The rate of hydrated electron reaction with neutral and anionic scavengers in concentrated salt solutions
The rate of hydrated electron reaction with neutral and anionic scavengers in concentrated salt solutions
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浓盐溶液中水合电子与中性和阴离子清除剂的反应速率
DOI：
10.1021/j100541a007
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发表时间：
1977
期刊：
影响因子：
--
通讯作者：
D. Schulte‐Frohlinde
中科院分区：
文献类型：
--
作者：
E. Hankiewicz;D. Schulte‐Frohlinde
e/sub aq//sup -/ 与硝基苯、IrCl/sub 6//sup 2 -/ 和 Fe(CN)/sub 6//sup 3 -/ 反应的速率常数 k/sub obsd/ 已在水中以及浓度高达 14 M LiCl 和 6 M CsCl 的 LiCl 和 CsCl 溶液中测量，并且发现是扩散控制的。 CsCl 溶液的粘度与 CsCl 浓度无关，而在 LiCl 溶液的情况下，粘度的对数随浓度线性减小。由于硝基苯的速率常数的对数 log k/sub obsd/ 随 LiCl 浓度线性降低，因此粘度是速率决定参数。在 CsCl 溶液中，速率常数不随盐浓度变化。铱酸盐和铁氰化物在 LiCl 浓度分别高于 1 和 6 M 时表现得像中性物质；在这些LiCl浓度以上，它们的速率常数和硝基苯的速率常数对盐浓度的依赖性是高盐浓度下的Smoluchowski-Debye方程。
The rate constants, k/sub obsd/, of the e/sub aq//sup -/ reaction with nitrobenzene, IrCl/sub 6//sup 2 -/, and Fe(CN)/sub 6//sup 3 -/ have been measured in water, and in LiCl and CsCl solutions up to a concentration of 14 M LiCl and 6 M CsCl and were found to be diffusion controlled. The viscosity of CsCl solutions is independent of CsCl concentration whereas in the case of LiCl solutions the logarithm of the viscosity decreases linearly with concentration. Since the logarithm of the rate constant, log k/sub obsd/, with nitrobenzene decreases linearly with LiCl concentration the viscosity is the rate-determining parameter. In CsCl solutions the rate constants do not vary with salt concentration. Iridate and ferricyanide behave like neutral species at LiCl concentrations above 1 and 6 M, respectively; above these LiCl concentrations the dependence of their rate constants and that of nitrobenzene on salt concentration is Smoluchowski--Debye equation at high salt concentration.