College of Chemical Engineering, China University of Mining and Technology, Xuzhou, P R China.
Phys Chem Chem Phys. 2012 Jan 28;14(4):1502-6. doi: 10.1039/c2cp22972b. Epub 2011 Dec 12.
In a continuous flow stirred tank reactor (CSTR), the reaction of thiourea-iodate-sulfite (TuIS) exhibits a rich variety of complex oscillations in pH. The transitions from 1(n) type oscillations to 1(3), 1(2) type and simple oscillations were observed on decreasing the flow rate gradually in small steps at 30.2 °C and 20.5 °C, respectively. The transitions from 1(n) type oscillations to 1(0)1(4), 1(0)1(3) type and simple oscillations were observed as well on increasing the temperature in small steps at a given flow rate. Based on the analogous iodate-sulfite-thiosulfate system a simple empirical rate law model is suggested to give a sound agreement between the experimental and simulated results on the complex oscillatory behaviour. A possible explanation of the emergence of the simple empirical rate law model from the mechanism of the individual reactions of the TuIS system is also discussed.
在连续搅拌釜式反应器(CSTR)中,硫脲-碘酸盐-亚硫酸盐(TuIS)的反应在 pH 值上表现出丰富多样的复杂振荡。在 30.2°C 和 20.5°C 下,分别通过逐渐减小流速的小步骤,观察到从 1(n)型振荡到 1(3)、1(2)型和简单振荡的转变。在给定流速下,通过小步骤升高温度,也观察到从 1(n)型振荡到 1(0)1(4)、1(0)1(3)型和简单振荡的转变。基于类似的碘酸盐-亚硫酸盐-连二亚硫酸盐体系,提出了一个简单的经验速率定律模型,该模型在复杂振荡行为的实验和模拟结果之间具有良好的一致性。还讨论了从 TuIS 体系的各个反应的机制中出现简单经验速率定律模型的可能解释。