Rustici M, Lombardo R, Mangone M, Sbriziolo C, Zambrano V, Turco Liveri M L
Faraday Discuss. 2001(120):39-51; discussion 85-104. doi: 10.1039/b103532k.
The behaviour of the Ce(IV)-catalyzed Belousov-Zhabotinsky (BZ) system has been monitored at 20.0 degrees C in unstirred batch conditions in the absence and presence of different amounts of the non-ionic micelle-forming surfactants hexaethylene glycol monodecyl ether (C10E6) and hexaethylene glycol monotetradecyl ether (C14E6). The influence of the non-ionic surfactants on both the kinetics of the oxidation of malonic acid (MA) by Ce(IV) species and the behaviour of the BZ reaction in stirred batch conditions has also been studied over a wide surfactant concentration range. The experimental results have shown that, in unstirred batch conditions, at surfactant concentrations below the critical micelle concentration (c.m.c.) no significant change in the dynamics of the Belousov-Zhabotinsky system occurs. Beyond this critical concentration the presence of micelles forces the BZ system to undergo a chaos-->quasi-periodicity-->period-1 transition. Thus, the surfactant concentration has been considered as a bifurcation parameter for a Ruelle-Takens-Newhouse (RTN) scenario. Addition of increasing amounts of non-ionic surfactants has no significant effect on the kinetics of the reaction between MA and Ce(IV), but it influences the oscillatory parameters of the stirred BZ system. At surfactant concentrations below the c.m.c. all the oscillatory parameters are practically unaffected by the presence of surfactant, while beyond this critical value the induction period is the same as in aqueous solution but both the oscillation period and the duration of the rising portion of the oscillatory cycle decrease. In all cases, the experimental trends have been ascribed to the enhancement in the medium viscosity due to the presence of micelles.
在20.0摄氏度下,于未搅拌的间歇条件下,在不存在和存在不同量的非离子型形成胶束表面活性剂六甘醇单癸醚(C10E6)和六甘醇单十四烷基醚(C14E6)的情况下,监测了铈(IV)催化的贝洛索夫-扎博廷斯基(BZ)体系的行为。还在较宽的表面活性剂浓度范围内,研究了非离子表面活性剂对铈(IV)物种氧化丙二酸(MA)的动力学以及搅拌间歇条件下BZ反应行为的影响。实验结果表明,在未搅拌的间歇条件下,当表面活性剂浓度低于临界胶束浓度(c.m.c.)时,贝洛索夫-扎博廷斯基体系的动力学没有显著变化。超过这个临界浓度,胶束的存在迫使BZ体系经历混沌→准周期性→1周期转变。因此,表面活性剂浓度被视为鲁埃尔-塔肯斯-纽豪斯(RTN)情景的分岔参数。增加非离子表面活性剂的量对MA与Ce(IV)之间反应的动力学没有显著影响,但会影响搅拌的BZ体系的振荡参数。在表面活性剂浓度低于c.m.c.时,所有振荡参数实际上不受表面活性剂存在的影响,而超过这个临界值时,诱导期与在水溶液中相同,但振荡周期和振荡周期上升部分的持续时间都缩短了。在所有情况下,实验趋势都归因于胶束的存在导致介质粘度增加。