Peralta Catalina, Frank Claudia, Zaharakis Alex, Cammalleri Carolyn, Testa Matthew, Chaterpaul Stephen, Hilaire Christian, Lang Daniel, Ravinovitch Daniel, Sobel Sabrina G, Hastings Harold M
Department of Chemistry, Hofstra University, Hempstead, New York 11549-1510, USA.
J Phys Chem A. 2006 Nov 9;110(44):12145-9. doi: 10.1021/jp062512r.
The purpose of this research was to explore the unstirred, ferroin-catalyzed Belousov-Zhabotinsky (BZ) reaction as an experimental model for the response of excitable media to small perturbations (slightly larger than the threshold for excitations). Following Showalter et al. (Showalter, K.; Noyes, R. M.; Turner, H. J.Am. Chem. Soc. 1979, 101, 7463-69), we used a positively biased silver electrode to release silver ions into a BZ reaction mixture, removing bromide ions and causing an excitation if sufficient bromide was removed. We found (1) a scaling region in which the delay before activation increased linearly as the size of the perturbation decreased, qualitatively consistent with but not fully explained by the Oregonator of Field et al. (Field, R. J.; Körõs, E.; Noyes, R. M. J. Am. Chem. Soc. 1972, 94, 8649-64); (2) evidence for a 10 s oligomerization time scale; and (3) that activations were always delayed until after the end of a pulse of current, with the delay essentially constant for sufficiently long pulses, an effect not seen in simple ODE models but consistent with the anomalously large current apparently required for activation (Showalter, K.; Noyes, R. M. J. Am. Chem. Soc. 1976, 98, 3730-31) and explainable by bromide transport. Overall, the BZ system appeared to be well-suited as an experimental prototype, despite its complexity.
本研究的目的是探索未搅拌的、亚铁离子催化的贝洛索夫-扎博京斯基(BZ)反应,作为可兴奋介质对小扰动(略大于激发阈值)响应的实验模型。遵循绍沃尔特等人(绍沃尔特,K.;诺伊斯,R. M.;特纳,H. J.《美国化学会志》1979年,101卷,7463 - 69页)的方法,我们使用带正电的银电极将银离子释放到BZ反应混合物中,去除溴离子,若去除的溴离子足够,则引发一次激发。我们发现:(1)一个标度区域,其中激活前的延迟随着扰动大小减小而线性增加,定性上与菲尔德等人的俄勒冈模型(菲尔德,R. J.;科罗斯,E.;诺伊斯,R. M.《美国化学会志》1972年,94卷,8649 - 64页)一致,但未得到该模型的充分解释;(2)有证据表明存在一个10秒的寡聚时间尺度;(3)激活总是延迟到电流脉冲结束之后,对于足够长的脉冲,延迟基本恒定,这种效应在简单的常微分方程模型中未见到,但与激活显然所需的异常大电流(绍沃尔特,K.;诺伊斯,R. M.《美国化学会志》1976年,98卷,3730 - 31页)一致,并且可以用溴离子传输来解释。总体而言,尽管BZ系统很复杂,但它似乎非常适合作为一个实验原型。
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