Electroactivity of nitriles on platinum electrodes and its use in chromatographic detection

Acetonitrile yields two oxidative peaks, first at ca. +0.30 and second at ca. +1.15 V vs. Ag/AgCl in cyclic voltammetry with platinum electrodes in 0.10 M methanesulfonic acid (MSA) containing 0.05–5 mM concentrations of acetonitrile. This electroactivity of the nitrile group was used for a direct detection of nitriles after their chromatographic separation. Three organic nitriles (acetonitrile, propionitrile and butanenitrile) were separated with an IonPac ICE-AS 1 column, eluted with 0.10 M MSA and detected on a platinum electrode via pulsed amperometric detection. Analytical performance was evaluated with a three potential waveform (+0.30 V, +1.15 V, −0.30 V vs. Ag/AgCl, current integration at +1.15 V). Numerical values of detection limits, linearity of calibration and reproducibility are reported for all three organic nitriles.