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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Kinetics and mechanism of the chromium(vi) catalyzed decomposition of hypochlorous acid at elevated temperature and high ionic strength
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Kinetics and mechanism of the chromium(vi) catalyzed decomposition of hypochlorous acid at elevated temperature and high ionic strength

机译：铬（VI）的动力学和机制催化在升高的温度和高离子强度下次氯酸分解

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摘要

An important reaction step in the industrial production of NaClO3 (electrochemical chlorate process) is the thermal decomposition of HOCl/OCl- to yield ClO3- and Cl-. It is widely accepted that this reaction is accelerated by aqueous chromium(vi) species. A detailed kinetic study was conducted under industrially relevant conditions, i.e. at high ionic strength (6.0 M) and elevated temperature (80 degrees C), to investigate this phenomenon. The decomposition of hypochlorous acid was followed in the presence of Cr(vi) or phosphate (PO43-) or without any additive. In addition to the beneficial pH buffering effect of Cr(vi), the CrO42- form of chromium(vi) was found to slightly catalyze the decomposition of hypochlorous acid. The overall rate of HOCl decomposition can be expressed as -dc(HOCl)/dt = k(dec)[HOCl](2)[OCl-] + k(cat)[HOCl](2)[CrO42-]. The corresponding rate constants were determined, k(dec) = 9.4 +/- 0.1 M-2 s(-1) and k(cat) = 4.6 +/- 0.8 M-2 s(-1), and mechanistic interpretation of the catalytic rate law is given. The contribution of the catalytic path to the overall rate of decomposition changes from ca. 30% at pH = 8 to ca. 70% at pH = 6.
机译：NaClO3（电化学氯酸盐工艺）工业生产中的重要反应步骤是Hocl / OCL-产生ClO3和Cl-的热分解。众所周度地接受该反应通过铬（VI）物种加速。在工业上相关条件下进行详细的动力学研究，即在高离子强度（6.0μm）和升高的温度（80℃）下进行，以研究这种现象。在Cr（VI）或磷酸盐（PO43-）存在下或没有任何添加剂的情况下遵循次氯酸的分解。除了Cr（VI）的有益pH缓冲效果之外，发现CRO 42-铬（VI）的形式略微催化次氯酸的分解。 Hocl分解的总速率可以表示为-dc（hocl）/ dt = k（dec）[hocl]（2）[accl-] + k（猫）[hocl]（2）[cro42-]。确定相应的速率常数，K（DEC）= 9.4 +/- 0.1M-2 S（-1）和K（猫）= 4.6 +/- 0.8 M-2 S（-1），以及机械解释给出了催化税率定律。催化路径对来自CA的整体分解率的贡献。 pH = 8至CA时30％。 pH = 6时70％。

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