–5411. doi:10.1021/ja01022a014.

[2] [2]
Misochko, Eugenii Ya, Alexander V. Akimov, Charles A. Wight. Infrared spectroscopic observation of the stabilized Intermediate complex FO₃ formed by reaction of mobile Fluorine atoms with ozone molecules Trapped in an Argon Matrix. The Journal of Physical Chemistry A. 1999, 103 (40): 7972–7977. Bibcode:1999JPCA..103.7972M. doi:10.1021/jp9921194.

[:0-3] [3]
Streng, A. G. The Oxygen Fluorides. Chemical Reviews. 1963, 63 (6): 607–624. doi:10.1021/cr60226a003.

[4] [4]
Streng, A. G., A. V. Grosse. Two New Fluorides of Oxygen, O₅F₂ and O₆F₂. Journal of the American Chemical Society. 1966, 88: 169–170. doi:10.1021/ja00953a035.

[5] [5]
Jäger, Susanne et al. Fluorine and Oxygen. Fluorine. Berlin, Heidelberg: Springer. 1986: 1–161.

[:1-6] [6]
Nikitin, Igor Vasil'evich, and V. Ya Rosolovskii. Oxygen Fluorides and Dioxygenyl Compounds. Russian Chemical Reviews. 1971, 40 (11): 889–900. Bibcode:1971RuCRv..40..889N. doi:10.1070/rc1971v040n11abeh001981.

[7] [7]
Lawless, Edward W., Ivan C. Smith. Inorganic high-energy oxidizers: synthesis, structure, and properties. M. Dekker. 1968.

[8] [8]
Marx, Rupert, Konrad Seppelt. Structure investigations on oxygen fluorides. Dalton Transactions. 2015, 44 (45): 19659–19662. PMID 26351980. doi:10.1039/c5dt02247a.

[:2-9] [9]
Solomon, Irvine J. Research on Chemistry of ${\ce {O3F2}}$ and ${\ce {O2F2}}$ . No. IITRI-C227-6. IIT RESEARCH INST CHICAGO IL, 1964.

[10] [10]
Goetschel, Charles T. et al. Low-Temperature Radiation Chemistry. I. Preparation of Oxygen Fluorides and Dioxygenyl Tetrafluoroborate. Journal of the American Chemical Society. 1969, 91 (17): 4702–4707. doi:10.1021/ja01045a020.

[11] [11]
De Marco, Ronald A., and Jean'ne M. Shreeve . "Fluorinated Peroxides." Advances in Inorganic Chemistry and Radiochemistry. Vol. 16. Academic Press, 1974. 109-176.

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