FORMATION AND DECAY OF H2O3 AND HO2 IN ELECTRON-IRRADIATED AQUEOUS SOLUTIONS
FORMATION AND DECAY OF H2O3 AND HO2 IN ELECTRON-IRRADIATED AQUEOUS SOLUTIONS
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DOI：
10.1021/j100804a050
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发表时间：
1963-01-01
影响因子：
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通讯作者：
BIELSKI, BHJ
中科院分区：
文献类型：
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作者：
CZAPSKI, G;BIELSKI, BHJ
过羟基自由基，HO 2，之间的反应动力学进行了研究，在23。用货车de Graaff加速器产生的电子束在快速流动的含溶解氧的水中产生自由基，并通过与含四硝基甲烷的溶液快速混合来测定辐照后任何时间的剩余量，该溶液与HO 2自由基反应。发现的速率常数为kso，+ho 2 = 2.2 X 106 Af-1秒- 1和ko 2-+ oy= 1.5 × 107 Af-1秒- 1，并且发现H 02的pK为4.4±0.4。另一个中间体，据信是H2 O3的动力学理由，被发现表现出伪一级disaps-pepersion，一级速率常数是酸度的函数。使用硫酸亚铁作为清除剂溶液发现了该中间体。H2 O3的半衰期达到最大值2秒。在0.02 Af（H+）中，降低至小于0.1秒。1和10-4 M（B>）。该动力学与酸碱催化H2 O3分解生成H2O+（X.
The kinetics of the reaction between perhydroxyl radicals, HO2, have been studied at 23. The radicals were generated in rapidly flowing water containing dissolved oxygen by an electron beam from a Van de Graaff ac-celerator, and the quantity remaining at any time after irradiation was determined by rapid mixing with a solu-tion containing tetranitromethane, which reacts with HO2 radicals. The rate constants found were kso,+ ho2= 2.2 X 106 Af-1 sec.-1 and ko2-+ oy= 1.5 X 107 Af-1 sec.-1, and the pK of H02 was found to be 4.4±0.4. Another intermediate, believed to be H203 on kinetic grounds, was found to exhibit pseudo-first-order disap-pearance, the first-order rate constant being a function of acidity. This intermediate was found using ferrous sulfate as the scavenger solution. The half-life of H2O3 reaches a maximum of 2 sec. in 0.02 Af (H+), decreasing to less than 0.1 sec. in 1 and 10-4 M (B>). The kinetics are shown to agree well with acid-and base-catalyzed decomposition of H2O3 to form H20+(X.