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B-Z化学振荡反应及其在苯胺类物质检测中的应用
B-Z Oscillating Chemical Reactions and Their Applications in Determining Aniline Compounds
【作者】 刘静；
【作者基本信息】 西北师范大学 ， 分析化学， 2010， 硕士
【摘要】 化学振荡现象由来已久,有关化学振荡反应以及相关的非线性化学动力学更广泛领域的研究在近20年得到了人们愈来愈多的关注,B-Z化学振荡反应是目前最受分析工作者青睐的实验研究和理论分析的对象。本文利用锰催化的酒石酸-丙酮化学振荡体系的非平衡定态和规则振荡分别检测了对硝基苯胺以及邻、间、对苯二胺;并总结了几种苯胺类物质对锰催化的B-Z化学振荡体系的扰动规律。论文包括四个部分。第一部分:绪论详细介绍了B-Z化学振荡反应的类型及其发生的条件,简要阐述了利用化学振荡反应不同行为进行检测的原理,并综述了近几年来振荡反应在分析检测领域的应用。第二部分:利用酒石酸-丙酮有机双底物化学振荡体系的非平衡定态检测对硝基苯胺本文利用酒石酸-丙酮-Mn2+-KBrO3-H2SO4化学振荡体系的非平衡定态检测对硝基苯胺,以温度为控制参数优化检测条件,建立了检测对硝基苯胺的新方法。结果表明,当温度为33.5℃,反应体系的组成为3.5mL 0.06 mol·L-1酒石酸（TA）, 4.0mL 0.7 mol·L-1 H2SO4, 1.5mL 1.5×10-4 mol·L-1 MnSO4, 4.0mL 0.4 mol·L-1丙酮（Act）及7.0mL 0.05 mol·L-1 KBrO3时,对硝基苯胺对体系扰动的灵敏度最高。当对硝基苯胺浓度在2.50×10-73.75×10-5 mol·L-1范围内时,体系振幅的变化量与所加入对硝基苯胺浓度的负对数呈良好的线性关系,检测限为2.50×10-8 mol·L-1。第三部分:苯胺及其衍生物对锰催化的B-Z化学振荡体系的扰动研究了苯胺及其衍生物对优化条件的锰（II）催化的B-Z化学振荡体系的扰动情况。结果表明,由对苯二胺引起的扰动最大,苯胺次之,扰动最小的为对硝基苯胺。同时对扰动机理进行了讨论,发现外加干扰物主要与体系中的Br2发生亲电取代反应,并且,苯胺类物质环上的电子云密度越大,就越容易发生亲电取代,引起振幅的变化就越大。第四部分:利用酒石酸-丙酮有机双底物化学振荡体系的规则振荡检测邻、间、对苯二胺提出了利用酒石酸-丙酮有机双底物化学振荡体系检测邻、间、对苯二胺的新方法。结果表明,邻、间、对苯二胺的浓度分别在5.00×10-73.75×10-5 mol·L-1,1.00×10-51.00×10-3 mol·L-1和5.00×10-61.00×10-3 mol·L-1范围内时,体系振幅的变化量与所加入邻、间、对苯二胺浓度的负对数呈良好的线性关系,相关系数分别为0.9992,0.9990和0.9989,最低检测限分别为2.50×10-8 mol·L-1,1.00×10-6 mol·L-1和5.00×10-7 mol·L-1。同时,对可能的扰动机理进行了讨论。
【Abstract】 Oscillating chemical reaction has been of long standing, the extensive studies of which and nonlinear chemical dynamics related with this have attracted considerable attention of researchers in recent two decades. Furthermore, analysis operators pay more attention to B-Z oscillating chemical reaction, which is considered to be an optimum object of experimental study and theoretical analysis. This dissertation reports the determination of p-nitroaniline and o-, m-, p-phenylenediamine by using non-equilibrium stationary state and regular oscillation of tartrate-acetone double substrate oscillating system respectively, and summaries the perturbation regularity of aniline and some of its derivates on Mn（II） catalyzed B-Z oscillating system. It includes four parts.Part I: IntroductionClassifications and occurrence conditions of B-Z oscillating chemical system are introduced in detail. Determination principles of different behaviors in chemical oscillation are described in brief, and their applications in analytical determination in recent years are also reviewed.Part II: Determination of p-nitroaniline by the tartrate-acetone-Mn2+-KBrO3- H2SO4 double organic substrate oscillating system using non-equilibrium stationary stateA highly sensitive method is proposed for the determination of p-nitroaniline by using non-equilibrium stationary state of tartrate-acetone-Mn2+-KBrO3-H2SO4 double organic substrate oscillating system. Under the optimum conditions, temperature was chosen as a control parameter to design the bifurcation point. Results showed that the system consisting of 3.5mL 0.06 mol·L-1 tartrate, 4.0mL 0.7 mol·L-1 H2SO4, 1.5mL 1.5×10-4 mol·L-1 MnSO4, 4.0mL 0.4 mol·L-1 acetone and 7.0mL 0.05 mol·L-1 KBrO3 was very sensitive to the surrounding at 33.5℃. A well linear relationship between the potential difference and the negative logarithm concentration of p-nitroaniline was obtained to be in the range of 2.50×10-73.75×10-5 mol·L-1 with a lower detection limit of 2.50×10-8 mol·L-1.Part III: Perturbation of aniline and its derivates on Mn（II）-catalyzed B-Z oscillating chemical systemThe perturbation of aniline and three its derivates on B-Z oscillating chemical system catalyzed by Mn（II） was investigated. It was found that disturbance caused by p-phenylenediamine was the biggest one, the next was aniline and that of p-nitroaniline was the smallest among them. Perturbation mechanism was discussed and the results indicated that the analytes mainly took place electrophilic substitution reaction with Br2 in the system. Furthermore, the higher the electron density of ring of aniline compounds, the bigger change in oscillating amplitude was.Part IV: Determination of o-, m-, p-phenylenediamine by using regular oscillation of tartrate-acetone double organic substrate oscillating systemA new method for the determination of o-, m-, p-phenylenediamine is established that is based on the perturbation of tartrate-acetone-Mn2+-KBrO3-H2SO4 double organic substrate oscillating system with different amounts of them. Results showed that a well linear relationship was existed between the potential difference and the negative logarithm concentration of o-, m-, p-phenylenediamine in the range of 5.00×10-73.75×10-5 mol·L-1, 1.00×10-51.00×10-3 mol·L-1 and 5.00×10-6 1.00×10-3 mol·L-1, with the correlation coefficients were 0.9992, 0.9990 and 0.9989, respectively. The detection limit of 2.50×10-8 mol·L-1, 1.00×10-6 mol·L-1 and 5.00×10-7 mol·L-1 were also obtained. At the same time, a possible perturbation mechanism was discussed in brief.
【Key words】 B-Z oscillating chemical reaction； non-equilibrium stationary state； regular oscillation； determination； perturbation；