Date of Award

8-2012

Degree Name

Master of Science

Department

Chemistry

First Advisor

James J. Kiddle

Second Advisor

Elke Schoffers

Third Advisor

Andre Venter

Access Setting

Masters Thesis-Open Access

Restricted to Campus until

3-1-2013

Abstract

Determination of hydroxyl radical rate constants are essential to ensure adequate degradation of contaminants in wastewater. Hydrazines are an important class of organic contaminants and are the focus of this research. Ten 1,1-dialkylhydrazines are synthesized by the zinc reduction of the corresponding N-nitrosamines. Their hydroxyl radical rate constants are determined using the linear accelerator at the Notre Dame Radiation Laboratory at pH 4, 7, and 10.

Their rate constants are found to depend on the protonation state of the molecule. At pH 4 the molecules are fully protonated and hydrogen atom abstraction is favored from the alkyl chains. At pH 7 the molecules exist in both the protonated and freebase forms and their rate constants are a sum of the rate constants at pH 4 and 10. In the fully freebase form at pH 10 hydrogen atom abstraction occurs from amine hydrogens. A NMR study was also done to fully characterize a series of N-nitrosamines. Interesting results including a splitting of 15N NMR signals for N-alkylbenzylnitrosamines were observed.

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