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首页> 外文期刊>Journal of the Indian Chemical Society >Iodide mediated oxidation of arsenic(III) by cerium(IV) in aqueous sulphuric acid and sulphate media - A kinetic and mechanistic study
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Iodide mediated oxidation of arsenic(III) by cerium(IV) in aqueous sulphuric acid and sulphate media - A kinetic and mechanistic study

机译：碘化物介导的硫酸和硫酸盐介质中铈（IV）氧化铈（IV）的动力学和机理研究

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摘要

A minute (10~(-8) mol dm~(-3)) quantity of iodide mediated oxidation of arsenic(III) by cerium(IV) in an aqueous sulphuric acid and sulphate media has been studied spectrophotometrically at 25 °C. The stoichiometry is 1 : 2, i.e. one mole of arsenic(III) requires two moles of cerium(IV). The reaction is first order each in cerium(IV) and iodide concentrations. The order with respect to arsenic(III) is less than unity. Increase in sulphuric acid concentration increased the rate. In situ H~+ ion concentration is calculated by the knowledge of equilibrium constants and the order with respect to H~+ ion concentration is found to be less than unity. The ionic strength did not have any significant effect on the rate of reaction, whereas rate constant increased with decreasing dielectric constant of the medium. Added products cerium(III) and arsenic(v) did not have any significant effect on the reaction rate. The active species of oxidant and reductant are Ce(SO4)~(2+) and AsI~(2+) respectively. A suitable mechanism is proposed. The catalytic constant and activation parameters are determined. The results obtained in the present study are similar to that of bromide, chloride and iodide mediated oxidation of antimony(III) by cerium(IV) in aqueous sulphuric acid-sulfate media and are compared and discussed.
机译：在25°C下用分光光度法研究了微量的（10〜（-8）mol dm〜（-3））碘化物介导的铈（IV）氧化铈（IV）。化学计量比为1：2，即一摩尔的砷（III）需要两摩尔的铈（IV）。该反应在铈（IV）和碘化物浓度中均为一级。关于砷（III）的顺序小于1。硫酸浓度增加的速率增加。通过平衡常数的知识就地计算出H〜+离子浓度，发现相对于H〜+离子浓度的阶次小于1。离子强度对反应速率没有任何显着影响，而速率常数随介质介电常数的降低而增加。添加的产物铈（III）和砷（v）对反应速率没有任何显着影响。氧化剂和还原剂的活性种类分别为Ce（SO4）〜（2+）和AsI〜（2+）。提出了合适的机制。确定催化常数和活化参数。在本研究中获得的结果类似于在硫酸硫酸盐介质中溴化铈，氯化铈和碘化物介导的铈（IV）氧化锑（III）的结果，并进行了比较和讨论。

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