Accession Number : ADA192825

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

Descriptive Note : Technical rept. no. 68, 1 Oct 86-30 Sep 87,

Corporate Author : PURDUE UNIV LAFAYETTE IN DEPT OF CHEMISTRY

Personal Author(s) : Milner, David F ; Weaver, Michael J

PDF Url : ADA192825

Report Date : 25 Sep 1987

Pagination or Media Count : 34

Abstract : 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. Keywords: Digital simulation analysis, Uncompensated solution resistance, Electrochemical rate constants, Cyclic voltammetry.

Descriptors :   *REACTION KINETICS, *ELECTRICAL RESISTANCE, ALTERNATING CURRENT, CAPACITANCE, COMPENSATION, CONSTANTS, CYCLES, DIGITAL SIMULATION, ELECTROCHEMISTRY, ELECTRODES, LAYERS, PARAMETERS, RESISTANCE, SOLUTIONS(GENERAL), VOLTAMMETRY, ELECTRICAL IMPEDANCE

Subject Categories : Physical Chemistry

Distribution Statement : APPROVED FOR PUBLIC RELEASE