Physical Sciences and Mathematics Commons^™

Thermochemical Hydrogen-Deuterium Isotope Effects, Wayne C. Duer

Doctoral Dissertations

"The heats of solution at 25.0 ± 0. 1°C for each member of hydrogen-deuterium isotopic pairs (chloroform/chloroform-d, acetone/acetone-d₆, methanol/methanol-d₁, ethanol/ethanol-d₁, and water/heavy water) have been determined as a function of molality in a variety of solvents. The heats for most of the systems could be described as a linear function of average molality with an average deviation in fit of less than one per cent. Using these linear equations, heats of solution at infinite dilution were obtained by extrapolation to zero molality. The heats of solution at infinite dilution of the hydrogen containing compounds were subtracted from those of the …

The Reaction Of N-Sulfinylamines With Diazoalkanes, Harry R. Musser

Doctoral Dissertations

"The photochemical decomposition of diphenyldiazomethane in the presence on N-sulfinylamines leads to ketimines. By-products include tetraphenylethylene, benzophenone, thiobenzophenone, and benzophenone azine. This reaction is the first example of carbene addition to a non-carbon containing multiple bond system. Evidence indicates that the carbene adds to the N=S bond of the N-sulfinylamine to give the corresponding thiaziridine-S-oxide which spontaneously decomposes to give ketimine and SO. In the dark N-sulfinylaniline catalyzes the decomposition of diazoalkanes to carbenes. This decomposition presumably takes place through a thiatriazole-1-oxide intermediate. The carbene then reacts either with N-sulfinylaniline to form ketimine, after loss of SO, or with diazoalkane …

Substitution And Photolytic Rearrangements In Three-Member Ring Compounds, Joseph Terril Bohanon

Doctoral Dissertations

"An investigation into the substitution and photolytic rearrangements of 1,2,3-triphenylcyclopropenes was conducted. Triphenylcyclopropenyl t̲-butyl ether was found to undergo alkyl group exchange with refluxing methanol, ethanol, or 2-propanol to yield the corresponding 1,2,3-triphenylcyclopropenyl alkyl ether when a trace impurity of a 1,2,3-triphenylcyclopropenium halide is present to catalyse the reaction. This forms hydrogen halide with solvent. Upon standing for long periods of time, the 1,2,3-triphenylcyclopropenyl ethers were observed to partially rearrange to new products. A sample of 1,2,3-triphenylcyclopropenyl methyl ether was subjected to photolysis in hexane and yielded 3-methoxy-1,2-diphenylindene, 2,3- diphenylindenone, tolane, benzoic acid, 1,2,3-triphenylpropen-1-one and a polymer. Samples of 1,2,3-triphenylcyclopropene, …

The Electrochemical Behavior Of The Lead-Thallium System In Acidic Sulfate Solutions, Pedro Juan Aragon

Doctoral Dissertations

"Although the literature involving the corrosion of pure lead in sulfuric acid solutions is extensive, such studies still constitute an active field of investigation and debate. Much of the effort expended on this subject is due to the need of a better understanding of the reaction in lead storage batteries as well as of the mode of electrocrystallization processes. The resistance of lead to attack by sulfuric acid renders it an important coating material in this media. It is also often used in electrochemical synthesis because of its overvoltage characteristics. Unfortunately its mechanical properties are poor, and many ways have …

Identification Of Decomposition Products Of Tropyl Azide And Interaction Of Tropylium Ion With Nucleophiles, James Joseph Ward

Doctoral Dissertations

"An investigation of the structures of several of the products resulting from the decomposition of tropyl azide (I) and of the chemistry of related processes has been undertaken. Irradiation of samples of (I) in the vapor phase with low intensity UV G.E. Sun Lamps furnished a low melting white solid identified as tropyl troponimmonium azide (II). Earlier experiments of a similar nature reported to furnish (III) were not repeatable (Chem. Commun 276 (1967))...

Upon standing, solutions of (I) slowly formed troponimmonium azide (IV) in the cold (J. Chem. Soc. (D), 220 (1970)). The structures (II) and (IV) were confirmed by …

A Fundamental Investigation Of The Gas Phase Polymerization Of Styrene And Vinyl Type Monomers In A Low Power Inductively Coupled 4 Mhz Rf Plasma, L. F. Thompson

Doctoral Dissertations

"A study has been made on the plasma polymerization of styrene and vinyl type monomers in a cold, low power, inductively-coupled RF plasma. All vinyl type monomers yielded an insoluble, crosslinked film which was slightly colored. A kinetic study is reported for styrene. The effects of power level, bleed rate of monomer, pressure and reactor geometry on the rate of polymer formation are reported. A mechanism is postulated for plasma polymerization. It was found that the initiation step was the rate controlling step and that the reaction followed a cationic polymerization scheme. Both crosslinking and discoloration of the polymers occur …

The Electrochemical Oxidation Of 1-Pentyne On Platinum And Gold, Michael Jensen Danielson

Doctoral Dissertations

"The anodic oxidation of 1-pentyne was studied at 70°C on Pt and Au electrodes in solutions of H₂SO₄, K₂SO₄, K₂CO₃, and KOH. Pt was studied in a pH range of 0.35 - 12.7 and Au in a range of 10.9 - 12.7. Reaction rates were measured as a function of potential, pH, temperature, and 1-pentyne partial pressure. The coulombic efficiencies for the oxidation to CO₂ were 77 percent in 1 N H₂SO₄ and 69 percent in 1 N KOH on Pt and 43 percent in 1 N KOH on Au. The kinetic parameters on Pt were [partial derivative]V/[partial derivative]log i …