C2(X1Σg+)自由基与不饱和碳氢化合物反应的温度效应

引用本文: 胡仁志, 谢品华, 张群, 司福祺, 陈旸. C₂(X¹Σ_g⁺)自由基与不饱和碳氢化合物反应的温度效应[J]. 物理化学学报, doi: 10.3866/PKU.WHXB201302046 shu

Citation: HU Ren-Zhi, XIE Pin-Hua, ZHANG Qun, SI Fu-Qi, CHEN Yang. Temperature Dependence of C₂(X¹Σ_g⁺) in Reactions with Unsaturated Hydrocarbons[J]. Acta Physico-Chimica Sinica, doi: 10.3866/PKU.WHXB201302046 shu

C₂(X¹Σ_g⁺)自由基与不饱和碳氢化合物反应的温度效应

胡仁志 ^1, ,
谢品华 ^1, ,
张群 ^2, ,
司福祺 ^1, ,
陈旸 ^2,

基金项目:
国家自然科学基金(61108031, 21173205) (61108031, 21173205)

国家重点基础研究发展规划项目(973) (2010CB923302) (973) (2010CB923302)

中国科学院知识创新工程(KJCX2-YW-N24)资助 (KJCX2-YW-N24)

摘要:

运用脉冲激光光解-激光诱导荧光(PLP-LIF)的方法在293-573 K的温度范围内测量了C₂(X¹Σ_g⁺)自由基与不饱和碳氢化合物(C₂H₄和C₂H₂)气相反应的双分子反应速率常数. 获得的速率常数可以用Arrhenius 公式表达如下(单位: cm³·molecule^-1·s^-1): k(C₂H₄)=(1.16±0.10)×10^-10exp[(290.68±9.72)/T], k(C₂H₂)=(1.36±0.02)×10^-10exp[(263.85±7.60)/T], 误差为2σ. 由获得的双分子反应速率常数及其所呈现的负温度效应, 我们认为在293-573 K温度范围内C₂(X¹Σ_g⁺)自由基和不饱和碳氢化合物的反应遵循加成机理.

关键词:

English

Temperature Dependence of C₂(X¹Σ_g⁺) in Reactions with Unsaturated Hydrocarbons

1.
1 Key Laboratory of Environmental Optics & Technology, Anhui Institute of Optics and Fine Mechanics,Chinese Academy of Science, Hefei 230031, P. R. China;
2 Hefei National Laboratory for Physical Sciences at the Microscale, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, P. R. China
Received Date: 30 November 2012
Available Online: 25 March 2013
Fund Project:
国家自然科学基金(61108031, 21173205)

国家重点基础研究发展规划项目(973) (2010CB923302)

中国科学院知识创新工程(KJCX2-YW-N24)资助

Abstract:

Bimolecular rate constants for the gas-phase reactions of C₂(X¹Σ_g⁺) with unsaturated hydrocarbons C₂H₄ and C₂H₂ were measured over the temperature range 293-573 K by pulsed laser photolysis/laserinduced fluorescence (PLP-LIF). The rate constants, in the unit of cm³·molecule^-1·s^-1, can be fitted by the normal Arrhenius expressions: k(C₂H₄)=(1.16±0.10)×10^-10exp[(290.68±9.72)/T], and k(C₂H₂)=(1.36±0.02)×10^-10exp[(263.85 ± 7.60)/T], where all error estimates are ± 2σ and represent the precision of the fit. The observed bimolecular rate constants along with the negative temperature dependences of k(T) allow us to conclude that the reactions of C₂(X¹Σ_g⁺) with these unsaturated hydrocarbons in the temperature range 293- 573 K proceed via an addition mechanism.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

C₂(X¹Σ_g⁺)自由基与不饱和碳氢化合物反应的温度效应

English

Temperature Dependence of C₂(X¹Σ_g⁺) in Reactions with Unsaturated Hydrocarbons

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