This thesis focuses on the development of new compounds or new processes that are more environmentally friendly and economical than those currently in use. The decomposition of hydrazine, a well established liquid rocket fuel for both the aerospace and defense industries, to the product ammonia is studied. Control of this reaction will allow hydrazine to be used as a propellant for both chemical and electric propulsion. From this a dual stage thruster will be developed that will be more efficient than current systems decreasing the amount of propellant needed and allowing for either a larger mission payload or a longer duration of individual missions. Hydrazine, while beneficial and well established, is also highly toxic, so other work in this thesis focuses on the synthesis of the novel molecule 1,1-dimethyl-2-[2-azidoethyl]hydrazine or DMAEH and its hydrazone intermediate 1,1-dimethyl-2-[2-azidoethyl]hydrazone or De-DMAEH as less toxic hydrazine replacements. Novel "switchable" ionic liquids have been investigated in this research. These are solvents that can change from molecular liquids to ionic liquids and back, simply with the addition or removal of CO₂ from the system. They can be used for a variety of applications, including as solvents for a reaction and separation system. Due to the recyclable nature of these solvents, waste is decreased making their development and implementation both environmentally and economically beneficial. Finally, the grafting reaction of vinyl silanes onto a hydrocarbon backbone is investigated. Fundamental work is being performed to study the graft distribution, selectivity and mechanism by which this reaction occurs. A more thorough understanding of how this reaction proceeds will allow for the development of a more efficient industrial process.

Cross-linked polyethylene has higher upper use temperature than normal polyethylene and is used as an insulating material for electricity carrying cables and hot water pipes. The most common method of inducing crosslinks is by reaction with silanes. After incorporation of silanes into polyethylene and upon hydrolysis with ambient moisture or with hot water, Si-O-Si crosslinks are formed between the various linear polyethylene chains. Industrially, this reaction is performed routinely. However, the efficiency of this reaction with respect to the silane is low and control of product distribution is difficult. A precise fundamental understanding is necessary to be able to manipulate the reactions and thus, allow for the facile processing of the polymers. Hydrocarbon models of polymers - heptane, dodecane - are being used to study this reaction in the laboratory. For the reaction, vinyltrimethoxysilane is used as the grafting agent along with di-tert-butyl peroxide as the radical initiator. MALDI, a mass spectrometric technique is used for the analysis of the product distribution after work-up. Advanced NMR techniques (COSY, HSQC, DEPT, APT, HMBC) are being conducted on the grafted hydrocarbon compounds to gain an in-depth understanding of the mechanism and regiochemistry of the grafting reaction. Scalable and cost effective methods to capture CO2 are important to counterbalance some of the global impact of the combustion of fossil fuels on climate change. The main options available now include absorption, adsorption and membrane technology. Amines, especially monoethanolamine, have been the most commercialized technology. However, it is not without disadvantages. House et al have investigated the energy penalty involved in the post-combustion CO2 capture and storage from coal-fired power plants and found that 15-20% reduction in the overall electricity usage is necessary to offset the penalty from capturing and storing 80% of United States coal fleet's CO2 emssions1. Novel non-aqueous amine solvents, developed by the Eckert Liotta group, react with CO2 to form ionic liquids. The ionic liquids readily desorb CO2 upon heating, regenerating the reactive amines and this cycle can be carried out multiple times. An iterative procedure is being adopted to develop amine solvents for CO2 capture. Thermodynamic information like reversal temperature and boiling point of the solvents are collected; they are then used to formulate structure property relationships which allow for new molecules to be engineered. On reaction with CO2, there is a sharp increase in viscosity which is unfavorable from a processing standpoint. Many approaches to mitigate and control viscosity are being studied as well. 1House et al, Energy Environ Sci, 2009, 2, 193-205