2,2′-联吡啶基催化铬(VI)氧化乳酸的动力学与机理研究

J. Shan, L. Fan, S. Huo, H. M. Liu, S. Shen
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引用次数: 0

摘要

用分光光度法研究了2,2′-联吡啶(bpy)在25 ~ 40◦C的酸性水溶液中催化铬(VI)氧化乳酸(Lac)的动力学和机理。该反应对Cr(VI)为准一级反应,对乳酸为准一级反应。伪一阶速率常数随[H+]和[bpy]的增加而增加。有弱的负盐效应,没有检测到自由基。因此,HCrO4被认为是Cr(VI)的主要存在种类。根据实验结果,提出了一种可能的氧化反应机理。由该机理导出的速率方程可以解释所有的实验现象。计算了反应的活化参数和速率决定步骤的速率常数。
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A Kinetic andMechanistic Study of 2,2'- Bipyridyl the Catalyzed Chromium(VI) Oxidation of Lactic Acid
The kinetics and mechanism of 2,2′-bipyridyl (bpy) catalysis of the chromium(VI) oxidation of lactic acid (Lac) in aqueous acidic medium was studied with spectrophotometry in a temperature range of 25∼40 ◦C. The reaction was found to be pseudo-first order with respect to Cr(VI) and first order to lactic acid. It was found that the pseudo-first order rate constantkobs increased with the increase in [H+] and [bpy]. There is a weak negative salt effect and no free radicals are detected. Thus, HCrO4 is assumed the main existing species of Cr(VI). Based on the experimental results, a probable reaction mechanism of oxidation is proposed. The rate equation derived from the mechanism can explain all the experimental phenomena. The activation parameters, along with rate constants of the rate-determining step, have been calculated.
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