Thesis (Ph. D.)--University of Chicago, 1940. / Reproduced from type-written copy. "Private edition, distributed by the University of Chicago libraries, Chicago, Illinois." Includes bibliographical references.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1967. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

No description available.

No description available.

Thesis (Ph. D.)--University of Nebraska, 1934.

Incorporation of water molecules in the crystal structure of an organic compound has strong effects on its physical and chemical properties. Therefore, the study on stability of water-incorporated pharmaceutical compounds and mechanisms of hydration and dehydration is very important for the pharmaceutical industries. The main goals of the present research project were quantitative description of the crystallization and solid-state transformations of pseudopolymorphs of sodium naproxen in order to provide fundamental information concerning stability of the pseudopolymorphic forms. Furthermore, macroscopic phenomena of size reduction and anisotropic water-removal by dehydration were rationalized by microscopic aspects of crystal lattice structures. The heats of solution for each pseudopolymorph were estimated by fitting the solubility data with the vant Hoff equation, and their use was extended by the thermodynamic cycle developed in the present study. According to the thermodynamic cycle, for an enantiotropic system, a form with a lower degree of hydration always has the lower heat of solution than a form with a higher degree of hydration, implying that a form with a lower degree of hydration is more stable. The relative stabilities of the dihydrated, the monohydrated, and the anhydrous sodium naproxen at 0% relative humidity were investigated by dehydration of the dihydrated form and powder X-ray diffraction. The monohydrate is more stable than the dihydrate and the result was supported by isothermal TGA experiments. This research explained why powder-like crystals of the anhydrous sodium naproxen were produced by dehydration of hydrated forms. The surfaces of the dehydrated crystals displayed cracks aligned along the b-axis of the monohydrate. These cracks made the anhydrous crystals, which were produced from the monohydrated species, very brittle and, eventually, such crystals were disrupted into much smaller entities. In addition, the existence of water channels in the unit cells of the monohydrate facilitates the dehydration in a direction more rapidly, especially, along the b-axis of the monohydrate. Rapid removal of water in a specific direction caused anisotropic dehydration.

Thesis (Ph. D.)--Brigham Young University. Dept. of Chemical Engineering, 2005. / Includes bibliographical references (p. 145-156).

Log K values, valid at zero ionic strength are reported for the interaction in aqueous solution of CN- with Ni2+ and Hg2+ at 10°, 25° and 40°C, and with Pd2+ at 25°C. ∆H° and ∆S° values valid at zero ionic strength and 25°C are also reported for the interaction of CN- with Hg2+ and for the reaction Pd(CN)42- + CN- = Pd(CN)53-. In connection with the study of Pd2+ - CN- interaction, log K values for the hydrolysis of Pd2+ to give PqOH+ and Pd(OH)2 and an E° value for the reaction Pd(s) = Pd2+ + 2e- are reported. A least squares computational method is developed for the calculation of the equilibrium constants, enthalpy changes and entropy changes for metal-ligand interactions from a single thermometric titration curve (Entropy Titration). This method has been tested by determining log K, ∆H° and ∆S° values for the interaction of Ag+ and Cu2+ with pyridine, Hg(CN)2 with CN- and HgCl2 with Cl-. The results indicate that both the computational method and entropy titration technique are applicable to the determination of the thermodynamics of interaction of metal-ligand systems. Log K, ∆H° and ∆S° values have been determined for the interaction of SO42+ with H+ and thirty +1, +2 and +3 metal ions. The results are compared to electrostatic predictions and deviations from electrostatic predictions are attributed to specific solvent interactions. Log K, ∆H° and ∆S° values are reported for the interaction of Hg(CN)2 with thiourea in water-ethanol solvent mixtures. The results indicate that there is a significant change in the solvolysis of the species in solution at approximately 20 mole per-cent ethanol.

A new isothermal titration calorimeter has been designed to facilitate the study of heats of reaction and heats of solution at constant temperature. With this calorimeter, endothermic or exothermic processes can be studied at temperatures constant to ±0.0002°C. Heat effects are compensated by balancing the heat effect of the process taking place in the calorimeter against a variable heat and a constant cooling Peltier device. The calorimeter was tested by measuring the heat of ionization of water and the heat of dilution of aqueous HClO_4 solutions. For these systems heats were measured to an accuracy of ±0.02 calorie. Log K, ΔH°, ΔS° and ΔCp° values valid at zero ionic strength have been reported for the interaction of CN^- with Ni^2+ , Zn^2+ , Cd^2+ and Hg^2+ in aqueous solution at 10, 25 and 40°C. The results were compared to electrostatic predictions and it was found that electrostatic considerations do not predict the metal-ligand behavior in solution. The effect of temperature upon the behavior of ΔG, ΔH and ΔS is predicted using the ΔCp values determined in this study. Log K, ΔH°, ΔS° and ΔCp° values were determined for the glycinate complexes of bivalent Mn, Fe, Co, Ni, Cu, Zn and Cd. The results indicate that solvent effects for the various metal complexes are similar (based on ΔCp values) and that the temperature dependence of the thermodynamics of the metal glycinate complexes are similar for each of the metal glycinate systems.

The heats of immersion in n-alcohols of zeolites NaY, 5A and ZSM-5 and the kinetics of the immersion process have been determined using a Calvet MS-70 microcalorimeter. The specific heat of immersion decreased non-linearly as a function of chain length of alcohol for NaY and 5A. In contrast, the specific heat of immersion passed through a maximum at n-pentanol for ZSM-S. The specific immersion time as a function of chain length of alcohol showed an apparent linear increase in the order 5A > ZSM-S > NaY. NaY showed almost no increase. The effects of sample evacuation temperature and butyl alcohol isomer bulk on the heats of immersion were also investigated. These results were interpreted in terms of molecular accessibility of the wetting liquid into the pores of the zeolites and in terms of the Si/Al ratio of the zeolites. The overall kinetics of immersion appears to be first order. / Master of Science