Determination of the capacitance of solid-state potentiometric sensors: An electrochemical time-of-flight method.

A dual microelectrode electrochemical time-of-flight technique in which diffusion flux of Ag+, Cl-, or H+ ions electrochemically produced at a generator electrode is measured by recording potential-time transients with Ag, Ag/AgCl, or iridium oxide potentiometric microsensors, respectively, is developed. The generator and microsensor electrodes are typically spaced by 50-100 microm and are incorporated in the lithographically fabricated thin-layer-type devices. Under conditions of moderate rates of the ion electrogeneration, the potential-time (E-t) transients recorded with the three microsensors show excellent agreement with theory involving linear diffusion equations and the experimentally determined Nernstian slopes of the microsensors. However, when the generator current, or the initial concentration of the primary ion of interest is low, appreciable delays in the recorded E-t transients are observed due to the finite capacitance of the micropotentiometric sensors. The recorded delay in the E-t transients can be quantitatively accounted for by including the sensor capacitance (C) in the theoretical description of the transients. Direct comparison between the theoretical and the experimental E-t transients yields the sensor's capacitance. This capability of our new technique is unique in that it allows determination of the capacitance of a potentiometric sensor at open circuit. In the cases of silver electrodes, this method results in C = 31 +/- 2 microF/cm2, a value that is in agreement with those obtained by other methods. The results for silver chloride sensors yield a C in the range of 100-140 +/- 10 microF/cm2. The specific values depend on sensor preparation and the resulting roughness of the Ag/AgCl interface. Iridium oxide sensors show a capacitance that linearly depends on the thickness of the film. Specific capacitance of these microporous films was determined to be 59 +/- 6 F/cm3.