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首页> 外文期刊>The journal of physical chemistry, B. Condensed matter, materials, surfaces, interfaces & biophysical >Surface Alloying of Lead as a Step in the Cathodic Generation of the Pb_9~(4-) in KI and RbBr Liquid Ammonia Solutions
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Surface Alloying of Lead as a Step in the Cathodic Generation of the Pb_9~(4-) in KI and RbBr Liquid Ammonia Solutions

机译：铅的表面合金化是在KI和RbBr液氨溶液中阴极生成Pb_9〜（4-）的步骤

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摘要

Reduction of lead in liquid ammonia solutions of KI and RbBr at -70 ℃ was studied using voltammetry as well as potentiostatic and galvanostatic techniques. It was found that the only soluble reduction product was the Zintl ion Pb_9~(4-). Transitionally two intermetallic phases were also formed via direct incorporation of the alkali metal into lead, but they eventually dissolved in liquid ammonia. The alkali metal (M)-rich phase had the Pb:M molar ratio around 0.4 for both K and Rb, whereas the ratio for the lead-rich phase was between 0.8:1 and 1: 1 for potassium and around 0.7:1 for rubidium. The alkali metal-rich phase was unstable and easily transformed into the lead-rich phase by the reaction with solid lead. This reaction plays a crucial role both in the alkali metal incorporation and in the solid-phase dissolution reaction. A model mechanism of the lead reduction is presented.
机译：利用伏安法，恒电位和恒电流技术研究了在-70℃下KI和RbBr液氨溶液中铅的还原。发现唯一的可溶性还原产物是Zintl离子Pb_9〜（4-）。通过将碱金属直接掺入铅也形成了过渡的两个金属间相，但最终它们溶解在液氨中。富碱金属（M）相的K和Rb的Pb：M摩尔比约为0.4，而富铅相的比例对于钾为0.8：1至1：1，而对于钾为0.7：1铷。富含碱金属的相不稳定，并且通过与固体铅的反应容易转变成富含铅的相。该反应在碱金属结合和固相溶解反应中都起着至关重要的作用。提出了减少铅的模型机制。

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