Determining kinetic parameters from pulse voltammetric data

Abstract

A nonlinear least-squares method of analyzing pulse voltammetric data suitable for use with a small laboratory computer is presented. The method, which is applicable to all forms of pulse voltammetry, is based upon a nonlinear simplex optimization of the parameters of the problem in a normalized space derived from linear regression of the measured current on a calculated dimensionless current function. Hence, in contrast with procedures employing working curves, no extraneous scaling factors or biases are required to compare models directly with experimental data. The method also provides an efficient computation of the confidence ellipsoid surrounding the optimal values of the kinetic parameters. © 1986 American Chemical Society.