Abstract

The changes in indicator-electrode potential and (quasi)equilibrium solution composition in the anodic compartment of a model electrolyzer initially filled with aqueous electrolyte containing 0.5 M concentration of bromide anions are calculated under the condition that pH 2 is maintained constant in this compartment. The theoretical analysis is carried out for three different hypotheses concerning the possible depth of electrolysis and the nature of processes involved: (1) no bromine compounds with positive degree of oxidation are formed; (2) bromine compounds with the degree of oxidation not higher than +1 are formed; (3) the process can involve the formation of both bromate ions and bromine compounds with the lower degrees of oxidation (\({\text{Br}}_{{\text{3}}}^{ - },\)\({\text{Br}}_{{\text{5}}}^{ - },\) Br₂, BrO^–, HBrO) in solution as well as the liquid phase of bromine \(\left( {{\text{Br}}_{{\text{2}}}^{{{\text{liq}}}}} \right).\) All electrochemical and chemical reactions involving bromine-containing species taken into account within the framework of hypotheses of system evolution 1, 2, and 3 are assumed to be (quasi)equilibrium, and the electric current through the cell separator is assumed to be provided by supporting electrolyte ions. Methods are proposed for experimental determination of the version of evolution of Br-containing anolyte during electrolysis.

中文翻译：

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溴化物阳极电解过程中溶液成分变化的理论分析

抽象的

在使该电解槽中的pH 2保持恒定的条件下，计算初始填充有0.5 M浓度溴离子的含水电解质的模型电解槽的阳极槽中的指示电极电势和（准）平衡溶液组成的变化。针对可能的电解深度和所涉及过程的性质，针对三种不同的假设进行了理论分析：（1）没有形成具有正氧化度的溴化合物；（2）形成氧化度不大于+1的溴化合物；（3）该过程可能涉及形成具有较低氧化度的溴酸根离子和溴化合物（\（{\ text {Br}} _ {{\ text {3}}} ^ {-} \\ （{\ text {Br}} _ {{\ text {5}}} ^ {-} \}溶液中的Br ₂，BrO ^–，HBrO以及溴的液相\（\ left（{{\ text {Br}} _ {{\ text {2}}} ^ {{{\ text {liq} }}}} \ right）。\）在系统演化1、2和3的假设框架内，所有涉及含溴物质的电化学和化学反应都被认为是（准）平衡，并且电流假定通过支持电解质离子提供了穿过电池隔板的通道。提出了用于实验确定电解过程中含溴阳极电解液演变形式的方法。