{"title":"亚氯酸盐离子极谱法","authors":"L. Gierst, L. Vandenberghen , E.T. E. Nicolas","doi":"10.1016/0022-0728(66)80125-0","DOIUrl":null,"url":null,"abstract":"<div><p>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 <em>desorption</em> process.</p><p>The present work shows that this pre-wave is related to traces of ferrate ions, which are almost always present in unpurified hydroxide solutions.</p><p>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) + <em>e</em> ⇌ Fe(+II) Fe(+II) + 2<em>e</em> ⇌ 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.</p><p>The rate-determining step FeO<sub>2</sub>H<sup>−</sup> + ClO<sub>2</sub><sup>−</sup> → proceeds with a rate constant of the order of 1.7·10<sup>8</sup><em>M</em><sup>−1</sup> 1 sec<sup>−1</sup>.</p><p>The main wave, which follows the dip, corresponds to the direct irreversible discharge of ClO<sub>2</sub><sup>−</sup>, the rate constant of which satisfactorily obeys the Frumkin theory, with α<em>n</em><sub>α</sub> ⋍ 0.37.</p></div>","PeriodicalId":100778,"journal":{"name":"Journal of Electroanalytical Chemistry (1959)","volume":"12 5","pages":"Pages 462-476"},"PeriodicalIF":0.0000,"publicationDate":"1966-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/0022-0728(66)80125-0","citationCount":"11","resultStr":"{\"title\":\"Polarographie de l'ion chlorite\",\"authors\":\"L. Gierst, L. Vandenberghen , E.T. E. Nicolas\",\"doi\":\"10.1016/0022-0728(66)80125-0\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>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 <em>desorption</em> process.</p><p>The present work shows that this pre-wave is related to traces of ferrate ions, which are almost always present in unpurified hydroxide solutions.</p><p>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) + <em>e</em> ⇌ Fe(+II) Fe(+II) + 2<em>e</em> ⇌ 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.</p><p>The rate-determining step FeO<sub>2</sub>H<sup>−</sup> + ClO<sub>2</sub><sup>−</sup> → proceeds with a rate constant of the order of 1.7·10<sup>8</sup><em>M</em><sup>−1</sup> 1 sec<sup>−1</sup>.</p><p>The main wave, which follows the dip, corresponds to the direct irreversible discharge of ClO<sub>2</sub><sup>−</sup>, the rate constant of which satisfactorily obeys the Frumkin theory, with α<em>n</em><sub>α</sub> ⋍ 0.37.</p></div>\",\"PeriodicalId\":100778,\"journal\":{\"name\":\"Journal of Electroanalytical Chemistry (1959)\",\"volume\":\"12 5\",\"pages\":\"Pages 462-476\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"1966-11-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://sci-hub-pdf.com/10.1016/0022-0728(66)80125-0\",\"citationCount\":\"11\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Electroanalytical Chemistry (1959)\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/0022072866801250\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Electroanalytical Chemistry (1959)","FirstCategoryId":"1085","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/0022072866801250","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 11
摘要
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。
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 αnα ⋍ 0.37.
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