Influence of Uncompensated Solution Resistance on the Determination and Standard Electrochemical Rate Constants Using Cyclic Voltammetry, and Some Comparisons with AC Voltammetry

摘要

A digital simulation analysis is presented of the deleterious effects of uncompensated solution resistance, Rus, upon the evaluation of standard rate constants, k2ob, using cyclic voltammetry. The results are expressed in terms of systematic deviations of 'apparent measured' rate constants, k2ob(app), evaluated in the conventional manner without regard for Rus, from the corresponding actual values, k2ob (true), as a function of Rus and other experimental parameters. Attention is focused on the effects of altering the electrode area and the double-layer capacitance upon the extent of the deviations between kob (app) and ksob (true), and on comparisons with corresponding simulated results obtained from phase-selective ac impedance data.