利用减秩因子分析法同时优化确定化学反应级数和速率常数  

Simultaneous Estimation of Reaction Order and Rate Constant by Rank Annihilation Factor Analysis

作　　者：朱仲良[1] 程文治[1] 赵怡[1] 夏骏[1] 

机构地区：[1]同济大学化学系,上海200092

出　　处：《分析化学》2003年第7期820-823,共4页Chinese Journal of Analytical Chemistry

基　　金：国家自然科学基金 (No .2 9975 0 19);同济大学理科发展基金资助项目

摘　　要：通过对反应过程中在线测得的动力学谱 光谱二维数据矩阵进行主成分分析 ,可确定化学反应过程存在的组分数。提出用优化动力学参数 减秩因子分析法解析二维数据矩阵 ,对未知动力学模型的复杂反应可同时优化求解第一步反应的级数和速率常数。模拟二维数据验证了该方法的可行性。该方法用于高锰酸钾氧化溴化钠的反应过程中测得的二维数据的解析 ,结果表明 :高锰酸钾的还原过程符合 0级反应模型。Based on the two-way kinetic-spectral data measured on-line during the chemical reaction, the number of species existed in the reaction process can be determined by principal component analysis (PCA). A new method was proposed for estimating kinetic parameters combined the optimization algorithm and rank annihilation factor analysis (RAFA). After kinetic-spectral data were processed by the proposed method, the reaction order and rate constant of the first step of complicated reaction could be estimated simultaneously without previous knowledge of the kinetic model. The effectiveness of the method was proved by both the synthetic and the actual reaction data. The oxidation process of sodium bromide by potassium permanganate was studied and the result indicated that the reduction of potassium permanganate was 0 order.

关 键 词：减秩因子分析法 优化 化学反应级数 速率常数 化学反应动力学 动力学谱-光谱二维数据矩阵 

分 类 号：O657.3[理学—分析化学]