We detail the operation mechanism and instrumental limitations for potentiometric-scanning ion conductance microscopy (P-SICM). P-SICM makes use of a dual-barrel probe, where probe position is controlled by the current measured in one barrel and the potential is measured in a second barrel. Here we determine the interaction of these two barrels and resultant effects in quantitation of signals. Effects due to the size difference in pipet tip opening are examined and compared to model calculations. These results provide a basis for quantitation and image interpretation for P-SICM.