13C16O、12C18O、12C17O和13C18O与OH及OD自由基的相对反应速率。
Relative rates of reaction of 13C16O, 12C18O, 12C17O and 13C18O with OH and OD radicals.
作者信息
Feilberg Karen L, Johnson Matthew S, Nielsen Claus J
机构信息
Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen OE, Denmark.
出版信息
Phys Chem Chem Phys. 2005 Jun 7;7(11):2318-23. doi: 10.1039/b503350k.
A relative rate experiment is carried out for four isotopomers of carbon monoxide (CO) and their reactions with OH and OD radicals. The relative reaction rates of 13C16O, 12Cl8O, 12C17O and 13C18O with OH and OD radicals are measured at 298 +/- 2 K and 1013 +/- 10 mbar. The OH/OD source in the reaction chamber is photolysis of ozone to produce O(1D) in the presence of molecular hydrogen: O(1D) + H2/D2 --> OH/OD + H/D. The relative reaction rates are determined as: k(OH) + 13C16O/k(OH) + 12C18O = 0.98 +/- 0.01, k(OH) + 12C17O/k(OH) + 12C18O = 0.990 +/- 0.008, k(OH) + 13C16O/k(OH) + 13C18O = 0.98 +/- 0.01, k(OD) + 13C16O/k(OD) + 12C18O = 0.99 +/- 0.01, k(OD) + 12C17O/ k(OD) + 12C18O = 1.000 +/- 0.008, k(OD) + 13C16O/k(OD) + 13C18O = 0.98 +/- 0.01. The errors represent 2sigma from the statistical analyses and do not include possible systematic errors. These are novel results for the kinetic isotope effects in the reactions of CO isotopomers with OD radicals. The results for the reactions of CO isotopomers with OH radicals constitute a repeat and a re-analysis of experimental data previously published by this group which have been found to be partly erroneous. This communication serves as a correction to the following paper: K. L. Feilberg, S. R. Sellevåg, C. J. Nielsen, D. W. T. Griffith and M. S. Johnson, Phys. Chem. Chem. Phys., 2002, 4, 4687.
对一氧化碳（CO）的四种同位素异构体及其与OH和OD自由基的反应进行了相对速率实验。在298±2 K和1013±10毫巴的条件下，测量了(^{13}C^{16}O)、(^{12}C^{18}O)、(^{12}C^{17}O)和(^{13}C^{18}O)与OH和OD自由基的相对反应速率。反应室中的OH/OD源是在分子氢存在下臭氧的光解以产生O(1D)：O(1D) + (H_2)/(D_2) --> OH/OD + H/D。相对反应速率确定为：(k(OH) + ^{13}C^{16}O)/(k(OH) + ^{12}C^{18}O) = 0.98±0.01，(k(OH) + ^{12}C^{17}O)/(k(OH) + ^{12}C^{18}O) = 0.990±0.008，(k(OH) + ^{13}C^{16}O)/(k(OH) + ^{13}C^{18}O) = 0.98±0.01，(k(OD) + ^{13}C^{16}O)/(k(OD) + ^{12}C^{18}O) = 0.99±0.01，(k(OD) + ^{12}C^{17}O)/(k(OD) + ^{12}C^{18}O) = 1.000±0.008，(k(OD) + ^{13}C^{16}O)/(k(OD) + ^{13}C^{18}O) = 0.98±0.01。这些误差代表统计分析中的2σ，不包括可能的系统误差。这些是CO同位素异构体与OD自由基反应中动力学同位素效应的新结果。CO同位素异构体与OH自由基反应的结果重复并重新分析了该小组之前发表的实验数据，发现部分数据有误。本通讯是对以下论文的更正：K. L. Feilberg、S. R. Sellevåg、C. J. Nielsen、D. W. T. Griffith和M. S. Johnson，《物理化学化学物理》，2002年，4，4687。
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