Thesis (Ph. D.) in Chemistry--University of Maine, 2002. / Includes vita. Includes bibliographical references (leaves 199-209).

Thesis--Wisconsin. / Vita. Includes bibliographical references (leaf 119).

Thesis (Ph. D.)--University of Wisconsin--Madison, 1976. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 211-215).

Thesis (Ph. D.)--University of Wisconsin--Madison, 1950. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

No description available.

A constant temperature room has been constructed in which the thermoregulator is controlled by a temperature-sensitive resistance. A thermostat has been constructed in which the 0 temperature is controlled to within 0.001°C. A precision conductance bridge has been built in a very convenient form. Improvements include the replacement of the telephone as null detector by a cathode ray oscilloscope, and the use of a resistance-capacity phase-shift oscillator, which gives a good wave-form. An automatic recycling conductance water still has been built which regularly gives water with a conductivity less than 0.09 micromhos per cm. The conductivities of dilute KCl solutions have been measured, taking special care to prevent errors due to the adsorption of KCl on the surface of glass. Two cells were used for these measurements : a modified Jones cell, and a special conductimetric titration cell. The modified Jones cell has given results in good agreement with the generally-accepted values. The results of the conductimetric titration cell do not agree well with the generally-accepted values; the greatest difference (for the most dilute solution) is 0.4%. The reason for this is not known.

After the publication of the paper by Gledhill and Malan in which precision conductance techniques were used for the first time in the determination of the solubility of silver chloride, Dr. N.H. Perton of Christchurch College, New Zealand, wrote to Gledhill and suggested that the same methods might be rewarding if applied to the determination of the solubility of mercurous chloride. A review of the Chemical literature showed that the values for the solubility of mercurous chloride were not at all consistent. Into., p. 1

Graphite ferric chloride, C₁₂FeCl₃, was prepared by heating anhydrous ferric chloride with graphite at 305°C. The purified compound containing 53% ferric chloride was not attacked by hot 6N hydrochloric acid or 6N sodium hydroxide solutions. X-ray diffraction measurements gave a powder pattern which was distinctly different from that of either graphite or ferric chloride and from which it was apparent that no free ferric chloride existed in the compound. The separation of the graphite layer-planes was increased from 3.36 to 9.4Å by the intercalation of the ferric chloride molecules. Tests for exchange between C₁₂FeCl₃ and Fe⁺⁺⁺ ion were made using radioactive Fe⁵⁹. In no instance was any measurable exchange observed. The compound was subjected to neutron irradiation and the Szilard-Chalmers yield of separable activity calculated and identified. The separated portion contained less than 1% of the total activity and consisted of Fe⁵⁹, P³² and S³⁵, free of detectable radiation decomposition products. The active Fe portion was separated by ether extraction. The lack of exchange and the low Szilard-Chalmers yield are both attributed to the formidable steric hindrance effects which result from the configuration of the "stacked layers" structure for graphite ferric chloride. / Science, Faculty of / Chemistry, Department of / Graduate

Isotherms of the ferric chloride-graphite system have been determined at 300°C, 310°C, and 350°C. It was found that C₇FeCl₃ is formed at all three temperatures, and in addition Cl₁₂FeCl₃ is formed at 350°C. C₇FeCl₃ has been isolated by preparing it in a bomb. Mossbauer studies on it showed that electron transfer is from graphite to iron chloride, and that all of the iron is in the same oxidation state. It has been shown that intercalated ferric chloride can be reduced to ferrous chloride by hydrogen at 375°C. Studies on graphite containing ferric chloride or chromyl chloride have shown that the threshold pressure for intercalation of Br₂, ICl, or CrO₂Cl₂ is higher than for pure graphite. It has been found that the uptake of chromyl chloride by graphite is dependent on the rate of pressure increase, and that in addition natural crystals of graphite vary in their reactivity with chromyl chloride. / Science, Faculty of / Chemistry, Department of / Graduate

The isolation of nitrilohexaphosphonitrilic chloride is reported in this work, and its structure shown to be a tricyclic condensed ring. The physical and chemical properties of this molecule are unlike the monocyclic phosphonitrilic chlorides. The reasons for this are not fully understood, but are thought to involve the weakness of the central P-N bond; the crystal structure and mass spectrum of the molecule show that this central bond is long and weak. Substitution reactions, common in the monocyclic chlorides, bring about either a partial or total break-down of the tricyclic P₆N₇ skeleton. In the case of electron-withdrawing substituents (e.g. -F,OMe), complete loss of the phosphonitrilic skeleton is achieved, and, in the case of electron-donating groups (-NMe₂), substitution onto the ring brings about cleavage of one of the internal P-N bonds. The molecule that is formed during the dimethylamination of P₆N₇Cℓ₉ is unique in phosphonitrilic chemistry and its suggested structure visually emphasizes the weakness of the central P-N bond in P₆N₇Cℓ₉. A series of molecular orbital calculations on the P₆N₇Cℓ₉ molecule were carried out in this study, and it is suggested that the observed structural trends in the molecule can be attributed to the properties of the phosphorus 3d[subscript]yz orbital on the bridgehead atoms. / Science, Faculty of / Chemistry, Department of / Graduate