Scanning electrochemical microscopy, 52. Bipolar conductance technique at ultramicroelectrodes for resistance...

The bipolar conductance, BICON, technique for the measurement of solution resistance, based on the application of microsecond current pulses, as originally described by Enke and co-workers for measurements with conventional electrodes, was extended for use with ultramicroelectrodes, with a focus on its application in scanning electrochemical microscopy (SECM). When the plateau time used to make the measurement lies within the BICON conditions, the solution conductance can be obtained directly from the output without the need for calibration curves. However, decreasing the size of the ultramicroelectrode decreases the range of values that satisfy these conditions, and one must resort to calibration curves to obtain solution conductance from the measured current, which was nevertheless found to be proportional to electrolyte concentration with electrodes as small as 5 mum in diameter. BICON/SECM approach curves over insulating substrates followed SECM negative feedback theory and approach curves in the presence of low (micromolar) or no added electrolyte are possible once the background conductivity is taken into account. Approach curves to a conducting substrate at open circuit potential are influenced by the solution time constant (solution resistance at the electrode tip x electrode double layer capacitance), which is a function of the tip/substrate distance, as well as the substrate size.