Simultaneous Determination of Nitrobenzene and Nitro-Substituted Phenols by Differential Pulse Voltammetry and Chemometrics

The voltammetric behaviour of five nitro-substituted aromatic compounds, such as nitrobenzene, 2-, 3-, 4-nitrophenol and 2,4-dinitrophenol, was investigated, and a method was developed for the simultaneous determination of these compounds, based on their reduction at a hanging mercury drop electrode (HMDE). It was found that by applying the differential pulse voltammetric (DPV) approach in a Britton–Robinson buffer of pH 5.4, nitrobenzene, 2-, 3- and 4-nitrophenol had well defined voltammetric reduction waves with peak potentials at −344, −284, −292 and −376 mV, respectively. However, 2,4-dinitrophenol had two peaks with potentials at −240 and −364 mV under the same conditions. For each compound linear calibration graphs were obtained in the general concentration range of 0.05–3.0 mg l−1. In mixtures of the five compounds, serious overlapping of voltammetric peaks was observed, and with conventional analytical methodology pre-separation steps would be required. In this study, chemometrics methods of data analysis, such as partial least squares (PLS), principal component regression (PCR) and classical least squares (CLS), were applied to resolve the overlapped voltammograms. Orthogonal experimental design was used for construction of the training sets containing the five aromatic compounds in the concentration range of 0.1–2.6 mg l−1. Five significant factors or principal components were modelled for prediction by the PLS and PCR methods, respectively. The percent of relative prediction error (RPE) was similar and acceptable for both methods being approximately ±10%. The percent of recoveries were within ±10% of the target value. The CLS method performed poorly (RPET=38%). The developed method was then applied to the analysis of these nitro-substituted aromatic compounds in field samples with similar satisfactory results