Determination of sulfite by pervaporation-flow injection with amperometric detection using copper hexacyanoferrate-carbon nanotube modified carbon paste electrode

A pervaporation-flow injection (PFI) method was developed for the determination of sulfite in selected food samples using a copper hexacyanoferrate-carbon nanotube (CuHCF-CNT)-modified carbon paste electrode. The electrochemical behavior of the modified electrode was observed using cyclic voltammetry in comparison to a CuHCF-modified carbon paste electrode and a bare carbon paste electrode at a scan rate of 100 mV s−1 in 0.10 M KNO3. The bare carbon paste electrode gave the lowest response to sulfite, while the presence of CuHCF made the detection of sulfite possible through electrocatalytic oxidation by the hexacyanoferrate in the modified electrodes. The presence of CNT in the CuHCF-CNT-modified sensor gave the most remarkable current for the detection of sulfite and was then used as a working electrode in the amperometric flow-through cell in the pervaporation flow injection system. The PFI method involves the injection of a standard or sample sulfite solution into a sulfuric acid donor stream to generate sulfur dioxide gas and evaporate into the headspace of the pervaporation unit. The sulfur dioxide diffuses through the PTFE hydrophobic membrane into a potassium nitrate acceptor stream and reverts to the sulfite form, which, subsequently, is transported to the electrochemical flow cell where it is analyzed amperometrically at a CuHCF-CNT-modified electrode at +0.55 V (vs. Ag/AgCl). The detection was determined to be applicable in the sulfite concentration range of 0.5–50 mg L−1. The sensitivity, detection limit, and sample throughput were determined to be 2.105 nA L mg−1, 0.40 mg L−1 and 11 h−1, respectively. The developed PFI method, coupled with the CuHCF-CNT-modified carbon paste electrode, was applied in the determination of sulfite content in sulfite-containing food products. The results agreed well with those obtained through the officially recommended differential pulse polarographic method.