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首页> 外文期刊>Cogent Chemistry >A spectroscopic investigation of kinetics and mechanism of ruthenium(III)-catalyzed oxidation of N-(2-hydroxyethyl)phthalimide by cerium(IV) in aqueous sulphuric acid and sulphate media
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A spectroscopic investigation of kinetics and mechanism of ruthenium(III)-catalyzed oxidation of N-(2-hydroxyethyl)phthalimide by cerium(IV) in aqueous sulphuric acid and sulphate media

机译：硫酸和硫酸盐介质中钌（III）催化铈（IV）催化钌（III）催化氧化N-（2-羟乙基）邻苯二甲酰亚胺的动力学和机理的光谱学研究

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The oxidation of N-(2-hydroxyethyl)phthalimide with cerium(IV) with a small amount of ruthenium(III) present as a catalyst has been studied by spectrophotometric means. The spectroscopic study has been carried out in aqueous H_(2)SO_(4) and SO 4 2 - media at constant ionic strength of I ?=?1.60?mol?dm~(?3). Stoichiometric analysis shows that one mole of NHEP reacts with two moles of cerium(IV). The oxidation products were identified by IR and GC–MS. Orders with respect to substrate, oxidant, ruthenium(III) and acid concentrations were determined. Increase in sulphuric acid concentration increases the rate. Effect of ionic strength and solvent polarity of the medium on the rate of the reaction was studied. The added product, cerium(III), has no significant effect on the rate of reaction. The active species of oxidant in sulphate medium and catalyst are Ce SO 4 2 + and [Ru(H_(2)O)_(6)]~(3+). Based on the experimental results a suitable mechanism is proposed. The activation parameters and the thermodynamic quantities are also determined and discussed.
机译：用分光光度法研究了用少量的钌（Ⅲ）作为催化剂的铈（Ⅳ）对N-（2-羟乙基）邻苯二甲酰亚胺的氧化作用。光谱研究是在H_（2）SO_（4）和SO 4 2-水溶液中以恒定的离子强度为I≥1≤≤1.60≤mol≤dm≤（≤3）进行的。化学计量分析表明，一摩尔的NHEP与两摩尔的铈（IV）反应。通过IR和GC-MS鉴定了氧化产物。确定有关底物，氧化剂，钌（III）和酸浓度的顺序。硫酸浓度的增加速率增加。研究了介质的离子强度和溶剂极性对反应速率的影响。所添加的产物铈（III）对反应速率没有显着影响。硫酸盐介质和催化剂中氧化剂的活性种为Ce SO 4 2 +和[Ru（H_（2）O）_（6）]〜（3+）。根据实验结果，提出了一种合适的机理。还确定并讨论了活化参数和热力学量。

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