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Relative rates of reaction of C-13 O-16, C-12 O-18, C-12 O-17 and C-13 O-18 with OH and OD radicals

机译:C-13 O-16,C-12 O-18,C-12 O-17和C-13 O-18与OH和OD自由基的相对反应速率

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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 C-13 O-16, C-12 O-18, C-12 O-17 and C-13 O-18 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(D-1) in the presence of molecular hydrogen: O(D-1) + H-2/D-2 -> 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 2 sigma 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:.
机译:对一氧化碳(CO)的四种异构体及其与OH和OD自由基的反应进行了相对速率实验。在298 +/- 2 K和1013 + /下测量C-13 O-16,C-12 O-18,C-12 O-17和C-13 O-18与OH和OD自由基的相对反应速率-10毫巴。反应室中的OH / OD源是臭氧的光解,在分子氢存在下产生O(D-1):O(D-1)+ H-2 / D-2-> OH / OD + H / D.相对反应速率确定为: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)(+ 13 C 18 O)= 0.98 +/- 0.01。误差代表统计分析得出的2 sigma,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异位异构体与OH自由基反应的结果构成了对该组先前发表的实验数据的重复和重新分析,发现该数据部分是错误的。此通信是对以下论文的更正:

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