carboxylium | 638-71-1

• 分子结构分类: 有机化合物 - 有机氧化合物 - 有机氧化物
• 英文名称: carboxylium
• CAS: 638-71-1
• 化学式: CHO₂
• 分子量: 45.0177
• InChiKey: CLJFDRKGHKJAKZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.39
• 重原子数：
  3.0
• 可旋转键数：
  0.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  37.3
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  二氧化碳 在 氢气 作用下， 生成 carboxylium
  参考文献：
  名称：

  An absolute proton affinity scale in the ∼130–140 kcal mol⁻¹ range

  摘要：

  The dependences on temperature of the rate coefficients for the endothermic proton transfer reactions of HBr+ with CO2 and CH4 have been obtained in a variable-temperature selected ion flow tube. The measurements have been used to determine the 300 K proton affinity of CO2, P.A.(CO2), =128.5±1.0 kcal mol−1, utilizing the literature value of P.A.(Br)=131.8 kcal mol−1, obtained from the dissociation energy of HBr+, as a primary standard. The proton affinity difference between CO2 and CH4 has been substantiated by equilibrium constant measurements as a function of temperature for proton transfer between CO2 and CH4. Similar equilibrium constant measurements have been used to determine the proton affinities of HCl, N2 O, HBr, and CO, giving a proton affinity ladder ordered (in kcal mol−1) as CO(141.4), HBr(138.8), N2 O(137.3), HCl(133.0), Br(131.8), CH4 (130.0), and CO2(128.5). Proton affinities have also been determined for Br2(140.0), NO(127.0), and CF4(126.5), the last two values being obtained from selected ion flow drift tube measurements. An upper limit to P.A.(SF6) of 127 kcal mol−1 has been inferred from the instability of SF6 H+ towards dissociation into SF+5 and HF.

  DOI：

  10.1063/1.456834
• 作为试剂：
  描述：

  methane 在 carboxylium 作用下， 生成 甲烷离子
  参考文献：
  名称：

  Determination of proton affinities from the kinetics of proton transfer reactions. VII. The proton affinities of O₂, H₂, Kr, O, N₂, Xe, CO₂, CH₄, N₂O, and CO

  摘要：

  The flowing afterglow and selected ion flow tube techniques are applied in a room temperature study of the kinetics of proton-transfer reactions of the type XH++Y?YH++X for X or Y=He, H2, O2, Kr, O, N2, Xe, CO2, CH4, CD4, N2O, OH, and CO, and for the deuteration of O2 by D3+. Equilibrium constants are determined and changes in thermodynamic state properties (ΔG°, ΔH°, ΔS°) are derived for the reactions with X/Y=H2/O2, O2/Kr, H2/Kr, H2/N2, O/N2, N2/Xe, Xe/CO2, CO2/CH4, CH4/N2O, and N2O/CO. Proton affinities are reported for O2, H2, Kr, O, N2, Xe, CO2, CH4, N2O, and CO, together with the heats of formation of their protonated species. Also a correlation is presented between the kinetic and thermodynamic results obtained in this study.

  DOI：

  10.1063/1.439975

文献信息

• Reactions of CO2 +, CO2CO2 + and H2O+ ions with various neutral molecules
  作者：Asit B. Rakshit、Peter Warneck

  DOI：10.1039/f29807601084

  日期：——

  A drift chamber mass spectrometer apparatus was used to determine products and rate coefficients at 300 K for reactions of CO2+, CO2CO2+ and H2O+ with H2, CH4, SO2, O2, C2H2, C2H4, COS, CS2, NH3, NO2 and NO. Charge transfer is the predominant reaction channel in most cases. Reaction efficiencies are discussed by comparison with rate coefficients calculated from the capture mechanism according to averaged

  使用漂移室质谱仪设备确定在300 K下CO 2 +，CO 2 CO 2 +和H 2 O +与H 2，CH 4，SO 2，O 2，C 2 H反应的产物和速率系数2，C 2 H 4，COS，CS 2，NH 3，NO 2和不。在大多数情况下，电荷转移是主要的反应通道。通过与根据平均偶极子定向理论从捕获机制计算出的速率系数进行比较，讨论了反应效率。
• Ionic and Neutral Species in Pulse Radiolysis of Supercritical CO₂. 1. Transient Absorption Spectroscopy, Electric Field Effect, and Charge Dynamics
  作者：Ilya A. Shkrob、Myran C. Sauer、Charles D. Jonah、Kenji Takahashi

  DOI：10.1021/jp021494k

  日期：2002.12.1

  350−1500 nm spectra are decomposed into the contributions from the solvent radical cation, solvent radical anion, and a long-lived neutral product that we associate with singlet carbon trioxide, CO3(1A1). These three species are characterized by their optical spectra, chemical behavior, kinetics, and the response of these kinetics to external electric field. The following mechanism for radiolysis of sc CO2

  瞬态吸收光谱用于研究致密、类液体超临界 (sc) CO2 (T = 41 °C, ρ = 0.84 g/cm3) 的辐射分解机制。350-1500 nm 光谱分解为溶剂自由基阳离子、溶剂自由基阴离子和与单线态三氧化碳相关的长寿命中性产物 CO3(1A1) 的贡献。这三种物质的特征在于它们的光谱、化学行为、动力学以及这些动力学对外部电场的响应。提出了以下用于 sc CO2 辐射分解的机制：溶剂的电离产生 ≈5 对/100 eV。这些对中的大多数由溶剂空穴和热化的准自由电子组成；CO3- 的即时产率小于总离子产率的 3%。电子在 <200 ps 内被溶剂捕获。由于电子迁移率高，这种俘获大部分发生在电荷逃离彼此的库仑场之后。由于电子与非配子的交叉复合...
• Measurements of the dissociative recombination coefficients for several polyatomic ion species at 300 K
  作者：Nigel G. Adams、David Smith

  DOI：10.1016/0009-2614(88)87081-7

  日期：1988.2

  The dissociative recombination coefficients, α, have been measured at 300 K for several polyatomic positive ion species using a flowing afterglow/Langmuir probe (FALP) apparatus. The α range from 1.1 × 10−7 cm3 s−1 for H2F+ to 2.2 × 10−6 cm3 s−1 for the clustered species H+(CH3OH)3. Several of the ionic species included in this study are considered to be involved in the synthesis of interstellar molecules

  使用流动的余辉/ Langmuir探针（FALP）装置，对几种多原子正离子物种在300 K下测量了离解重组系数α。对于H 2 F +，α的范围为1.1×10 -7 cm 3 s -1；对于簇状物种H +（CH 3 OH）3，α的范围为2.2×10 -6 cm 3 s -1。这项研究中包括的几种离子物质被认为与星际分子的合成有关。
• Ion–Molecule Reactions of State Selected HCl+ Ions with Carbon Dioxide and Ethene
  作者：M. Malow、K. Brembs、Karl-Michael Weitzel

  DOI：10.1524/zpch.2001.215.6.737

  日期：2001.1.1

  The ion–molecule reactions of state selected HCl

  离子-分子反应的状态选择的HCl
• Ion-molecule reactions involving hydronium, water(1+), hydroxyl(1+) at thermal energy
  作者：R. J. Shul、R. Passarella、L. T. DiFazio、R. G. Keesee、A. W. Castleman

  DOI：10.1021/j100328a025

  日期：1988.8