Blagojević Slavica M, Anić Slobodan R, Cupić Zeljko D, Pejić Natasa D, Kolar-Anić Ljiljana Z
Faculty of Pharmacy, Department of Physical Chemistry, University of Belgrade, Vojvode Stepe 450, Belgrade, 11000, Serbia.
Phys Chem Chem Phys. 2008 Nov 28;10(44):6658-64. doi: 10.1039/b804919j. Epub 2008 Sep 30.
The influence of the initial malonic acid concentration [MA]0 (8.00 x 10(-3) < or = [MA]0 < or = 4.30 x 10(-2) mol dm(-3)) in the presence of bromate (6.20 x 10(-2) mol dm(-3)), bromide (1.50 x 10(-5) mol dm(-3)), sulfuric acid (1.00 mol dm(-3)) and cerium sulfate (2.50 x 10(-3) mol dm(-3)) on the dynamics and the kinetics of the Belousov-Zhabotinsky (BZ) reactions was examined under batch conditions at 30.0 degrees C. The kinetics of the BZ reaction was analyzed by the earlier proposed method convenient for the examinations of the oscillatory reactions. In the defined region of parameters where oscillograms with only large-amplitude relaxation oscillations appeared, the pseudo-first order of the overall malonic acid decomposition with a corresponding rate constant of 2.14 x 10(-2) min(-1) was established. The numerical results on the dynamics and kinetics of the BZ reaction, carried out by the known skeleton model including the Br2O species, were in good agreement with the experimental ones. The already found saddle node infinite period (SNIPER) bifurcation point in transition from a stable quasi-steady state to periodic orbits and vice versa is confirmed by both experimental and numerical investigations of the system under consideration. Namely, the large-amplitude relaxation oscillations with increasing periods between oscillations in approaching the bifurcation points at the beginning and the end of the oscillatory domain, together with excitability of the stable quasi-steady states in their vicinity are obtained.
在30.0摄氏度的间歇条件下,研究了在溴酸盐(6.20×10⁻² mol dm⁻³)、溴化物(1.50×10⁻⁵ mol dm⁻³)、硫酸(1.00 mol dm⁻³)和硫酸铈(2.50×10⁻³ mol dm⁻³)存在的情况下,初始丙二酸浓度[MA]₀(8.00×10⁻³ ≤ [MA]₀ ≤ 4.30×10⁻² mol dm⁻³)对贝洛索夫-扎博廷斯基(BZ)反应动力学和动力学的影响。通过先前提出的便于研究振荡反应的方法分析了BZ反应的动力学。在仅出现大幅弛豫振荡的定义参数区域内,确定了丙二酸整体分解的准一级反应,相应的速率常数为2.14×10⁻² min⁻¹。由包括Br₂O物种的已知骨架模型进行的BZ反应动力学和动力学的数值结果与实验结果吻合良好。通过对所考虑系统的实验和数值研究,证实了在从稳定准稳态过渡到周期轨道以及反之亦然的过程中已经发现的鞍结无限周期(SNIPER)分岔点。具体而言,在接近振荡域开始和结束时的分岔点时,振荡之间的周期增加的大幅弛豫振荡,以及其附近稳定准稳态的兴奋性都被观察到。