title: Simultaneous kinetic determination of thiocyanate and sulfide using eigenvalue ranking and correlation ranking in principal component-wavelet neural network.
abstract: In this work, two toxic compound, sulfide and thiocyanate were determined simultaneously using kinetic spectrophotometry. These anions have shown the catalytic effects on the reaction between iodine and azide. Since the system was nonlinear, a nonlinear model, principal component-wavelet neural network (PC-WNN) was used as the multivariate calibration method. The principal component analysis was used to decrease the dimension of the original matrix. In other words, the scores of the PCs, 5, instead of the original variables, 301, were used as the input for the model. Two methods were used to select the most relevant principal components: eigenvalue ranking and correlation ranking. In this work, eigenvalue and correlation ranking methods have shown better results for thiocyanate and sulfide, respectively, and it can be concluded that these methods are complementary. The WNN has several advantages relative to other types of neural network such as better convergence ability. The data set was divided to calibration, prediction and validation sets. Each set was selected so that the concentrations of the analytes were approximately covered the entire ranges of the analytes. Mean relative error for thiocyanate and sulfide in validation set were 8.5 and 10.6, respectively. Thiocyanate and sulfide can be determined in the range of 60-700ng ml(-1) and 20-400ng ml(-1), respectively. The proposed method was applied for the determination of sulfide and thiocyanate in real samples such as tap, waste and river waters with satisfactory results.
authors.affiliation: College of Chemistry, Isfahan University of Technology, Isfahan 84156-83111, Iran. Ensafi@cc.iut.ac.ir
authors.forename: Ali A
authors.initials: AA
authors.lastname: Ensafi
authors.forename: T
authors.initials: T
authors.lastname: Khayamian
authors.forename: R
authors.initials: R
authors.lastname: Tabaraki