Graduate Thesis Or Dissertation

 

Experimental and theoretical investigation of the ability of oxygen-containing molecules to accept charge Public Deposited

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  • The question of why carboxylic acids and phenols are stronger acids than alcohols has been investigated experimentally and theoretically. The experimental approach involves comparison of gas-phase acidities and core-ionization energies. The theoretical treatment uses calculated point potentials and acidities. The ease of proton removal is related to two factors known as initial- and final-state effects. Initial-state factors influence the process in neutral molecules; anything that makes the potential near the acidic hydrogen more positive will make the molecule more acidic. Final-state effects influence the process during and after proton removal. As the proton is removed, the electrons and protons redistribute to better accommodate the negative charge. Anything that can help accommodate the negative charge and stabilize the anion will make the molecule more acidic. Both the experimental and theoretical results of this study indicate that initial-state effects are the dominant factors in determining the relative acidities of alcohols, phenols, and carboxylic acids. Final-state differences were found to contribute negligibly to the relative acidity. These results are in conflict with the currently accepted resonance-delocalization theory, in which resonance delocalization of the negative charge in the anions of unsaturated molecules (a final-state effect) is considered to be the major contributor to the overall acidity difference between carboxylic acids and alcohols and between phenols and alcohols. Linear correlations have been found between experimental and theoretical gas-phase acidities, and between experimental oxygen is ionization energies of hydroxyl-containing molecules and the corresponding methoxy- and ethoxy-containing molecules. These correlations make it possible to predict accurate acidities and oxygen is coreionization energies of compounds for which measurements would be difficult or impossible. The series of molecules, isopropyl alcohol, isopropenyl alcohol, and acetic acid is discussed. Isopropenyl alcohol is a transient molecule; its acidity and oxygen is ionization energy were determined from the linear correlations discussed above. Initial- and final-state differences are discussed with respect to isopropyl alcohol and acetic acid.
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