【作者】 索南；

【导师】 高锦章； 杨武；

【作者基本信息】 西北师范大学 ， 分析化学， 2003， 硕士

【摘要】 近年来非线性热力学和化学振荡现象已成为许多科技工作者研究的热点问题。化学振荡反应具有特别的宏观现象及特殊的机理，因此成为分析化学进行微量检测的有效工具。本文利用化学振荡反应首次建立了巴比妥酸、茚三酮、海洛因的动力学检测方法，结果满意。论文由四部分组成。 第一部分：化学振荡反应在药物分析中的应用 阐述了化学振荡反应的基本概念及FKN机理，研究了与之有关的热力学基本理论和化学振荡反应具备的条件。对几类化学振荡反应，特别是B-Z振荡反应在分析检测中的应用进行了详细介绍。系统地列举了1978-2003年间化学振荡反应在药物分析检测应用中取得的进展。 第二部分：巴比妥酸对B-Z振荡反应的影响及其应用 研究了巴比妥酸对B-Z振荡反应的影响，结果表明，巴比妥酸的加入明显改变了振荡体系的周期和振幅，且巴比妥酸的浓度与振荡周期改变值ΔT及振幅改变值ΔA均呈现良好的线性关系，线性范围为6.4×10^-7～3.1×10^-3mol／L，相关系数分别为0.9921和0.9954，对其扰动机理进行了初步探讨。 第三部分：茚三酮对B-Z振荡反应的影响及其应用 研究了茚三酮对B-Z振荡体系的影响，考察了振幅和周期的改变值与茚三酮浓度的关系。结果表明，在6.9×10^-7～4.2×10^-2mol／L范围内，第一振幅改变值与茚三酮浓度有良好的线性关系，相关系数为0.9977。依据FKN模型，对此反应机理进行了初步探讨。 第四部分：利用APP技术及H₂O₂-CuSO₄-KSCN振荡反应测定海洛因 首次报道了利用Cu（Ⅱ）催化过氧化氢氧化硫氢化钠的敞开振荡体系测定海洛因的新方法。加入海洛因的浓度与振荡周期的改变值具有良好线性关系，检测下限达1.2×10^-6mol／L，浓度范围6.0×10^-6～1.2×10^-4M，相关系数为0.9971。对温度、流速、反应各组分浓度对扰动的影响，及其作用的可能机理进行了探讨。更多还原

【Abstract】 The subject of "nonlinear dynamics" and the phenomenon of oscillating chemical reaction, in particular, have become of great interest across of wide range of scientific research in recent years. Oscillating chemical reactions exhibit exotic behavior and unusual mechanisms. Consequently, they have been considered a useful tool for the determination of trace amounts of chemical compounds. This work develops new methods using oscillating chemical reaction for quantitative analytical determinations of barbituric acid, ninhydrin, and heroin for the first time; the accuracy and selectivity of these methods are well pleasing. The main content consists of four parts:Part I. Oscillating chemical reactions and applications for pharmaceuticalanalysisIn this part, we describe the basic concepts of oscillating chemical reactions and FKN mechanism, studies some basic thermodynamic theory related, and gives the conditions of occurring oscillating chemical reactions. Some oscillating chemical reactions that were used in analytical determinations, especially B-Z chemical oscillation, are reported in details. The research progress in applications for pharmaceutical analysis from 1978 to 2003 is discussed systematically through representative examples.Part II. Effect of barbituric acid on the B-Z the oscillating chemicalreaction and its analytical applicationThe effect of barbituric acid on the B-Z oscillating chemical reaction was studied. Results show that the adding of heroin can perturb both the oscillating period and amplitude, the changes of the oscillating period or the amplitude are linearly proportional to the concentration of barbituric acid, which over the range of 6.4×10-7-3.1×10-3 mol/L, and the related coefficient to be 0.9921 and 0.9954, respectively. The possible reaction mechanism has been explained using the FKN mode.Part III. Effect of ninhydrin on the B-Z oscillating reactionThe effect of ninhydrin on the B-Z oscillating chemical reaction was studied. The dependence of the period and the amplitude change on the injected concentration was reported. Results show that the change of the first oscillation period is linearly proportional to the concentration of ninhydrin, which over the range of 6.9×10-7 ~ 4.2×10-2mol/L, and the related coefficient is 0.9977. The possible reaction mechanism has been studied as well as Field-K6r6s-Noyes (FKN) mechanism.Part IV . Determination of heroin using H2O2-CuSO4-KSCN oscillating chemical reaction by the analyze pulse perturbation technique (APP)A new analytical method for the determination of heroin by the sequential perturbation caused by different amounts of heroin on the chemical oscillating system involving the Cu (Il)-catalyzed reaction between hydrogen peroxide and sodium thioyanate in an alkaline medium with the aid of continuous-flow stirred tank reactor (CSTR) is proposed. The method relies on the linear relationship between the changes in the oscillation period of the chemical system and the concentration of heroin, with a detecting limit of 1.2×10-6M. The calibration curve fits a linear equation very well when the concentration of heroin over the range 6.0×10~6 to 1.2×10-4 M (r=0.9971). Influence of temperature, injection points, flow rate and reaction variables are investigated and the possible mechanism of the action of heroin in the chemical oscillating system is discussed. .更多还原