Statistical Properties of a Procedure for Analyzing Pulse Voltammetric Data.

O'Dea et al. (1983, J. Phys. Chem. 97, 3911-3918) proposed an empirical procedure for obtaining estimates and confidence intervals for kinetic parameters in a model for pulse voltammetric data. Their goal was to find a procedure that would run in real time, not necessarily one that would have well-defined statistical properties. In this paper we investigate some of the statistical properties of their procedure. We show that their estimation method is equivalent to maximum likelihood estimation, and their confidence intervals, while related to likelihood ratio confidence regions, have a coverage probability that is not fixed and that is potentially quite large. We suggest modifications of their procedure that lead to more traditional confidence intervals. We examine the effect on their procedure of the presence of nuisance paramters. Finally we discuss the possibility of serially correlated errors.