Amperometric detection with microelectrodes in flow injection analysis: theoretical aspects and application in the...

The construction of a wall-jet cell with amperometric detection using a set of disc electrodes whose radii ranged from 5 to 750 mum has been proposed. The influence of some experimental parameters like flow rate and electrode radius on hydrodynamic voltammograms recorded for a 0.5 mmol dm(-3) potassium ferrocyanide solution also containing 0.1 mol dm(-3) KCl has been discussed. Some considerations regarding the current signals obtained from flow injection experiments using both a 5- and a 750-mum radius platinum electrode were carried out in order to achieve the lowest limit of detection, a value of 0.03 mumol dm(-3) ferrocyanide being calculated by using the 5-mum radius microelectrode as amperometric detector. The wall-jet cell has been used in the determination of nitrite in saliva by quantifying the triiodide formed in the reaction of the analyte with excess iodide in acidic medium. A 12.5-mum platinum disc microelectrode maintained at +0.2 V vs. Ag/AgCl was used as amperometric detector. Peaks obtained in fiagrams after injection of diluted saliva to the carrier stream containing 0.1 mol dm(-3) sulphuric acid and 20 mmol dm(-3) potassium iodide were compared to an analytical curve obtained in the same conditions (r(2)=0.997) for a nitrite concentration in the range 1-10 mumol dm(-3). The concentration of nitrite in the saliva sample after the appropriate correction for dilution was found to be 2.3 ppm (0.05 mmol dm(-3)), in a good agreement with results obtained by using a standard spectrophotometric procedure (2.5 ppm). The limit of detection of the method was calculated as 0.2 mumol dm(-3), and the reproducibility was checked by measuring the peak current for 19 injections of 10 muM nitrite, the standard deviation being 3.7%.