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A simple and accurate method has been developed for the field and laboratory analysis of four highly toxic substances found in certain industrial wastes in high concentrations. Trinitrobenzenesulfonic acid (TNBS) was used as a colorimetric reagent for 1,4-phenylenediamine (p-PD), 1,2-phenylenediamine (o-PD), 1,3-phenylenediamine (m-PD), and aniline in phosphate buffer of pH 7.4 to form relatively stable compounds that had high absorbance near 430 nm. With sodium sulfite present in the solution at 2 mmol·L–1 or above, higher extinction coefficients were attained and good linear relationships of absorbance with PDs and aniline concentrations were observed. Test times required to achieve maximum absorbance were 60 min for p-PD and m-PD, 30 min for aniline, and 200 min for o-PD. The reliable quantitation ranges were 2–20 µmol·L–1 for p-PD and m-PD and 2–40 µmol·L–1 for o-PD and aniline with the standard error of the estimates being less than 5% in these ranges. Key words: phenylenediamine, aniline, trinitrobenzenesulfonic acid, colorimetric test method.

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