Journal of Electroanalytical Chemistry, Vol.432, No.1-2, 159-169, 1997
Hydrodynamic Modulation Using Vibrating Electrodes - Application to Electroanalysis
Microband (10 mu m x 2 mm), multiple parallel microband (spacing 20 mu m) and planar (similar to 1 mm(2)) electrodes, fabricated by screen printing and vibrated (2-50 Hz; 1-2 mm amplitude) either continuously or in pulsed motion parallel to the short axis of the band and perpendicular to the face of the planar electrodes, are described. The band electrodes were made by printing successive layers of gold and insulator onto a ceramic substrate then snapping along a pre-scribed line to expose a fresh surface. A clean and repeatable electrode surface for a disposable device was obtained by this simple expedient. The resulting microband electrodes when vibrated showed the signal enhancement characteristic of vibrated wire electrodes, the modulation depth and signal enhancement being smaller than those characteristic of a vibrated microwire but larger than those from larger diameter wires. The printed bands have the major advantages of ease of preparation and use and of low cost and repeatability in bulk manufacture. Reagents were also printed onto the devices and were rapidly dissolved and mixed into the test solution by the vibration. A low-cost, single-use device for analysis, without prior calibration, of chlorine in water has been demonstrated with detection limit around 0.3 mu mol dm(-3) (0.02 ppm) and linearity into the mmol dm(-3) range. Multiple microband electrodes have been used to implement, in a simple and inexpensive way, generator-collector methods of electrochemical titration, exemplified by the determination of ascorbic acid using electrogenerated Fe(III). The analytical methods are repeatable and practical, although the hydrodynamics of these systems are complex. The current to planar electrodes oriented vertically and vibrated along the surface normal is not modulated : a uniform circulating flow appears to be set up. The current to microband electrodes vibrated parallel to the short axis is strongly modulated. For sinusoidal motion the current waveform is an amplitude-and frequency-dependent superposition of a number of waves, each perfectly periodic in a simple multiple of the vibration frequency. The mean and maximum current an independent of the amplitude of the motion. A qualitative description of the hydrodynamics of the vibrating electrodes is given and the predicted dependence of mean current on (vibration frequency)(1/2) demonstrated, despite the complexity of the current waveforms. The idea of using pulsed motion to renew periodically the concentration boundary conditions is discussed briefly.