title: Surprising effect of uncompensated resistance on the cyclic voltammetric responses for a reversible surface-confined and uniformly accessible redox couple.
abstract: A traditional diagnostic for cyclic voltammetric responses is the plot of the peak current i(peak) vs the scan rate |v| or vs |v|(1/2). For a reversible redox couple with redox moieties freely diffusing in bulk solution, a plot of i(peak) vs |v|(1/2) will be linear; for a surface-confined and uniformly accessible reversible couple, a plot of i(peak) vs |v| will be linear; however, if there is significant uncompensated resistance, it is the plot of i(peak) vs |v|(1/2) that will be linear even if the redox species are surface confined. The present work offers a theoretical basis for this result.
authors.affiliation: Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973-5000, United States.
authors.forename: Stephen W
authors.initials: SW
authors.lastname: Feldberg