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Chlorine Dioxide-Iodide-Methyl Acetoacetate Oscillation Reaction Investigated by UV-Vis and Online FTIR Spectrophotometric Method

机译:紫外可见-在线FTIR分光光度法研究二氧化氯-碘化物-乙酰乙酸甲酯的振荡反应

摘要

In order to study the chemical oscillatory behavior and mechanism of a new chlorine dioxide-iodide ion-methyl acetoacetate reaction system, a series of experiments were done by using UV-Vis and online FTIR spectrophotometric method. The initial concentrations of methyl acetoacetate, chlorine dioxide, potassium iodide, and sulfuric acid and the pH value have great influence on the oscillation observed at wavelength of 289 nm. There is a preoscillatory or induction period, and the amplitude and the number of oscillations are associated with the initial concentration of reactants. The equations for the triiodide ion reaction rate changing with reaction time and the initial concentrations in the oscillation stage were obtained. Oscillation reaction can be accelerated by increasing temperature. The apparent activation energies in terms of the induction period and the oscillation period were 26.02 KJ/mol and 17.65 KJ/mol, respectively. The intermediates were detected by the online FTIR analysis. Based upon the experimental data in this work and in the literature, a plausible reaction mechanism was proposed for the oscillation reaction.
机译:为了研究新型二氧化氯-碘离子-乙酰乙酸甲酯反应体系的化学振荡行为和机理,采用紫外可见和在线FTIR分光光度法进行了一系列实验。乙酰乙酸甲酯,二氧化氯,碘化钾和硫酸的初始浓度以及pH值对在289 nm波长下观察到的振荡有很大影响。存在振荡前或诱导期,并且振幅和振荡次数与反应物的初始浓度有关。得到了三碘化物离子反应速率随反应时间和振荡阶段初始浓度变化的方程式。振荡反应可以通过提高温度来加速。表观活化能以诱导期和振荡期计分别为26.02 KJ / mol和17.65 KJ / mol。通过在线FTIR分析检测中间体。基于这项工作和文献中的实验数据,提出了一种合理的振荡反应机理。

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