Electrode Kinetic Studies Using a Computerized Data Acquisition and Analysis System

Citation

Abel, Roger Henry (1971) Electrode Kinetic Studies Using a Computerized Data Acquisition and Analysis System. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/HT2Z-3059. https://resolver.caltech.edu/CaltechTHESIS:03092018-170506721

Abstract

The first section of this dissertation introduces the basic concepts that are necessary for the quantitative description of electrode kinetics. The refinements and corrections in the rate equation that are due to a detailed model of the electrical double layer, and to the potential step relaxation technique are introduced and discussed.

A discussion of the non-linear statistical analysis techniques that are necessary for a rigorous analysis of rate equation is presented in the second section. The estimates of the precision of the desired parameters obtained by using statistical methods can be used as a measure of the efficiency of an experiment. Their use as measures of "kinetic information density" is developed and illustrated by comparing charge and current measurement in the potential step technique. Previous approaches to the subject of "kinetic information density" are discussed and compared to the results from statistical analysis.

The third section describes the computerized data acquisition and analysis system that was designed and used for the study of electrode kinetics.

The final section presents the results of the kinetic studies undertaken on the Zn⁺²/Zn(Hg) system in 1 F NaNO₃, 1 F NaClO₄, and 1 F NaCl supporting electrolytes. Ensemble averaging is used in these studies to increase precision and its values is illustrated.

The results that are obtained for the rate constants in the various supporting electrolytes are compared and it is shown that the rates are comparable in NaNO₃ and NaClO₄ supporting electrolytes but significantly greater in 1 F NaCl. These results are compared with results of previous investigators and the quality of the results of this thesis are compared to those of previous investigators.

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