Picosecond Pulse Radiolysis. III. Reaction Rates and Reduction in Yields of Hydrated Electrons
Picosecond Pulse Radiolysis. III. Reaction Rates and Reduction in Yields of Hydrated Electrons
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皮秒脉冲辐射分解。
DOI：
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发表时间：
1971
期刊：
影响因子：
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通讯作者：
J. Hunt
中科院分区：
文献类型：
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作者：
J. Aldrich;M. Bronskill;R. Wolff;J. Hunt
在20-350PSEC的时间范围内，测定了水合电子与包括简单盐和氨基酸在内的多种化合物的反应速率常数。在几乎所有的情况下，与水合电子反应的二级速率常数在所研究的浓度范围内都没有变化。然而，测得的速率常数与稀溶液中测得的速率常数大体不同，这是由于反应前水合电子周围的离子气氛没有完全形成所致。除了氢离子HAq+，几乎所有化合物都降低了初始水合电子产率：在所有情况下，这种下降都表现出与浓度的指数依赖关系。在降低水合电子产率方面最有效的化合物是胱氨酸和镉盐，这两种情况下都需要0.39摩尔/升才能将初始产率降低到37%。降低初始产率的能力与相应的水合电子速率没有直接关系。这是一个..。
Rate constants for reactions of the hydrated electron with a wide range of compounds, including simple salts and amino acids, have been measured in the time region 20–350 psec. In nearly all cases the second‐order rate constant for reaction with the hydrated electron did not change in the concentration range studied. However, the measured rate constant was in general different to that obtained in dilute solutions, and this was attributed to incomplete formation of the ionic atmosphere around the hydrated electron before reaction. Apart from the hydronium ion, Haq+, nearly all compounds decreased the initial hydrated electron yield: in all cases this decrease showed an exponential dependence on concentration. Compounds most efficient at decreasing the hydrated electron yield were cystine and cadmium salts, in both cases 0.39 mole/liter being needed to reduce the initial yield to 37%. The ability to reduce the initial yield showed no direct correlation with the corresponding hydrated electron rates. This an...