Thesis (Ph. D.)--University of Wisconsin, 1966. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographies.

Thesis (M.Ch.E.)--University of Delaware, 2006. / Principal faculty advisor: Jingguang G. Chen. Includes bibliographical references.

Thesis (doctoral)--Swedish University of Agricultural Sciences, 2006. / Thesis documentation sheet inserted. Appendix reprints four papers and manuscripts co-authored with others. Includes bibliographical references. Also partially issued electronically via World Wide Web in PDF format; online version lacks appendix.

Thesis (Ph.D.) - University of Queensland, 2005. / Includes bibliography.

Thesis (Ph. D.)--Oregon Graduate Center, 1986.

Thesis (Ph. D.)--Massachusetts Institute of Technology and Woods Hole Oceanographic Institution, 1985. / Bibliography: p. 218-234.

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The crystal structure of the complex 2SbCl3.p-xylene (space group: P21/c; a=9.13Å, b=8.44Å, c=12.79A, β=125°21') was investigated at low temperatures, and it proves to be a layer structure with packing p-xylene molecules. The compound C5H5NH+ Sbcl4− (space group; C2/c; a=13.12Å, b=13.07Å, c= 7.44Å, β =122°19') was identified as a hydrolysis product of' the Sbcl3/pyridine system by means of a partial structure analysis. The complex 2Sbcl3.C5H5N (space group: Pca21; a=26.14Å, b=11.93Å, o=7.51Å) was prepared and its structure elucidated. Its general structural features include an infinite Sb - C1 chain, pyridine ligands attached to the antimony atom, and the presence, in addition, of a "solvating" pyridine molecule. The complex 2Sbcl3.C5H5N (space group; P1; a=10.93A, b=8.92Å, c=9.30Å, ∝ = 106°48', β = 192°48', ⋈ = 116 °36') was prepared. This has an extensively bridged Sb - Cl system and non-bonding pyridine molecules, occurring in alternate layers. The complex SbCl3.C5H5N (space group: P21/c; a=13.00Å., b=17.87Å, c=12.17Å, β=121°11') was prepared.

This thesis reports the investigation of liquid-to-gas and liquid-to-solid phase transitions of liquid hydrocarbon fuels and their ethanol blends, both in the bulk phase and as single droplets. The key point has been to develop an understanding of the fuels' macroscopic behavior by studying them at the molecular and at the single droplet level. A key work in this thesis is the investigation of different ratio ethanol/gasoline blends at the molecular level. At the macroscopic level, the vapor pressure, and hence the evaporation of the blends, is influenced by the strength of intermolecular interactions. Thus, information on the molecular interactions between ethanol and gasoline are inferred by using IR and excess IR spectroscopy. The spectroscopic data suggest that the hydrogen bonding between ethanol molecules is weakened upon gasoline addition, but the hydrogen bonds do not disappear. This can be explained by a formation of small ethanol clusters that interact via Van der Waals forces with the surrounding gasoline molecules. In addition, Raman spectroscopy is performed on the same blends, and the Raman spectra are compared with the IR ones. Two different approaches for data evaluation, with the scope of determining the ethanol content in the blends, are tested and compared: Firstly, the calibration of the intensity ratio of characteristic peaks as function of composition; secondly, a principal component regression (PCR). Both methods are found to have comparable uncertainty. For the evaluation of the Raman spectra, the PCR method yielded better accuracy than the intensity ratio approach. In addition, a detailed investigation of the influence of noise in the signal is presented. When the full IR spectra were evaluated by PCR, even high noise levels did not reduce the measurement accuracy significantly. Later, with the aim of studying the evaporation dynamics of fuel blends, at the single droplet level, electrodynamic balance (EDB) and optical tweezers are used to trap ethanol/gasoline droplets, containing different ethanol percentages. A longer lifetime is observed for droplets containing a greater fraction of ethanol. In order to explain the experimental evaporation trends obtained, a theoretical model is used to predict the evaporation rates of pure ethanol and pure gasoline droplets in dry nitrogen gas. Also a theoretical estimation of the saturation of the environment, with other aerosols, in the tweezers is carried out. Lastly, the liquid-to-solid phase transition of some long chain alkanes, commonly present in diesel or gasoline, is investigated both at the molecular and at the single droplet level. Firstly, by using Raman spectroscopy the solidification of these hydrocarbons in the bulk phase is observed. Distinctive features associating the solid even hydrocarbons to a triclinic structure and the odd ones to an orthorhombic structure can be observed in the spectra. Secondly, the liquid-to-solid phase transition of single hydrocarbons droplets is investigated. Freezing time and surface area resulted to be inversely proportional in dodecane droplets. This might suggest a surface freezing mechanism. Furthermore, differences in the scattering patterns, depending on the freezing mechanism, are pointed out. Droplets freezing homogeneously show a different scattering pattern with respect to droplets that froze heterogeneously.

D.Sc. (Chemistry) / Two different projects with the central theme of oxidation are discussed, namely the ozonation of saturated hydrocarbons and the total synthesis of an unusual steroid glycoside. The oxidation of saturated hydrocarbons by ozone with the so-called dry ozonation technique was investigated. This study led to the development of improved procedures in which the rate, yield and selectivity of the reaction between ozone and various saturated substrates could be controlled. Subsequently the dry ozonation of a broadspectrum of long straight chain saturated hydrocarbons, including waxes, was investigated. Reaction with these highly unreactive compounds gave almost exclusively ketones as products in high yields. The average amount of keto functionalities in the products is dependent on the reaction conditions as well as the chain length of the substrate. Therefore, a reliable method has been developed for the selective oxidation of straight chain saturated hydrocarbons, a process that is of great chemical, industrial as well as commercial importance. The dry ozonation of various straight chain monoketo compounds was also studied. Poliketo compounds are mainly formed in these reactions. This investigation showed that keto functionalities in the substrates exert a deactivating effect on neighbouring methylene groups, so that oxidations do not take place at these positions. Therefore, it was possible to predict the product distribution formed during the dry ozonation of shorter chain length monoketo compounds (Cg) . An effective synthesis of an unusual steroid glycoside similar to orbicusides A-C, compounds that contain extraordinary carbohydrate and A-ring moieties, was developed. Oxidation reactions played a prominent role in this reaction sequence. A substantial effort was also directed towards obtaining the correct stereochemistry at the various stereocentres of the carbohydrate moiety. This facilitated ring closure to a final product that contained carbohydrate and A-ring moieties similar to orbicusides A-C. As a result of this work, a method was developed for the introduction of a vicinal cis-diol on the sterically hindered face of an alkene. This method is especially suited for substrates where acid labile functional groups are present.