Electronic Theses and Dissertations

Date of Award

1-1-2022

Document Type

Dissertation

Degree Name

Ph.D. in Chemistry

First Advisor

Charles L. Hussey

Second Advisor

Saumen Chakraborty

Third Advisor

Walter Cleland

School

University of Mississippi

Relational Format

dissertation/thesis

Abstract

In this work, the characterization of lanthanide elements (Dy, Er, Gd, Ho, Tb, Tm, Yb) in various RTIL solvents based on the ubiquitous bis(trifluoromethylsulfonyl)amide anion (Tf2N-) was investigated. The effect of cation structure on the mass transport and electron transfer properties of Yb3+ in [X]-Tf2N RTILs is considered, where [X] is one of six quaternary ammonium cations with varying structure and chemical properties. Cyclic staircase voltammetry (CSV), rotating disk electrode voltammetry (RDEV), and electrochemical impedance spectroscopy (EIS) experiments are used for this purpose. For each RTIL, the dependence of the redox reaction is examined at each of the working electrodes: glassy carbon, platinum, gold, and tungsten. In addition, the effect of temperature on the mass transport of Yb3+ and the heterogenous rate constant of the quasireversible Yb3+/2+ redox reaction is examined. It is shown that mass transport depends on the cation structure, whereas the heterogeneous rate constant depends primarily on the working electrode material.

Concentration/Emphasis

Chemistry

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