The kinetics for the reaction of the oxidation of acetaldehyde by chromic acid in aqueous medium has been studied in an attempt to extend the present knowledge of oxidation by chromic acid. In particular, these experiments were undertaken in order to see if there are any similarities between this reaction and the oxidation of isopropyl alcohol in aqueous medium, which other investigators have studied. The main runs were carried out at 25°, at an ionic strength of 0.3. The reaction was followed by the decrease in chromic acid concentration as determined with the Beckman Spectrophotometer. In all of the runs, the concentrations of acetaldehyde and H⁺ were in excess of the chromic acid concentrations. It was found that the oxidation of acetaldehyde is first order in acetaldehyde and first order in HCrO₄⁻, (but not strictly first order in total chromic acid). The reaction is roughly second order in H⁺. Mn⁺² has an inhibitory effect upon the rate, as has been found in the isopropyl alcohol oxidation. Because of the similarity in kinetic behavior between acetaldehyde and isopropyl alcohol, the mechanisms are probably very similar. This mechanism for acetaldehyde oxidation has been discussed in some detail. / Master of Science

In 1947, while working on the aromatic cyclodehydration of ketones to their corresponding substituted anthracenes, Vingiello (1a) attempted to prepare 9-cyclohexylanthracene using this method. It was evident in the cyclization of o-benzylcyelohexyl-phenone (I) that the hydrol (II) postulated as an intermediate could lose water in two ways, yielding two different compounds 9,10-dihydro-9-cyclohexenylanthracene (IV) and 9-cyclohexyl-anthracene (III). This is shown in Chart I. Since a carbon, hydrogen analysis gives the same result for both compounds it is obvious that some other method of identification is necessary. It is the purpose of this part of the investigation to attempt to identify the existing structure by ultra-violet absorption analysis, and formation of derivatives and also to attempt to prepare 9-cyclohexylanthracene by an unequivocal method. / Master of Science

Master of Science

The y1ide anion, lithiotriphenylphosphenylacetylmethylene was obtained by treatment of triphenylphosphineacetylmethylene with 1.2 molecular equivalents of n-butyllithium in tetrahydrofuran-hexane under a nitrogen atmosphere at -78º. This ylide anion reacted selectively with alkyl halides to form γ-substituted 13-keto phosphonium ylides. Subsequent ionization of triphenylphosphine-(3-phenylpropionyl)methylene with n-butyllithium at -78° followed by alkylation produced γ,γ-disubstituted ylides. Condensation of the ylide anion with various aldehydes and ketones afforded δ-hydroxy-β-keto ylides in reasonable yields, uncontaminated by normal Wittig products. Reaction of the ylide anion with o-phthalaldehyde resulted in terminal aldol condensation accompanied by an intramolecular Wittig reaction to give 4,5-benzotropone. The condensation of lithiotriphenylphosphineacetylmethylene with 2-cyclohexene-1-one gave the 1,2-addition product, although it could not be completely purified. Attempts to form potassiotriphenylphosphineacetylmethylene by means of potassium amide in liquid ammonia gave the unexpected product, acetonyldiphenylphosphine oxide. An earlier proposed mechanism for this reaction was partially verified by detection of benzene as a by product. An unidentified compound was isolated from these potassium amide reactions. / Master of Science

Quantitative data concerning the state of solvation of cellulose derivatives dispersed in solvent-non solvent systems is rather limited. Since such derivatives possess a high commercial importance largely because of their ability to be dispersed and regenerated from solvent-non solvent systems by manipulation of the solution phase of the system, such data are highly desirable from the purely practical viewpoint. Likewise, from the purely theoretical viewpoint, such data are desirable in the investigation of problems involving fractional precipitation techniques, studies in film and filament formation and in the elucidation or a number of similar basic phenomena of current interest. Specifically, the aim of this investigation is to study, quantitatively, the changes in solvation of a sample of cellulose nitrate in an acetone-water solvent-non solvent system as the composition of the liquid phase is varied over a range from solvent rich to solvent poor. / Master of Science

Master of Science

McWeeny has developed a method which utilizes the steepest descent technique in solving the Hartree-Fock equations. The mathematical development is presented and discussed. The method achieves convergence for several otherwise recalcitrant systems. The following systems are investigated and discussed: 1. the π-electron systems of p-benzoquinone and calicene, 2. the all-valence-electron systems of the calicene dianion, nitrobenzene and m-chloronitrobenzene, 3. the first complete SCFMO binding energy curves for the Cl₂-benzene charge-transfer complex, including several configurations, 4. studies of selectivity for the protonation of (addition of Bronsted acids to) propylene, and the chlorination of nitrobenzene and m-chloronitrobenzene (These studies proved to be far more complex than initially foreseen, and firm conclusions were not obtained.). Recommendations for further investigation of these systems are also given. / Master of Science

Master of Science

The National Aeronautics and Space Administration's Space Shuttle employs a solid rocket propellant. Combustion of the solid propellant produces hydrogen chloride as one of the major products. In this thesis, the hydrogen chloride/silica system was investigated. Silica was chosen as a model compound to represent ground debris transported into the exhaust cloud as a result of convection. The silica adsorbent was characterized by x-ray diffraction, infrared spectroscopy, and surface area. Interaction of hydrogen chloride with silica (𝔞-quartz) was studied by various techniques including adsorption/readsorption isotherms, ESCA, and calorimetry. Adsorption of hydrogen chloride at 30°C was found to be dependent on the outgas temperatures and reversibility was dependent on the reoutgas temperatures. ESCA analysis on silica after exposure to HCl. indicated the presence of chloride ion. Angular probe studies showed that the chloride ion resides on the surface of silica rather than in the bulk of the sampling region. Calorimetric work was performed to measure heats of immersion of silica outgassed at various temperatures in different concentration of hydrochloric acid. Heats of immersion were found to increase with increasing outgas temperature and concentration of acid. Similar investigation of the hydrogen chloride/silica system was then extended to ground debris samples from the Kennedy Space Center. These samples were characterized by SEM/EDAX. The amount of HCl adsorption per unit area was more than three times greater than on pure silica. Apparently, HCl has a greater affinity towards some component of the ground debris other than silica. / Master of Science

N,N’-Bis (pentafluorosulfanyl )urea was synthesized from. thiazyl trifluoride, carbonyl fluoride, and either anhydrous hydrogen chloride. Attempts at reacting the urea with ethyl malonate, malonic acid, malonyl chloride, carbon suboxide, and ethyl crotonate all failed. The urea was found to be unstable in both acidic and basic media. N,N’-Bis(pentafluorosulfanyl)malonamide was prepared from pentafluorosulfanylamine and carbon suboxide by mixing them either as gases or in a solvent. The malonamide was found to decompose with tertiary amines such as pyridine. Attempts to react the malonamide with carbonyl chloride, fluoride, and sulfide to form a barbiturate were unsuccessful. N-Phenyl-N’-pentafluorosulfanyl was prepared from pentafluorosulfanyl isocyanate and aniline. Attempts to prepare the mixed urea from pentafluorosulfanylamine and phenyl isocyanate failed. A possible product from a reaction of thiazyl trifluoride and aniline was either ΦN=S(F₂) ≡ N. Attempts to prepare N-pentafluorosulfanylurea from the reaction of SF₅NCO and NH₃ or SF₅NH₂ and HNCO failed. / Master of Science