Instituto de Química, Universidade Federal do Rio de Janeiro, Rio de Janeiro, 21941-909 Rio de Janeiro, Brazil.
Inorg Chem. 2022 Jan 17;61(2):1178-1187. doi: 10.1021/acs.inorgchem.1c03522. Epub 2021 Dec 29.
Mixing iodide and perchloric acid solutions with an excess of chlorate inside a diode-array spectrophotometer led to the observation of an abrupt decrease of the absorbance at the 215 nm isosbestic point after an induction period. The clock time decreases by increasing the initial concentrations of chlorate and acid, but increasing the initial iodide concentration has an opposite effect. The proposed mechanism simulates the experimental results and considers the interaction of UV light with iodide, producing iodine and triiodide ion. The autocatalytic core of this mechanism is the same as that employed to explain the autocatalytic behavior of chlorine dioxide-iodine reaction, but considering HIO as the reactive species rather than HOI, being a more realistic mechanism for acid conditions.
在二极管阵列分光光度计中,将碘化物和高氯酸溶液与过量的氯酸盐混合,在诱导期后观察到 215nm 等吸收点的吸光度突然下降。随着初始氯酸盐和酸浓度的增加,时钟时间减少,但增加初始碘化物浓度则会产生相反的效果。所提出的机制模拟了实验结果,并考虑了紫外光与碘化物的相互作用,生成碘和三碘化物离子。该机制的自催化核心与用于解释二氧化氯-碘反应的自催化行为的核心相同,但考虑到 HIO 是反应性物质而不是 HOI,对于酸性条件来说,这是一个更现实的机制。