Some Investigations in Theoretical and Experimental Electrochemistry

Citation

Flanagan, James Brian (1978) Some Investigations in Theoretical and Experimental Electrochemistry. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/kb90-ht51. https://resolver.caltech.edu/CaltechTHESIS:01302017-163917597

Abstract

This thesis is composed of three distinct topics. Chapters II, III and IV are concerned with the analytical consequences of adsorption of reactants at the electrode surface with d.c. polarography and normal and differential pulse polarography. Theoretical behavior was calculated by means of digital simulation and Laplace transform techniques. The effects of nonlinear adsorption isotherms and uncompensated resistance on current-potential response was calculated. The reaction Cd⁺²/Cd (Hg) with adsorption induced by the presence of iodide was used as a test system.

Chapters V and VI are concerned with the electrochemical behavior of molecules with more than one center for electron transfer. Classical statistical methods were used with computer calculation of results, Problems considered include concentration- and current-potential behavior of: (1) polymeric species with no interaction between centers; (2) dimers with interactions; and (3) asymmetric binuclear molecules.

Chapter VII discusses data analysis techniques for "large step" coulostatics in the study of electron transfer kinetics. The merits of the technique in electrochemistry are discussed. A method for the use of a numerically generated function as the basis function for nonlinear regression is discussed.

Chapter VIII presents a study of alternative methods of "small step" coulostatic data analysis. Strong cross-correlation was found between double layer capacitance, charge transfer parameters and diffusional parameters.

Thesis Files