Trifluoromethanol nitrate | 135659-54-0

• 分子结构分类: 有机化合物 - 有机氧化合物 - 有机含氧阴离子化合物
• 英文名称: Trifluoromethanol nitrate
• 英文别名: trifluoromethyl nitrate
• CAS: 135659-54-0
• 化学式: CF₃NO₃
• 分子量: 131.011
• InChiKey: TYRSOEVURVXMSR-UHFFFAOYSA-N

物化性质

• 沸点：
  19.5±40.0 °C(Predicted)
• 密度：
  1.625±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  8
• 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：
  55
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  Trifluoromethoxide 在 五氧化二氮 作用下， 21.9 ℃ 、53.33 Pa 条件下， 生成 Trifluoromethanol nitrate
  参考文献：
  名称：

  Reactions of CF₃O^- with Atmospheric Trace Gases

  摘要：

  The rate coefficients and product yields for the reactions of CF3O- with ClONO2, HNO3, HCl, N2O5, So(2), HI, and H2O were measured at 295 K and similar to 0.4 Torr using the flowing afterglow technique. The reactions of CF3O- with HO(2)NO2 and H2SO4 were also studied qualitatively. CF3O- reacts rapidly with ClONO2, HO2NO2, SO2, and HCl by only fluoride transfer and with HNO3, HI, and H2SO4 by both fluoride and proton transfer. CF3O- also reacts with HI to form IF2- and with N2O5 to produce NO3-. CF3O- undergoes a slow clustering reaction with H2O and is transformed within water clusters into F-. HF and F-.(HF)(2). CF3O- is unreactive with CH3NO3, CH3C(O)O2NO2, O-3, NO2, CO2, and O-2. These results demonstrate that CF3O- is an excellent candidate as a reagent ion for the selective detection of ClONO2, HCl, and HNO3 in the upper troposphere and stratosphere with a chemical ionization mass spectrometer. The observed reaction of CF3O- with H(2)0 within water clusters indicates that CF3O- will hydrolyze in aqueous solution to form F-, HF, and CO2. This provides insight into the mechanism for the heterogeneous loss of CF3OH in the atmosphere.

  DOI：

  10.1021/jp951928u

文献信息

• Kinetic study of the pressure dependence of the reaction CF3O+NO2at 298 K Rate constant measurements (P=0.5–9Torr) and competition between association (CF3ONO2)and disproportionation (CF2O+FNO2)channels
  作者：Francoise Caralp、Marie-The´rèse Rayez、Wendell Forst、Christine Bourbon、Mikhael Brioukov、and Pascal Devolder

  DOI：10.1039/a703761i

  日期：——

  The kinetics of the reaction of the CF3O radical with NO2 has been studied at 298 K at low pressure (0.5–9 Torr of helium) by fast-flow–laser-induced fluorescence (LIF), pyrolysis of a dilute mixture of CF3OOCF3 and He being used as the source of the CF3O radical. In good agreement with the results of Zellner and co-workers (obtained in the pressure range 5–100 Torr), the rate constant has been found to be pressure dependent. All the experimental data were analysed by a multichannel RRKM procedure using the results of abinitio calculations as input data. This revealed that two reaction channels, the association CF3O + NO2 → CF3ONO2 (1a) and the disproportionation CF3O + NO2 → CF2O + FNO2 (1b), must be invoked and they proceed via a common energized adduct CF3ONO2*. The pressure dependence of the branching ratio was predicted by this calculation: the disproportionation channel would be negligible near atmospheric pressure and becomes the major channel at pressure below ca. 0.3 Torr, with a calculated second-order limiting low-pressure value of the rate equal to 3.2 × 10−12 cm3 molecule−1 s−1. The high-pressure limit rate constant obtained is k∞ = (1.65 ± 0.2) × 10−11 cm3 molecule−1 s−1. An analytical representation of the pressure dependence of the rate constant at 298 K is proposed using the conventional Troe expression with an added constant.

