Some Applications of Time‐Dependent Rate Constant Theory to Radiation Chemistry
Some Applications of Time‐Dependent Rate Constant Theory to Radiation Chemistry
复制标题
时变速率常数理论在辐射化学中的一些应用
DOI：
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发表时间：
1971
期刊：
影响因子：
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通讯作者：
H. Schwarz
中科院分区：
文献类型：
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作者：
H. Schwarz
众所周知，扩散限制反应的速率常数在实验开始后随着时间的推移而降低，这是由于建立每种反应物围绕另一种反应物的扩散梯度所需的时间造成的。它指出，离子之间的缓慢反应也表现出时间依赖性，因为需要一个有限的时间来建立玻尔兹曼分布的每种类型的离子周围的其他。后一种效应表现为相反电荷的离子之间的反应速率常数随时间增加，而相似电荷的离子则随时间减少。这些随时间变化的效应被应用于Wolff等人的丙酮和酸溶液中电子形成和衰变的皮秒脉冲辐解结果，以及Czapski和Peled的一些竞争实验。它们归因于水合电子的前体反应的效应被证明与水合电子本身的时间依赖性现象的预期后果相似。
It is well known that rate constants for diffusion‐limited reactions decrease with time after the start of an experiment, an effect due to the time required to establish a diffusion gradient of each reactant around the other. It is pointed out that slow reactions between ions also exhibit a time dependence because a finite time is required to establish the Boltzmann distribution of each type of ion around the other. The latter effect appears as an increase of rate constant with time for reactions between ions of opposite charge and a decrease for ions of similar charge. These time dependent effects are applied to the picosecond pulse radiolysis results of Wolff et al. on electron formation and decay in acetone and acid solutions, and to some competition experiments of Czapski and Peled. Effects attributed by them to reactions of a precursor of the hydrated electron are shown to be similar to expected consequences of time‐dependent phenomena of the hydrated electron itself.