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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >CO Chemiluminescence and Kinetics of the C_2 + O_2 Reaction
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CO Chemiluminescence and Kinetics of the C_2 + O_2 Reaction

机译：CO化学发光和C_2 + O_2反应动力学

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摘要

The reaction CiXlk,. a3ll) + 0_2(X_3k)- CO(Xlk, Aill, a' 3k; d3L', e3k) + CO(Xlk) has been studied in two types of reactors. A pyrexsteady-state fast-flow reactor at approximately 500 K was used to obtain the spectral distributions of the CO (AIll-Xlk) emissions in the vacuum ultraviolet (VUV) and the CO triplet states emissions in the visible and near-IR (vis) wavelength region. The -UV emission had not previously been positively identified. The C_2 was produced from the C_2C_4 +K reaction. In a pseudostatic high-temperature photochemistry (HTP) reactor C_2 was made by 193 nm multiphoton dissociation of C_2C_14. That apparatus was used for quenching and rate coefficient experiments in the time domain. The VUV quenching measurements confirm the orbital symmetry argument that the reaction proceeds through excited C_20_2 intermediates. Reaction schemes for C_2(Xl_2) and for C_2(a3ll) are presented. The results are compared to those from the O + C_2H_2 reaction, which leads via C_2O + O to the same band systems emissions, ~nd the differences are discussed. Measurements of the overall rate coefficients from the decrease of the vis chemiluminescence intensities with time yielded kvis(298-711 K) = 1.1 x 10-11 exp(-381 Kn') cm3 molecule-1 S-I, with 2a precision limits of around +-5% and corresponding estimated accuracy limits of about +-21%. This expression is in -excellent agreement with earlier rate coefficient valuesdeterrnined by different methods. The VUV experiments yielded slightly higher values, the reason for which is uncertain. It is speculated that an apparent continuum observed in the VUV spectra could be 1C_20_2 excimer radiation to the repulsive ground state.
机译：反应CiXlk。已经在两种类型的反应器中研究了a3ll）+ 0_2（X_3k）-CO（Xlk，Aill，a'3k; d3L'，e3k）+ CO（Xlk）。使用约500 K的热定型快速流动反应器来获得真空紫外（VUV）中CO（AIll-Xlk）发射的光谱分布以及可见光和近红外（vis ）波长区域。先前尚未明确确定 -UV发射。 C_2由C_2C_4 + K反应产生。在伪静态高温光化学（HTP）反应器中，通过C_2C_14的193 nm多光子离解制得了C_2。该装置用于时域中的淬灭和速率系数实验。 VUV淬灭测量证实了轨道对称性论点，即反应通过受激的C_20_2中间体进行。给出了C_2（Xl_2）和C_2（a3ll）的反应方案。将结果与O + C_2H_2反应的结果进行比较，后者通过C_2O + O导致相同波段的系统发射，并讨论了差异。从可见光化学发光强度随时间的降低来测量总速率系数，得出kvis（298-711 K）= 1.1 x 10-11 exp（-381 Kn'）cm3分子-1 SI，2a精度极限为+ -5％以及相应的估计精度极限（大约+ -21％）。该表达式与通过不同方法确定的较早速率系数值非常一致。 VUV实验得出的值略高，原因尚不确定。推测在VUV光谱中观察到的表观连续体可能是至排斥基态的1C_20_2受激准分子辐射。

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