Pulse-radiolysis study of some unstable complexes of iron
Pulse-radiolysis study of some unstable complexes of iron
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DOI：
10.1039/tf9696502453
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发表时间：
1969
影响因子：
--
通讯作者：
G. G. Jayson-G.;J. P. Keene;D. Stirling;A. Swallow
中科院分区：
文献类型：
--
作者：
G. G. Jayson-G.;J. P. Keene;D. Stirling;A. Swallow
高氯酸亚铁在高氯酸（1 M）中的含氧溶液的脉冲辐解能够观察到三价铁氢过氧化物复合物Fe 3 +HO-2的形成和消失。在pH 0-2.1范围内，HO_2自由基与游离亚铁离子反应生成的速率常数为2.1 ± 0.4 × 106 M ~（-1）s ~（-1）。络合物在一级反应中消失，其速率常数在0-2.1范围内与pH无关。它在280-600 nm区域内表现出宽吸收，Iµ430 nm= 280 ± 30 M-1 cm-1。在没有氧的情况下，可以看到不同的吸收物种，归因于氢化铁络合物，Fe 3 +H-。这是由氢原子与自由亚铁离子反应形成的，k= 7.5 ± 2 × 106 M-1 s-1。它与氢离子反应后消失，k= 1.06 ± 0.1 × 104 M-1 s-1。其吸收光谱在325 nm处显示最大值，Iµ325= 650 ± 65 M-1 cm-1。
Pulse radiolysis of oxygen-containing solutions of ferrous perchlorate in perchloric acid (l M) enables the formation and disappearances of a ferric hydroperoxide complex, Fe3+HO–2, to be observed. The rate constant for its formation by reaction of HO2 radicals with free ferrous ions is 2.1 ± 0.4 × 106 M–1s–1 in the pH range 0–2.1. The complex disappears in a first-order reaction with a rate constant independent of pH in the range 0–2.1. It exhibits a broad absorption in the region 280–600 nm, with Iµ430 nm= 280 ± 30 M–1 cm–1. In the absence of oxygen, a different absorbing species can be seen, attributed to a ferric hydride complex, Fe3+H–. This is formed by the reaction of hydrogen atoms with free ferrous ions with k= 7.5 ± 2 × 106 M–1 s–1. It disappears by reaction with hydrogen ions, with k= 1.06 ± 0.1 × 104 M–1 s–1. Its absorption spectrum exhibits a maximum at 325 nm, Iµ325= 650 ± 65 M–1 cm–1.