Abstract
A new method of hydrodynamic modulation voltammetry (HMV) is introduced, based on the microjet electrode (MJE) with an oscillating nozzle position. In MJE-HMV a jet of solution is fired at high velocities from a nozzle (with a typical diameter in the range 25−50 μm) onto the surface of a disk ultramicroelectrode (UME). The mass transport rate to the electrode is modulated by oscillating the lateral position of the jet between two different coordinates: one where the jet impinges directly on the electrode surface and the other where the flowing stream (largely) misses the electrode. The resulting modulated (transport-limited) current in phase with the moving jet is quantitative and discriminates effectively against background processes. Studies of iridium (III) hexachloride (IrCl63-) oxidation at a Pt MJE serve to demonstrate the general capabilities of the technique. For this system, detection limits are estimated to be ∼5 × 10-9 mol dm-3. In its present form, modulation frequencies of as much as 20 Hz c...
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