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高氯酸氯

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高氯酸氯
IUPAC名
Chlorine perchlorate
别名 Dichlorine tetroxide
识别
CAS号 27218-16-2  checkY
PubChem 168667
ChemSpider 147540
SMILES
 
  • ClOCl(=O)(=O)=O
性质
化学式 Cl2O4
摩尔质量 134.904 g·mol⁻¹
外观 苍绿色液体
密度 1.81 g/cm3
熔点 -117±2 °C
沸点 25 °C时分解
溶解性 反应
危险性
主要危害 氧化剂
若非注明,所有数据均出自标准状态(25 ℃,100 kPa)下。

高氯酸氯是分子式为Cl2O4无机化合物。这种氯氧化物是不对称的,一个氯原子氧化态为+1而另一个为+7,准确的化学式应为ClOClO3。它可以用436nm的紫外线在室温下照射二氧化氯来制备:[1][2]

2 ClO2 → ClOClO3

高氯酸氯是一个苍绿色的液体(《无机化学》丛书第六卷(P342)上在介绍这种物质的颜色的时候写的是“浅黄色”),常温下就会分解。

性质

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高氯酸氯的化学性质十分活泼,在受热或振动时易爆。高氯酸氯的热稳定性小于高氯酸氟,大于高氯酸溴:

2 ClOClO3O2 + Cl2 + Cl2O6

高氯酸氯与许多金属氯化物反应得到无水高氯酸盐:

CrO2Cl2 + 2 ClOClO3 → 2 Cl2 + CrO2(ClO4)2
TiCl4 + 4 ClOClO3 → 4 Cl2 + Ti(ClO4)4

其他反应见下表[3]

和高氯酸氯的反应物 条件 产物或部分产物
加热 六氧化二氯(80%)、二氧化氯氯气氧气
紫外线照射 七氧化二氯、氯气、氧气[4]
氯化银 高氯酸银、氯气
碘化铯 -45 Cs[I(OClO3)4][註 1]
ClOSO2F或ClF MClO4(M=Cs或NO2)[註 2]
-45 高氯酸溴(BrOClO3)[註 2]
(0.33mol) -50 I(OClO3)3[註 3][5]

註:

  1. ^ Cs[I(OClO3)4]为浅黄色的盐,室温下较稳定,该离子包含一个平面正方形的IO4单元。
  2. ^ 2.0 2.1 MClO4(M=Cs或NO2)可以和BrOSO2F在-20℃反应,转化为高氯酸溴(BrOClO3),而高氯酸溴可以和溴化氢在-70℃反应,生成单质和高氯酸
  3. ^ 目前等摩尔量的碘和高氯酸氯制备高氯酸碘(I)(IOClO3)的反应尚未成功,碘直接由+1价氧化成了+3价。[來源請求]

用途

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制备碘和溴的高氯酸盐

参考资料

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  1. ^ A. J. Schell-Sorokin, D. S. Bethune, J. R. Lankard, M. M. T. Loy, P. P. Sorokin. Chlorine perchlorate a major photolysis product of chlorine dioxide. J. Phys. Chem. 1982, 86 (24): 4653–4655. doi:10.1021/j100221a001. 
  2. ^ M. I. Lopez, J. E. Sicre. Ultraviolet spectrum of chlorine perchlorate. J. Phys. Chem. 1988, 92 (2): 563–564. doi:10.1021/j100313a062. 
  3. ^ 《无机化学》丛书.第六卷.P343.(c)卤素高氯酸盐.张青莲 主编
  4. ^ Rao, Balaji; Anderson, Todd A.; Redder, Aaron; Jackson, W. Andrew. Perchlorate Formation by Ozone Oxidation of Aqueous Chlorine/Oxy-Chlorine Species: Role of ClxOy Radicals. Environmental Science & Technology. 2010-04-15, 44 (8): 2961–2967. ISSN 0013-936X. PMID 20345093. doi:10.1021/es903065f. 
  5. ^ Gomberg, M. The Reaction Between Silver Perchlorate and Iodine. Chlorine Tetra-Oxide. Journal of the American Chemical Society. 1923-02-01, 45 (2): 398–421. ISSN 0002-7863. doi:10.1021/ja01655a017. 
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高氯酸氯
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