Validation of a tubular bismuth film amperometric detector

A tubular bismuth film electrode (BFE), installed as part of a multisyringe flow injection system, was used as an amperometric detector to determine the concentration of diclofenac sodium in pharmaceutical formulations. A tubular voltammetric detection cell was employed, in which the hydrodynamic flow conditions were not disturbed. This automated method allows the continuous regeneration of the BFE, preventing passivation of the detector and improving the sensitivity of detection. The influence of several variables on this sensitivity, such as the injection volume, deposition time and flow rate were evaluated; a two-level factorial experimental design was employed for this. In optimal conditions, the linear range of the calibration curve varied from 6.0-50.0 μmol L−1, with a detection limit of 4.3 μmol L−1. A sampling rate of 90 determinations/h was achieved; the relative standard deviation of analytical repeatability was <3.5%. After 30 injections the bismuth film on the electrode surface was automatically renewed. The method was validated by comparing the results obtained with those provided by RP-HPLC; no significant difference were seen (p < 0.05).