高氯酰氟

高氯酰氟
Perchloryl fluoride
	IUPAC名; Perchloryl fluoride
别名	Chlorine oxyfluoride, Perchlorofluoride, Chlorine fluorine oxide, Trioxychlorofluoride, Perchloric acid fluoride
识别
CAS号	7616-94-6
PubChem	24258
ChemSpider	22680
SMILES	FCl(=O)(=O)=O;
InChI	1/ClFO3/c2-1(3,4)5;
InChIKey	XHFXMNZYIKFCPN-UHFFFAOYAO
EINECS	231-526-0
RTECS	SD1925000
性质
化学式	ClO3F
摩尔质量	102.4496 g·mol⁻¹
外观	无色气体
氣味	甜味
密度	1.434 g/cm3
熔点	−147.8 °C（125 K）
沸点	−46.7 °C（226 K）
溶解性（水）	0.06 g/100 ml (20 °C)
蒸氣壓	10.5 atm (20°C)
黏度	3.91 x 10−3 Pa.s (@ melting point)
结构
分子构型	四面体
热力学
ΔfHm⦵298K	-21.42 kJ/mol
S⦵298K	278.97 J/(mol*K)
危险性
主要危害	腐蚀性，氧化性，毒性
NFPA 704	0 3 3
PEL	TWA 3 ppm (13.5 mg/m3)
TLV	3 ppm
	致死量或浓度：
LC50（中位浓度）	385 ppm (rat, 4 hr); 451 ppm (dog, 4 hr)
LCLo（最低）	2000 ppm (rat, 40 min); 451 ppm (dog, 4 hr)
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

高氯酰氟^[5]是具有化学式ClFO
3的活泼气体，具有类似于汽油和煤油的独特甜味^[6]。有毒，是一种强大的氧化剂和氟化剂。是高氯酸的酸性氟化物。

事实速览 高氯酰氟, 识别 ...

关闭

尽管高氯酰氟的生成焓_^（ ΔH_f^°=-5.2千卡/摩尔）很小，但它是热力学稳定的，在400℃才分解。^[2]^:380对还原剂和阴离子具有很强的反应性，但氯原子充当亲电体。^[2]^:382 与还原剂如金属酰胺、金属、氢化物等发生爆炸性反应^[6]。与氯酰氟不同，其在水中的水解非常缓慢。

高氯酰氟主要由氟化高氯酸盐产生。常用五氟化锑作为氟化剂： ^[2]^:372–373

ClO−
4 + 3 HF + 2 SbF
5 → ClO
3F + H
3O+
+ 2 SbF−
6

ClO
3F与醇反应生成烷基高氯酸盐，这是对震动极其敏感的炸药。 ^[7] 在路易斯酸存在下，它可用于通过亲电芳香取代将–ClO
3基团引入芳香环。 ^[8]

高氯酰氟在有机化学中用作温和的氟化剂。^[2] ^:383 它是第一种工业上的亲电氟化剂，自20世纪60年代起用于生产氟化类固醇。^[7] 在氯化铝存在下，它也被用作芳族化合物的亲电子高氯化试剂。^[9]

研究了高氯酰氟作为高性能液体火箭燃料氧化剂的用途。^[10] 与五氟化氯和五氟化溴相比，它具有明显更低的比冲，但不会腐蚀容器。不需要低温储存。火箭燃料化学家John Drury Clark在他的书《Ignition！》中报道称 ^[11]高氯酰氟与全卤素氧化剂如三氟化氯和五氟化氯完全混溶，这种混合物提供了适当燃烧含碳燃料所需的氧气。

它也可以作用于光電火焰光度計（英语：Photoelectric flame photometer）的激发源。 ^[12]

高氯酰氟氟化物是有毒的，TLV（英语：Threshold limit value）为3ppm。^[13] 它对肺和眼睛具有强烈的刺激性，能够灼伤暴露的皮肤。其IDLH水平为100 ppm。^[14] 接触的症状包括头晕、头痛、晕厥和紫绀。暴露于毒性水平会导致严重的呼吸道炎症和肺水肿。^[10]

