686. Glow-discharge electrolysis. Part I. The anodic formation of hydrogen peroxide in inert electrolytes
686. Glow-discharge electrolysis. Part I. The anodic formation of hydrogen peroxide in inert electrolytes
复制标题
686.辉光放电电解。
DOI：
10.1039/jr9520003595
复制
发表时间：
1952
期刊：
影响因子：
--
通讯作者：
A. Hickling
中科院分区：
文献类型：
--
作者：
R. A. Davies;A. Hickling
本文研究了惰性电解质稀溶液的电解，通过向液面放出减压放电，使阳极从溶液中抽出。最初形成的主要阳极产物是过氧化氢，其量与所传递的电量成正比；当过氧化氢在溶液中积累时，就会发生分解反应，最终得到稳定的过氧化氢浓度。在给定电量通过后存在于溶液中的过氧化氢的量基本上与所使用的电流和影响放电性质的因素无关，并且可以用(H，O)当量的形式精确地表示。=V(L-EF)/k其中Q是法拉第的电量，V是溶液的体积，k是分解反应的速度系数，以及a是表示对于每通过的电量初始形成的过氧化氢当量的系数(值1.1-1.9)。对于p H从1到9的不同溶液，这个过程基本上是相同的，但是，在这个范围的极端情况下，过氧化氢的生成量有所减少；在强碱性溶液中，没有检测到过氧化氢，这可能是因为它容易通过释放过氧化氢离子进行阳极分解。电解的一般特征被解释为羟基自由基在溶液中的初级形成，主要是通过电解作用，尽管不排除水分子的一些直接解离的可能性；然后发生二聚化产生过氧化氢，当过氧化氢达到足够的浓度时，它通过与羟基自由基的相互作用迅速分解。
The electrolysis of dilute solutions of inert electrolytes has been investigated, with an anode withdrawn from the solution, by passing an electrical discharge at reduced pressure to the liquid surface. The main anodic product initially formed is hydrogen peroxide in amount proportional to the quantity of electricity passed; as this accumulates in the solution a decomposition reaction sets in and ultimately a stationary concentration of hydrogen peroxide is attained. The amount of hydrogen peroxide present in the solution after the passage of a given quantity of electricity is substantially independent of the current used and of factors affecting the nature of the discharge, and it can be accurately expressed by an equation of the form (H, O,) equivs.= V (l-eF)/k where q is the quantity of electricity in faradays, V is the volume of the solution, k is a velocity coefficient for the decomposition reaction, and a is a factor (value 1.1-1.9) expressing the number of equivalents of hydrogen peroxide initially formed for each faraday of electricity passed. The process is fundamentally the same for different solutions varying in p H from 1 to 9, with, however, some decrease in the amount of hydrogen peroxide formed at the extremes of this range; in strongly alkaline solutions no hydrogen peroxide can be detected, probably owing to its ready anodic decomposition by discharge of the perhydroxyl ion. The general features of the electrolysis are interpreted by the primary formation in solution of the hydroxyl radical, mainly by electrolytic action although the possibility of some direct dissociation of water molecules is not excluded; dimerisation then occurs to give hydrogen peroxide, which, when it attains a sufficient concentration, decomposes by interaction with hydroxyl radicals as fast as it is formed.