Thesis (Ph. D.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2007. / Committee Chair: Prof. Charles L. Liotta; Committee Member: Prof. Arthur J. Ragauskas; Committee Member: Prof. Charles A. Eckert; Committee Member: Prof. John D. Muzzy; Committee Member: Prof. Rigiberto Hernandez.

Hydrazine (HZ) and monomethylhydrazine (MMH) are used extensively as hypergolic propellants at Kennedy Space Center. These highly reactive fuels are considered highly toxic, and potentially carcinogenic. Consequently, the transport, handling, and disposal of hydrazines is strictly regulated to protect personnel and the environment. Currently, KSC generates large volumes of hydrazine-laden wastewater for disposal. This waste is contained and shipped on public highways for subsequent disposal by incineration presenting a potentially catastrophic threat to the environment and the general public in the event of an accidental release. Other existing remediation methods include oxidative and reductive pathways as well as biodegradation in fixed film reactors. Each of these methods has associated drawbacks and limitations that make them unsuitable for industrial use. Recently, hydrazine neutralization by reaction with alpha-ketoglutaric acid (AKGA) to form the stabilized pyridazine derivatives PCA and mPCA has been explored. The applicability of this technique for use at KSC has been established and procedural considerations for implementation have been addressed. Experimental evidence based on worst case scenario decontamination processing simulations and reaction characterization has suggested that AKGA can cost effectively function as a drop-in replacement for current neutralizers with minimal modification to existing infrastructure and operating procedures. Further work will be necessary to satisfy permitting iv requirements and verify that the reaction product stream is non-hazardous in light of limited toxicity data.

Hydrazine and monomethylhydrazine are widely used as propellants in aerospace and defense industries. However these chemicals are volatile, carcinogenic, and sensitive to impact, which impose serious threats during their usage. In this thesis, we have demonstrated two novel ways to immobilize hydrazine chemicals. In one approach hydrazine, monomethylhydrazine have been gelled using carbon dioxide. Chemical and structural properties of these gels are studied by NMR (1H, 15N, 13C), diffusion-ordered NMR spectroscopy, and Cryo-HRSEM. Thermal reversibility of these gels is also demonstrated. In another approach, hydrazine, monomethylhydrazine and 1,1-dimethylhydrazine are reacted with 5-methyltetrazole to form ionic liquids. Synthesis of novel tetrazole monomers and polymers, .and new method for encapsulating sodium azide have also reported in this thesis