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通过新型碘化物选择性电极测量次碘酸浓度以及一种新方法制备 HOI。监测 Briggs-Rauscher 振荡反应中的 HOI 水平。

Measurement of hypoiodous acid concentration by a novel type iodide selective electrode and a new method to prepare HOI. Monitoring HOI levels in the Briggs-Rauscher oscillatory reaction.

机构信息

Department of Physical Chemistry, Babes-Bolyai University, RO-400028 Cluj-Napoca, Romania.

出版信息

J Phys Chem A. 2012 Jun 28;116(25):6630-42. doi: 10.1021/jp3015673. Epub 2012 Jun 6.

Abstract

A new type of iodide selective electrode prepared by dipping a silver wire into molten silver iodide is reported. The electrode was calibrated for silver and iodide ions and the measured electromotive force for various Ag(+) and I(-) concentrations was close to the theoretical within a few millivolts. Besides Ag(+) and I(-) ions, however, the electrode also responds to hypoiodous acid. Thus, the electrode was calibrated for HOI as well, and for that purpose a new method of hypoiodous acid preparation was developed. To explain the close to Nernstian electrode response for HOI and also the effect of hydrogen ion and iodine concentration on that response, the corrosion potential theory suggested earlier by Noszticzius et al. was modified and developed further. Following oscillations in the Briggs-Rauscher reaction with the new electrode the potential crosses the "solubility limit potential" (SLP) of silver iodide. Potentials below SLP are controlled by the concentration of I(-), but potentials above SLP are corrosion potentials determined by the concentration of HOI. Finally, the measured HOI oscillations are compared with calculated ones simulated by a model by Furrow et al.

摘要

一种新型的碘化物选择电极,是通过将银丝浸入熔融碘化银中制备的。该电极对银离子和碘离子进行了校准,并且在几毫伏的范围内,各种 Ag(+)和 I(-)浓度的测量电动势与理论值非常接近。然而,除了 Ag(+)和 I(-)离子外,该电极还对次碘酸根离子有响应。因此,该电极也对 HOI 进行了校准,为此开发了一种新的次碘酸制备方法。为了解释 HOI 的接近 Nernst 响应以及氢离子和碘浓度对该响应的影响,Noszticzius 等人早先提出的腐蚀电势理论进行了修正和进一步发展。在新电极的 Briggs-Rauscher 反应的振荡之后,电势会穿过银碘化物的“溶解度极限电势”(SLP)。低于 SLP 的电势由 I(-)浓度控制,但高于 SLP 的电势是由 HOI 浓度决定的腐蚀电势。最后,将测量的 HOI 振荡与 Furrow 等人的模型模拟的计算振荡进行了比较。

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