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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Experimental and mechanistic investigation of an iodomalonic acid-based Briggs-Rauscher oscillator and its perturbations by resorcinol
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Experimental and mechanistic investigation of an iodomalonic acid-based Briggs-Rauscher oscillator and its perturbations by resorcinol

机译：基于碘化丙二酸的Briggs-Rauscher振荡器及其间苯二酚干扰的实验和机理研究

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摘要

Classic Briggs-Rauscher oscillators use malonic acid (MA) as a substrate. The first organic product is iodomalonic acid. Iodomalonic acid (IMA) can serve as a substrate also; thus, the first product in that case is diiodomalonic acid (I_2MA). Nonoscillating iodination kinetics can be followed by absorbance at 462 nm in acidic KIO_3 so long as IMA is in substantial excess over [I_2]. At 25 °C, simulations lead to the two most important rate laws, and related rate constant estimates are reported. I _2MA eventually decomposes by unknown processes, but I_2, O_2, H_2O_2, and Mn~(2+) speed up that decomposition, liberating most of the iodine back to the solution. Resorcinol is an effective inhibitor of oscillations both in MA oscillators and in IMA oscillators. Response of an IMA oscillator to varying amounts of resorcinol is shown herein and is similar to that for MA-based oscillators. The inhibitory effect of resorcinol is diminished by addition of IMA to a MA-based oscillator. The iodination reaction between IMA and resorcinol is too slow (0.043 M ~(-1) s~(-1)) to account for the decreased inhibitory effectiveness of resorcinol. Rather, the decomposition of I_2MA is responsible for the inhibition decrease.
机译：经典的Briggs-Rauscher振荡器使用丙二酸（MA）作为底物。第一种有机产物是碘羟丙酸。碘丙二酸（IMA）也可以用作底物;因此，在这种情况下，第一产物是二碘代丙二酸（I_2MA）。只要IMA显着超过[I_2]，在酸性KIO_3中，在462 nm处的吸光度可以跟踪非振荡碘化动力学。在25°C下，模拟得出两个最重要的速率定律，并报告了相关的速率常数估算值。 I _2MA最终会被未知过程分解，但是I_2，O_2，H_2O_2和Mn〜（2+）加速了分解过程，将大部分碘释放到溶液中。间苯二酚是MA振荡器和IMA振荡器中振荡的有效抑制剂。本文示出了IMA振荡器对不同量的间苯二酚的响应，并且与基于MA的振荡器的响应相似。通过将IMA添加到基于MA的振荡器中，间苯二酚的抑制作用会减弱。 IMA和间苯二酚之间的碘化反应太慢（0.043 M〜（-1）s〜（-1））不能说明间苯二酚的抑制效果降低。相反，I_2MA的分解是抑制作用降低的原因。

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