Rossi Federico, Lombardo Renato, Sciascia Luciana, Sbriziolo Carmelo, Liveri Maria Liria Turco
Dipartimento di Chimica Fisica "F. Accascina", Università degli Studi di Palermo, Viale delle Scienze, Parco d'Orleans II, Pad. 17, 90128 Palermo, Italy.
J Phys Chem B. 2008 Jun 19;112(24):7244-50. doi: 10.1021/jp8003739. Epub 2008 May 24.
The effects of the anionic surfactant sodium dodecyl sulfate (SDS) on the spatio-temporal and temporal dynamics of the ferroin-catalyzed Belousov-Zhabotinsky (BZ) reaction have been studied over a wide surfactant concentration range. For the first time, investigations were performed also for unstirred systems. The presence of SDS in the reaction mixture influences the oscillatory parameters to an extent that significantly depends on the surfactant concentration. The trend of the wave speed v upon the increasing amount of SDS was found to have a maximum at [SDS] = 0.075 mol dm (-3) ( v = 0.071 mm s (-1)), after which the speed decreased to 0.043 mm s (-1) at [SDS] = 0.5 mol dm (-3), which is below the value found in the absence of the surfactant ( v = 0.055 mm s (-1)). The response of the oscillatory BZ system to the addition of SDS has been ascribed to two different causes: (a) the peculiar capability of the organized surfactant assemblies to affect the reactivity by selectively sequestering some key reacting species and (b) the modifications induced by SDS on the physical properties of the medium. These hypotheses have been corroborated by performing spectrophotometric investigations on the stirred BZ system. Complementary viscosity measurements gave useful hints for the clarification of the surfactant role.
研究了阴离子表面活性剂十二烷基硫酸钠(SDS)在较宽的表面活性剂浓度范围内对亚铁离子催化的贝洛索夫-扎博廷斯基(BZ)反应的时空动力学和时间动力学的影响。首次对未搅拌体系也进行了研究。反应混合物中SDS的存在对振荡参数有影响,且这种影响程度很大程度上取决于表面活性剂的浓度。发现随着SDS量的增加,波速v的趋势在[SDS]=0.075 mol dm⁻³时达到最大值(v = 0.071 mm s⁻¹),之后在[SDS]=0.5 mol dm⁻³时速度降至0.043 mm s⁻¹,该值低于在无表面活性剂时测得的值(v = 0.055 mm s⁻¹)。振荡BZ体系对添加SDS的响应归因于两个不同原因:(a)有组织的表面活性剂聚集体通过选择性螯合一些关键反应物种来影响反应性的特殊能力;(b)SDS对介质物理性质的改变。通过对搅拌的BZ体系进行分光光度研究,证实了这些假设。补充的粘度测量为阐明表面活性剂的作用提供了有用的线索。