Date of Award

1990

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

First Advisor

Robert J. Gale

Abstract

In part one, an analytical model for the growth kinetics of the anodic oxidation of Si at constant voltage is developed. The theoretical model derived for the film growth rate is consistent with the existing empirical relation reported earlier. Electronic current density, the major total current component, is shown to be nonohmic and space charge limited. Equations are derived, each as a function of time, for the total current density, the electronic current density, and the ionic efficiency during anodic oxidation. These theoretical predictions are in good agreement with the available experimental data. In part two, the high frequency conductances of three binary electrolytes: NaCl, K$\sb2$S0$\sb4$, and K$\sb3$Fe(CN)$\sb6$ have been measured in aqueous solution by a spectrum analyzer. A maximum conductance at a specific high frequency has been observed at certain concentrations for each electrolyte. The cell used for the experiments is a capacitive cell, or so-called condenser-type cell. A theoretical circuit model, which incorporates the Debye-Falkenhagen effect, has been developed for this type of cell and low field conditions. The calculations based on the classical electrostatic interactions of ions are in satisfactory agreement with experimental results. Some aspects of the high frequency conductance in capacitive cells, such as the role of the Debye-Falkenhagen effect, which has been ignored or misrepresented previously, are clarified. In part three, the characteristics of the metal-insulator-electrolyte interface (MIE), under quasi-equilibrium conditions, have been studied theoretically. Mathematical models of the MIE have been developed for two cases: ideal, and non-ideal. By combining MIE characteristics and the electroosmotic effect in a capillary, a novel effect called field effect electroosmosis can be postulated. Based on this effect, a new device called a metal-insulator-electrolyte-electrokinetic field effect device (MIEEKFED) can be designed. Finally, two new fundamental equations for Micellar-Electrokinetic Capillary Chromatography (MECC) have been derived, which are the corresponding Capillary Zone Electrophoresis (CZE) equations for the resolution and the migration time. A Van Deemter-like equation to describe the theoretical plate height for MECC has also been derived. MECC optimal resolution has been found for neutral solutes in three cases: where the migration mobility of the micelle is negative, zero, and positive.

Pages

175

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