  在 298 K 低压（0.5â9 托氦气）条件下，通过快速流激光诱导荧光（LIF）研究了 CF3O 自由基与 NO2 的反应动力学，CF3OOCF3 和 He 的稀释混合物的热解被用作 CF3O 自由基的来源。与 Zellner 和合作者的研究结果（在 5â100 托压力范围内获得）完全一致，发现速率常数与压力有关。以 abinitio 计算结果为输入数据，采用多通道 RRKM 程序对所有实验数据进行了分析。结果表明，必须调用两个反应通道，即联合反应 CF3O + NO2 â CF3ONO2 (1a) 和歧化反应 CF3O + NO2 â CF2O + FNO2 (1b)，它们通过一个共同的通电加合物 CF3ONO2* 进行。该计算预测了支化率的压力依赖性：歧化通道在接近大气压时可以忽略不计，而在压力低于约 0.3 托时则成为主要通道，计算得出的二阶极限低压速率值等于 3.2 à 10â12 cm3 molecâ1 sâ1。高压极限速率常数为 kâ = (1.65 ± 0.2) à 10â11 cm3 moleculeâ1 sâ1。利用带有附加常数的传统特罗（Troe）表达式，提出了 298 K 时速率常数随压力变化的分析方法。
• Peeters, J.; Vertommen, J.; Langhans, I., Berichte der Bunsen-Gesellschaft, 1992, vol. 96, # 3, p. 431 - 436
  作者：Peeters, J.、Vertommen, J.、Langhans, I.

  DOI：——

  日期：——
• Kinetic and Mechanistic Studies of the Reactions of CF₃O Radicals with NO and NO₂
  作者：Chr. Fockenberg、H. Somnitz、G. Bednarek、R. Zellner

  DOI：10.1002/bbpc.199700001

  日期：1997.10

  AbstractThe reactions of CF3O radicals with (1) NO and (2) NO2 were studied using two different experimental techniques. A laser photolysis/LIF detection method was applied for measuring the rate constants as a function of temperature (T = 222–302 K) and total pressure (ptot = 7–107 mbar). Whereas the reaction with (1) NO was found to be independent of temperature and pressure with k1 = (4.5±1.2)×10−11 cm3 s−1, the reaction with (2) NO2 was found to be dependent on both of these variables. The temperature dependence of k2 in the high pressure limit can be given by the expression k2,∝ (T) = (8±5)×10−13 exp ((863±194) K/T) cm3 s−1. The product distributions of the two reactions were determined in separate experiments using steady‐state photolysis combined with FTIR spectroscopy. For reaction (1) only CF2O was found as a reaction product with a yield of 0.93±0.10, independent of temperature. For reaction (2) several products (CF3ONO2, CF2O, FNO2) were identified, the overall yield, however, is dominated (≥90%) by the recombination product CF3ONO2. A theoretical analysis of the detailed mechanisms of both reactions was made by performing ab initio energy and geometry predictions in combination with RRKM calculations. Both reactions were found to proceed via an initial addition mechanism involving the CF3ONOx (x = 1, 2) intermediate and a four‐center transition state. A direct abstraction of an F atom by NO or NO2 can be excluded.
• Reactions of CF₃O^- with Atmospheric Trace Gases
  作者：L. Gregory Huey、Peter W. Villalta、Edward J. Dunlea、David R. Hanson、Carleton J. Howard

  DOI：10.1021/jp951928u

  日期：1996.1.1

  The rate coefficients and product yields for the reactions of CF3O- with ClONO2, HNO3, HCl, N2O5, So(2), HI, and H2O were measured at 295 K and similar to 0.4 Torr using the flowing afterglow technique. The reactions of CF3O- with HO(2)NO2 and H2SO4 were also studied qualitatively. CF3O- reacts rapidly with ClONO2, HO2NO2, SO2, and HCl by only fluoride transfer and with HNO3, HI, and H2SO4 by both fluoride and proton transfer. CF3O- also reacts with HI to form IF2- and with N2O5 to produce NO3-. CF3O- undergoes a slow clustering reaction with H2O and is transformed within water clusters into F-. HF and F-.(HF)(2). CF3O- is unreactive with CH3NO3, CH3C(O)O2NO2, O-3, NO2, CO2, and O-2. These results demonstrate that CF3O- is an excellent candidate as a reagent ion for the selective detection of ClONO2, HCl, and HNO3 in the upper troposphere and stratosphere with a chemical ionization mass spectrometer. The observed reaction of CF3O- with H(2)0 within water clusters indicates that CF3O- will hydrolyze in aqueous solution to form F-, HF, and CO2. This provides insight into the mechanism for the heterogeneous loss of CF3OH in the atmosphere.