High-pressure falloff curves and specific rate constants for the reactions atomic hydrogen + molecular oxygen .dblharw. perhydroxyl .dblharw. hydroxyl + atomic oxygen
High-pressure falloff curves and specific rate constants for the reactions atomic hydrogen + molecular oxygen .dblharw. perhydroxyl .dblharw. hydroxyl + atomic oxygen
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DOI：
10.1021/j100248a033
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发表时间：
1985-01
期刊：
影响因子：
--
通讯作者：
C. Cobos;H. Hippler;J. Troe
中科院分区：
文献类型：
--
作者：
C. Cobos;H. Hippler;J. Troe
复合反应 H + O/sub 2/ + M ..-->.. HO/sub 2/ + M 在 1 至 200 bar 的压力下，通过激光闪光光解在 M = Ar、N/sub 2/ 和 CH/sub 4/ 浴槽气体中进行研究。通过衰减曲线的外推，在 298 K 下得出极限高压速率系数 k/sub infinity/ = 7.5 x 10/sup -11/ cm/sup 3/ molecular/sup -1/ s/sup -1/。根据统计绝热通道模型对此结果进行分析，得到类似排序的 0.94 A/sup -1/ 的松散参数。构建了 HO/sub 2/ 解离的相应特定速率常数 k(E,J) 并与轨迹计算进行比较。结果还与反应 HO + O ..-->.. H + O/sub 2/ 的数据进行了比较，该反应的预测几乎与温度无关的速率常数为 2.8 x 10/sup -11/ cm/sup 3/ molecular/sup -1/ s/sup -1/。对与能量传递特性相关的极限低压速率系数进行了分析。结果与激发的 H2O/sub 2/ 的能量转移轨迹计算进行了比较。 77 篇参考文献、8 张图、5 个表格。
The recombination reaction H + O/sub 2/ + M ..-->.. HO/sub 2/ + M is studied by laser flash photolysis in the bath gases M = Ar, N/sub 2/, and CH/sub 4/ at pressures between 1 and 200 bar. By extrapolation of the falloff curves, a limiting high-pressure rate coefficient k/sub infinity/ = 7.5 x 10/sup -11/ cm/sup 3/ molecule/sup -1/ s/sup -1/ is derived at 298 K. An analysis of this result in terms of the statistical adiabatic channel model leads to a looseness parameter of a similarly ordered 0.94 A/sup -1/. The corresponding specific rate constants k(E,J) for dissociation of HO/sub 2/ are constructed and compared with trajectory calculations. The results are also compared with data on the reaction HO + O ..-->.. H + O/sub 2/ for which a nearly temperature-independent rate constant of 2.8 x 10/sup -11/ cm/sup 3/ molecule/sup -1/ s/sup -1/ is predicted. An analysis of the limiting low-pressure rate coefficients with respect to energy-transfer properties is made. The results are compared with trajectory calculations of energy transfer of excited HO/sub 2/. 77 references, 8 figures, 5 tables.