Oxidation of the iodide ion is an important facet of the solar cells such as perovskite solar cells and dye‐sensitized solar cells. The rate of reaction undoubtedly depends upon several factors. Such parameters include reaction media, electrolyte, and the nature of solvents, and electrolyte. If these factors are optimized then the rate of the reaction can be controlled and could be used to get the maximum benefit out of it such as economically and industrially cost‐effective uses of the reaction and globally environmentally benign. We studied the kinetics of the oxidation of the iodide ion in the binary solvent system that consisted of 10% (v/v) tertiary butyl alcohol and water. The transition metal complex such as dicyanobis(phenanthroline)iron(III) oxidizes the iodide ion spontaneously without any external triggering with a fast rate at 293 ± 1 K. The reaction was probed under the pseudo–first‐order condition with an excess concentration of the iodide ion over dicyanobis(phenanthroline)iron(III) at 0.06 M ionic strength. The reaction was observed independent of the concentration of dicyanobis(phenanthroline)iron(III), that is, the zero order and third order with respect to the iodide ion in the selected solvent system. An overall third‐order was observed for the redox reaction. The value of the multiplication product of the molar absorptivity (ɛ), path length of the cuvette (b), and overall rate constant (k) was deduced to be 1.59 × 10⁶ M⁻³ s⁻¹. The observed zero‐order rate constant of the reaction was increased by the fractional (1.5) power of the concentration of protons in the excess concentration of acid 1 mM to 0.1 M. The multiplication product of ɛ⋅b to the fractional order rate constant (k′) was found 0.773 M^−1.5 s⁻¹ that confirms protonation of triiodide in acidic‐10% (v/v) tertiary butyl alcohol‐water. The effect of ionic strength showed a similar impact in different compositions of solvents such as 5, 10, and 20% (v/v) tertiary butyl alcohol‐water. The observed zero‐order rate constant was decreased upon increasing the ionic strength in each medium consisting of the binary solvent system.

中文翻译：

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二元体系中双氰基（菲咯啉）铁（III）氧化碘化物的动力学

碘离子的氧化是诸如钙钛矿太阳能电池和染料敏化太阳能电池等太阳能电池的重要方面。反应速度无疑取决于几个因素。这样的参数包括反应介质，电解质以及溶剂和电解质的性质。如果优化了这些因素，则可以控制反应的速率，并可以从中获得最大的收益，例如在经济和工业上具有成本效益的反应使用以及对环境无害。我们研究了由10％（v / v）叔丁醇和水组成的二元溶剂体系中碘离子氧化的动力学。过渡金属络合物，例如双氰基双（菲咯啉）铁（III），自发地氧化碘离子，而没有任何外部触发，并且在293±1 K的快速速率下进行反应。离子强度为0.06 M的双氰基双（菲咯啉）铁（III）上的碘离子。观察到该反应与双氰基双（菲咯啉）铁（III）的浓度无关，即相对于所选溶剂体系中碘离子的零级和三级。整个氧化还原反应观察到三阶。摩尔吸收率（ɛ）与比色皿的路径长度（反应在拟一级条件下进行，离子强度为0.06 M时，碘离子的浓度超过双氰基双（菲咯啉）铁（III）。观察到该反应与双氰基双（菲咯啉）铁（III）的浓度无关，即相对于所选溶剂体系中碘离子的零级和三级。整个氧化还原反应观察到三阶。摩尔吸收率（ɛ）与比色皿的路径长度（反应在拟一级条件下进行，离子强度为0.06 M时，碘离子的浓度超过双氰基双（菲咯啉）铁（III）。观察到该反应与双氰基双（菲咯啉）铁（III）的浓度无关，即相对于所选溶剂体系中碘离子的零级和三级。整个氧化还原反应观察到三阶。摩尔吸收率（ɛ）与比色皿的路径长度（b），并且总速率常数（k）被推导为1.59×10 ⁶  M ^-3 s ^-1。反应所观察到的零级速度常数增加了在酸为1mM的过量浓度的质子的浓度的分数（1.5）功率至0.1 M.ɛ⋅的乘积b到分数阶速率常数（发现k'）0.773 M ^-1.5 s ^-1证实了三碘化物在酸性10％（v / v）叔丁醇-水中的质子化作用。离子强度的影响在溶剂的不同组成（例如5、10和20％（v / v）的叔丁醇-水）中显示出相似的影响。随着在由二元溶剂系统组成的每种介质中离子强度的增加，观察到的零级速率常数会降低。