Nanosecond Pulse Radiolysis and Nonhomogeneous Kinetics Involving Hydrated Electrons
Nanosecond Pulse Radiolysis and Nonhomogeneous Kinetics Involving Hydrated Electrons
复制标题
纳秒脉冲辐射分解和涉及水合电子的非均匀动力学
DOI：
10.1063/1.1671667
复制
发表时间：
1969
期刊：
影响因子：
--
通讯作者：
D. Walker
中科院分区：
文献类型：
--
作者：
G. A. Kenney;D. Walker
对浓度约为 10−4M 的水合电子行为的纳秒脉冲放射分解研究表明，大约第一个半衰期（~110 纳秒）期间的衰变特征在于速率常数与第二个半衰期期间的速率常数显着不同。后者的速率似乎遵循二级动力学。最初的衰减归因于物种的不均匀分布以及系统变得真正均匀之前涉及 eaq− 的轨道内反应。非均匀周期的定性计算与实验过渡时间一致。显然，在一些脉冲放射分解研究中，人们无法合理地根据光密度测量评估的浓度计算二阶速率常数。这些实验是在纯脱气水中进行的，该水受到来自 Febetron 加速器的 0.5 MeV 电子的 3 纳秒强脉冲的影响。通过使用非常小的反应体积进行分光光度分析...
Nanosecond pulse‐radiolysis studies on the behavior of hydrated electrons at concentrations of about 10−4M showed that the decay during approximately the first half‐life (∼110 nsec) was characterized by a rate constant significantly different from that during the second half‐life. The latter rate appeared to follow second‐order kinetics. The initial decay is attributed to nonuniform distributions of species and to intratrack reactions involving eaq− before the system became truly homogeneous. Qualitative calculations on the period of nonhomogeneity were in agreement with the experimental transition time. It is apparent that in some pulse‐radiolysis studies one cannot justifiably calculate second‐order rate constants from concentrations evaluated from optical‐density measurements. The experiments were performed on pure deaerated water subjected to an intense 3‐nsec pulse of 0.5‐MeV electrons from a Febetron accelerator. Spectrophotometric analyses were conducted over very small reaction volumes by using th...