dichloromethane, chloridic acid | 109026-11-1

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 卤代烷
• 英文名称: dichloromethane, chloridic acid
• 英文别名: trichloroketone；oxychloroform
• CAS: 109026-11-1
• 化学式: CCl₃O
• 分子量: 134.369
• InChiKey: FOIGFJARRSTTCM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  5
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  1
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  三氯甲基过氧自由基 生成 dichloromethane, chloridic acid
  参考文献：
  名称：

  CCl 3 O 2和CHCl 2 O 2自由基自反应的动力学，机理以及与HO 2的反应

  摘要：

  反应的动力学和机理CCl 3 O 2 + CCl 3 O 2 →2CCl 3 O + O 2（1），CHCl 2 O 2 + CHCl 2 O 2 →2CHCl 2 O + O 2（2a），CHCl 2 O 2 + CHCl 2 O 2 →CHCl 2 OH + CCl 2 O + O 2（2b），CCl 3 O 2 + HO 2 →产物（3）和CHCl 2 O 2 + HO在总压力为700-760托时，研究了2 →产物（4）与温度的关系。使用了两种补充技术：用于动力学测量的快速光解/紫外吸收和用于最终产品分析的连续光解/ FTIR光谱。在220至280nm之间测定CHCl 2 O 2和CCl 3 O 2的紫外吸收光谱；它们的形状类似于其他烷基过氧自由基，但具有较宽和较弱的谱带。由氯原子在氯原子引发的氯原子氧化链中CCl 2 O的形成速率确定速率常数k 1在273和460 K之间，其中反应1是限速步骤；k

  DOI：

  10.1021/jp960572z

文献信息

• Kinetic study of the reaction trichloromethyl + oxygen + M .fwdarw. trichloromethylperoxo + M from 1 to 760 Torr and from 233 to 333 K
  作者：F. Danis、F. Caralp、M. T. Rayez、R. Lesclaux

  DOI：10.1021/j100172a037

  日期：1991.9

  The kinetics of reaction 1, CCl3 + O2 + M --> CCl3O2 + M, has been investigated in detail as a function of temperature and over a large pressure range. At low pressure, 0.8-12 Torr, the reaction was investigated by laser photolysis and time-resolved mass spectrometry, while at high pressure (760 Torr), flash photolysis with UV absorption spectrometry was employed. At the low-pressure limit, the rate expression, k1(0) = (1.6 +/- 0.3) x 10(-30)(T/298)-(6.3 +/- 0.5) cm6 molecule-2 s-1 (M = N2), exhibits a quite strong negative temperature coefficient. The obtained strong collision rate expression, 7.0 x 10(-30)(T/298)-4.3 cm6 molecule-2 s-1, using either RRKM calculations or Troe's factorized expression, is unable to reproduce the experimental temperature dependence, unless an unreasonably strong temperature dependence is assigned to the collisional efficiency factor: beta-c = 0.23(T/298)-2.0 (M = N2). Similar results are obtained for other chlorofluoromethyl radicals. The falloff curves were constructed by using RRKM calculations obtained by adjusting beta-c and the transition-state model, in order to reproduce the experimental data. The rate expression at the high-pressure limit was derived from these calculations k1(infinity) = (3.2 +/- 0.7) x 10(-12)(T/298)-(1.2 +/- 0.4) cm3 molecule-1 s-1. All the parameters to be used in Troe's analytical expression for calculating the bimolecular rate constant at any pressure and temperature are given. The rate constant at the low-pressure limit k1(0) is more than an order of magnitude lower than for the CF3 radical. The RRKM calculations show that this arises from a large difference in the C-O bond dissociation energies in the corresponding peroxy radicals: 81.9 kJ mol-1 for CCl3O2 instead of almost-equal-to 145 kJ mol-1 for CF3O2.
• Kinetics and thermochemistry of the equilibrium trichloromethyl radical + oxygen .dblarw. peroxotrichloromethane
  作者：J. J. Russell、J. A. Seetula、D. Gutman、F. Danis、F. Caralp、P. D. Lightfoot、R. Lesclaux、C. F. Melius、S. M. Senkan

  DOI：10.1021/j100371a012

  日期：1990.4