High-performance liquid chromatography of selected organic peroxides with oxidative amperometric detection.

Reversed-phase high-performance liquid chromatography with oxidative amperometric detection was optimized for the determination of several organic peroxides in drinking water under ideal conditions. The determinations were performed under isocratic conditions using acetonitrile and methanol as the organic modifiers with 0.05 M potassium phosphate buffer solution. The oxidative amperometric response of the organic peroxides was dependent on the concentration of organic modifier and the electrode potential. The optimum electrode potential (EOxAPP), for the simultaneous determination of the organic peroxides was approximately +1.150 +/- 0.05 V versus the Ag/AgCl reference electrode. The maximum analytical signal for butan-2-one peroxide and tert-butyl hydroperoxide, when using acetonitrile, was obtained with 20% v/v organic modifier. For cumene hydroperoxide, the maximum analytical signal was achieved with approximately 35% v/v acetonitrile. The retention time of cumene hydroperoxide, on an octyldecylsilane column (250 x 4 mm id), decreased sharply from > 100 to < 10 min when the organic modifier concentration was varied from 5 to 50% v/v. The retention time of butan-2-one and tert-butyl hydroperoxide, under the same conditions, varied by < 10 min. The calibration curves for the aliphatic peroxides and aromatic peroxide were linear from 2 to 200 ng and from 0.2 to 200 ng injected, respectively.