| 150716-79-3

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机氯化物
• CAS: 150716-79-3
• 化学式: C₂H₄ClO₂
• 分子量: 95.5056
• InChiKey: VDILQDAWQSBIKW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 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：
  10.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  生成 α-chloroethyl radical
  参考文献：
  名称：

  1-氯乙基自由基与分子氧反应的动力学和热化学

  摘要：

  The kinetics of the reaction CH3CHCl + O-2 reversible arrow CH3CHClO2 --> products (1) has been studied at temperatures 296-839 K and He densities of(3-49) x 10(16) molecule cm(-3) by laser photolysis/photoionization mass spectrometry. Rate constants were determined in time-resolved experiments as a function of temperature and bath gas density. At low temperatures (298-400 K) the rate constants are in the falloff region under the conditions of the experiments. Relaxation to equilibrium in the addition step of the reaction was monitored within the temperature range 520-590 K. Equilibrium constants were determined as a function of temperature and used to obtain the enthalpy and entropy of the addition step of the reaction (1). At high temperatures (750-839 K) the reaction rate constant is independent of both pressure and temperature within the uncertainty of the experimental data and equal to (1.2 +/- 0.4) x 10-(14) cm(3) molecule(-1) s(-1). Vinyl chloride (C2H3Cl) was detected as a major product of reaction 1 at T = 800 K. The rate constant of the reaction CH3CHCl + Cl-2 --> products (6) was determined at room temperature and He densities of(9-36) x 10(16) molecule cm(-3) using the same technique. The value obtained is k(6) = (4.37 +/- 0.69) x 10(-12) cm(3) molecule(-1) s(-1). An estimate of the high-pressure limit for reaction 1 was determined using this measured k(6) and the k(1)/k(6) ratio obtained by Kaiser et al.: K-1(infinity) (T = 298K) (1.04 +/- 0.22) x 10(-11) cm(3) molecule(-1) s(-1). In a theoretical part of the study, structure, vibrational frequencies, and energies of nine conformations of CH3CHClO2 were calculated using ab initio UHF/6-31G* and MP2/6-31G** methods. The theoretical results are used to calculate the entropy change of the addition reaction Delta S degrees(298) = -152.3 +/- 3.3 J mol(-1) K-1. This entropy change combined with the experimentally determined equilibrium constants resulted in a CH3CHCl-O-2 bond energy Delta H degrees(298) = -131.2 +/- 1.8 kJ mol(-1). The room-temperature entropy (S degrees(298) = 341.0 +/- 3.3 J mol(-1) K-1) and the heat of formation (Delta H-f degrees(298) = -54.7 +/- 3.7 kJ mol(-1)) of the CH3CHClO2 adduct were obtained.

  DOI：

  10.1021/j100001a036
• 作为产物：
  描述：

  α-chloroethyl radical 在 氧气 作用下， 生成
  参考文献：
  名称：

  1-氯乙基自由基与分子氧反应的动力学和热化学

  摘要：

  The kinetics of the reaction CH3CHCl + O-2 reversible arrow CH3CHClO2 --> products (1) has been studied at temperatures 296-839 K and He densities of(3-49) x 10(16) molecule cm(-3) by laser photolysis/photoionization mass spectrometry. Rate constants were determined in time-resolved experiments as a function of temperature and bath gas density. At low temperatures (298-400 K) the rate constants are in the falloff region under the conditions of the experiments. Relaxation to equilibrium in the addition step of the reaction was monitored within the temperature range 520-590 K. Equilibrium constants were determined as a function of temperature and used to obtain the enthalpy and entropy of the addition step of the reaction (1). At high temperatures (750-839 K) the reaction rate constant is independent of both pressure and temperature within the uncertainty of the experimental data and equal to (1.2 +/- 0.4) x 10-(14) cm(3) molecule(-1) s(-1). Vinyl chloride (C2H3Cl) was detected as a major product of reaction 1 at T = 800 K. The rate constant of the reaction CH3CHCl + Cl-2 --> products (6) was determined at room temperature and He densities of(9-36) x 10(16) molecule cm(-3) using the same technique. The value obtained is k(6) = (4.37 +/- 0.69) x 10(-12) cm(3) molecule(-1) s(-1). An estimate of the high-pressure limit for reaction 1 was determined using this measured k(6) and the k(1)/k(6) ratio obtained by Kaiser et al.: K-1(infinity) (T = 298K) (1.04 +/- 0.22) x 10(-11) cm(3) molecule(-1) s(-1). In a theoretical part of the study, structure, vibrational frequencies, and energies of nine conformations of CH3CHClO2 were calculated using ab initio UHF/6-31G* and MP2/6-31G** methods. The theoretical results are used to calculate the entropy change of the addition reaction Delta S degrees(298) = -152.3 +/- 3.3 J mol(-1) K-1. This entropy change combined with the experimentally determined equilibrium constants resulted in a CH3CHCl-O-2 bond energy Delta H degrees(298) = -131.2 +/- 1.8 kJ mol(-1). The room-temperature entropy (S degrees(298) = 341.0 +/- 3.3 J mol(-1) K-1) and the heat of formation (Delta H-f degrees(298) = -54.7 +/- 3.7 kJ mol(-1)) of the CH3CHClO2 adduct were obtained.

