Kinetics and mechanistic approach to electron transfer from renewable isosorbide to Ce (IV) in HClO4 medium

IF 2.218 Q2 Chemistry

Chemical Data Collections Pub Date : 2023-11-30 DOI:10.1016/j.cdc.2023.101105

Ahmed Fawzy , Nizar El Guesmi , Basim H. Asghar

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引用次数: 0

Abstract

Kinetics of isosorbide (S) oxidation by Ce(IV) in aqueous HClO₄ medium has been examined via spectrophotometric technique at fixed ionic strength and temperature. The reaction showed a 1: 2 stoichiometry (S: Ce(IV)). The reaction was studied under pseudo-first order conditions. The dependency of the rate of oxidation reaction on the reactants’ concentrations showed that the reaction was first order in [Ce(IV)], whereas in both [H⁺] and [S], its order was lower than unity. The oxidation rate was directly proportional to ionic strength as well as dielectric constant of the reaction medium. However, it should be mentioned that adding Ce(III) had remarkably not affect the rate. The isosorbide oxidation product was recognized as (1S,4S,5R)-4-hydroxy-2,6-dioxabicyclo[3.3.0]octan-8-one). A mechanistic scheme for oxidation coherent with the observed kinetics was proposed. The rate-law expression was derived which was agreed with the acquired outcomes. The calculated activation quantities recommended construction of a rigid intermediate through the reaction and such process was endothermic and non-spontaneous.

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HClO4介质中可再生异山梨酯向Ce (IV)电子转移的动力学和机理研究

用分光光度法研究了在固定离子强度和温度下，Ce(IV)在HClO4水溶液中氧化异山梨酯(S)的动力学。反应呈1:2的化学计量(S: Ce(IV))。在拟一级条件下研究了该反应。氧化反应速率与反应物浓度的关系表明，[Ce(IV)]为一级反应，而[H+]和[S]为低一级反应。氧化速率与反应介质的离子强度和介电常数成正比。然而，应该提到的是，添加Ce(III)对反应速率没有显著影响。异山梨酯氧化产物为(1S,4S,5R)-4-羟基-2,6-二恶沙环[3.3.0]辛烷-8- 1)。提出了与观察到的动力学一致的氧化机理方案。得到了与所得结果一致的速率律表达式。计算出的活化量建议通过反应构建刚性中间体，该过程是吸热的，非自发的。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Chemical Data Collections Chemistry-Chemistry (all)

CiteScore

6.10

自引率

0.00%

发文量

169

审稿时长

24 days

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