Thesis (M.S. in Chemical Engineering)--University of California, Berkeley, Sept. 1960. / Includes bibliographical references (leaf 56).

Thesis (Ph. D.)--University of Wisconsin--Madison, 1969. / Typescript. Vita. Description based on print version record. Includes bibliographical references.

Thesis (M.S.)--University of North Carolina at Wilmington, 2005. / Includes bibliographical references (leaf: [36] )

Thesis (PH. D.)--University of Michigan, 1926. / Reprinted from two articles by Alfred L. Ferguson and Egbert K. Bacon, published in the Journal of the American Chemical Society, v. 49, August, 1927.

Thesis--Liège. / Summaries in Dutch, English, German, and Italian. Includes bibliographical references (p. [127]-130).

Thesis (M. Sc.)--University of Canterbury, 2007. / Typescript (photocopy). Includes bibliographical references (leaves 76-78). Also available via the World Wide Web.

The solid state and solution phase photochemistry of three bridgehead-substituted dibenzobarrelene-11,12-diesters and a 2,3-naphthobarrelene diester derivative were investigated. These compounds were expected to undergo the di-π-methane rearrangement via their triplet excited states, and a rearrangement to a cyclooctatetraene (COT) derivative via their singlet excited states. All compounds investigated underwent smooth photoreactions in the solid state to produce the same products as observed in the corresponding solution phase photolyses. One exception to this was a bridgehead dimethyl- substituted dibenzobarrelene diester. In this case an unusual photo-product which was characterized as a dibenzopentalene derivative, was obtained in the solid state along with lesser amounts of the normal-solution products. The mechanism proposed for the formation of this product involves a 1,4-biradical intermediate which undergoes a novel double 1,2-ester migration. It was recognized that this biradical intermediate could also undergo fragmentation to produce a cyclooctatetraene (COT) derivative which differs in its symmetry from that of the COT expected based on the mechanism proposed by H. E. Zimmerman for similar transformations observed in the cases of benzo- and naphthobarrelenes. Thus, there are two structures possible for the COT formed which cannot be distinguished based on their spectral properties. For this reason, single crystal X-ray diffraction analysis of the COTs formed in each case was performed. Of the four COT structures determined by X-ray crystallography, three COTs had structures that were consistent with the fragmentation mechanism, while one had a structure consistent with the Zimmerman mechanism. In light of the possible unusual photorearrangements observed, it was thought desirable to establish the molecular structures of all photo-products obtained. To this end, crystal and molecular structures of 11 photoproducts were determined. Also, in an attempt to establish structure-reactivity relationships, crystal and molecular structures of four starting materials were determined. A bridgehead chloromethyl-substituted dibenzobarrelene diester was also found to produce dibenzopenatalene-like photoproducts in the solid state or in chloroform solution; these photoproducts were also characterized based mainly on X-ray crystallography. These results add to the generality of the unusual photobehavior of some dibenzobarrelene derivatives. In the solution phase photolysis of a bridgehead dichloro-substituted dibenzobarrelene diester, a novel cyclic peroxide product was obtained. This was rationalized as being derived from photolysis of the primary di-π-methane photoproduct followed by trapping of the resulting 1,3-biradical by traces of molecular oxygen present in the reaction mixture. Thus, in the present study it was found that bridgehead substituted dibenzobarrelene derivatives undergo di-π-methane rearrangement via their T₁ states as expected, but that their S₁ states may undergo unusual rearrangements to produce cyclooctatetraene derivatives with unexpected structures, and dibenzopentalene derivatives in some cases. / Science, Faculty of / Chemistry, Department of / Graduate

The purpose of this thesis is to analyze the thermochemical properties of solutes in nonelectrolyte pure solvents and to develop mathematical expressions with the ability to describe and predict solution behavior using mobile order theory. Solubilities of pesticides (monuron, diuron, and hexachlorobenzene), polycyclic aromatic hydrocarbons (biphenyl, acenaphthene, and phenanthrene), and the organometallic ferrocene were studied in a wide array of solvents. Mobile order theory predictive equations were derived and percent average absolute deviations between experimental and calculated mole fraction solubilities for each solute were as follows: monuron in 21 non-alcoholic solvents (48.4%), diuron in 28 non-alcoholic solvents (60.1%), hexachlorobenzene (210%), biphenyl (13.0%), acenaphthene (37.8%), phenanthrene (41.3%), and ferrocene (107.8%). Solute descriptors using the Abraham solvation model were also calculated for monuron and diuron. Coefficients in the general solvation equation were known for all the solvents and solute descriptors calculated using multilinear regression techniques.

No description available.

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.