【作者】 魏晓霞；

【导师】 高锦章； 杨武；

【作者基本信息】 西北师范大学 ， 分析化学， 2008， 硕士

【摘要】 近年来，非线性现象已经成为许多科学工作者研究的最热门问题之一，化学振荡行为作为一种典型的非线性现象越来越受到人们的关注并被深入研究，而化学振荡反应用于检测具有仪器简单、操作简便、较宽的线性检测范围和较低的检测限等优点。论文阐述了利用Ce（IV）催化的规则B-Z化学振荡反应在封闭体系中检测1-萘胺和Fe（phen）₃²⁺催化的B-Z体系的混沌状态下检测了一些金属离子，并讨论了可能的反应机理，最后还用非平衡定态（分岔）检测了Cu²⁺和1-萘胺，并且与规则振荡和混沌状态下的检测结果进行了比较。第一章：绪论简单介绍了经典B-Z化学振荡体系的反应机理及Oregonator数学模型，综述了化学振荡的各种行为在分析检测中的应用，展望了应用前景。第二章：利用B-Z化学振荡反应检测1-萘胺研究了1-萘胺对KBrO₃-CH₂（COOH）₂-Ce（SO₄）₂-H₂SO₄化学振荡体系的扰动以及影响振荡体系的诸多因素。结果表明，1-萘胺浓度的对数与扰动后的振荡周期和振幅的差值T，A存在良好的线性关系，可作为定量分析的依据。其线性范围分别为7.08×10^-57.08×10^-6 mol·L^-1和7.08×10^-51.0×10^-6 mol·L^-1，最低检测限分别为8.25×10^-8 mol·L^-1和5.64×10^-9 mol·L^-1，相关系数为0.9922（n=11）和0.9955（n=12），最后讨论了其可能的反应机理。第三章：利用B-Z振荡体系的瞬时混沌检测痕量金属离子研究了一个在Fe（phen）₃²⁺催化下的B-Z化学振荡反应中高灵敏检测金属离子的方法，通过对反应条件的优化，发现金属离子浓度的负对数与加样后的最大Lyapunov指数和诱导期的乘积存在良好的线性关系，可作为定量分析的基础，最后分析了可能的反应机理。第四章：利用B-Z化学振荡的非平衡定态检测铜离子和1-萘胺研究了利用Fe（phen）₃²⁺催化的B-Z化学振荡体系的分岔形态检测铜离子和1-萘胺，这种方法是建立在分岔点附近的非平衡定态，在优化条件下对其进行检测。实验结果表明,铜离子和1-萘胺浓度的负对数与加样后振幅的改变存在一定的线性关系。并将检测结果与同体系下的规则振荡和混沌进行了比较,该方法具有快速、简便和检测限低等优点。更多还原

【Abstract】 In recent years, non-linear phenomenon has become a hot topic in many fields in which one is oscillating chemical reaction. Although this reaction is just chemical rather than biological oscillator, studying this reaction will help us to understand easily the life organism, a complex system. Thus, scientists coming from various subjects are interesting in discussing the non-linear behavior from all sides. The present work will only focus our attention on the application to analytical chemistry. As we know, the apparatus used in oscillating chemical reaction is simple and easy to operate. As an analytical method, it has some characterics such as a wide linear range and lower detection limit.In this paper, 1-naphthylamine was determined using the regular B-Z oscillating chemical reaction catalyzed by Ce（IV） in a closed system, some metal ions were determined using the B-Z oscillating chemical reaction catalyzed by Fe（phen）₃²⁺ in the chaotic regime and a possible reaction mechanism was discussed; Finally, determining Cu²⁺ and 1-naphthylamine using the non-equilibrium stationary state （bifurcation）, and compared with the results of the regular and chaotic oscillations. Chapter I: IntroductionA brief introduction has been made for mechanism of classical B-Z oscillation chemical reaction and corresponding Oregonator mathematical model. The application in analytical determination was described. Finally, the prospective of oscillation chemical reaction research and application are prospected. Chapter II: Determination of 1-naphthylamine by using B-Z oscillating chemical reactionUsing 1-naphthylamine to perturb the classical B-Z oscillating chemical system was observed and the variables were also investigated in detailed. The results show that the changes both in oscillating period and amplitude were linearly proportional to the logarithm of the concentration of 1-naphthylamine （logC） very well ranging from 7.08×10-5 to 7.08×10^-6 mol·L-1 and 7.08×10-5 to 1.0×10^-6 mol·L-1, with the detection limit are 8.25×10^-8 mol·L^-1 and 5.64×10^-9 mol·L^-1, corresponding regression coefficient are 0.9922（n=11） and 0.9955（n=12）, respectively, and the possible mechanism was discussed.Chapter III: Determination of trace amounts of some metal ions by transient chaotic regime in the B-Z oscillating systemIn this part, a determination of trace amounts of some metal ions in the batch B-Z oscillating chemical reaction catalyzed by ferroin was made. The optimum conditions for the determination have been examined. The transient chaotic regime is quantified by the product of the largest Lyapunov exponent and induction period, which is linearly proportional to the negative logarithm of concentration of metal ions. A possible mechanism was also discussed.Chapter IV: Determination of Cu²⁺ and 1-naphthylamine using the perturbation of non-equilibrium stationary state in the B-Z oscillating chemical reactionA highly sensitive method is proposed for the determination of Cu²⁺ and 1-naphthylamine in the batch B-Z oscillating chemical reaction catalyzed by ferroin., And a non-linear chemical system far from thermodynamic equilibrium is also described. The method is based on the non-equilibrium stationary state close to a bifurcation point. The optimum conditions for the determination have been examined. The results show that the change in oscillating amplitude was linearly proportional to the negative logarithm of the concentration of Cu²⁺ and 1-naphthylamine from 1.3×10^-5 to 6.5×10^-10 mol·L^-1 and 7.5×10^-5 to 1.5×10^-6 mol·L^-1 respectively. Meanwhile, the results obtained were compared with other determination methods.更多还原