Polarographie de l'ion chlorite

Journal of Electroanalytical Chemistry (1959) Pub Date : 1966-11-01 DOI:10.1016/0022-0728(66)80125-0

L. Gierst, L. Vandenberghen , E.T. E. Nicolas

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引用次数: 11

Abstract

It is known that the polarographic behaviour of the chlorite ion in alkaline media is characterized by a kinetic pre-wave, followed by a dip, which has been assumed to reflect a desorption process.

The present work shows that this pre-wave is related to traces of ferrate ions, which are almost always present in unpurified hydroxide solutions.

At potentials of the order of −1.0 V/S.C.E., ferrite ions are produced; these are catalytically reoxidised by the chlorite ions. The dip is explained by the direct reduction to metallic iron. The kinetic characteristics of the reactions: Fe(+III) + e ⇌ Fe(+II) Fe(+II) + 2e ⇌ Fe(O) and 4Fe(+II) + Cl(+IV) → 4 Fe(III) + Cl(−I) have been elucidated, taking into account the effects of concentration, cation composition and pH.

The rate-determining step FeO₂H⁻ + ClO₂⁻ → proceeds with a rate constant of the order of 1.7·10⁸M⁻¹ 1 sec⁻¹.

The main wave, which follows the dip, corresponds to the direct irreversible discharge of ClO₂⁻, the rate constant of which satisfactorily obeys the Frumkin theory, with αn_α ⋍ 0.37.

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亚氯酸盐离子极谱法

众所周知，绿泥石离子在碱性介质中的极谱行为的特征是动力学前波，然后是一个浸入，这被认为反映了一个解吸过程。目前的工作表明，这种前波与高铁离子的痕迹有关，高铁离子几乎总是存在于未纯化的氢氧化物溶液中。在−1.0 V/S.C.E.数量级的电位下，产生铁氧体离子;它们被亚氯酸盐离子催化再氧化。这种倾斜可以用直接还原为金属铁来解释。研究了Fe(+III) + e + Fe(+II) Fe(+II) + 2e + Fe(O)和4Fe(+II) + Cl(+IV)→4Fe(III) + Cl(−I)反应的动力学特征，考虑了反应浓度、阳离子组成和ph的影响，确定了FeO2H−+ ClO2−→的速率常数为1.7·108M−1 1 sec−1。主波与ClO2−的直接不可逆放电相对应，其速率常数为αnα⋍0.37，符合Frumkin理论。

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

Journal of Electroanalytical Chemistry (1959)

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