首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >The Light-Perturbed Ru-Catalyzed Belousov-Zhabotinsky Reaction: Evidence for Photochemically Produced Bromous Acid and Bromide Ions by Phase Response Analysis
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The Light-Perturbed Ru-Catalyzed Belousov-Zhabotinsky Reaction: Evidence for Photochemically Produced Bromous Acid and Bromide Ions by Phase Response Analysis

机译:光扰动的Ru催化的Belousov-Zhabotinsky反应:通过相反应分析光化学生产溴酸和溴离子的证据

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摘要

Phase response analysis of light-perturbed closed and aging Ru-catalyzed Belousov-Zhabotinsky (BZ) reactions with malonic, methyl-, ethyl-, butyl-, and phenylalonic acids as organic substrates suggests two major responses of the light-pertubed Ru-catalyzed BZ system. One is the photoproduction of bromous acid (HBrO_2) in the beginning of the reaction when little bromoorganic species are prsent, while another response is the photoproduction of bromode ions in the presence of bromomalonic acid or bomomalonic acid derivatives. From this analysis of the light-induced production of bromide ions directly from bromate can be excluded. The experimentally observed phase response curves agree well with calculations performed with the Oregonator model. An oxidative quenching mechanism for the photoproduction of bromide is suggested. Interestingly, during illumination of the Ru(II)/MA subsystem, i.e., in the absence of BrMA and bromate, the oxidative quenching does also occur.
机译:光干扰的封闭和老化的Ru催化的Belousov-Zhabotinsky(BZ)反应以丙二酸,甲基,乙基,丁酸和苯丙酸作为有机底物的相响应分析表明,光催化的Ru催化的两个主要反应BZ系统。一种是在反应开始时存在少量溴有机物时的溴酸(HBrO_2)的光产生,而另一种响应是在存在溴代丙二酸或溴代丙二酸衍生物的情况下溴代离子的光产生。从光诱导直接由溴酸盐产生溴离子的这种分析中,可以排除这种情况。实验观察到的相位响应曲线与用Oregonator模型执行的计算非常吻合。提出了一种用于光致溴化物的氧化猝灭机理。有趣的是,在照亮Ru(II)/ MA子系统期间,即在不存在BrMA和溴酸盐的情况下,也确实发生了氧化猝灭。

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