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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >High-temperature reactions of OH radicals with benzene and toluene
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High-temperature reactions of OH radicals with benzene and toluene

机译：OH自由基与苯和甲苯的高温反应

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摘要

The rate constants for the reactions of OH radicals with benzene and toluene have been measured directly by a shock tube/pulsed laser-induced fluorescence imaging method at high temperatures. The OH radicals were generated by the thermal decomposition of nitric acid or tert-butyl hydroperoxide. The derived Arrhenius expressions for the rate constants were k(OH + benzene) = 8.0 x 10(-11) exp(-26.6 kJ mol(-1)/RT) [908-1736 K] and k(OH + toluene) = 8.9 x 10(-11) exp(-19.7 kJ mol(-1)/RT) [919-1481 K] in the units of cubic centimeters per molecule per second. Transition-state theory (TST) calculations based on quantum chemically predicted energetics confirmed the dominance of the H-atom abstraction channel for OH + benzene and the methyl-H abstraction channel for OH + toluene in the experimental temperature range. The TST calculation indicated that the anharmonicity of the C-H-O bending vibrations of the transition states is essential to reproduce the observed rate constants. Possible implications to the other analogous H-transfer reactions were discussed.
机译：OH自由基与苯和甲苯的反应速率常数已通过激波管/脉冲激光诱导的荧光成像方法在高温下直接测量。 OH自由基是通过硝酸或氢过氧化叔丁基的热分解而生成的。速率常数的导出的Arrhenius表达式为k（OH +苯）= 8.0 x 10（-11）exp（-26.6 kJ mol（-1）/ RT）[908-1736 K]和k（OH +甲苯）= 8.9 x 10（-11）exp（-19.7 kJ mol（-1）/ RT）[919-1481 K]以立方厘米每分子每秒的单位。基于量子化学预测的高能学的过渡态理论（TST）计算证实了在实验温度范围内OH +苯的H原子抽象通道和OH +甲苯的甲基H抽象通道的优势。 TST计算表明，过渡态C-H-O弯曲振动的非谐性对于重现观察到的速率常数至关重要。讨论了对其他类似的H转移反应的可能含义。

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