Thesis (Ph. D.)--Ohio state University, 1928. / Autobiography.

Thesis (Ph. D.)--Columbia University, 1924. / Vita.

Thesis (Ph. D.)--Columbia University, 1944. / Lithoprinted, Edwards brothers, inc. Vita. Bibliography: p. 30-32.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1970. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

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

Thesis (Ph. D.)--Syracuse University, 2006. / "Publication number AAT 3241611."

Thesis (Ph. D.)--University of Washington, 2000. / Vita. Includes bibliographical references (leaves 100-108).

A major industrial use of pyrotechnic compositions is as delay fuses in electric detonators. Suitable delay times may be achieved through (i) choice of chemical components (ii) adjustment of composition of the system chosen and, finally, (iii) adjustment of the length of fuse used. This study forms part of a survey of binary fuel/oxidant combinations in an attempt to provide some fundamental information on the first step above: (i) choice of chemical components. The complete survey has included studies of a single fuel in combination with one of a variety of oxidants, and studies of the oxidation of one of several different fuels separately by barium peroxide and strontium peroxide. This study is part of this second approach and the fuels chosen were iron and zinc powders, mainly for chemical reasons (including the potential for use of thermomagnetometry on the iron systems), but also for possible environmental advantages. The mixed oxide products of pyrotechnic combustion could also have some scientific and/or commercial value. The techniques used included thermal analyses of mixtures and their individual components, and measurements of temperature-time profiles during combustion. Thermodynamic and kinetic information was obtained under a variety of conditions and scanning electron microscopy and X-ray diffraction and microprobe analyses provided additional information. Possible mechanisms of reactions are discussed in detail. The practical conclusions were that any potential use which the Fe/peroxide systems may have as delay compositions, with burning-rates of from 3-30 mm s⁻¹, is offset by the susceptibility of the oxidants to reaction with water and CO₂ in the atmosphere. The Zn/BaO₂ and Zn/SrO₂ systems did not burn under compaction, and combustion of uncompacted powders was erratic. Zinc liquid (and probably zinc vapour) take part in the reaction and the gaseous nature of the combustion makes zinc-fuelled pyrotechnic systems unsuitable for delay applications. All the techniques used showed the heterogeneity of the solid residues of combustion. If these residues were to be of any value, they would need further conventional treatment involving grinding of the residue, possible adjustment of compositions, and calcining to produce uniform materials.

The possibility of separating homologous phenols by liquid-liquid extraction with aqueous sodium hydroxide has been considered. In particular, phenol-o-cresol mixtures have received attention and the system phenol, o-cresol, water, and sodium hydroxide has been defined both with respect to the boundary of the two-phase region and the phase equilibria involved. Some qualitative and quantitative considerations have been given to possible extraction operations. It is concluded that extraction in the quaternary system is likely to be attractive only in the case of particular alkaline phenolic feeds. / Applied Science, Faculty of / Chemical and Biological Engineering, Department of / Graduate

Petroleum, one of the most complex mixtures on Earth, has been extensively studied for decades. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and the ultrahigh resolution it provides, however, has dramatically transformed our understanding of petroleum by providing detailed molecular characterization. Nevertheless, many properties of crude oil, and the molecular characteristics that drive them, remain poorly understood, especially in regards to the role and impact of oxygen in oils. In the work presented here in-depth characterization of oxygen in petroleum is explored, to augment understanding of petroleum behavior due to oxygen. Although current FT-ICR MS instrument easily provides ultrahigh resolution, there is a constant for more as the complexity of petroleum means there is also some molecule just out of the obtainable analytical reach. Spectral segmenting on petroleum, in which narrow mass windows are acquired instead of all masses at once as in conventional broadband mass spectrometry, was performed in order to increase resolution and dynamic range to explore the species typically “missed” in conventional FT-ICR MS analysis. From the performance improvements provided by spectral segmenting, it was observed that molecules with high heteroatom content, including extensive oxygen content, are observed at low abundances, and that they may play a critical role in petroleum behavior despite their low abundances. Because of this the behavior of oxygen in petroleum is further explored. Naphthenic acids (carboxylic acids) in petroleum are known to be corrosive, yet no known correlation between naphthenic acid content and specific petroleum corrosivity has ever been established, other than more acidic crudes are generally more corrosive. In one proposed corrosion mechanism, a ketone is formed with a structure related to the structure of the corrosive acid. A method to detect and characterize these ketones in petroleum is developed and validated with model acids in an oil matrix, and then applied to more complex mixtures of naphthenic acids and acids derived from a vacuum gas oil to provide insight into which acids are most corrosive. Oxygen in petroleum plays an important role when petroleum is exposed to the environment. FT-ICR MS is used with traditional gas chromatography mass spectrometry (GC/MS) techniques to highlight how it is possible to use oxygen, in addition to other properties and heteroatoms, to track the relation of petroleum as it flows from reservoir to an oil seep and ultimately at the sea surface. In addition to highlighting petroleum subterranean connectivity, an initial characterization is obtained from which information about how petroleum transforms as it migrates is provided. Asphaltenes are perhaps the most poorly understood fraction of petroleum, with their molecular structures under intensive debate. Analysis by high resolution GC/MS of pyrolysis products of “classical” asphaltenes from bitumen and of “environmental” asphaltenes from a tarball is performed. It is found that high resolution is necessary for accurate characterization of even “simple” pyrolysis products, and that environmental asphaltenes are enriched in oxygen relative to the classical bitumen asphaltenes. The exact oxygen structures observe also provides insight into the weathering processes that the tarball underwent in its formation. / A Dissertation submitted to the Department of Chemistry and Biochemistry in partial fulfillment of the requirements for the degree of Doctor of Philosophy. / Spring Semester 2018. / January 17, 2018. / Corrosion, FT-ICR MS, GC-MS, Petroleum, Solid Phase Extraction / Includes bibliographical references. / Alan G. Marshall, Professor Directing Dissertation; Jinfeng Zhang, University Representative; Christian Bleiholder, Committee Member; Wei Yang, Committee Member; Ryan P. Rodgers, Committee Member.