双periodatocuate (III)在碱性介质中氧化3-氨基-1-丙醇的动力学及机理

J. Shan, C. Han, S. Huo, L. Fan
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引用次数: 1

摘要

用分光光度法研究了双periodatocuate (III) (DPC)在298.2 K - 313.2 K的碱性水介质中氧化3-氨基-1-丙醇(3-AP)的动力学。DPC和1 < nap < 2 ~ 3-AP均为准一级反应。在伪一阶条件下([3-AP] 0 [DPC]0),不同浓度的[OH−]对反应速率常数的影响是不同的。在低[OH−]时,kobs随[OH−]的增加而降低,而在高[OH−]时,kobs随[OH−]的增加而增加,高碘酸盐对反应速率有延缓作用。存在微弱的负盐效应。通过现场试验对主要产品进行了鉴定。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。测定了反应的活化参数和速率决定步骤的速率常数。
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Kinetics and Mechanism of Oxidation of 3-Amino-1-propanol by Diperiodatocuprate(III) in Alkaline Medium
The kinetics of oxidation of 3-amino-1-propanol (3-AP) by diperiodatocuprate(III) (DPC) in aqueous alkaline medium have been studied by spectrophotometry in the temperature range 298.2 K–313.2 K. The reaction was found to be pseudo-first order with respect to DPC and 1 < nap < 2 to 3-AP. It was found that under pseudo-first order conditions ([3-AP] 0 [DPC]0), the observed rate constant kobschanged differently under different concentration of [OH −]. At low [OH−], kobsdecreased with increase in [OH−], but at higher [OH−], kobs increase with increase in [OH −], and periodate had a retarding effect on the reaction rate. There is a weak negative salt effect. The main products were identified by spot tests. 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 the rate constants of the rate-determining step, were determined.
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