The thermochemical copper-chlorine (Cu-Cl) cycle for hydrogen production includes three chemical reactions of hydrolysis, decomposition and electrolysis. The decomposition of copper oxychloride establishes the high-temperature limit of the cycle. Between 430 and 530 oC, copper oxychloride (Cu2OCl2) decomposes to produce a molten salt of copper (I) chloride (CuCl) and oxygen gas. The conditions that yield equilibrium at high conversion rates are not well understood. Also, the impact of feed streams containing by-products of incomplete reactions in an integrated thermochemical cycle of hydrogen production are also not well understood. In an integrated cycle, the hydrolysis reaction where CuCl2 reacts with steam to produce solid copper oxychloride precedes the decomposition reaction. Undesirable chlorine may be released as a result of CuCl2 decomposition and mass imbalance of the overall cycle and additional energy requirements to separate chlorine gas from the oxygen gas stream. In this thesis, a new phase change predictive model is developed and compared to the reaction rate kinetics in order to better understand the nature of resistances. A Stefan boundary condition is used in a new particle model to track the position of the moving solid-liquid interface as the solid particle decomposes under the influence of heat transfer at the surface. Results of conversion of CuO*CuCl2 from both a thermogravimetric (TGA) microbalance and a laboratory scale batch reactor experiments are analyzed and the rate of endothermic reaction determined. A second particle model identifies parameters that impact the transient chemical decomposition of solid particles embedded in the bulk fluid consisting of molten and gaseous phases at high temperature and low Reynolds number. The mass, energy, momentum and chemical reaction equations are solved for a particle suddenly immersed in a viscous continuum. Numerical solutions are developed and the results are validated with experimental data of small samples of chemical decomposition of copper oxychloride (CuO*CuCl2). This thesis provides new experimental and theoretical reference for the scale-up of a CuO*CuCl2 decomposition reactor with consideration of the impact on the yield of the thermochemical copper-chlorine cycle for the generation of hydrogen. / UOIT

Hydrogen appears to be a clean and sustainable fuel for transportation vehicles, including internal combustion engine vehicles. In this research, a 1986 GMC Sierra truck with a 350CID 5.7L V8, 4 barrel carbureted Chevrolet gasoline engine is converted to burn hydrogen as a sustainable and envirnmentally benign fuel with a shorter energetic cycle. It demonstrates that the problems of backfire can be eliminated using several less expensive methods, such as employing cold spark plugs with reduced spark gap and low temperature cooled valves along with the introduction of water vapor to the mixture. In the experiments, the internal combustion engine was tested for two fuels: (i) octane 95 gasoline, and (ii) gaseous hydrogen at 99% purity. The vehicle underwent dynamometer tests using both the gasoline and hydrogen fuels for performance comparisons. A comprehensive thermodynamic analysis, through energy and exergy, of the engine is conducted for both cases: (i) with the octane 95 gasoline fuel and (ii) with hydrogen gaseous fuel. The performance results through energy and exergy efficiencies are compared for possible improvements. The mileage and energy efficiencies calculated and tested using this engine showed that it is more efficient operating on gasoline fuel rather than hydrogen. This is explained fully in the thesis as to the properties of hydrogen and gasoline fuels that differ, and the particular vehicle technology makes this difficult to achieve a reasonable mileage and efficiency. / UOIT

The main goal of this thesis was to explore the role of H-bonding interactions in ferrocene peptide conjugates at the molecular and supramolecular level. With the help of detailed spectroscopic and crystallographic studies, the intermolecular association of a range of conjugates was studied and described here. It was shown that C-terminal modifications directed the supramolecular assembly. In the case of Fc[CO-Gly-Val-OH]2, the C-terminal carboxylate group directed intermolecular interactions, causing formation of a supramolecular architecture that was characterized by large solvent-filled hydrophobic channels. In the absence of this directional group, as was the case in Fc[CO-Leu-Val-OMe]2 extended β-sheets were formed. Hierarchical self-assembly of disubstituted ferrocene peptide conjugates possessing Gly-Val-Phe and Gly-Val-Phe-Phe peptide substituents gave rise to nano- and micro-sized assemblies. Spontaneous self-assembly of Fc-peptides through intra-and intermolecular hydrogen bonding interactions induced supramolecular building blocks, which further associated to fibers, large fibrous crystals, and twisted ropes. Next, intermolecular H-bonding interactions were studied using a surface-based approach. A fragment of the amyloid-beta (Aβ) peptide was bound to a gold surface through a C-terminal Cys. Various aspects of the peptide film were examined using different electrochemical and surface analytical techniques. The interaction of Congo red and of Lys-Leu-Val-Phe-Phe with the immobilized Aβ fragment was studied using electrochemical methods, showing responses that indicated intermolecular interactions. This surface approach was used to probe the interaction of a series of ferrocene peptides (Fc-CO-Leu-Val-Phe-Phe-OX and Fc-CO-Lys(Boc)-Leu-Val-Phe-Phe-OX with X=H and Me) with the surface-bound Aβ fragment. Biomolecular interactions between Fc-peptides and the Aβ-modified surface were studied by electrochemical methods. The current response of the Fc redox process was modulated by the interaction with the Aβ-modified surface.

We have prepared a new class of polybenzoxazine based nanocomposites through DNA-like self-complementary multiple hydrogen bonding. At first, benzoxazine containing thymine (Bz-T), PEO containing adenine (PEO-A) group and POSS containing adenine (POSS-A) have been successfully synthesized, respectively. Those chemical structures were confirmed by 1H and 13C NMR and FT-IR spectroscopies. DSC and TGA analyses showed that the Bz-T had lower cross-link temperature and higher thermostability than benzoxazine containing methyl acrylate (BZ-ac) group. Moreover, TEM and WAXD provided a new evidence for linearly structure and self-assembly polybenzoxaine through self-complementary multiple hydrogen bonding of its T units. Then, PEO-A/PBz-T and POSS-A/PBz-T hybrid materials were prepared. SAX, WAXD, TEM and AFM analyses indicated that the size of PEO domain in PBz-T matrix was significantly decreased and the new type phase separation boundary (discrete domain through non-convent bonds) was obtained. Finally, we were using WAXD, TEM, DSC and nanoindenter to study properties of POSS-A/PBz-T nanocomposite. The presence of self-assembly nano-lamellate structure and enhance the mechanical properties on thin film, because of well-dispersion of POSS in PBz-T matrix through strong hydrogen bonding between A-T interactions.

Use of hydrogen bonding as internuclear connecting information to better determine molecular structure or dynamics.

Thesis (M.S.)--University of Florida, 2004. / Title from title page of source document. Document formatted into pages; contains 60 pages. Includes vita. Includes bibliographical references.

Thesis (M.S.)--University of North Carolina at Wilmington, 2004. / Includes bibliographical references (leaves : [56]-57).

Thesis (Ph.D)--Mechanical Engineering, Georgia Institute of Technology, 2009. / Committee Chair: Andrei Fedorov; Committee Member: Srinivas Garimella; Committee Member: Timothy Lieuwen; Committee Member: William Koros; Committee Member: William Wepfer. Part of the SMARTech Electronic Thesis and Dissertation Collection.

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

The primary subject of this thesis is the study of warm dense hydrogen by means of pulsed laser heating in the pressure region 1 to 2 Mbar and temperatures above the melting line, where a liquid-liquid phase transition from the insulating molecular fluid to a conducting atomic hydrogen fluid, so called plasma phase transition (PPT), was predicted to take place. The first evidence of the PPT under static compression is reported. The observations are in agreement with the negative slope phase line predicted by ab initio methods. / Physics