方波阳极溶出伏安法同时测定溶液中Cd(Ⅱ)、Pb(Ⅱ)、Cu(Ⅱ)、Bi(Ⅲ)离子的多元校正方法  

Simultaneous Determination of Cd(Ⅱ),Pb(Ⅱ),Cu(Ⅱ) and Bi(Ⅲ)by Square Wave Anodic Stripping Voltammetry and Multivariate Calibration

作　　者：范清杰 杜国荣[1] 涂家润[1] 

机构地区：[1]南开大学化学学院,天津300071

出　　处：《天津大学学报》2013年第2期145-149,共5页Journal of Tianjin University(Science and Technology)

基　　金：科技部科技型中小企业技术创新资助项目(09ZXCXGX17100;10ZXCXSY09400);天津市科技支撑计划重点资助项目(08ZCKFSF03500)

摘　　要：方波阳极溶出伏安法同时测定Cd(Ⅱ)、Pb(Ⅱ)、Cu(Ⅱ)和Bi(Ⅲ),由于谱峰重叠面无法直接进行分析,为此提出一种基于化学计量学同时定量分析的方法.在0.1,mol/L柠檬酸铵溶液中,以银基汞膜电极为工作电极,采用方波阳极溶出伏安法结合偏最小二乘(PLS)回归方法,用于同时定量分析溶液中Cd(Ⅱ)、Pb(Ⅱ)、Cu(Ⅱ)和Bi(Ⅲ)离子.由于Cu(Ⅱ)和Bi(Ⅲ)离子的溶出峰严重重叠,采用偏最小二乘回归方法进行定量分析.以39个样品作为训练集建立了PLS回归模型,各离子浓度范围分别是Cd(Ⅱ)0.10～2.56,μg/mL、Pb(Ⅱ)0.20～2.66,μg/mL、Cu(Ⅱ)0.10～2.56,μg/mL、Bi(Ⅲ)0.60～3.06,μg/mL.采用另外10个样品作为验证集对模型进行了评价,得到4种离子的回收率分别为92.3%～103.0%、94.7%～106.0%、89.0%～105.0%和94.8%～108.0%.与传统的单变量校正方法相比,多元校正方法可以用于重叠溶出伏安信号的定量分析.In contrast to the conventional method which cannot directly simultaneously determine Cd （II）, Pb （H）, Cu （11）and Bi （m） by wave anodic stripping voltammetry due to the overlap of the peaks, a method based on chemometrics was proposed to simultaneously determine the four ions. Cd （ 11 ）, Pb （ I1 ）, Cu （ I1 ） and Bi （III） were determined simultaneously by square wave anodic stripping voltammetry with a silver-mercury film electrode in 0.1 mol/L ammonium citrate. Partial least squares （PLS） regression was applied to resolve quantitatively the strongly overlapping peaks in the voltammograms of Cu （ II ） and Bi （11I） ions. A PLS regression model was set up by a 39- sample training set with a concentration range of 0.10--2.56 ktg/mL for Cd（ II ）, 0.20--2.66 lag/mL for Pb（ II ）, 0.10--2.56/~g/mL for Cu （ 11 ） and 0.60---3.06/ag/mL for Bi （11I）. A validation set consisting of 10 samples was used to assess the model. The recoveries obtained were 92.3%--103.0%, 94.7%--106.0%, 89.0%--105.0% and 94.8%-- 108.0% for the four ions, respectively. The comparison with conventional univariate calibration method shows that, with the multivariate calibration, components with overlapping voltammetric curves can be determined simultane- ously without a prior separation.

关 键 词：同时测定 化学计量学 重金属 方波阳极溶出伏安法 

分 类 号：O657[理学—分析化学]