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Batch pH Oscillations in the Belousov-Zhabotinsky Reaction

机译:Belousov-Zhabotinsky反应中的分批pH振荡

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摘要

No single-phase system has been previously reported to give significant pH oscillations in a closed (batch) reactor. We report here sustained pH oscillations in batch for the Belousov-Zhabotinsky reaction using much lower [H+](0) and much higher [BrO3-](0) than in traditional studies of this reaction. In fact, pH oscillations were obtained in the presence of only BrO3-, malonic acid (MA), and Mn2+. The amplitude, frequency, and duration of oscillations tend to depend primarily on the ratio of [BrO3-](0) to [MA](0). A critical part of the proposed mechanism involves the reversible formation of a manganese(III) complex with bromomalonic acid, followed by two-electron oxidation to tartraric acid and Mn2+. Estimates of the corresponding rate constant values for these reactions have been obtained by simulation. It is suggested that the presence of a supercatalytic reaction in H+ may be a sufficient, if not necessary, requirement for the occurrence of pH oscillations in a batch system.
机译:先前没有报道单相系统以在封闭(批量)反应器中提供显着的pH振荡。 我们在此报告批量生为PH振荡,用于使用远低[H +](0)和更高的[Bro3 - ](0)比在对该反应的传统研究中进行的Belousov-Zhabotinsky反应。 实际上,在仅在Bro3,丙酸(MA)和Mn2 +存在下获得pH振荡。 振幅,频率和持续时间倾向于主要取决于[BRO3 - ](0)至[MA](0)的比率。 所提出的机制的关键部分涉及与溴alonicAc酸的锰(III)络合物的可逆形成,其次是双电子氧化至塔拉瑞酸和MN2 +。 通过模拟获得了这些反应的相应速率常数值的估计。 建议在H +中存在超催化反应可以是足够的,如果不是必需的,则需要在批量系中发生pH振荡的要求。

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