Development and Evaluation of a Pseudoreference Pt//Ag/AgCl Electrode for Electrochemical Systems

The use of standard reference electrodes, such as Ag/AgCl or saturated calomel electrodes, in potentiometric and amperometric studies involving miniaturized electrochemical systems, or those operating under positive hydraulic pressure, is often impractical. Placement of the reference electrode in the direct vicinity of the working electrode is often prohibited by the dimensions or layout of the electrochemical cell, while the alternative strategy of locating the reference electrode in a separate compartment often leads to electrolyte leakage and contamination of the system. In the present study, we have investigated the functionality of a pseudoreference electrode comprising a platinum wire, one end of which was maintained in intimate contact with the internal solution of an Ag/AgCl reference electrode while the other was connected, via a BNC connector, to a platinum probe located within the electrochemical cell. Linear and cyclic voltammetric studies, involving both aqueous and nonaqueous electrolytes, were carried out using the pseudoreference electrode and an electrochemical cup-type cell with three electrodes or an electrochemical flow reactor. In all cases, the functionality of the Pt//Ag/AgCl system was similar to that of a conventional Ag/AgCl reference electrode. Variations in the electrolyte did not alter the potential or voltammetric profile recorded when using the pseudoreference system, although peak currents were generally improved and potential values shifted by approximately +350 mV in comparison with the Ag/AgCl electrode, therefore, the system pseudoreference can be applied in any electrochemical system due to the constant potential difference. It is concluded that the pseudoreference electrode can be used with advantage to obtain potentiometric and amperometric measurements in both simple and complex electrochemical systems.

A New Method of Current Switching for Linear Wide-Range Measurement Systems

This new and general method here called overflow current switching allows a fast, continuous, and smooth transition between scales in wide-range current measurement systems, like electrometers. This is achieved, using a hydraulic analogy, by diverting only the overflow current, such that no slow element is forced to change its state during the switching. As a result, this approach practically eliminates the long dead time in low-current (picoamperes) switching. Similar to a logarithmic scale, a composition of n adjacent linear scales, like a segmented ruler, measures the current. The use of a linear wide-range system based on this technique assures fast and continuous measurement in the entire range, without blind regions during transitions and still holding suitable accuracy for many applications. A full mathematical development of the method is given. Several computer realistic simulations demonstrated the viability of the technique.