[1]
NIOSH Pocket Guide to Chemical Hazards. #0490. NIOSH.
[2]
Harry Julius Emeléus; A. G. Sharpe. Advances in inorganic chemistry and radiochemistry, Volume 18. Academic Press. 1976. ISBN 0-12-023618-4.
[3]
NIST Chemistry WebBook, SRD 69. 2018 [2019-08-24]. （原始内容存档于2020-06-03）. |article=被忽略 (帮助)
[4]
Perchloryl fluoride. Immediately Dangerous to Life and Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
[5]
Chemical Science and Technology Laboratory. Perchloryl fluoride. National Institute of Standards and Technology. [2009-11-28]. （原始内容存档于2020-06-03）.
[6]
Jared Ledgard. The Preparatory Manual of Explosives 3rd. Lulu.com. 2007: 77. ISBN 0-615-14290-7.
[7]
Peer Kirsch. Modern fluoroorganic chemistry: synthesis, reactivity, applications. Wiley-VCH. 2004: 74. ISBN 3-527-30691-9.
[8]
Peter Bernard David De la Mare. Electrophilic halogenation: reaction pathways involving attack by electrophilic halogens on unsaturated compounds. CUP Archive. 1976: 63. ISBN 0-521-29014-7.
[9]
Inman, C. E.; Oesterling, R. E.; Tyczkowski, E. A. Reactions of Perchloryl Fluoride with Organic Compounds. I. Perchlorylation of Aromatic Compounds1. Journal of the American Chemical Society. 1958-10-01, 80 (19): 5286–5288. ISSN 0002-7863. doi:10.1021/ja01552a069.
[10]
John Burke Sullivan; Gary R. Krieger. Clinical environmental health and toxic exposures 2nd. Lippincott Williams & Wilkins. 2001: 969. ISBN 0-683-08027-X.
[11]
存档副本 (PDF). [2019-08-24]. （原始内容存档 (PDF)于2019-07-16）.
[12]
Schmauch, G. E.; Serfass, E. J. The Use of Perchloryl Fluoride in Flame Photometry. Applied Spectroscopy. 1958, 12 (3): 98–102. Bibcode:1958ApSpe..12...98S. doi:10.1366/000370258774615483.
[13]
National Institute for Occupational Safety and Health. NIOSH Pocket Guide to Chemical Hazards. Centers for Disease Control and Prevention. [2013-10-31]. （原始内容存档于2013-11-03）.
[14]
National Institute for Occupational Safety and Health. Documentation for Immediately Dangerous To Life or Health Concentrations (IDLHs). Centers for Disease Control and Prevention. [2013-10-31]. （原始内容存档于2013-11-03）.

[PGCH-1] [1]
NIOSH Pocket Guide to Chemical Hazards. #0490. NIOSH.

[emeleus1976-2] [2]
Harry Julius Emeléus; A. G. Sharpe. Advances in inorganic chemistry and radiochemistry, Volume 18. Academic Press. 1976. ISBN 0-12-023618-4.

[NIST-3] [3]
NIST Chemistry WebBook, SRD 69. 2018 [2019-08-24]. （原始内容存档于2020-06-03）. |article=被忽略 (帮助)

[IDLH-4] [4]
Perchloryl fluoride. Immediately Dangerous to Life and Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).

[5] [5]
Chemical Science and Technology Laboratory. Perchloryl fluoride. National Institute of Standards and Technology. [2009-11-28]. （原始内容存档于2020-06-03）.

[ledgard2007-6] [6]
Jared Ledgard. The Preparatory Manual of Explosives 3rd. Lulu.com. 2007: 77. ISBN 0-615-14290-7.

[kirsch2004-7] [7]
Peer Kirsch. Modern fluoroorganic chemistry: synthesis, reactivity, applications. Wiley-VCH. 2004: 74. ISBN 3-527-30691-9.

[8] [8]
Peter Bernard David De la Mare. Electrophilic halogenation: reaction pathways involving attack by electrophilic halogens on unsaturated compounds. CUP Archive. 1976: 63. ISBN 0-521-29014-7.

[9] [9]
Inman, C. E.; Oesterling, R. E.; Tyczkowski, E. A. Reactions of Perchloryl Fluoride with Organic Compounds. I. Perchlorylation of Aromatic Compounds1. Journal of the American Chemical Society. 1958-10-01, 80 (19): 5286–5288. ISSN 0002-7863. doi:10.1021/ja01552a069.

[sullivan2001-10] [10]
John Burke Sullivan; Gary R. Krieger. Clinical environmental health and toxic exposures 2nd. Lippincott Williams & Wilkins. 2001: 969. ISBN 0-683-08027-X.

[11] [11]
存档副本 (PDF). [2019-08-24]. （原始内容存档 (PDF)于2019-07-16）.

[12] [12]
Schmauch, G. E.; Serfass, E. J. The Use of Perchloryl Fluoride in Flame Photometry. Applied Spectroscopy. 1958, 12 (3): 98–102. Bibcode:1958ApSpe..12...98S. doi:10.1366/000370258774615483.

[13] [13]
National Institute for Occupational Safety and Health. NIOSH Pocket Guide to Chemical Hazards. Centers for Disease Control and Prevention. [2013-10-31]. （原始内容存档于2013-11-03）.

[14] [14]
National Institute for Occupational Safety and Health. Documentation for Immediately Dangerous To Life or Health Concentrations (IDLHs). Centers for Disease Control and Prevention. [2013-10-31]. （原始内容存档于2013-11-03）.

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高氯酰氟

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合成与化学

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参考文献