  DOI：

  10.1021/j100001a036

文献信息

• Rate coefficients and mechanisms of the reaction of cl-atoms with a series of unsaturated hydrocarbons under atmospheric conditions
  作者：John J. Orlando、Geoffrey S. Tyndall、Eric C. Apel、Daniel D. Riemer、Suzanne E. Paulson

  DOI：10.1002/kin.10135

  日期：——

  Rate coefficients and/or mechanistic information are provided for the reaction of Cl-atoms with a number of unsaturated species, including isoprene, methacrolein (MACR), methyl vinyl ketone (MVK), 1,3-butadiene, trans-2-butene, and 1-butene. The following Cl-atom rate coefficients were obtained at 298 K near I atm total pressure: k(isoprene) = (4.3 ′ 0.6) x 10 - 1 0 cm 3 molecule - 1 s - 1 (independent

  为 Cl 原子与许多不饱和物质的反应提供速率系数和/或机理信息，包括异戊二烯、甲基丙烯醛 (MACR)、甲基乙烯基酮 (MVK)、1,3-丁二烯、反式-2-丁烯、和 1-丁烯。以下 Cl 原子速率系数在 298 K 接近 I atm 总压力下获得：k(异戊二烯) = (4.3 ' 0.6) x 10 - 1 0 cm 3 分子 - 1 s - 1（与 6.2 至 760 Torr 的压力无关); k(MVK) = (2.2 ′ 0.3) × 10 - 1 0 cm 3 分子 - 1 s - 1 ; k(MACR) = (2.4 ′ 0.3) x 10 - 1 0 cm 3 分子 - 1 s - 1 ；k(trans-2-butene) = (4.0 ′ 0.5) × 10 - 1 0 cm 3 分子 - 1 s - 1 ；k(1-butene) = (3.0 ′ 0.4) × 10 - 1
• Evidence for the three-center elimination of hydrogen chloride from 1-chloroethoxy
  作者：M. Matti Maricq、Jichun Shi、Joseph J. Szente、L. Rimai、E. W. Kaiser

  DOI：10.1021/j100140a027

  日期：1993.9

  Time-resolved IR spectral photography and transient diode laser absorption measurements reveal a yield of HCl from the photolysis of Cl2 in the presence of C2H5Cl and O2 which is 78% larger than expected from Cl + C2H5Cl. The HCl formation occurs in two steps: a rapid rise to [HCl] = [Cl]0, followed by a secondary rise to [HCl] = 1.78[Cl]0 with a rate constant of k3 = (5.2 +/- 1.3) X 10(-12) cm3 S-1. In the presence of NO, the rate of secondary HCl formation is greatly enhanced, but its yield (84%) is comparable to that in the absence of NO. The secondary HCl is explained as an elimination product from the CH3CHClO, which can be generated by the reaction of CH3CHClO2 with itself or with NO. The fact that the secondary HCl yield increases by 12% when using CD3CH2Cl shows that the secondary HCl is formed mainly by three-center elimination from the 1-chloroethoxy radical. We also report UV absorption cross sections for CH3CHClO2, which has a broad maximum of sigma(max) = 0.029 angstrom2 from 215 to 248 nm, and CH2ClCH2O2, with sigma(max) = 0.045 angstrom2 at 240 nm. The self-reaction rate constants are (5.2+/-1.3) X 10(-12) cm3 s-l and (6.04-0.8) X 10(-12) cm3 s-1, respectively. Finally, the rate constant for the reaction Cl + C2H5Cl = C2H4Cl + HCl (1) is determined to be k1 = (7.3 +/- 0.9) X 10(-12) cm3 s-1.
• Kinetics and Thermochemistry of the Reaction of 1-Chloroethyl Radical with Molecular Oxygen
  作者：Vadim D. Knyazev、Akos Bencsura、Ilia A. Dubinsky、David Gutman、Carl F. Melius、Selim M. Senkan

  DOI：10.1021/j100001a036

  日期：1995.1

  The kinetics of the reaction CH3CHCl + O-2 reversible arrow CH3CHClO2 --> products (1) has been studied at temperatures 296-839 K and He densities of(3-49) x 10(16) molecule cm(-3) by laser photolysis/photoionization mass spectrometry. Rate constants were determined in time-resolved experiments as a function of temperature and bath gas density. At low temperatures (298-400 K) the rate constants are in the falloff region under the conditions of the experiments. Relaxation to equilibrium in the addition step of the reaction was monitored within the temperature range 520-590 K. Equilibrium constants were determined as a function of temperature and used to obtain the enthalpy and entropy of the addition step of the reaction (1). At high temperatures (750-839 K) the reaction rate constant is independent of both pressure and temperature within the uncertainty of the experimental data and equal to (1.2 +/- 0.4) x 10-(14) cm(3) molecule(-1) s(-1). Vinyl chloride (C2H3Cl) was detected as a major product of reaction 1 at T = 800 K. The rate constant of the reaction CH3CHCl + Cl-2 --> products (6) was determined at room temperature and He densities of(9-36) x 10(16) molecule cm(-3) using the same technique. The value obtained is k(6) = (4.37 +/- 0.69) x 10(-12) cm(3) molecule(-1) s(-1). An estimate of the high-pressure limit for reaction 1 was determined using this measured k(6) and the k(1)/k(6) ratio obtained by Kaiser et al.: K-1(infinity) (T = 298K) (1.04 +/- 0.22) x 10(-11) cm(3) molecule(-1) s(-1). In a theoretical part of the study, structure, vibrational frequencies, and energies of nine conformations of CH3CHClO2 were calculated using ab initio UHF/6-31G* and MP2/6-31G** methods. The theoretical results are used to calculate the entropy change of the addition reaction Delta S degrees(298) = -152.3 +/- 3.3 J mol(-1) K-1. This entropy change combined with the experimentally determined equilibrium constants resulted in a CH3CHCl-O-2 bond energy Delta H degrees(298) = -131.2 +/- 1.8 kJ mol(-1). The room-temperature entropy (S degrees(298) = 341.0 +/- 3.3 J mol(-1) K-1) and the heat of formation (Delta H-f degrees(298) = -54.7 +/- 3.7 kJ mol(-1)) of the CH3CHClO2 adduct were obtained.