The kinetics of OH(ν = 0) and OH(ν = 1) have been followed using pulsed photolysis of H₂O or HNO₃ to generate hydroxyl radicals, and time-resolved, laser-induced fluorescence to observe the rates of their subsequent removal in the presence of HCl or HBr. The experiments yield the following rate constants (cm³ molecule⁻¹ s⁻¹) at 298 ± 4 K: OH(ν = 0) + HCl: k_o = (6.8 ± 0.25) × 10⁻¹³; OH(ν = 0) + HBr: k_o = (11.2 ± 0.45) × 10⁻¹²; OH(ν = 1) + HCl: k₁ = (9.7 ± 1.0) × 10⁻¹³; OH(gn = 1) + HBr; k₁ = (8.1 ± 1.05) × 10⁻¹² For OH(ν = 1), the measurements do not distinguish between loss by reaction and relaxation, and the fact that k₁ > k_o for HCl is tentatively attributed to relaxation, probably by near-resonant vibrational—vibrational energy transfer. Clearly, neither of these exothermic, low-activation-energy reactions is enhanced to any great extent, if at all, by vibrational excitation of the OH radical.ft]*|Present address: Battelle/Pacific Northwest Laboratories, P.O. Box 999, Richland, Washington 99352, USA.

中文翻译：

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用HCl和HBr对OH（ν= 0）和OH（ν= 1）的动力学进行时间分辨的lif研究

使用脉冲光解H ₂ O或HNO ₃产生羟基自由基，跟踪OH（ν= 0）和OH（ν= 1）的动力学，并通过时间分辨的激光诱导荧光观察其随后的速率在HCl或HBr的存在下进行脱除。实验在298±4 K时产生以下速率常数（cm ³分子^-1 s ^-1）：OH（ν= 0）+ HCl：k _o =（6.8±0.25）×10 ^-13；OH（ν= 0）+ HBr：k _o =（11.2±0.45）×10 ^-12 ; OH（ν= 1）+ HCl：k ₁ =（9.7±1.0）×10 ^-13 ; OH（gn = 1）+ HBr; ķ ₁=（8.1±1.05）×10 ^-12对于OH（ν= 1），测量结果无法区分反应损失和弛豫之间的差异，而HCl的k ₁ > k _o暂时归因于弛豫，可能是由于接近-共振振动-振动能量传递。显然，通过OH自由基的振动激发，这些放热的低活化能反应都不会得到很大程度的增强。[ft] * |当前地址：Battelle / Pacific Northwest Laboratories，PO Box 999，Richland ，华盛顿99352，美国。