基于改进计时电流法精确模型的数值解仿真及实验验证  

Numerical Simulation Based Accurate Models of Improved Chronoamperometry and Its Experimental Validation

作　　者：陈旭海[1,2] 刘绍丽[2,3] 陈敬华[4] 杜民[2] 林新华[4] 

机构地区：[1]福州大学电气工程与自动化学院,福州350000 [2]福建省医疗器械和医药技术重点实验室,福州350000 [3]福州大学物理与信息工程学院,福州350000 [4]福建医科大学药学院,福州350000

出　　处：《物理化学学报》2012年第4期877-884,共8页Acta Physico-Chimica Sinica

基　　金：国家高技术研究发展规划项目(863)(2008AA02Z433);国家自然科学基金(21105012);福建省科技计划项目(2010I0017);福建省高校杰出青年科研人才培育计划(JA11105);福建省自然科学基金(2011J01028)资助~~

摘　　要：根据电极表面被测物浓度变化经验公式所建立的改进计时电流法的理论模型,只能定性分析响应电流峰值与被测物浓度关系,无法准确描述响应电流峰值与反应体系及激励电势中其它参数的关系.为解决该问题,利用能斯特方程与扩散定律,建立了描述电极表面被测物浓度与响应电流关系的积分方程,通过数值分析方法求解得到该积分方程数值解.进而利用数值仿真得到精确的电流与时间关系曲线,分析了电流峰值与试剂浓度、惯性时间常数、参比电极标准电势、激励电势初始值以及稳态值之间的关系.最后,利用改进计时电流法的电路装置对K3[Fe(CN)6]试剂进行测试,实验结果表明该数值模型比经验模型更接近真实情况,也验证了由该模型推导得到的各参数之间关系的正确性.Based on the empirical formula for concentration change of a detected molecule on the surface of a electrode,an approximate mathematical model of improved chronoamperometry was established.The relationship between the working current and detection reagent concentration was analyzed qualitatively.Parameters for the electrode reaction and excitation potential were not included.To solve this problem,the Nernst equation and Fick＇s law were applied to construct an integral equation for the specific concentrations of the oxidant and reductant on the surface of the electrode.The current-time curve obtained numerically was used to investigate the relationship between the peak current and concentration of reagent,inertia time constant,standard potential of the reference electrode,initial value and steady state value of the voltage excitation.Using the improved chronoamperometry device,we studied the electrochemical behavior of K3[Fe（CN）6].The experimental results showed that the simulation results from the numerical model were much closer to the actual situation than the empirical model.The experimental results also confirmed the parameter relationships that were derived using the model.

关 键 词：改进计时电流法 精确模型 数值分析 能斯特方程 菲克扩散定律 

分 类 号：O646.5[理学—物理化学]