Chronopotentiometric analysis of highly resistive media

Reciprocal derivative chronopotentiometry is shown to be well suited for performing electrochemistry in highly resistive solutions in connection to conventional-sized electrodes. The fundamentally different operational principles of reciprocal derivative chronopotentiometry (compared to controlled-potential voltammetry) reduces its susceptibility to solution resistance effects. The influences of the electrolyte concentration and constant current upon the reciprocal derivative chronopotentiometric peak area and potential are examined in different solvents. Well-defined, analytically useful peaks are observed in highly resistive media (with low electrolyte/analyte ratios). Narrower peaks, shifted to higher potential values, are observed upon increasing the solution resistance. Yet, the analytical signal (square root of the peak area) is nearly independent of the ohmic drop. The experimental results are compared with the theoretical predictions. Considerable ohmic drop distortions are observed in analogous voltammetric experiments. The defined chronopotentiometric peaks permit convenient quantitation of micromolar analyte concentrations in highly resistive media. Such observations open the door to new electrochemical applications of conventional electrodes that were previously restricted to ultramicroelectrodes.