Date of Award

Spring 2023

Document Type

Open Access Dissertation

Department

Chemistry and Biochemistry

First Advisor

Ken D. Shimizu

Abstract

The main topics of this dissertation are: 1) the development and discussion of a new molecular balance for measuring alkyl-alkyl interactions in a wide array of organic solvents, 2) the development of linear solvation energy relationships between solvent interaction parameters and solvent accessible surface area (SASA) in CH-arene interactions, and 3) the development of online resources for helping undergraduate students perform organic chemistry mechanisms problems well.

The solvophobic effect, that is the forced association between two solutes due to intermolecular attraction of the solvent molecules, is ubiquitous in organic chemistry and responsible for many significant phenomena thereof. However, there is a lack of experimental data on the effect due to its weak nature. Therefore, an intermolecular torsional balance system was developed specifically to isolate and measure the solvophobic effect across a wide range of organic solvents. The SASAs of the balances were altered to gauge how the solvophobic effect changes with the size of the solvent-solute interface. From the data collected, a predictive model correlating solvent cohesion, solute association energy, and solvent-solute interface area was developed which accurately predicted the association energy of the hydrophobic effect from previous literature.

Like solvent cohesion, the Kamlet-Taft, Catalán, and Laurence solvent parameters have been closely related with various solute-solvent association properties. Using a set of molecular torsional balances, we correlated the relationships between solvent parameters, solute-solvent interface area, and solvent-solute association energy of different CH-arene interactions. Results demonstrated a similar solvophobic effect between both CH-π interactions and CH- aromatic edge interactions, and that similar solvent parameters dominate the interactions.

College level organic chemistry presents itself as a major difficulty to many undergraduate students. In response, we surveyed a sample of underperforming exams to assess which areas were the most troublesome in writing electron-pushing formalisms (EPF). Online tutorial modules were then developed which instructs students in a step-by-step procedure on how to accomplish EPF problems with specific focus on the most prevalent problem areas. Furthermore, additional notes linking to problem to fundamental concepts of organic chemistry were addended within the example problems in order to facilitate the transition of students from understanding organic chemistry from rote memorization to a relational understanding of the principles.

Rights

© 2023, Alexander N. Manzewitsch

Included in

Chemistry Commons

Share

COinS